HAND-BOOK
OF
CHEMISTRY
3Y
LEOPOLD GMELIN
QD
28
G573
VOL. XVII.
CAYNIDISH SOCIETY
A 589740
1

ARTES
1837
SCIENTIA
VERITAS
LIBRARY
OF THE
UNIVERSITY OF MICHIGAN
E-PLURIBUS-UNUM
TUROOR
SI-QUAERIS PENINSULAM AMOENAM
CIRCUMSPICE
:
ļ
QD
23
G573
WORKS
OF THE
CAVENDISH SOCIETY.

FOUNDED 1846.
HAND-BOOK
OF
CHEMISTRY.
BY
LEOPOLD GMELIN.
VOL. XVII.
ORGANIC CHEMISTRY.
VOL. XI.
ORGANIC COMPOUNDS CONTAINING FROM 34 TO 46 ATOMS OF CARBON.
TRANSLATED BY
HENRY WATTS, B.A., F.R.S., F.C.S.
LONDON:
HARRISON, 59, PALL MALL.
Bookseller to the Queen, and H.R.H. the Prince of Wales.
MDCCCLXVI.
LONDON:
PRINTED BY HARRISON AND SONS, ST. MARTIN'S LANE.
:
"
}
:
CONTENTS OF VOL. XVII.
(VOL. XI OF ORGANIC CHEMISTRY.)
APPENDIX TO 34-CARBON COMPOUNDS (continued.)
Blue and Red Colouring Matters (continued.)
Blue and Red Colouring Matters of Roots (continued)
Leaf-red
Leaf-green or Chlorophyll
****
Green Colouring Matters.
Phyllocyanin and Phylloxanthin....
Older Investigations by Berzelius :
...
....
442
....
....
....
a. Leaf-green having the colour of fresh leaves
B. Leaf-green having the colour of dried leaves....
y. Third modification of Leaf-green
Green colouring matter of Euchema spinosum, Cetraria islandica, &c.
Green colouring matter of Thistle-tops, Artichokes, and undeveloped
Flower-buds
Colouring matter of Monotropa Hypopitys·
....
....
Page
1
1
3
4
567
7
7
7
00
8
COMPOUNDS CONTAINING 36 AT. CARBON.
Primary Nucleus C36H18.
Retene, C36H18
Retene with Picric acid....
44.
Retene with Picric acid and Benzene
8
...
10
11
Conjugated Compounds of Retene.
Sulphoretene, C36H20S2O8 = C36H18,2SO³,2HO
Retene-bisulpholic acid, C36H18S4012 C36H18,4SO3
Baryta-salt, C36H16Ba²S4O¹². — Lead-salt, C36H16Рb²S4O¹2……..
VOL. XVII.
-
b
0441
4.4
11
12
13
招
​vi
Helenene, C36H24 ?
Carotin, C36H24,02
CONTENTS.
Primary Nucleus C36H24.
...
....
Chlorine-nucleus C36C14H20.
Quadrichlorocarotin, C36C14H20,02
Page
13
14
16
....
Primary Nucleus, C36H26; Oxygen-nucleus C36H2006.
Alkanet-red? C36H2008
=
C36H2006,02
40
Appendix to Alkanet-red :
1. Chica-red
17
18
...
***
2. Red colouring matter of the root-bark of Lithospermum arvense ……..
3. Resinous red of Spanish Pepper
4. Nucin
20
20
....
20
...
Oxygen-nucleus C36H16010.
Cetraric acid, C36H16016 C36H10,06
=
....
Cetrarate of Ammonia, 2NH3,C36H16016
Cetrarate of Lead, C36H14Pb2O16
....
Oxygen-nucleus C36NH1906.
21
24
...
24
Pelosine, C3NH2106
=
C36NH¹906,H2
....
....
Hydrochlorate, C36NH2106, HCl.
2aq.
....
Chromate, C36NH2¹06,2CrO³ +
....
Chloro-aurate. Chloroplatinate, C36NH2106, HCl,PtCl²
Appendix to Pelosine: Pelluteïne
Codeine, C36NH2106
C36NH1906, H2
Amorphous Codeine
Bihydrated Codeine, C36NH2¹06,2HO
Teriodide of Codeine, C36NH2¹06,31 ....
....
Carbonate of Codeine. - Phosphate, C36NH21O6,3HO,PO5
Sulphate of Codeine, C36NH2106,HO,SO³
Iodate of Codeine
....
....
Hydriodate of Codeine, C³NH³¹Q6,HI + 2aq.
Perchlorate of Codeine
....
Hydrochlorate of Codeine, C36NH²¹O6,HCl + 3aq.
Nitrate of Codeine, C3NH2¹O¤,HO,NO5
25
....
26
27
....
27
.....
28
30
...
31
....
32
32
33
****
33
33
33
....
33
34
34
....
34
35
Chromate, Mercury-salt, and Gold-salt of Codeine
Chloroplatinate of Codeine, C6NH2¹06,HCl,PtCl²
Chloropalladite, Hydrocyanate, Hydroferrocyanate, and Hydroferri-
cyanate of Codeine ....
....
CONTENTS.
Hydrosulphocyanate of Codeine, C36NH2¹06,C²NHS²
Acetate of Codeine
Oxalate of Codeine, C36NH2¹06,C²Ã²04
Tartrate, Gallate, and Tannate of Codeine ....
Compounds of Codeine with Alkalis
....
....
Oxy-iodo-azo-nucleus C30NH¹712O6.
Biniodocodeine, C36NH191206 = C36NH¹71206,H²....
Oxy-bromo-azo-nucleus CNH18ВrО6.
Bromocodeine, C36NH20BrO6 = C36NH18BrO6,H²
Hydrobromate, C36NH20BrO6,HBr + 2aq.
vii
Page
35
36
....
****
36
36
...
36
Hydrochlorate. - Chloroplatinate
Oxy-bromo-azo-nucleus C6NH¹¤Br³O.
36
36
36
38
38
38
•
....
39
Terbromocodeine, C36NH¹³Br³06
=
C36NH16Br306,Ħ²
Hydrobromate, C36NH18Br³06,3HBr
Hydrochlorate. - Chloroplatinate
....
Oxy-chloro-azo-nucleus C36NH18C106.
Chlorocodeine, C36NH20C1O6 C36NH¹8C106,H²
Hydrated Chlorocodeine
=
...
Sulphate, C36NH2°C10°,HO,SO³ + 4aq.
Chloroplatinate, C36NH20 C106,HCl,PtCl²
Oxy-nitro-azo-nucleus C36NH18X06.
Nitrocodeine, C36N2H20010
C36NH18X06,H²
Sulphate, C36NH²ºXO6,HO,SO³. — Hydrochlorate.
nate, C36NH20XO6,HCl,PtCl³. — Oxalate
****
Conjugated Compounds of Codeine.
Bicyanocodeine, C40N3H2106 = C36Сy³AdH¹706,H²
Ethyl-codeine, C40NH2506
=
C36N (C4H5) H1806,H2
O
Hydriodate, C40NH2506,HI
Primary Nucleus C36H28.
Sycocerylic Alcohol, C6H30O2 = C36H28,H2O2
Acetate of Sycoceryl, C40H3204 С36H29О,C4H³ ³
Benzoate of Sycoceryl, C50H34O4 = C36H29O,C¹4H50³
Sycoretin....
****
....
...
39
39
40
40
40
Chloroplati-
41
42
***
42
42
A
43
44
45
...
46
....
b2
Vili
CONTENTS.
Axinic acid, ?C36H2804 C36H28,04
=
Aginin. — Age or Axin ....
Oxygen-nucleus C36H18010¸
Usnic acid, ?C36H¹014 — C36|18(10,04
....
Usnates of Ammonia. - Usnate of Potash, C36H¹7KO¹4
Usnate of Soda. — Usnate of Baryta, C38H¹BaO¹¹
禽畜
​....
....
Page
46
47
48
51
51
Usnates of Lead, Silver and Iron. - Usnate of Copper, C36H¹7CuO¹* 51
Oxy-azo-nucleus C36N2H22O4.
Menispermine, ?C36N2H2404 C36N2H2204,H²
Sulphate
Paramenispermine.....
=
....
52
ུ་
52
53
Primary Nucleus C36H30
Hydrocarotin, C36H3002 C36H3002
DI
Iodine-nucleus C361H29.
Iodo-hydrocarotin, C36IH29O2 = C36IH29,O²
Bromine-nucleus C36Br³H²7.
Terbromo-hydrocarotin, C36Br³H270² C36 Br³H27,02
=
Chlorine-nucleus C36C14H26.
Quadrichloro-hydrocarotin, C36C14H2602
C36C14H26,02 ....
Primary Nucleus C36H32; Oxygen-nucleus C36H2606.
Glycyrretin ? C36H26O8
Glycyrrhizin ? C48H36010
C'36H2606,02
Glucoside of Glycyrretin.
...
....
Compounds of Glycyrrhizin with Metallic Oxides
Appendix to Glycyrrhizin.
Ononis-glycyrrhizin ? C36H22O16
****
Oleic acid, C36H3404
Primary Nucleus C36H34.
=
C36H34,04....
Sources, Preparation and Purification
....
53/
...
54
....
55
14
55
56
14
....
60
62
62
63
88893
CONTENTS.
ix
Page
Properties
Decompositions
Oleates: SOAPS
....
Oleate of Ammonia
*
...
....
Oleates of Potash: a. Mono-acid, C36H33K04
Bi-acid
....
Oleate of Soda, C36H39NaO4. — Soda-soap
D
Oleates of Baryta, C6H33BaO¹ and C36H33BaO4, C36H3404
....
66
64
65
69
69
69
70
****
70
71
Oleate of Strontia, C36H33SrO4.- Oleate of Lime, C6H33CaO4 71
Oleate of Magnesia, C6H33MgO¹. Oleate of Chromium.
Oleate of Zinc, C36H33ZnO4. Oleates of Lead, C36H33PbO4,
PbO, and C36H33PbO4. - Oleate of Iron
Oleate of Cobalt. - Oleate of Nickel. Oleate of Copper,
C¹36H 33 CuO+. Oleates of Mercury: Mercurous salt,
C36H33Hg204. - Mercuric salt, C36H33Hg04. Oleate of
Silver
....
D
Table of the melting-points of mixtures of Oleic and Margaric acids,
according to Chevreul
....
Acids nearly identical with Oleic Acid.
1. Walter's Moringic Acid. 2. Filixolic acid
Elaïdic acid, C36H³¹O¹ C36H34,04
=
....
Elaïdates: Ammonia and Potash-salts
....
***
Soda-salts, C36H33 NaO4 and C36H33 NaО4,C36H3404
72
73
74
22:
74
74
77
77
77
....
....
78
Baryta-salt, C36H33BaO4. — Magnesia-salt. — Lead-salt,
C36H33PbO4. — Silver-salt, C36H³³ AgO¹
Stearidic acid, C36H34O4
...
....
C56H³³AgO¹
Appendix to Oleic Acid, and Supplement to xiii, 374.
...
Azelaic acid, C18H1608
Azelaates
****
....
....
....
38
79
80
Conjugated Compounds of the Primary Nucleus C36 H34.
Oleate of Methyl, C38H3604
=
=
C2H30,C363303
C2H30,C36H3303
Elaïdate of Methyl, C38H3604
Oleate of Ethyl, C40H3O4 C4H5O,C36H3303
Elaïdate of Ethyl, C40H3804 C4H5O,C36H3303
Monolein, C42H408
C6H7O5,C36H3303
Diolein, C78H74012
C6H8O6,2C36H3303
Triolein, C14H104 (12
=
C6H503,30363303
....
Appendix to Triolein.
I. Decomposition of Olive-oil by Oil of Vitriol
....
1444
82
....
82
....
83
84
....
84
85
....
85
87
*
CONTENTS.
a. Oleosulphuric acid
b. Margarosulphuric acid
c. Metamargaric acid
d. Metoleic acid
e. Hydromargaritic acid
f. Hydroleic acid
g. Hydromargaric acid
....
....
....
II. Fatty Oils occurring in Nature
1. Olive oil
2. Almond oil ....
....
....
...
****
....
Page
88
88
***
88
88
88
....
89
....
89
90
4.
91
92
....
3. Fatty Ant oil.
4. Oil of Anacardium orientale.—5. Oil of
the seeds of Argemone mexicana. - 6. Oil of Aspidium Filix
mas
....
....
....
....
93
....
7. Oil of the Almonds of Azadirachta indica. 8. Oil of Barley-
meal. 9. Oil of Beech-nuts.- 10. Oil of the seeds of Butea
frondosa. 11. Oil of the seeds of Calophyllum inophyllum. -
12. Oil from the nuts of Canarium commune. 13. Oil of the
almonds of Cassuvium pomiferum. 14. Oil of Cotton-seed
....
....
....
94
4.
95
96
15. Croton oil.-16. Oil of the seeds of Daphne Mezereum.
17. Oil of Earth-almond
18. Oil of Eggs. — 19. Oil of Ergot-of-rye. — 20. Oil of Euphorbia
Lathyris
21. Hazel-nut oil. 22. Oil of Horse-chestnuts. - 23. Oil of the
fruit of Mesua ferrea. -- 24. Oil of Morels. — 25. Oil of the
seeds of Nigella sativa. 26. Fatty oil of the root and seeds
of Paris quadrifolia. - 27. Oil of Parsley
28. Oil of Plum-kernels. - 29. Oil of the seed of Pongamia glabra.
30. Sesame oil. — 31. Fatty oil of Silkworms: -32. Spindle-
tree oil
...
97
98
....
=
Elaidin, C4H10412
Mannitic Bioleate, C84H76014 C12H¹008,2C36H3303
33. Oil of the seeds of Sterculia fœtida. 34. Oil of various species
of Thea or Camelia. — 35. Fatty oil of Truffles ....
99
C6H503,3C36H3303
99
....
A
100
Bromine-nucleus C36Br2H32.
Bromoleic acid, C36Br²H³2,04
101
....
Chlorine-nucleus C36C12H32.
Chloroleic acid, C36C12H32,04
101
Oleamide, C36NH3502
Elaidamide, C36NH3502
Amidogen-nucleus C36 Adн33.
С36 AdH33,02
101
=
С36 дан 33,02
102
.
CONTENTS.
xi
"
Primary Nucleus C36H36.
Page
Stethal, C36H3802
=
C36H 36, H2O2.
C36H36,04
Stearic acid, C36H3804
Stearates
=
Stearate of Ammonia
...
....
Stearate of Potash. A. Mono-acid, C36H35KO+
B. Bi-acid, C36H35 KO4, C36H360±
C. Triacid and Quadriacid?
Stearate of Soda: A. Mono-acid, C36H35 NaO+
B. Biacid, C6H35 NaO+,C6H3604
**
....
164
94
103
...
103
107
107
108
109
109
...
109
110
110
110
....
Stearate of Baryta, C36H35BaO¹
Stearate of Strontia, C3H3SrO¹
Stearate of Lime, C36H35CaO¹.
Stearates of Lead: A. Biplumbic, C6H35PbO¹,PbO. — B. Mono-
Stearate of Magnesia, C6H3MgO 111
plumbic, C36H35PbO+
Stearate of Copper, CH³CuO±
Stearates of Mercury
Stearate of Silver, C36H35 AgO4
4994
+4
111
112
1
112
112
Melting points of mixtures of Stearic acid and other fatty acids 113
Conjugated Compounds of the Primary Nucleus С36Ħ36.
Stearate of Methyl, C3H8O4
>
=
C²H³O,C36H3503
C+H50, C36H3503
Stearate of Ethyl, CH¹O±
Bistearate of Ethylene, C76H7408
Monostearin, C42H4208
=
Distearin, C78H78012
=
C4H402,2C36H35O3
C6H705, C36H3503
C6H8O6,2C36H3503
Tristearin, C1 H110 12 C6H5O3,3C36H3503
1040
....
Stearochlorhydrin, C42H¹¹CIO6 C6H6C103,C36H3503
Stearate of Amyl, C6H4604
=
C10H¹¹O,C36H3503
=
Benzostearic Anhydride, C50HO6 C¹4H50³, C36H 350³....
Stearate of Orcin, C50H4206 C¹4H703,C36H3503
=
Stearate of Capryl, C52H52O+
Stearate of Opianyl, C92H78O12
Stearate of Camphyl, C56H5204
Bistearate of Pinityl, C8+HO¹4
C16H170,C36H303
=
=
****
114
*
115
116
117
$114
....
117
118
122
123
123
124
+
124
124
125
....
125
....
C12H12O10,4C36H3503
126
126
126
127
127
128
C12H806,4C36H3503
128
128
129
C20H8O6,2C36H3503
C20H¹70,C36H 3503
C12H10OS, 2C36H3503
Quadristearate of Pinityl, C156H152022
=
Bistearate of Quercityl, CsH800¹4 C12H1008,2C36H3503
Bistearoglucose, C84H7SO¹4 C12H808,2C36H3503
044
Quadristearate of Mannityl, C156H152022 C12H22O10,4C36H3503
Sexstearate of Mannityl, C228H216(22 C¹2H6O+,6C36H35O3
Bistearate of Dulcityl, Cs+H800¹4 = C12H10O8,2C36H3503
Quadristearate of Dulcityl, C156H14SQ18
=
Stearate of Cetyl, C68H68O1 C32H330, C36 H3503
Stearone, C70H7002
C36H 360², C3+H3±
xii
CONTENTS.
Bromastearone, C70Br2C6802
Stearic Anhydride, C72H7006
Page
=
C36H3602, C34 Br2H32....
C36H3503, C36H3503
130
...
131
Oxygen-nucleus С36H³40%.
Ricinoleic acid, C36 H3406
C36H3402, 04
Ricinoleate of Baryta, C36H33BaO6
Ricinoleate of Strontia, C36H³³SrO6;
....
- of Lime, C36H33 CaO6;
Magnesia, C36H33MgO¤; of Zinc, C36H33ZnO¤
Ricinoleate of Lead, C36H33PbO6; — of Silver, C36H33 AgО¤
Ricinelaïdic acid, C36H3402,04
Ricinelaïdates, C36H33MO6
TA
....
Appendix to Ricinoleic and Ricinelaïdic Acids.
I. Castor oil
19.
....
R
3.
2. Oil of Jatropha Curcas: Oleum Cicinum
3. Oil of the fruit of Jatropha glauca and J. glandulifera
4. Spongy residue from the dry distillation of Castor oil
5. Pyroricinic acid, C36H3407? Lead-salt, C36H3PbO¹ ?
6. Ricinine
...
Ricinoleate of Ethyl, C40H3806
Ricinelaïdate of Ethyl, C40H³O6
Ricinelaïdin, C78H720¹4
=
=
C4H50, C36H3305
C450,С36 335
C6H604,2036H3305
131
133
....
of
134
135
135
....
136
137
140
....
***
141
141
***
142
་་
143
143
144
144
Bromine-nucleus C38BrH35.
Bromostearic acid, C36BrH35,0* ....
145
Bromine-nucleus C3Br2H34.
Bibromostearic acid, C36Br2H34,04
146.
Chlorine-nucleus C38C110026
Chlorostearic acid, C36C11026,0*....
→
....
146
Stearamide C36NH3702
Stearanilide, C48NH4102
=
Amidogen-nucleus C36 Adͳ.
=
C36 AdH35,02
C3(NH,C2H5)H3,O?
Oxy-amidogen-nucleus C36 AdH³O².
Ricinoleamide, C36NH3504
***
C36 AdH3302,02;
Ricinelaïdamide, C36 NH35O4 = C¹36 AdH3302,02
....
44
147
147
147
148
CONTENTS.
xiii
1
COMPOUNDS CONTAINING 38 AT. CARBON.
Primary Nucleus C3820; Oxygen-nucleus C³Œ¹¹06.
Vulpic acid, C8H14010 C38H1406,04
Vulpate of Ammonia, C³³H¹³ (NH¹)O¹º + 2aq.
Vulpate of Potash, C38H13KO10
Vulpate of Baryta, C38H13BaO10
13
Vulpate of Silver, C38H¹³ AgO¹0
....
Page
150
150
...
151
151
....
ADDENDA TO vol. xiii., p. 8.
1. Alphatoluic acid, C¹6H8O4
Silver-salt, C¹6H7AgO¹....
2. Oxatolylic acid, C32H1606
Baryta-salt, C32H15BaO6.
salt, C32H1 AgO
Lead-salt, C32H¹5PbQ6 + 4aq. - Silver-
Oxatolylate of Ethyl, C36H2006 = C4H5O,C32H1505....
....
....
Primary Nucleus C36H24; Oxygen-nucleus C36 H2004.
Guaiaconic acid, C36H2010
=
C36H 2004,06 ....
...
Lead-salt, C36H¹8Pb2¹0,2HO
Oxyazo-nucleus C38NH1508.
Chelerythrine, CNH¹708
=
C38NH150S, H²
4449
4444
151
153
153
154
154
155
....
156
15.6
159
160
161
162
162
162
....
163
163
163
Phosphate, Sulphate, Hydrochlorate, Chloroplatinate, and Acetate
of Chelerythrine
1. Glaucopiprine ...
2. Glaucine
4.
....
Appendix to Chelerythrine.
....
3. Second alkaloïd of Sanguinaria
....
....
4. Third alkaloïd of Sanguinaria: Puccine
5. Acrid alkaloïd of Escholtzia
6. Bitter alkaloïd of Escholtzia ....
***
....
7. Colouring matter of the flowers of Glaucium luteum ....
8. Chelidoxanthine
....
Oxyazo-nucleus C38N3H1506.
Cheledonine ? C3SN3H1706
=
Salts of Chelidonine
C3SN3H1506,H2
***
....
...
..
164
165
xiv
CONTENTS.
Primary Nucleus C38H26; Oxygen-nucleus C35H2204.
Page
Pyroguaiacin, C¹³SH2206
=
C38H2204,02
166
....
Potassium-compound, C38H21KO6 + 3aq.
+3aq. Sodium-compound,
C38H21NaO6, 21aq.
167
....
....
Oxyazo-nucleus C³NH1906.
Thebaine, C3NH2106 CNH!O,H
Sulphate. — Hydrochlorate, CNH2¹06,HCl + 2HO
Chloroplatinate, CNH2¹06,HCl,PtCl² + 2HO
C3NH19O,H
....
Sulphate, C3NH2¹06,HSO4. — Hydrochlorate, C3NH2106,HC).
-
Bebirine, C3NH2106
=
Appendix to Bebirine :
1. Sipeerine.-2. Bebiric acid. - 3. Buxine
Chloroplatinate, C38NH2¹06,HCl,PtCl²
Primary Nucleus C38H30; Oxygen-nucleus C38H140¹6.
Daphnetin, C38H14018
=
C38N14016, 02....
***
Daphnin, C62H3438
=
Lead-compound, C38H¹ºPb4018
C38H14018,2C12H¹0010
...
A
....
Hydrated or Crystallised Daphnin, C62H34033 + 8aq.
Resin and Acrid Principle of the Daphnads....
Primary Nucleus C38H36.
Doeglic acid, C33H36,04
Baryta-salt, C³³H³5BaO4
Doeglic ether, C42H4004
Doegling Train-oil
J
....
C33L35(C4H5)O
....
Fatty acid, C38H 38,04
Primary Nucleus C38H38,
....
167
169
170
170
172
173
174
176
176
178
****
178
179
•
179
180
180
COMPOUNDS CONTAINING 40 ATOMS OF CARBON.
Primary Nucleus C40H22; Oxygen-nucleus C40H12010,
GY
Euxanthone, C4H¹2012
=
C40H12010,02
....
Appendix: 1. Porphyric acid, C20 (NO4)2H4Oº ?
2. Oxyporphyric acid
181
181
183
184
CONTENTS.
XV
Oxychlorine-nucleus C40C1³H9O10,
Chloreuxanthone, C40C13H9O10,02
440
Primary Nucleus C40H34; Oxyazo-nucleus C40NH1508.
Page
184
Berberine, C40NH1708
C40NH¹508,H²
185
....
Hydrated or Crystallised Berberine, C40NH¹708 + 9aq?
Ammonia-compound of Berberine ?
189
189
....
189
190
Sulphate of Berberine, C40NH1708,2HSO4
Hydriodate, C40NH¹708,HI. — Iodo-hydriodate, C40NH¹708,12,HI
Hydrobromate, C¹ºNH¹708,HBr. — Hydrochlorate, C40NH¹70³,HCl.
Chlorate, C40NH¹708,HCIO
Nitrate, C40NH¹O,HNO.
....
Chromate, C40NH¹708,HO,2CrO³.
191
Phosphomolybdate. Chloromercurate, C40NH¹708,HCl,HgCl 192
Berberine with Oxide of Silver, C40NH7O8,AgO?
....
....
....
....
193
193
194
4014
194
194
Hyposulphite of Berberine and Silver, C40NH1708,HO,S²O² + AgO,S20² 193
Chloroaurate of Berberine, CNH¹708,HCl,AuCl³
Chloroplatinate of Berberine, C⁰NH¹OS,HCl,PtCl²
Hydrocyanate of Berberine, C40NH¹70,HCy
Hydroferrocyanate of Berberine, 2C40NH¹708,H2FeCy³
Hydroferricyanate, 3C4ºNH¹70, H³Fe²Cyº. —Hydrochlorate of Berberine
with Cyanide of Mercury, C40NH¹708,HCl,HgCy. - Hydrosulpho-
cyanate of Berberine, C40NH1708, C2NHS?. Acetate. Oxalate,
C40N H¹70s, C4H2Os. — Hydrochlorate of Berberine with Glycocoll,
C40NH¹708, HCl,C4NH403
Succinate of Berberine, C40NH1708, CH6O8. - Tartrate, C40NH1708,
C40NH170$,C»HŝO®.
CSH6O12. Tartrate of Berberine and Antimony, C40NH¹70s,HO,
Sbo³, CH40¹0. — Picrate of Berberine, CNH¹70s, C¹²X³H³02
Appendix to Berberine: Oxyacanthine, C32NH23011 ?
....
C40NH7O8,C¹²X³Í³O²
195
196
...
198
Sulphate and Hydrochlorate of Oxyacanthine ...
Iodomercurate, Nitrate, Chloroplatinate, Acetate, Oxalate, and
198
Picrate of Oxyacanthine
199
***
Primary Nucleus C40H26; Oxyazo-nucleus C40N2H2O².
Cinchonine, C40N2H240² = C40N2H22O3,H2
199
....
Salts of Cinchonine (also ADDENDA, p. 610). - Determination of
Cinchonine in its salts ...
205
....
Carbonate of Cinchonine. - Phosphate, 2040N2H2402,3HO,PO5 +
24aq. Hyposulphite, C40N2H2402,HO,S2O2 + 2aq. - Hypo-
sulphate....
206
...
Sulphates. A. Mono-acid, C40N2H2402,HO,SO³ + 2aq.
206
Bi-acid, C40N2H2402,2 (HO,SO³) + 8 aq.
207
Iodate, C40N2H2402,HO,IO5.- Periodate.-Hydriodate, C40N2H240°,
HI + 2aq. — Chlorate, CN2H2O²,HO,ClO5 + aq.
208
.
xvi
CONTENTS.
Perchlorate, C40N2H2402,2C1HOS + 2aq. - Hydrochlorates,
C40N2H2402,HCl + 4aq. and C40N2H2402,2HCI
Hydrofluate, C4ºNH2402,HF.- Nitrate
....
....
Chromate, CN2H2402,HO,2CrO³. Arseniate, 2040N2H2402,3HO,
As05 + 24aq. Chlorocadmiate, C40N2H4O2,HCl,CdCl + aq.
Chlorostannite, C40N2H2402,2HCl,2SnCl. -Iodomercurate,
C40N2H2402,2HI,2HgI ....
į
1...
Hydriodate of Cinchonine with Chloride of Mercury?
Chloromercurate, CN2H2O2,2HCl,2HgCl
Chloroplatinate, C40N2H2402,2HCl,2PtCl²
....
....
Page
209
210
211
212
212
212
Hydrocyanate. — Hydroferrocyanate, C40N2H2402,2Cy³FeH² + 4aq. 213
Hydroferricyanate, C40N2H24O2, Cy°Fe2H6 + 4aq.
214
Compounds of Hydriodate and Hydrobromate of Cinchonine with
Cyanide of Mercury
214
....
Cyanoplatinate, C40N2H2O2,HCy,PtCy
214
Hydrosulphocyanate, C40N2H2O2, CyHS ....
215
Formate. Acetate. Oxalate, 2040N2H4O2, C4H2O8 + 4aq.
Cyanurate. Oxalurate. — Mellitate, C40N2H2402,2C8H2O³.— Suc-
cinate, C40N2H2402,C$H6O8 + 3aq. — Aspartate
215
216
Tartrates. — A. Dextrotartrates, 2C40N2H2402,CH6O¹² + 4aq. and
C40N2H240², CH6O¹² + 8aq.
217
....
....
Antitartrate, C40N2H24O2, C8H6O12 + 2aq. — Tartrate of Cinchonine
and Antimony
218
Croconate and Rhodizonate.
Urate, C40N2H2402, C10N4H406
218
+ 8aq.
219
****
1440
Citrates, 3040N2H2402,C¹²H8O14 + 8aq. and 2C40N2H2402,C¹2H8014
Picrate, 2C40N2H2402,3C12X3H3O2. - Benzoate, C40N2H2402, C14H6O*.
Kinate.
Hippurate. Gallate. Tannate
Roccellate
219
220
220
....
223
224
Cinchonidine, C42N2H2O2 C40N2H2O2,H2 (also ADDENDA, p. 610)
Phosphate of Cinchonidine, 3C40N2H2402,2(PO5,3HO) + 24aq.
Hyposulphite. Sulphates, C40N2H2402,SO³,HO and C40N2H240²,
2(SO³,HO) + 10aq. Chlorate
....
Hydrochlorate, C40N2H2402,HC1 and C40N2H2402,HCl + 2aq.
Hydrofluate. Nitrate
Iodomercurate. Chloromercurate, C40N2H2402,2HC1,2HgCl.
Chloroplatinate, C40N2H2402,2HC1,2PtCl2
Sulphocyanide. — Formate. Acetate. Oxalate. Butyrate.
Tartrates. Valerate. - Citrate. - Hippurate. — Kinate
Appendix to Cinchonidine.
225
....
226
227
1. Wittstein's Cinchonidine, C36N2H2002
228
Sulphates Neutral, C36N2H2002,HO,SO3 + 3aq.
Hydrochlorate, C36N2H2O2,2HCl + 14aq.
Acid
228
228
*
CONTENTS.
Nitrate, C36N³H2002,HO,NO5 + 8aq.- Acetate, C36N2H20O²,C4H404
+5aq. - Tartrate
2. Pseudoquinine..
xvii
Page
229
229
Conjugated Compounds and Derivatives of Cinchonine and Cinchonidine.
=
C40N2H22O2,H2
Hydrocinchonine, C40N2H26O2
Cinchonicine, C40N2H2402
Oxycinchonine, C40N2H2404
2PtC12
*
=
C40N2H2402, H2
C40N2H2204, H2
....
***
Sulphate, C40N2H²¹O¹‚HO,SO³.--Chloroplatinate, C40N2H2404,2HCl,
....
Cinchonine-sulphuric acid, C40N2H2402,SO3
Methyl-cinchonine, C42N2H2602
Hydriodate, C42N2H2602,HI
Methyl-cinchonidine, C38N2H2402
Hydriodate, CasN2H2402,HI
C40N2H21(C2H3)O²,H² ...
C36N2H19 (C2H³) O²,Hª ?
....
...
Acetyl-cinchonine, C44N2H26O4 = C40N2H23 (C4H³O²) 02
Benzoyl-cinchonine, C54N2H28O4 = C40N2H23 (C¹4H502) O²
Oxybromazo-nucleus C40N2BrH2¹02.
Bromocinchonine, C40N2BrH23O2 = C40N2BrH2103, H2
Sesqui-bromocinchonine, C80N4Br³H45O¹ ?
Oxybromazo-nucleus C40N2Br2H2002.
=
Bibromocinchonine, C40N2Br H²O² C40N2B12H2002,H²
Hydrochlorate, C4°N²Br²H2O2,2HCl ....
Oxychlorazo-nucleus C40N2C12H2O².
Bichlorocinchonine, C40N2C12H22O2
―
C40N2C12H2002, H2....
Hydrobromate, C40N2C12H22O2,2HBr ....
Hydrochlorate, CN2C12H22O2,2HC1. Nitrate.
C40N2H22O2,2HC1,2PtCl2 + 2aq.
M
****
230
230
231
232
232
....
232
233
233
233
***
234
•
234
SU
***
235
235
....
....
236
237
237
....
237
Chloroplatinate,
238
{
Primary Nucleus C40H28.
Blue Galbanum-oil, C40H30O2
Galbanum-resin
....
C40H28,H2O2
238
...་
....
239
C¹² H602,02
240
Addendum to vol. xi, p. 379: Resorcin, C2H604
Oxygen-nucleus C4—260².
Guaiaretic acid, C40H26OS = C40H2602,06
....
Potash-salt, C40H24K2O8 + 4HO and + 6HO; and C40H25KO8 +
2HO
....
....
Soda-salt, C40H24 Na2OS + 4HO and C40H25 NaO8,2HO
Baryta-salt, C40H24Ba208. - Lead-salt, C40H22Pb¹OS
241
244
244
245
YOGA
xviii
CONTENTS.
Oxybromine-nucleus C40Br¹H2202.
Bromoguaiaretic acid, C40Br4H2408 C40 Br4H2202,06
=
Appendix to Guaiaretic Acid.
1. Guaiac Beta-resin
2. Guaiac yellow
3. Guaiac resin
....
....
....
Page
245
246
....
....
246
247
Addenda to the products from Guaiac resin previously described.
1. To Guaiacene (x, 411)
....
2. Guaiacic acid (xi, 397)
3. Guaiacol or Pyroguaiacic acid (xii, 350)
FIES
1040
251
252
W
252
Oxyazo-nucleus C40NH1908.
Hydroberberine, C40NH2108
C40NH1908,H2
***
....
Sulphates of Hydroberberine, C40NH2¹08,HO,SO³ ; 2040NH210s,
3(HO,SO³) + 8aq.; and C40NH2¹08,2 (HO,SO³)
Hydriodate, C40NH2¹08,HI. Hydrobromate. - Hydrochlorate,
C40NH2108,HCI
....
Nitrate, C40NH2108,HO,NO5. — Chloroplatinate, C40NH2108,HCl,
Ethyl-hydroberberine C4NH25O8
PtC12
....
==
Papaverine, C40NH2108
C40NH20 (C4H5)05
C49NH1908, H²
Carbonate. Sulphate
....
....
253
254
255
256
256
....
257
258
259
....
259
260
****
Papaverine with Iodine, C40NH2108,31 and C40NH2108,51
Hydriodate, C20NH2¹08,HI. - Hydrochlorate, C40NH2108,HCl
Nitrate, C40NH2108,HNO6. Iodomercurate. Chloroplatinate,
C40NH2108,HCl,PtCl²
Oxynitrazo-nucleus C4ºNX͹808.
Nitropapaverine, C40N2H20O¹2
=
C40NXH1808,H2
....
....
Sulphate. Nitrate of Papaverine, C40N2H20O12,HNO6. — Chloro-
platinate, C40N2H20012, HCl,PtC12
....
260
261
....
Oxybromazo-nucleus C40NBrH¹808.
Bromopapaverine, C40NBrH2008
=
C40NBrH¹80s, H²
261
262
Hydrobromate, C¹ºNBrH²ºO,HBr. — Hydrochlorate
Oxyazo-nucleus C4ºN2H22O4.
Quinine, C40N2H2404
C40N2H2204,H²
....
....
History. Sources
Preparation of Quinine and Cinchonine
Purification of Quinine and Cinchonine
....
....
262
....
263
264
....
....
265
CONTENTS.
xix
:
Separation of Quinine and Cinchonine
Various modes of Preparation: a. Exhaustion of the Bark.
b. Precipitation
c. Further treatment of the Precipitate
...
Estimation of Quinine and Cinchonine in Cinchona-barks
Properties of Quinine
....
Decompositions: 1. By Heat.
...
2. By Solar Light.
Electric Current. 4. By Nitrite of Potash.
acid. — 6. By Chromic acid
....
B
...
....
Page
266
266
267
268
269
A
3. By the
269
5. By Nitric
7. By Permanganate of Potash. 8. By Peroxide of Lead.
9. By Zinc and dilute Sulphuric acid.-10. By Heating
with Water in sealed tubes.-11. By Sulphuric acid and
Ferrocyanide of Potassium; also by Sulphuric acid alone.
11a. By Anhydrous Phosphoric acid
12. By Iodine, Iodic acid and Periodic acid
13. By Iodine and Sulphuric acid
14. By Chlorine
....
14a. By Chlorine-water and Ammonia
Dalleiochine, Rusiochine, and Melanochine
146. By Chlorine and Ferrocyanide of Potassium
....
....
....
****
....
270
270
270
270
....
271
272
272
273
15. By Potash. 16. By Methylic Iodide.-17. By Acetic
and Benzoic Chlorides
Combinations. A. With Water: Hydrate of Quinine, CN2H2404
+ 2aq. and + 6aq. — B. With Acids: Quinine-salts (also AD-
DENDA, p. 615)
....
....
Carbonate, C40N2H2404,2CO² + 2aq. - Hypophosphite, C40N2H2404,
PH304
Pyrophosphate. Phosphate, 3C40N2H2404,2PO³,6HO. - Hyposul-
phite, C40N H2404,HO,S²O² ....
Hyposulphate
Sulphite.
•
****
Sulphate: A. Mono-acid, C40N2H2404,HO,SO3 + 4aq. and + 15aq.
Bi-acid, C40N2H2404,2 (HO,SO³) + 15aq.
Iodate. Periodate, CON²H²O¹‚IO² + 18HO and + 12HO.
Hydriodate, C40N2H2404,HI....
4.
....
....
....
Chlorate. Perchlorate, C40N2H2404,2CIHOS + 14aq.
Hydrochlorate: Mono-acid, C40N2H2404,HCl. Bi-acid
Hydrofluate. — Nitrate, C40N2H2404,HO,NO5
Chromates. C40N2H2404,CrO3 and C40N2H2404,2CrO³ + 16aq.
...
Perchromate.. Arseniate. Antimoniate ?
Sulphate
Quinine and Iron. - Quinine with Iodide of. Iron ?
....
4.
274
275
276
277
....
280
281
282
....
283
283
of
284
....
285
Chloromercurate, C40N2H2404,2HCl,2HgCl
Nitrate of Quinine, with Oxide of Silver, AgO,C40N2H2404,NO5 285
Chloroplatinate, C40N2H2404,2HC1,2PtCl². Chloriridiate. - Hy-
..
....
....
-
drocyanate
Hydroferrocyanate, C40N2H2O+,Cy6Fe³H4 + 6aq. - Hydroferricya-
286
XX
CONTENTS.
Page
nate, C40N2H2401,Cy Fe2H3 + 3aq. -Hydrocyanate of Quinine
with Cyanide of Platinum, 3C40N2H2404,2HCy,2PtCy and
C40N2H2404,2HCу,2PtCy
Hydrosulphocyanate
Formate.
....
•
Acetates, C40N2H2404,C4H4Oª and C40N2H2404,2C¹H¹¹,
+ 2aq. and 6aq.- Oxalate, 2C40N2H2404,C4H2O8. — Cyanurate.
Mellitate
Aspartate. — Valerate, C40N2H2404,C10H10O4 + 3aq. and 24aq.
Dextrotartrate, 2040N2H2404,C8H6O12 and C40N2H2404,C8H6O12 +
2aq. Antitartrate. Tartrate of Quinine and Potash.
Croconate and Rhodizonate. — Urate, C40N2H2404,C'¹ºN2H4O6
Orcin with (Sulphate of?) Quinine.-Citrate of Quinine, 2C40N2H4O4,
C12H8O14. Lactate. Picrate
Compound of Anethol and Quinine, 2C40N2H2404,С20H120² + 4aq.
Tannate. Moritannate. Compound of Cinchona-red and
Quinine....
Kinate. - Oleate
Quinidine, C40N2H2404
....
....
=
C40N2H2204,H2
Varieties
....
Occurrence
Preparation. - Properties
....
Decompositions
....
....
....
....
287
288
289
290
291
292
....
293
294
....
294
295
....
296
297
298
298
298
299
Hydrate of Quinidine, C40N2H2404,4HO
Quinidine-salts
..
....
....
ARA
Sulphates: Mono-acid, C40N2H2404,HSO4 + 6aq. — Bi-acid.— Hy-
driodates. Hydrobromate
Hydrochlorates, C40N2H2404,HCl and C40N2H2404,2HCl. — Nitrate.
- Zinc-compounds, C40N2H2404,2HCl,2ZnCl and C40N2H2404,
HCl,ZnCl. Chloromercurate, C40N2H2404,2HCl,HgCl.
Quinidine with Nitrate of Silver, C40N2H2404,AgNO6
Chloroaurate, C40N2H2404,2HC1,2AuCl³.-Chloroplatinate, C40N2H24O4,
2HCl,2PtCl² + 4aq.-Acetate. -Oxalates, 2C40N2H2404,C4H2O8
+ 2aq. and C40N2H2404,C4H2O8 + 2aq.
Succinate. Tartrate. Tartrate of Quinidine and Potash? — Tar-
trate of Quinidine and Antimony, C40N2H2404,HO,SьО³,С8н40¹0.
-Picrate of Quinidine
Quinicine, C40N2H2404
Quinoïdine.:
C40N2H22O4, H2
Appendix to Quinidine and Quinicine.
a. Containing Quinidine, with smaller quantities of Quinine, Cin-
chonine and Resin
300
301
302
302
303
....
....
....
B. Consisting chiefly of uncrystallisable transformation-products of
the Cinchona-bases
304
Winckler's Amorphous Quinine.
305
CONTENTS.
xxi
:
Page
Conjugated Compounds of Quinine or Quinidine and Compounds derived
therefrom.
Hydroquinine, C40N²H26O6 = C40N2H2406,H²
....
Oxyquinine, CN2H2406 C40N2 H2206,H²
Quinine-sulphuric acid, C40N2H24SO7 C40N2H2404,SO³
Methyl-quinine, C42N2H264 C40N2H21 (C2H3) O¹,H²
=
=
Ethyl-quinine, C44N2H28O4 C40N2H21(C4H5)04,H²
Sulphates, C44N2H2804,HSO4 and C4N2H2O*,2HSO+. — Hydriodate,
C44N2H2804,HI.- Hydrochlorate, C4N2H2804,HCI.
Chloroplatinate, C4N2H2SO4, 2HCl,2PtCl²
Ethyl-quinidine, CN2H28O4 C40N2H2¹ (C4H5)04,H2
—
306
****
307
307
124
....
308
308
Nitrate.
309
310
310
310
311
312
Sul-
Sulphate. Hydriodate, CN2H2804,HI. - Chloroplatinate,
C44N2H2804,2HC1,2PtC12
....
C40N2H2¹ (C¹¹H5O²) O¹‚H²
Benzoyl-quinine, C54N2H28O6
Compounds of the Cinchona-bases with Iodine and Sulphuric acid
Sulphate of Iodo-quinine, 240N2H2404,3HSO4,31
Sulphate of Iodethyl-quinine. -Sulphate of Iodo-quinidine.
phate of Iodethyl-quinidine. Sulphate of Iodo-quinicine. -
Sulphate of Iodocinchonine. - Sulphate of Iodocinchonidine
Appendix to the Cinchona-bases.
313
70
1. Cinchona-yellow
....
2. Bitter Alkaloid of Carapa-bark
3. Alkaloid from Copalche-bark
4. Jamaïcine....
5. Surinamine
6. Percirine
7. Pitoyine
314
314
314
314
316
317
317
Sylvic acid, C40H3004
Ammonia-salt
=====
Primary Nucleus CH30.
C+0H30,04
318
**
320
Potash-salts, CH2⁹KO¹, and CH2⁹KO¹,3CH300.- Lime-salt,
C40H29CaO¹. — Magnesia-salt
321
....
Lead-salt. Iron-salts.
M
C40H29 AgO
Pimaric acid, C¹ºH30O+
Copper-salt, CH²⁹CaO¹. — Silver-salt,
322
....
=
C40 H30, Of
323
....
Amorphous Pimaric acid
Laurent's Pyromaric acid
Nitromaric acid, CN2H26016 C40X2H2602,06
Copaivic acid, C40H3004 C40H30,Q+
Lime-salt, C4H2⁹CaО¹. Lead-salt, CHPьÒ¹
323
325
325
....
326
1
Silver-salt,
C40H9 Ago
227
C
xxii
CONTENTS.
Copaiba Balsam: 1. Brazilian Balsam
2. Thinner Copaiba Balsam
...
Resin of the Copaiba Balsam of Para
....
Lead-salt, C40H7PbO. - Silver-salt, C40H27 AgO6
Oxygen-nucleus C40H2208,
Mangostin, C40H22O10 C40H220$,02
Lead-compound, 2C40H22O10,5PbO + HO....
1004
Resin of Garcinia Mangostana
Dammaryl, C40H32....
Primary Nucleus C40H32.
....
Appendix to Dammaryl.
1. Semihydrate of Dammaryl, С8ºН650
2. Dammar-resins soluble in alcohol
3. Dammar-resin
....
Gutta (Gutta Percha), C40H32 (or C40H30)
Gutta Percha of Commerce
***
2C40H32,HO
..
Alban
Fluavil
Caoutchouc, C40H32
Caoutchouc oil
Vulcanised Caoutchouc
****
....
...
.....
Page
327
329
329
330
330
JALA
331
331
332
333
334
334
1
337
340
342
343
343
***
347
***
349
Appendix to Caoutchouc.
1. Milky sap of Tabernamontana utilis, from Guiana
2. Resins from the milk of the Cow-tree (Galactodendron utile)
3. Resin from the milk of Hura crepitans
4. Chinese India-rubber
....
5. Viscin
Viscautschin
....
Primary Nucleus C40034; Oxygen-nucleus C402806.
Wormwood-bitter, or Absynthiin ? C402808 C40H2806,02 ....
Tannate of Absynthiin....
路
​Oxygen-nucleus C40H26O8.
Asarone or Asarabacca-camphor, C¹ºH260³,0²
351
351
352
U
352
352
353
354
+
356
357
......
CONTENTS.
xxiii
Y"-" -་ -་
Oxynitro-azo-nucleus CN2XH200¹.
Cacotheline, C40N4H22O18 C40N2X2H20010,H2....
=
Sulphate. — Chloroplatinate, CN+H22O¹8,HCI,PtCl²
Cacotheline-baryta, CN2H22O18,BaO
...
Compounds of Cacotheline with Lead-oxide and Silver-oxide
ALL
Primary Nucleus C40H36; Oxygen-nucleus C40H3402.
Ursone, C40H3404
=
C40H340²,02
Arnicin? C40H30OS
....
Oxygen-nucleus C403006,
C40H3006,02
Resins of Arnica-root
Arnica-yellow
***
Elaterin, C40H2810
=
Oxygen-nucleus C40H2O³.
C40H2808,02
Appendix to Elaterin:
1. Prophetin? C46H36014
2. Ecbalin or Elateric acid
3. Hydro-elaterin....
4. Elateride ....
****
....
....
...
Oxygen-nucleus C40H24O12.
Coriamyrtin, C40H24014
=
C40H24012,02
1404
D
Page
358
359
360
360
4.
361
....
....
361
1640
363
364
364
365
....
367
367
367
368
1140
Primary Nucleus C40H38; Oxygen-nucleus C40H3404.
Asclepione, C40346
=
C40H3404,02 ....
***
Xanthoxylin, C40H24O16
=
Oxygen-nucleus C40Ħ24014.
C40H240 14,02
Primary Nucleus C4040.
Arachidic acid, C40H40,04
....
Arachidates, C4º°Ħ³⁹MO÷
Arachamide, C¹ºNH¹¹O² C40 AdH39,02
Arachidate of Methyl, CH04
**
C²H³O,C40H390(3
****
368
369
....
370
6194
371
372
373
c 2
xxiv
CONTENTS.
Arachidate of Ethyl, CHHHO1
C4H5O,C40H3903
Monoarachin, C4H6OS
-
Diarachin, CS6H86012
=
C6H705,CH3903
C6HSO6,2C40H3903
Triarachin, C126 H¹012
-
CCH503,3C40H3903
Arachidate of Amyl, C50H500+
=
CH¹¹O,CH3903
Oil of Earth-nuts
....
Page
373
373
....
374
374
375
375
Oxygen-nucleus CªH3604.
Lithofellic acid, CHH3608 C+0II360¹,0¹
=
375
Lithofellates
377
Oxygen-nucleus C÷H3+O6.
Flocks from Rottlera tinctoria
378
Resinous colouring matter of Rottlera
378
Resins of Rottlera tinctoria (Kamala)
378
Emetine? C40N2H30010
Violine
....
Oxyazo-nucleus C40N2H28010.
C40N2H28010, H2
Appendix to Compounds containing 40 atoms of Carbon.
1. Resins.
379
381
On Resins in general
382
A. Resins containing Benzoic or Cinnammic Acid.
1. Benzoin (also ADDENDA, p. 617)
2. Yellow Resin from Botany Bay
3. Dragon's Blood (also ADDENDA, p. 618)
4. Peru Balsam
5. Liquid Storax
6. Solid Storax
7. Tolu Balsam
383
386
...
...
387
389
391
...
392
+191
392
....
8. Mecca Balsam
9. Stearoptene from Oil of Cassia
393
395
B. Resins free from Benzoic Acid.
1. Alouchi-resin. 2. Gum Ammoniacum.
4. Resin from Arbol-a-Brea
5. Asafoetida
6. Bdellium
Volatile Oil of Asafoetida
-3. Gum Anime
396
397
398
399
402
یا
CONTENTS.
XXV
Page
....
7. Betulin or Birch-camphor
Betuloretic acid
•
8. Caranna. 9. Resin of Ceradia furcata
10. Resin of Ceroxylon Andicola
11. Copal
D
A. Hard kinds: Copal from Zanguebar, Sierra Leone, Benguela,
and Angola
B. Soft kinds: West Indian or Ball Copal. Kaurie Copal. Manilla
Copal
....
Separation of the Resins of Copal
12. Elemi-resin
13. Ivy-resin. 14. Euphorbium.
16. Gamboge. Gamboge-yellow
17. Gum-lac
....
18. Icica-resin: Brean. Icican. Colophan
19. Labdanum or Ladanum.
sopin
20. Resin of Laëtia resinosa. — 21. Ma-
402
403
....
404
...
405
...
....
....
405
405
....
406
201
1400
4.09
****
413
****
15. Gomart-resin
4444
415
1741
416
4
419
....
421
A
422
**
1000
22. Mastic
23. Myrrh
423
**
....
425
....
....
....
....
24. Olibanum. - 25. Opoponax
26. Varnish of the Pasto-Indians.-27. Sagapenum
+66
427
428
28. Sandarac
29. Tacamahac
429
430
****
+1
C. Fossil Resins containing Oxygen.
1. Amber
2. Ambrite.
3. Anthracoxene.
4. Asphalt
....
5. Berengelite. — 6. Boloretin.—7. Earth-resin from Bucaramanga
8. Copalin.-9. Euosmite.- 10. Fossil Caoutchouc
11. Guayaquillite. - 12. Hartin
...
....
Amorphous resin from the ethereal extract of Lignite
13. Jaulingite
....
14. Ixolyte.-15. Krantzite. — 16. Melanchym
17. Middletonite. - 18. Piauzite.
21. Retinite.-22. Schleretinite.
Northumberland
....
....
24. Tasmannite.-25. Peat-resins
26. Xyloretin
144
...
....
431
433
435
436
437
....
438
1940
438
....
439
440
441
....
.
442
443
***
.
443
....
449
444
445
19. Pyroretin.—Retinasphalt
23. Resin from Settling Stones in
27. Resins from the Lignite of Weissenfels
་་་་
....
1. Leucopetrin. - 2. Georetic acid. - 3. Geomyrin
4. Geoceric acid. -5. Geoceraïn. 6. Geocerinone
D. Resins extracted from Plants.
Resin of Anachuita-wood. — Resin of Angelica-root. - Resin of Angus-
tura-bark
446
$
2
xxvi
CONTENTS.
Page
Resin of the bark of Atherosperma moschatum.
Resin of Cannabis
indica. Resins of Cubebs
447
Resins of Juniper-berries
449
Resin of the bark of Lopez-root.
Acrid resin of Manna. - Resins of
Grana Paradisi. - Resin of Spanish Pepper
450
Kesins of Poplar-buds.
Turpetholic acid
Resins of Petasites vulgaris. — Resins of Pimpinella Saxifraga.—
Resin of Radix Sumbulus: Sumbul balsam
Turpeth-resin
Turpethin. — Turpethic acid
E. Aldehyde-resin
Second Appendix to Compounds containing 40 at. of Carbon.
Humous substances
Resins of Squill
451
4
453
453
****
454
455
456
...
458
...
A. Boullay's Ulmic acid
462
....
....
...
B. Substances produced by the action of Acids on Cane-sugar
Malaguti's Ulmin and Ulmic acid
C. Products of the action of Potash on Woody Fibre; Peligot's
462
Ulmic acid
466
D. Crenic acid
4.66
....
....
E. Apocrenic acid
469
F. Substances separated from Peat, Rotten Wood, and Vege-
table Mould: Sprengel's Humic acid
G. From Lignite: Herz's Carbo-humic and Carbo-ulmic acids
II. From Stable Manure: Braconnot's Azulmic acid; Thénard's
Fumic acid
471
....
476
476
....
COMPOUNDS CONTAINING 42 AT. OF CARBON.
Idryl, C42H¹4
Primary Nucleus C42H¹4.
...
Appendix to Idryl: Idrialin, C42H¹O
....
Oxyazo-nucleus C¹²N²H²º0+.
Strychnine, CEN²H²²O+ C42N2H2004, H2....
==
History. Occurrence. Preparation
Detection in cases of Poisoning
Properties
....
Decompositions
Combinations: A. With Water ...
...
B. With Iodine. C. With Acids
477
478
479
....
480
482
483
484
489
489
CONTENTS.
xxvii
Page
Carbonate of Strychnine
....
Phosphates, 2(CN2H22O+,HO), HO,PO5 and C42N2H22O¹,HO,PO³ +
....
....
2aq.
Hydrosulphate. Hyposulphite, C42N2H2204,HO,S²O² + aq.
Sulphates Neutral, C42N2H2204,HO,SO³, and Acid, C42N2H2204,
2(HO,SO³)
....
Sulphate of Iodostrychnine....
T
....
1000
490
490
491
492
....
492
Iodate of Strychnine. Periodate
492
Hydriodate, C42N2H22O+,HI. ·
Hydrobromate, C42N2H22O4, HBr
493
72:
Chlorate.
Perchlorate, CN2H2204,HO,C107 + 2aq. — Hydro-
chlorate, C42N2H22O4, HCl
493
Hydrofluate, C42N2H22O4,HF + aq.
494
Nitrate, C42N2H2O+,HO,NO5
:
Chromates Neutral, CENHO¹,HO,CrO³. — Acid
Arsenite, C42N2H2204,HO,AsO³
Arseniate, C42N2H2204,3HO,AsO5 + aq.
Chlorozincate, C42N2H22O4, HCl, ZnCl, and with 2HO
494
....
....
10
....
495
495
....
496
496
!
Chlorocadmiate, C42N2H2204,HCl,CaCl
Sulphate of Copper and Strychnine?
496
....
..
....
496
....
2.
Iodomercurate of Strychnine. — Bromomercurate.
....
Strychnine
with Mercuric Chloride, C2N2H2204,2HgCl. Sulphate of
Strychnine with Mercuric Chloride, C40N2H2204,HO,SO³ +
Chloromercurate of Strychnine, C42N2H2O4, HCl +
2HgCl.
2HgCl
....
...
...
Chloroplatinate, C¹²N²H²²O¹,HCl,PtCl². — Chloropalladite, C4N2H22O¹,
HCl,PdCl. — Chloroaurate, CN2H2O¹,HCl,AuC1³....
Hydrocyanate of Strychnine. - Hydroferrocyanates, 2(C42N2H≈O¹,
HCy),FeCy+ Saq. and C42N2H22O¹,HCy,2FeCy + 5aq.
Hydroferricyanate, 3 (CN2H22O4, HCy),Fe²Cy³ ÷ 12aq. and + 4aq.
- Strychnine with Mercuric Cyanide, CN2H2204,2HgCy
Hydrochlorate of Strychnine with Mercuric Cyanide, CN³H22O¹,
HCl + HgCy and C42N2H22O¹,HCl + 4HgCy. - Hydroplati-
nocyanate of Strychnine, CN HO¹‚HCy,PtCy + 2aq. — Hy-
drosulphocyanate, CN2H22O1,C2NHS²
Acetate. Oxalates, 20 N2H22O4, C4H2O8 and C2N2H22O¹,C+H208.
Melitate
...
....
....
Tartrates of Strychnine: A. Dextrotartrates, 2C NH2O+,C$H6O¹2
497
498
499
500
501
502
+ Saq. and C+NºH22O¹‚C$H6O¹² + 6aq. B. Antitartrates 503
Tartrate of Antimony and Strychnine, CN HO¹‚HO,SbO³¸CH¹010 504
Croconate, Picrate, Hippurate, and Betuloretinate of Strychnine
504
Strychnochromin
Appendix to Strychnine.
1034
505
с 3
xxviii
CONTENTS.
Conjugated Compounds and Derivatives of Strychnine.
Page
Oxystrychnine, C4N÷H28012
Bioxystrychnine, C42NHO¹
Methyl-strychnine, CчN÷H÷¹O+
=
....
C42N2H2¹ (C²H³) 04
Hydrobromate, CNHO,HBr
....
1
505
506
506
....
507
Hydrate, C4N2H²O¹ + 2HO
Phosphate, C¹N²H¾¹04,3HO,PO³. Sulphates, C44N2H2404,HO,
SO³, and CHN÷H404,2 (HO,SO3). - Hydriodate, C#N2H24O4,
HI.
Hydrochlorate, CN2H2404,HCl. Nitrate, CN2H2404,HO,NO5.
- Chromate. Chloromercurate, CNH404,HCl,5HgCl.—
Chloroplatinate.-Chloro-aurate, CNH2404,HCl,AuC¹³…...
Hydroferrocyanate. — Hydroferricyanate. Acetate. Oxalate
Ethylstrychnine, CN2H2O4
=
C42N2H2(C4H5) O+
....
508
509
510
....
510
Carbonates: Neutral. Acid, CN2H2604,2 (HO,CO2). —- Sul-
CNHO¹,2(HO,CO²).
phate.
Hydriodate, C46N2HO¹‚HI
....
Hydrochlorate. — Nitrate, C46N2H26O¹‚HO,NO5. · Chromate,
C46N2H4604,2(HO,CrO³). — Chloromercurate.
Chloroplatinate, C46N2H2604,HCl,PtCl²
...
Chloroaurate.
511
512
....
512
Compounds obtained from Strychnine and Ethylenic Bromide:
Bihydrobromate of Ethylene-strychnine, C42N2H20 (C4H¹) O4,2HBr
Hydrate of Strychnine-bromethylammonium, C42N²H²¹ (C¹H¹Br)0ª,
2HO. Sulphate, C46N2H2¹ (C4H¹Br) O¹,2 (HO,SO³).
Nitrate, CNH²¹ (C4H¹Br) O¹‚HO,NO5.
C¹²N²H²¹ (C¹H¹Br) O¹,HCl,PtCl³
Platinum-salt,
....
....
512
Hydrate of Ethylene-strychnine, C42N2H20 (CH4) O¹,2HO. - Tri-
chlorethylene-strychnine, CN2H¹7Cl³ (C4H4) O4. — Nitrate of
Nitro-ethylene-strychnine, CN÷H¹⁹X (C4H¹) O¹,HO,NO5
Chromate of Ethylene-strychnine, C42N2H20 (C4H¹) O¹,2 (HO,CrO³)
Amyl-strychnine, C5²N-HO± C42N2H21 (C10H¹¹) O±
Hydrochlorate, CNHO,HC
....
514
514
514
514
....
C52N³H³²O¹,2(HO,CrO³)
Nitrate, C5N H2O¹,HO,NO5. — Chromate, C52N2H3204,2 (HO,CrO³) 515
Oxychlorazo-nucleus C³²N²CI͹O¹.
Chlorostrychnine, CNCIH¹⁹0¹‚ز
....
Primary Nucleus C2H30; Oxygen-nucleus CHO8.
Scoparin, C2H2O¹0 =
C42H2208,02
Primary Nucleus CH; Oxygen-nucleus C2H300².
Cardol, CH3O+ C2H3O2,02
=
515
516
517
CONTENTS.
xxix
Page
Compound with Oxide and Acetate of Lead, C4H3PbO4, C42H300+,
ЗРЬО
519
Appendix to Cardol: Anacardic acid, CHH3207 ?
519
....
Oxygen-nucleus C42H2304.
Helenin, C2H2806
=
C42H2804,02 ?
....
Nitrohelenin
....
522
524
....
525
Chlorhelenin, C42H24C14O6
Philygenin, C42H24012
=
Oxygen-nucleus C42H22O¹0.
C24H22O10,H202
Glucoside of Philygenin: Philyrin, C54H34022
==
525
....
C42H24012,C12H10010
526
Primary Nucleus C42H34; Oxygen-nucleus C42H22O12.
=
C42H22O12,02
....
Columbin, C42H22O14
Appendix to Columbin Columbic acid, C2H22O12 + aq. ?
:
528
529
Primary Nucleus C42H36; Oxygen-nucleus C42H18018.
Euxanthic acid, C42H18022
=
C42H18018, 04
....
Hydrate of Euxanthic acid, C42H18022 + 2aq. and + 6aq.
Euxanthate of Ammonia, C42H¹7 (NH) 022 + 2aq. Potash-salt,
Magnesia-salt, C42HMgO22,MgO,HO.
Lead-salts, C42H¹7PbO,PbO,HO and CHPьО
C42H¹KO22 + 2aq.
-
Oxybromine-nucleus, CBr2H16018.
Bromeuxanthic acid, C2Br H16022
=
C42Br2H¹618,04
Oxychlorine-nucleus CªCl²H¹6018.
79-
Chloreuxanthic acid, C2C12H16022
=
C2C12H¹6O18,04
Oxynitro-nucleus C42XH¹7018.
Nitro-euxanthic acid, C42NH17026
Lead-salt, CXH¹PbO22,PbO
=
C42XH17018,04
....
530
532
534
....
535
....
536
....
....
Primary Nucleus C42H40; Oxygen-nucleus C42H4O16.
537
538
=
Beta-erythrin, C42H24O20 C42H24O16,04 (Appendix to vol. xiii, p. 150)
Lead-compound, C42H20Pb4O20
538
539
....
Appendix to vol. xiii, p. 150.
Beta-picroerythrin, C26H16012
....
....
539
XXX
Medullic acid, C¹²H¹²,0¹
CONTENTS.
Primary Nucleus C2H42.
Primary Nucleus C2H4; Oxygen-nucleus C2H32O12.
Bryoretin, C42134014 = CH 2012, H202
Glucoside of Bryoretin: Bryonin, C96H0O38 ?
***
COMPOUNDS CONTAINING 44 AT. OF CARBON.
Primary Nucleus CHH32; Oxygen-nucleus CHH20012.
СHн20О12,02
Brasilin or Sapan-red, CHHO¼
Hydrate, CHH044 + 3aq
....
....
Page
540
541
541
****
10.4
542
543
Primary Nucleus C4H34; Oxyazo-nucleus C4NH2¹012.
Hydrastine, CHNII23012
CHNH2¹0¹2,H²
Hydrochlorate, CHNH23012, HCI
3040
....
543
...
544
Chloro-aurate. - Chloroplatinate, CNH23012,HCI,PtC12.- Picrate 545
Primary Nucleus CHH36; Oxygen-nucleus C4H34О².
Gurgunic acid, CHITOS
=
C4H3102,06
****
545
Potash-salt, CHH32K208.- Baryta-salt, 2CHH32Ba208,3BaO,HO +
2aq. Lime-salt, CHICa O³. - Silver-salt, CHH32 Ag2O8 546
Primary Nucleus C4H3; Oxygen-nucleus C4Ĥ26O12.
****
Limonin ? CHI26014
=
CHI26012, 0º....
Appendix to Limonin: Hesperidin
Erucic acid, C¹H2O+
Erucates, CHH"MO"
Erucadic acid, CHHO¹
1. Sinapoleic acid
Primary Nucleus C¹¹².
C#H£,O¹
O
Appendix to Erucic Acid.
**
....
546
547
549
551
L
552
552
YA
I
CONTENTS.
xxxi
2. Crystalline Fat from Oil of Mustard
3. Simon's Sinapisine
•
4. Fatty Oil of Black Mustard
Page
552
553
553
553
-c. Oil of
5. Fatty Oil of White Mustard....
6. Brassica-oils: a. Oil of Winter Rape. b. Colza oil.
Summer Rape. d. Oil of Turnip-stemmed Cabbage. e. Oil of
Turnip
...
f. Oil of Chinese Radish
554
555
Oxygen-nucleus C4H32010.
Colocyntheïn? CHH320¹2
=
C44H32010,02
556
9040
Glucoside of Colocyntheïn: Colocynthin
556
Colocynthitin
558
•
Primary Nucleus C44H4.
Benic acid, C4H4404
=
CH*O*
Metallic Benates, C44H43MO¹
Benate of Ethyl, C4H404
C4H50,C4H4303
558
559
560
Bromine-nucleus C4B12H42.
Bromerucic acid, C44Br2H42,04
560
Lead-salt, C4Br2H"BaO4. - Lead-salt, C4Br Hª¹PbO4
561
COMPOUNDS CONTAINING 46 ATOMS OF CARBON.
Primary Nucleus C46H22; Azo-nucleus C4N4H¹8.
Aribine, C46N+H20
་
C46N4H18,H2
Hydrate, C46N¹H20,16aq
Sulphates, C46N4H20,2HSO4 and C46N+H20,4HSO¹
561
562
563
*
563
Hydrochlorate, C¹ºN¹H²º,2HCl. — Chloroplatinate, CN¹H20,2HCl,
2PtC12
,་
L
564
Primary Nucleus C46H30; Oxygen-nucleus C4H20010.
Ononetin, C46H22O12 = C46H20010,H202
Conjugated Compounds of Ononetin.
Formonetin, C48H20012
C46H1909,C2H03
565
xxxii
CONTENTS.
Onospin, C58IHQ21
C4622012,C¹2П12012
Ononin, CI34026
*
C4I²¹¹¹, C¹¹²¹2012,C2H03
Page
565
567
Primary Nucleus CH³¹; Oxyazo-nucleus CN2H24O8,
Aricine, CN20H26O8 C46N2H2408,H2
AA
Sulphates of Arcine: Neutral (?) and Acid, C46N2H26O8,2HSO4
Hydriodate, CN2H2O,HI. - Hydrochlorate, C46N2H2608,HC1
Chloroplatinate, CNHOS,HCl,PtCl²
...
Salts of Paricine
Appendix to Aricine: Paricine....
C46N2H2408,H2
+44
Brucine, CN2H26OS
Hydrate, CNºH2608 +8 aq.
4.
Iodides, 2C4N H2O8,31, and CN2H2608,31
Carbonate of Brucine.
g
...
....
Phosphate, 2C4N2H2608,3HO,PO5
Hyposulphite, CN2H6O8, HO,S2O2 + 4 aq.
Sulphate, CNH2608,HO,SO³. — Periodate
Iodate. Hydriodate, C4NHO,HI. Perchlorate, Chlorate,
Hydrochlorate, CNHO,HCI ....
....
568
570
570
571
571
572
A
572
577
577
579
579
K
579
...
580
581
582
582
583
583
584
...
....
584
584
585
Hydrofluate. Nitrate, C45NH260³, HO,NO". Chromate.
Iodomercurate. Chloromercurate, CNHOS,HCl,2HgCl
Chloroaurate. Chloroplatinate, C46N2H2608,HCl,PtCl². — Chlor-
iridiate
Hydroferrocyanate, 2 (CNHO,HCy),FeCy+ 2HO
Hydroferricyanate. Platino-hydrocyanate. Hydrosulphocya-
nate, CNH2GOs, CNHS2. Oxalate. Lactate
Tartrates: A. Dextrotartrates. a. 2046N2H260S, C8H6O12 +
11 aq. and + 16 aq.
b. C³N²H²ºOº, CSIO¹²....
B. Antitartrates: - a.
....
2C46N2H260,C8H6O2 + 28 aq.
b. C46N÷H2608,CsH6O12 + 10 aq.
N
Tartrate of Antimony and Brucine, CN2H2608,нO,SьO³,C8H4010
Compound of Brucine and Picrotoxin
....
Conjugated Compounds and Derivatives of Brucine.
Bromobrucine, C46N2BrH25OS
Methyl-brucine, CSNH2,08
C46N2BrH2308,Ħ².
CN²(C²H³) H2³0³‚H²
...
Sulphates, CISN÷HO³,HO,SO3 and CSNH28O8,2 (HO,SO³). -
Ilydriodate, C¹8N÷HO,HI. - Hydrobromate, CN2H808,
HBr
....
-
Hydrochlorate, C4$N÷HO³,HCl. -- Chloromercurate. - Chloropla-
tinate. Chloro-aurate
Ethyl-brucine, C5"N÷HOS
C®N²(C÷H³)H÷0³‚H²
585
586
586
587
587
CONTENTS.
xxxiii
Hydriodate, C50N2H3008,HI + HO
....
Page
587
588
588
588
589
589
589
Chloroplatinate, C50N2H30O8,HC1,PtCl²
Compounds obtained from Brucine and Bibromide of Ethylene :
Bihydrobromate of Ethylene-brucine, CN (CH) H2408,2HBr
Chloroplatinate of Bromethyl-brucine, CN(CH+Br) H2O, HCl,
PtC12
...
Hydrate of Ethylene-brucine
Sulphate of Ethylene-brucine,
4 aq.
....
...
C46N²(C+H+) H2O8,2(HO,SO³) +
Chloroplatinate of Ethylene-brucine, C46N2(CH4) H2408, HCl,PtC12
1. Igasurine
....
Oxy-igasurine
2. Curarine
Appendix to Brucine.
3. Conessine or Wrightine
4. Eserine
5. Oleandrine and Pseudocurarine
....
A
....
Primary Nucleus C4H46; Oxyazo-nucleus C¹NH27Q¹8.
Narceine, C46NH29018
=
C46NH27018,H³
Sulphate of Narceine
....
Hydrochlorate, C46N2H29O¹8,HCl. — Nitrate. - Chloromercurate.
Chloro-aurate. Chloroplatinate, CNH2O18,HCl,PtCl²
APPENDIX TO COMPOUNDS CONTAINING 46 AT. OF CARBON.
589
592
592
594
594
141
595
595
4
599
600
1. Colchicine, С³¹NH¹9¹0
601
....
2. Colchiceïne, C34NH19010
Tannate of Colchicine, 3C34NH19010, C54H22034
C3NH*O,H*
604
=
604
Barium-salt, C4NH18BaO¹0,- Copper-salt, C34NH¹CuO¹0
606
14
3. Corydaline
607
Cinchonidine....
Quinine ....
Quinidine
Resins
ADDENDA.
KA
610
615
616
41
617
ERRATA
Page 358, line 44, for 016 read 018.
5)
429,
>>
4,
""
alcohol,, ether.
499
5
22
23.
"}
APPENDIX TO 34-CARBON COMPOUNDS (continued).
Blue and Red Colouring Matters (continued).
THE roots of Atropa Belladonna yield a colouring matter which,
according to Hübschmann, is identical with that of the berries. To
obtain it, the roots are exhausted with alcohol of 90 p. c.; the tincture
when distilled, leaves a residue of brownish-yellow acid syrup,
together with resin. The latter is removed and the "syrup is mixed
with ammonia and filtered, when there remains on the filter a small
quantity of black granules, which are to be dissolved in acid, precipi-
tated with ammonia, and washed with water and alcohol. The black
powder thus obtained, Hübschmann's Atrosin, is insoluble in water,
alcohol, and ether, but dissolves with fine red colour in dilute mineral
acids, and in aqueous tartaric acid. (Hübschmann, Schureiz. Pharm.
Zeitschr; N. Jahrb. Pharm. 19, 369.)
3. Leaf-red.
The red colouring matter of autumn-reddened leaves, the Erythrophyll
of Berzelius is produced, according to Macaire-Princep, by the con-
tinued alteration of leaf-green which has first changed to leaf-
yellow. Wittstein also regards it as a product of the action of
sun-light on leaf-green, and terms it Cissotannic acid (xv, 516). ——
According to Schübler and Franck, autumn-reddened leaves contain
leaf-yellow aud a blue colouring matter which is reddened by acids;
the experiments of Berzelius, however, contradict this. Chatin and
Filhol (Compt. rend. 57, 39) seem to consider some kinds of leaf-red as
identical with Fremy's cyanin (xvi. 522).
Leaf-red occurs in the leaves of plants which bear red fruit,
especially in the leaves of Sorbus aucuparia, Prunus Cerasus, Ribes
rubrum, and Berberis vulgaris, and is closely related to the red colour
of the fruit (Berzelius). Autumn-reddened leaves occur, however, in
plants which do not bear red fruit, the coloration having also no con-
nection with the decay of the leaves (II. Mohl).
The red autumnal leaves of Rhus Coriaria and Pyrus communis,
and the calyx of Salvia splendens yield, when treated with hot alcohol,
a red resin which is turned green by alkalis and reddened again by
acids, and is insoluble in oils (Macaire-Princep). The brown autumnal
leaves of the hornbeam are not turned green by caustic potash
(Gmelin). A decoction of the leaves of Vitis hederacea is reddened by
acetic acid, and gives with neutral acetate of lead a violet precipitate,
which is turned green, but not dissolved, by caustic potash. When
to the decoction an excess of neutral acetate of lead is added, the
resulting precipitate is green; if, however, basic acetate of lead be
gradually added, a violet precipitate is produced, which, after washing,
is turned green by the neutral acetate (Legrip, J. Chim. méd. 23, 188)
See xv, 516.
The leaf-red of Berzelius is obtained from the reddened teaves of
VOL. XVII.
P
2
APPENDIX TO COMPOUNDS CONTAINING 34 AT. CARBON.
the cherry and of the currant. The leaves are exhausted with
alcohol; the alcohol is distilled off; and the remaining red liquid, after
filtering from resin and fat, is mixed with water, which produces no
cloudiness. Neutral acetate of lead is then added so long as the
resulting grass-green precipitate turns brown on standing. When the
colour no longer changes, the liquid is filtered and completely pre-
cipitated by neutral acetate of lead. The fine green precipitate is
washed on a filter, afterwards decomposed by hydrosulphuric acid, and
the solution is evaporated in a vacuum. Basic acetate of lead throws
down a little more leaf-red from the liquid previously precipitated by
the neutral acetate. Leaf-red is darker, and more blood-red than
the colouring matter of the cherry, which it otherwise resembles. Its
solution, when evaporated, throws down a red-brown deposit, which
forms pale red-brown compounds with bases. Unchanged leaf-red
dissolves in water and alcohol, and forms, with bases, compounds.
having a green or yellow colour, whilst those of the colouring matter
of the fruit are green or blue. When the aqueous solution of leaf-
red is half precipitated by lime-water, the supernatant liquid is red,
and not blue, as would be the case if leaf-red were a blue colouring
matter reddened by acids (Berzelius, Ann. Pharm. 21, 265; Pogg.
42, 428).
Red cabbage contains a colouring matter, which is turned red by
acids and green by alkalis, and seems to be identical with that
of violets. Metallic salts and boracic acid colour the fresh liquid
green, and that reddened by acids blue (Murray). Carbonic and
other acids colour the green alkaline liquid blue (Bowen, Schw. 43,
382; Robinet and Guibourt), Hydrosulphuric acid passed through
the liquid turns it green (Wolffgang, Scher. N. Bl. 1, 177); hydro-
sulphate of ammonia or protoxide of iron decolorises the liquid
which has been rendered green by alkalis (Kuhlmann, Ann. Pharm.
9, 286).
If the deposit thrown down from the expressed sap of the leaves
of Antidesma alexiteria be washed with cold water, warm ether after-
wards takes up therefrom a violet colouring matter, which is turned
green by alkalis and red by acids (Ridolfi, Brugn. Giorn. 17, 472).
The sap of Mercurialis perennis assumes in the air a blue colour, which
is reddened by acids (Runge). The sap of Orobus niger and Polygonum
ariculare, as well as the sap of Boletus lactifluus, turns blue only on
exposure to the air (Runge).
The nearly colourless sap expressed from the leaves of Aloe
soccotrina, when exposed to the air, even in the dark, gradually
assumes a red colour, passing at last to a splendid purple-violet.
Acids redden the sap and precipitate the colouring substance (Guyton-
Morveau. Fabroni, Scher. J. 2, 517 and 546).
The red colouring matter of the root-bark of Lithospermum arvense,
the red of Spanish pepper, chica-red, and nucin are treated of under
Alkanet-red (p. 17).
V. Green Colouring Matters.
Leaf-green.
PROUST. A. Gehl. 1, 490.
VAUQUELIN.
Ann. Chim. 83, 42.
LEAF-GREEN.
3
JOHN. Chem. Schriften, 4, 161; 5, 26.
PELLETIER and CAVENtou.
486; N. Tr. 3, 2, 313.
Ann. Chim. Phys. 9, 194; J. Pharm. 3,
MACAIRE-PRINCEP. Mem. de la Soc. de Phys. et d'hist natur. de Génève,
4, 43 ; N. Tr. 18, 2, 226.
MARQUART. Die Farben der Blüthen. Bonn, 1835.
BERZELIUS. Ann. Pharm. 27, 296.
MULDER. J. pr. Chem. 33, 478.
VERDEIL. Compt. rend. 33, 689; J. pr. Chem. 55, 187.
L. PFAUNDLER. Ann. Pharm. 115, 37.
FRÉMY. Compt. rend. 50, 405; Ñ. J. Pharm. 37, 241; J. pr. Chem.
87, 319.
LUDWIG and KROMAYER. N. Br. Arch. 106, 164.
Resinous leaf-green. Einhof's Vegetable Wax, Pelletier's Chlorophyll,
Macaire-Princep's Chromule verte.
Various substances extracted by alcohol or ether from different
plants, and coloured by leaf-green, were described by the older
chemists as leaf-green. Berzelius, however, obtained the green
colouring matter of leaves in a purer state. According to Frémy's
investigations, even this leaf-green must be regarded as a mixture of
a blue and a yellow colouring matter. The following views have also
been put forward
a. Leaf-green bears a great resemblance to the colouring matter of
the blood, and contains iron as an essential component (Verdeil). The
root, seeds, and white parts of plants contain iron in the form of pro-
toxide, which, when the parts become green, is converted into
sesquioxide, and occurs as such in the reddened parts of plants; in
leaf-green it occurs together with protoxide (E. Risler, Kopp's Jahresb.
1859, 560; extr. from N. Arch, ph. nat. 6, 206).
b. Leaf-green is a coloured substance, produced (probably by the
influence of iron) from a colourless or faintly coloured compound, pos-
sibly quercetin, æsculetin, luteolin, or a decomposition-product of
berberin, coloured by salts of iron (Hlasiwetz, Ann. Pharm. 112, 96;
115, 45). Pfaundler found that quercetin coloured by iron behaved
differently from leaf-green obtained from grass. Illasiwetz's view
may, nevertheless, be correct in some cases.
c. According to Morot, leaf-green has the composition represented
by the formula C18NH1003, and occurs, together with a fatty body,
CH70, from which it is formed by the action of ammonia and car-
bonic acid. It is not capable of producing either blue or red vegetable
colouring matters. His investigation, as well as that of Morren on
chlorophyll and erythrophyll, is known to us only in the form of an
extract (Kopp's Jahresb. 1859, 561) (Kr.).
Leaf-green is produced by the mixture of blue and yellow, and
may be split up into these colours. When leaf-green, extracted by
alcohol, is shaken with a mixture of two parts of ether and one part
of slightly diluted hydrochloric acid, the ether takes up the yellow
colour, whilst the hydrochloric acid beneath is coloured a splendid
blue. If the two layers be mixed by the intervention of alcohol, the
green colour is reproduced. The yellow colouring matter thus ob-
tained is designated by Frémy, Phylloxanthin; the blue colour le terms.
Phyllocyanin. A less complete separation of the two is effected by
adding to the alcoholic leaf-green hydrate of alumina, together with
B 2
APPENDIX TO COMPOUNDS CONTAINING 34 AT. CARBON.
small quantities of water, whereby, so long as the liquid is strongly
alcoholic, a dark-green lake is precipitated, the alcohol remaining of a
yellow colour. On treating this precipitate (or the yellowish-green
lake formed by adding more water) with ether, alcohol, or oil of tur-
pentine, the green colour is dissolved as a whole; bisulphide of carbon
dissolves first the yellow, and leaves the undissolved portion of a dark-
green colour.- Bases change leaf-green into yellow by the conversion
of phyllocyanin into phylloxanthin. The latter substance is soluble in
alcohol, and yields, with alumina, a yellow lake, from which alcohol,
ether, and bisulphide of carbon extract the colouring matter. The
alcoholic solution is turned green by hydrochloric acid; ether mixed
with hydrochloric acid decomposes it into blue and yellow. The
yellow colouring matter of young shoots and of etiolated leaves.
may also be split up, by means of ether and hydrochloric acid,
into blue and yellow. It is coloured green by hydrochloric acid
(Frémy).
When leaf-green is treated with hydrochloric acid, containing a
trace of nitric acid, a nearly pure blue liquid is obtained (Filhol, Compt.
rend. 50, 1182).
Phyllocyanin and phylloxanthin are obtained from the green colour
of the young leaves of wheat in the following manner: The expressed
sap mixed with alcohol is coagulated, and the coagulum, which retains
the colouring matter, is washed and exhausted with ether. The ether
is distilled off, and the residue first washed with cold, then dissolved
in hot alcohol, and boiled for a few seconds with alcoholic potash,
whereby the green colour is not altered. On dilution with water and
addition of hydrochloric acid, a yellow precipitate, and a splendid blue
liquid, copper-red by reflected light, are obtained. The latter, as the
alcohol evaporates, deposits dark-blue flocks of phyllocyanin, which
dry up to a dark-blue, brittle mass; or if the blue acid liquid be pre-
cipitated with basic acetate of lead, and the precipitate decomposed
with hydrosulphuric acid, the colouring matter goes down with the
sulphide of lead. The precipitate is then to be washed with ether to
remove the yellow, and exhausted with alcohol containing hydrochloric
acid; on evaporating the solution, dark-blue phyllocyanin remains.
Nitric acid turns it green, then orange-yellow; hydrochloric acid.
colours the alcoholic solution a splendid blue-green. When heated in
a glass tube, it yields a violet distillate. Contains, at 100°, 50.96
p. c. C, 8.52 II, 701 N, and 33:51 0, corresponding to the formula
CN2IIO (Ludwig & Kromayer). The yellow precipitate thrown
down by hydrochloric acid forms, after washing with alcohol, a yellow,
viscous mass. It is not altered by digestion with caustic soda. After
removing the soda, it forms with water a yellow emulsion, the colour-
ing matter of which is taken up by ether and hydrochloric acid when
shaken therewith. The ethereal solution, when evaporated, leaves a
residue, which is dissolved (excepting wax) by bisulphide of carbon,
and left on evaporation in the form of a tough, yellow mass. It is
coloured green by nitric acid (Ludwig & Kromayer).
131
T. According to Stokes (Proc. Roy. Soc. xiii, 144), the leaf-green
of land-plants is a mixture of four substances, two green and two
yellow, all possessing highly distinctive optical properties. The green
substances yield solutions exhibiting a strong red fluorescence; the
yellow substances do not. These four substances are soluble in the
same solvents, and three of them are very easily decomposed by acids,
LEAF-GREEN.
5
10
or even by acid salts, such as binoxolate of potash. Frémy's phillo-
cyanin is mainly the product of decomposition by acids of one of the green
bodies; his philloxanthin differs in composition and properties according
to the mode of preparation. Green sea-weeds agree with land-plants,
except as to the relative proportion of the colouring substances present;
but in olive-coloured sea-weeds (Melanospermea) the second green sub-
stance is replaced by a third green substance, and the first yellow
substance by a third yellow substance, to the presence of which the
dull colour of these plants is due. The red colouring matter of the red
sea-weeds (Rhodospermece) which the plants contain in addition to chloro-
phyll appears to be an albuminous substance. (See also Chem. Soc. J.
xvii, 309, 314. ¶)
T
-
Older investigations. By Berzelius. Leaf-green is a peculiar sub-
stance, which is not decomposed by acids and alkalis, but forms
definite compounds therewith. Like other colouring principles, it is
destroyed by light, air, and chlorine. It may be obtained in three
modifications.
a. Leaf-green having the colour of fresh leaves. The fresh leaves of
Crataegus Aria, collected in August, are bruised and exhausted with
ether; the dark-green tincture is distilled over a water-bath till nearly
the whole of the ether is removed; the solution is separated from the
deposit thereby produced; and the latter is washed with alcohol so
long as it imparts a dark-green colour thereto. The alcoholic tincture
contains leaf-green of the first modification, whilst the separated ethe-
real solution, and the portion of the deposit insoluble in alcohol, con-
tain leaf-green of the second modification. The alcoholic solution is
evaporated to dryness, and the residue treated with strong hydro-
chloric acid, which leaves a little dark substance (B). Water is added
to the dark-green filtrate so long as precipitation ensues, and the
precipitate is washed in succession with cold and hot water, the latter
being coloured yellow. The leaf-green thus obtained and dried, has
already undergone change, since it dissolves only with difficulty in
alcohol and ether, with black-green colour. It is, therefore, digested
for twelve hours in a weak solution of caustic potash, afterwards
diluted with twice the volume of water, and heated to the boiling-
point. The splendid grass-green liquid is filtered from the black
powder deposited, and slightly supersaturated with acetic acid, when
the leaf-green is thrown down in fine green flakes, which are collected,
washed, and dried.
Dark-green, earthy mass, casily triturable to a grass-green powder.
When heated to 200°, it does not fuse, and gives off merely a trace of
moisture. On treating this heated leaf-green with hydrochloric acid,
or caustic potash, a small quantity of black powder remains undis-
solved; the greater part, however, is still undecomposed.-Leaf-
green, submitted to dry distillation, melts, puffs up, and gives off first
a trace of moisture, then a colourless oil, together with a red non-
crystalline sublimate; at last a dark oil passes over, whilst a perfectly
combustible charcoal remains behind. The red sublimate dissolves in
water, hydrochloric acid, alcohol, and ether. It is not saponified by
caustic potash, and carbonises when heated, without again subliming.
Leaf-green is decolorised and converted into a fatty mass by a mix-
ture of hydrochloric acid and chlorate of potash. Nitric acid decom-
poses it.
Hot oil of vitriol turns it brown, and evolves sulphurous
+
6 APPENDIX TO COMPOUNDS CONTAINING 34 AT. CARBON.
acid. An alcoholic tincture of fresh leaves is bleached in a few
hours in sunshine. In one experiment leaf-yellow (xvi., 515) seemed
to be produced.
Leaf-green is insoluble in water, even when boiling. Cold oil of
vitriol dissolves it with magnificent green colour; the solution is per-
manent except when heated: it is precipitated by water. Hydro-
chloric acid of sp. gr. 1·14 dissolves it with deep emerald-green colour,
generally leaving behind a small quantity of pale-yellow fatty sub-
stance: the solution is partially precipitated by water, and completely
precipitated by neutralisation with carbonate of lime; it leaves the leaf-
green as a dark-green pellicle when evaporated. — Moist leaf-green
dissolves in ammonia and carbonate of ammonia, and in caustic potasli
and soda, with fine green colour, and is precipitated from the solutions
by acetic acid in large flocks, which appear emerald-green by trans-
mitted light. Dried leaf-green leaves a dark residue when dissolved
in caustic potash. The solution in ammonia and in the carbonates of
the alkalis has a dingy colour. The ammoniacal solution loses its am-
monia when evaporated; the solution in caustic potash or its carbonate
deposits, when concentrated, a potash-compound of leaf-green soluble
in water, but insoluble in alcohol. Lime- and baryta-water precipi-
tate ammoniacal leaf-green with pale-green colour. Alkaline leaf-green
precipitates solution of alum, with splendid green colour; the alcoholic
solution precipitates neutral acetate of lead with grass-green colour.
-
Leaf-green dissolves slightly in cold, more freely in boiling acetic
acid, and is precipitated from the solution by water. It dissolves in
alcohol with grass-green colour (the dried substance slowly with
blue-green colour), and is again thrown down by water. Soluble in
ether, oil of turpentine, and fixed oils (Berzelius).
Obtained from fresh
B. Leaf-green having the colour of dried leaves.
leaves in the preparation of a. The ethereal solution, obtained as de-
scribed, is added to the deposit insoluble in alcohol, and evaporated; and
the residue is again dissolved in ether and mixed with fuming hydro-
chloric acid, which is coloured an opaque green. So much ether is then
added that it is not completely taken up by the hydrochloric acid, and,
after shaking and standing for 24 hours, the deep-yellow solution is de-
canted, the remaining ethereal solution being rinsed out with a little
ether. The solution is warmed to drive off the ether held in solution,
and filtered; the fat remaining on the filter is washed with hydro-
chloric acid; and the acid solution is mixed with water as long as a pre-
cipitate is produced, then filtered, and saturated with marble, whereby
the leaf-green is thrown down. The precipitate produced by water is
treated with hydrochloric acid, which leaves leaf-green of the third mo-
dification behind; and the filtrate (now no longer precipitated by water,
since it contains only ẞ) is to be precipitated by marble as before.
ẞ leaf-green is of a dirty yellowish dark-green colour, like dry,
long-kept leaves. It is not precipitated from its solution in hydro-
chloric acid by water, except in presence of a or 7. It behaves in the
same manner as a with chlorine and nitric acid, and generally also with
solvents and precipitants; the solutions and precipitates, however,
exhibit other colours. The solution in dilute hydrochloric acid is de-
colorised by zinc. The solutions in acetic acid, alcohol, and ether
are grey-green in thin films and reddish-blue in thicker layers
(Berzelius).
、,::, (3,༤
-
LEAF-GREEN.
7
1. Third modification of leaf-green. Obtained in the preparation of
B, as a black residue, insoluble in hydrochloric acid of sp. gr. 114. It
is purified by washing with water, drying, dissolving in boiling alcohol
(which is effected with difficulty), and evaporating the dark-green
solution over the water-bath. It forms a shining residue, nearly
black by daylight, dark-green by artificial light. Hard, and easily
reduced to a dark-green power. Attracts moisture readily from the
air and becomes pasty. Dissolves very slightly in hydrochloric acid
with yellow colour, and is not thrown down again by water. Insoluble
in cold, slightly soluble in boiling acetic acid, forming a fine green
solution, from which it is deposited of a green colour on cooling.
Difficultly soluble in alcohol, and very slightly soluble in ether
(Berzelius).
Leaf-green prepared from poplar leaves, according to the directions
of Berzelius, contains, at 102°, 54.74 p. c. C., 4.82 II., 6·68 N., and
33.76 O. (Mulder).
The dark blue-green solution of leaf-green in oil of vitriol, when
covered with a layer of alcohol, assumes a dark indigo-blue colour,
which is imparted to the alcohol (Marquart).
Verdeil obtains his (ferruginous) leaf-green by exhausting leaves
with boiling alcohol, and mixing the tincture with hydrate of lime,
whereby the fatty bodies are retained in solution, and the leaf-green is
precipitated. The lime precipitate is treated with hydrochloric acid and
ether, which take up the leaf-green and leave it behind on evaporation.
When grass is expressed with water, the liquid heated to boiling,
and the albuminous leaf-green which separates exhausted with alcohol,
the tincture leaves on distillation a soft dark-green jelly. This is
agitated with boiling water; the liquid is decanted; the residue dis-
sclved in warm hydrochloric acid; and the solution, after cooling,
filtered and precipitated with hot water. The flocks thus precipitated,
form, when dried and triturated, a dark-blue powder, containing on the
average (after deducting 0.92 p. c. ash containing iron) 60-84 p. c.
carbon, 6.38 hydrogen, 32.78 oxygen, and an unimportant trace of
nitrogen (0-037 p. c.). When boiled with caustic potash, it does not
yield the decomposition-products of quercetin (Pfaundler).
Euchema spinosum Ag., a sea-weed from the East Indian Archipelago,
contains a variety of leaf-green which is soluble in alcohol and ether,
and insoluble in hydrochloric acid (Oudemanns, N. Br. Arch. 87, 292).
The leaf-green of Cetraria islandica, the tallochlor of Schnedermaun and
Knop, behaves in a similar manner. (See under Cetraric acid, C6H16016, p. 22).
A green colouring matter from infusoria, which, according to M. Schultz (Compt.
rend. 34, 683) agrees with leaf-green, but, according so Salm-Horstmar (Pogg. 94, 166)
differs therefrom, will be described in another place.
The two following green colouring matters differ from leaf-green.
Green colouring matter of Thistle-tops, Artichokes, and undeveloped
Flower-buds. When these parts of plants, while still white, are boiled
with water or pressed, colourless liquids, unchangeable in the air, are
obtained, which turn green in the air on addition of a little soda or
lime-water, and in presence of excess of alkali assume a yellow colour.
From these green solutions, alum, neutral acetate of lead, and stannic
oxide throw down fine dark-green lakes, which are not altered by
drying.
On decomposing the lead-precipitate with alcohol containing sul-
phuric acid, and mixing the brown yellow tincture with a large quan-
8
PRIMARY NUCLEUS 036H18.
tity of ether, the colouring matter is precipitated. When collected,
washed with water, and dried, it is yellowish-brown, infusible and non-
volatile, and contains nitrogen and traces of ash. The green colour
is insoluble in water, but soluble in oil of vitriol with fine red colour;
it is not affected by hydrochloric or acetic acid. The easily formed
solution in caustic alkalis and their carbonates is of a fine green colour,
and is precipitated by acids. It is decolorised by liquids in a state of
fermentation, and regains its colour on exposure to the air. - The
colour is slightly soluble in alcohol. It dyes prepared cotton-wool
(Verdeil, Compt. rend. 47, 442; J. pr. Chem. 77, 461).
Colouring matter of Monotropa Hypopitys. - Appears to be formed
by the action of the air on some colourless substance contained in the
plaut, the cut surfaces of the plant assuming a violet colour only on
exposure.
An aqueous decoction of the fresh plant deposits, on standing, a
dark blue-green powder consisting of microscopic, round, black granules.
The same powder is obtained by digesting the plant, without access
of air, in alcohol previously freed from air by boiling, and distilling the
tincture to remove the greater part of the alcohol, when a small quan-
tity of black granules is deposited. This substance appears to contain
nitrogen. When heated it evolves an odour of cloves, then gives off
vapours having the smell of tobacco, together with oily drops, and
leaves charcoal. It dissolves gradually in boiling water with brown
colour: the solution has an acid reaction, and is precipitated green by
acetate of iron, dirty-yellow by mercurous nitrate, and yellow by
neutral acetate of lead; tincture of iodine colours it a transient cherry-
red. — It dissolves in oil of vitriol without assuming a dark colour, and
is thrown down from the solution by water. Hydrochloric acid dissolves
it with emerald-green colour; the solution is not precipitated by water.
Cold nitric acid dissolves it with greenish colour. It dissolves easily
in aqueous ammonia and alkalis with black colour, and is precipitated
from the solutions by acids in cherry-red flocks. Insoluble in alcohol
and ether (Reinsch, Jahrb. pr. Pharm. 25, 193).
COMPOUNDS CONTAINING 36 ATOMS OF CARBON.
Primary Nucleus C6H18.
Retene.
C'36H18.
B. TROMMSDOrff. Ann. Pharm. 21, 126.
E. KRAUS. Pogg. 43, 141; Ann. Pharm. 28, 345.
STEENSTRUP (and FORCHHAMMER). Ann. Pharm. 41, 39; J. pr. Chem.
20, 459.
KNAUSS
FEHLING.
Ann. Pharm. 106, 391; J. pr. Chem. 82, 334.
Ann. Pharm. 106, 388; abstr. J. pr. Chem, 74, 507; Chem.
Centr. 1858, 513; Kopp's Jahresber, 1858, 439.
RETENE.
9
FRITZSCHE. Petersb. Acad. Bull. 17, 68; J. pr. Chem. 75, 281; abstr.
Ann. Pharm. 109, 250; Compt. rend. 47, 723; Rép. Chim. pure 1,
264; Kopp's Jahresb. 1858, 440. N. Petersb. Acad. Bull. 3, 88;
J. pr. Chem. 82, 321; abstr. Chem. Centr. 1861, 197; Kopp's Jahresb.
1860, 475.
Discovered by Fikentscher (Bericht über die Vers. deutscher Naturf. zu Prag,
1837) and Trommsdorff: described by Kraus as Scheererit, and by Steenstrup as
Phylloretin. A hydrocarbon obtained by Knauss, as a product of the distillation
of resin, was recognised by Fritzsche as identical with the above substances. Prin-
cipally investigated by Fritzsche.
Occurrence. In fossil pine-trunks, in deposits of peat and lignite;
in a peat-bed on the Fichtelberg (Fikentscher, Trommsdorff); in a
lignite deposit near Utznach, Canton St. Gall (Könlein, Kraus); in
Danish peat-bogs (Steenstrup). It forms a thin covering of small,
fatty, shining scales, soft to the touch, and is also diffused through
the wood. On the Fichtelberg and near Utznach it is found associated
with Fichtelite. A resin, melting at 108°, obtained by Herz (N.
Repert. 10, 506) iu very small quantity from the lignite of the Hohen-
peissenberg in Southern Bavaria, may possibly be retene.
Formation. In the dry distillation of pine-wood rich in resin, it
passes over with the tarry liquors, and separates therefrom in scales
having the appearance of paraffin (Knauss). By submitting colophony
to dry distillation and passing the vapour through a red-hot tube,
Fritzsche obtained several hydrocarbons forming compounds with
picric acid, amongst them probably retene: metanapthalin, which is
obtained in a similar manner, is perhaps impure retene (Fritzsche).
Preparation. From Fossil Wood. The comminuted wood is exhausted
by boiling with alcohol; the greater part of the alcohol is then dis-
tilled off; and the remainder of the decoction is evaporated to dryness
and treated with sulphide of carbon, which dissolves retene and other
substances, leaving a red-brown acid resin. The sulphide of carbon
is removed by distillation, and the residue dissolved, together with
picric acid, in benzene, when, on cooling, a compound of retene with
picric acid and benzene separates out in yellow needles. These are
pressed and recrystallised from alcohol, with addition of excess of
picric acid, and the compound of retenc and picric acid is decomposed
in a manner similar to that described at page 165, vol xvi: the sepa-
rated retene is recrystallised from alcohol (Fritzsche). Kraus boils the
wood in alcohol and purifies the retene which separates by recrystallisation. When
the crystals obtained from the wood-remains in Danish peat-bogs are dissolved in
boiling alcohol, tekoretin crystallises out first, and afterwards retene (Steenstrup).
Properties. Soft, shining laminæ, resembling boracic acid, unctuous
to the touch (Trommsdorff). Nacreous, less loose than napthalin
(Fehling). Melts at 87.5° (Steenstrup), at 98-99° (Fehling), at
107.5° (Trommsdorff), at 114° (Kraus). Fused retene solidifies at 90°,
the temperature rising to 95° (Fritzsche). Solidifies, on cooling, to a
white, very brittle mass. Evaporates gradually in the air and over
the water-bath; on melting it gives off white clouds, which condense
to a woolly sublimate (Kraus). Volatilises slightly with water-vapour.
Boils at a temperature about the boiling point of mercury, and distils
almost unchanged, the distillate becoming brown and the residue
10
PRIMARY NUCLEUS C36H18.
carbonising only towards the end of the distillation (Fritzsche, Fehling).
See below. Inodorous, tasteless. Sp. gr. after fusing and solidifying,
0.88 (Trommsdorff): according to Fehling, it sinks in cold, but floats
on boiling water.
H. Tromms- Kraus. Steen- Fehling.
36 C.... 216 92.31
18 H.... 18
....
7.69
....
dorff.
90.91
7.56
....
91.36
7.42
....
strup.
90.18
9.24
...
mean.
91.68
8.36
(36H18... 234 ....100.00 98.47 98.78 99-42 ....100.04
....
Polymeric with benzene (Trommsdorf, Kraus).
Fritzsche.
earlier.
mean.
later.
....
92.19
7.60
92.41
7.78
....
....
99.79.100-19
Decompositions. 1. Fused retene gives off, at 160°, a number of
small bubbles, boils at 200°, turning brown, and yields first a colour-
less (but altered), then a brown distillate, and at last a black tar,
charcoal being left behind. The distillate melts with the warmth of
the hand, and does not afterwards solidify when left at rest, but if
shaken, it partially solidifies in laminæ. By repeated distillation it is
obtained quite fluid, and no longer yields retene when dissolved in
alcohol. The crystals of the distillate, freed from retene, contain
85.91 p. c. C., 10.84 H.; the oil contains 86·18 p. c. C., and 11·2 H.,
the two are therefore isomeric (Kraus). This retene probably contained
fichtelite (Kr.). See above. 2. Retene burns with a bright smoky flame
(Trommsdorff, Kraus).—3. Nitric acid converts retene into a resin
(Fritzsche); more dilute acid also forms crystalline products
Fehling). Trommsdorff's retene is not attacked by fuming nitric acid; that of
Kraus is dissolved, and is thrown down from the solution by water white and
crystalline.-4. Retene forms coloured resins by treatment with chromic
acid (Fehling), and with hydrochloric acid and chlorate of potash
(Fritzsche).5. By prolonged contact with oil of vitriol, retene is
dissolved, evolving an odour of sulphurous acid, and forms retene-
bisulpholic acid, which crystallises out in combination with sulphuric
acid on standing. Retene heated with oil of vitriol yields sulpho-
retene (Fritzsche).
Knauss added retene to a mixture of fuming and ordinary oil of vitriol, warmed
the mixture to promote solution, and saturated the liquid, after dilution, with
carbonate of lead. In this way he obtained, on one occasion, a lead-salt, which
solidified to a jelly on cooling the concentrated solution, and contained, after pressing
and drying at 100°, 26 92 p. c. C., 2.30 H., and 42·82 PbO. Another time, on super-
saturating oil of vitriol with retene and diluting the solution, unchanged retene
separated, together with a white powder; the liquid when saturated with carbonate
of lead, yielded, besides the above salt, retene-bisulpholate of lead, and white flocks of
a third lead-salt, soluble only in boiling water, and containing 46·80 p. c. C., 4·47 H.,.
and 29 82 Pьo.
6. Retene is not acted upon by potassium (Trommsdorff, Steenstrup),
or by caustic potash, or lime (Fehling), even when distilled therewith.
Retene is insoluble in water. It dissolves with difficulty in cold,
and much more readily in boiling, alcohol. One part of retene dissolves in
28.6 pts. of boiling alcohol of 94 p. c. (Trommsdorff), in 40 pts. of 75 p. c.; on cool-
ing 1/800th remains in solution (Fritzsche).- Easily soluble in warm ether,
and in volatile and fixed oils.
Retene with Picric acid. Retene is dissolved together with three
parts of picric acid in hot alcohol or ether, and the crystals are col-
lected and pressed. Woolly, delicate, orange-yellow needles, darker
after fusion. Melts, when heated, to an orange-red liquid, which
solidifies at 125°.- Washing with alcohol decomposes it; alcohol of
:
SULPHORETENE.
11
:
75 p. c. dissolves picric acid and leaves retene behind; alcohol of 90 p. c.
dissolves a portion of the compound as a whole, and in the remainder
crystals of retene are deposited (Fritzsche).
48 C
3 N
21 H
14 O
C36H18, C12H³X³O²
288
42
62.20
....
....
21
112
463
100.00
....
9.07
4.54
24.19
Fritzsche.
mean.
earlier.
later.
62.67
62.40
....
4.55
4.73
Contains 51:38 p. c. retene and 18S 62 p. c. picric acid (Fritzsche). (Calc. 50 51
p. c. retene, 49-46 pieric acid).
Retene with Picric acid and Benzene. When a mixture of retene
and picric acid is dissolved in benzene, there separate on cooling
needles containing 13.90 to 14:47 p. c. benzene; they become opaque
in the air, and lose the whole of the benzene (Fritzsche).
Fritzsche.
C35H18
234
43-25
43.75
A
C12H6
78
14:42
1447
C12H3X302
229
42.33
42.35
C36H18, C126, C¹²H³X³O²
541
100.00
100.57
Conjugated Compounds of Retene.
Sulphoretene.
C13620208 = C6H18,2SO3,2HO.
FRITZSCHE. J. pr. Chem. 82, 339.
On diluting the solution of retene in oil of vitriol with an equal
volume of water, filtering the liquid from the crystals of a hydrated
compound of retene-bisulpholic acid and sulphuric acid which form on
cooling, and boiling the mother-liquor with more retene, Fritzsche.
found that the retene floated unattacked on the surface of the liquid;
he therefore added gradually twice the volume of oil of vitriol and
heated the mixture to 170° or 180°, till the retene disappeared. The
black-green liquid, after cooling, was decanted from the tar simultane-
ously produced, diluted with water, filtered, and neutralised with
ammonia, whereby sulphoretene was precipitated. The precipitate
was washed, dried, freed from admixed retene by treatment with ether,
and crystallised from boiling water or alcohol.
Properties. Deposited from water in thin laminæ, and from alcohol
as a light sandy powder or in crusts. Melts only at the point of
decomposition.
Fritzsche.
36 C .....
216
65.03
65.23
20 H
20
6.02
6.08
2 S
32
9.67
9.74
8 0.....
64
19.28
18.95
C36H18,SHO....
C6H18, S2H O³.... 332
100.00
100.00
12
PRIMARY NULLEUS C36HIS.
Decompositions. When heated it blackens and yields a solid distillate
which is easily soluble in ether and combines with picric acid, like
On digestion with oil of vitriol, it reddens, turns semi-fluid,
and dissolves with red colour. Water, gradually taken up by the
solution, precipitates flocks; added in larger quantity, it forms a clear
solution which deposits a large quantity of needles on cooling. The
solution is no longer precipitated by ammonia, but forms therewith
difficultly soluble granules, probably of retene-bisulpholate of ammonia.
Combinations. Sulphoretene is wetted with difficulty by cold
water and dissolves but slightly. Boiling water dissolves it abundantly
but slowly.
Dissolves abundantly in hot dilute mineral acids, and is deposited
from the solution, on cooling, in flocks or in the form of a jelly, or,
when ammonia is added to the hot solution, in laminæ.
With Hydrochloric acid. Obtained by boiling sulphoretene with
concentrated hydrochloric acid. It is deposited from the hot liquid as
a heavy oil, forming, on cooling, a crystalline solid which is immediately
decomposed by water.
With Oxalic acid. When aqueous oxalic acid is boiled with an
excess of sulphoretene, the filtrate first deposits unchanged retene,
and, on further cooling and standing, a white granulated powder, which
seems not to be decomposed by water.
With Picric acid. The solution of sulphoretene in hot aqueous
picric acid solidifies, on cooling, to a jelly, which dries up to a dark
orange-yellow, paper-like mass, and crystallises from alcohol in yellow
needles very difficultly soluble in benzene.
Sulphoretene dissolves freely in boiling aqueous ammonia, crystal-
lising therefrom on cooling. It dissolves slightly in solution of caustic
potash.
Soluble in cold, and much more freely in boiling alcohol. Nearly
insoluble in bisulphide of carbon, ether, and benzene.
Retene-bisulpholic Acid.
C26II18S4012 = C6H18,4SO³.
----
FRITZSCHE. J. pr. Chem. 82, 330.
KNAUSS. J. pr. Chem. 82, 334.
Retendisulfosäure. Disulforelensäure (sce p. 10).
Preparation. Retene is added to oil of vitriol slightly diluted with
water, and the solution is allowed to stand till it crystallises in a solid
mass; it is then diluted with water, neutralised with baryta and car-
bonate of baryta, filtered from the precipitated sulphate, and concen-
trated to crystallisation. The retene-bisulpholic acid is liberated from
the baryta-salt by sulphuric acid (Fritzsche).
The aqueous solution, when evaporated, yields a syrup which solidi-
fies, on cooling, to a tough, waxy mass of confused needles. The
alcoholic solution yields larger needles (Fritzsche).
HELENENE.
13
When subjected to dry distillation it puffs up, evolves sulphurous
acid, and yields a distillate which solidifies on cooling, and resembles
the baryta-salt (Fritzsche).
The acid dissolves in water. The solution of retene in oil of vitriol deposits,
on absorption of water, oily drops which dissolve in a larger quantity of water
(Fritzsche).
A solution of retene in moderately dilute oil of vitriol forms, on
standing, crystals of a compound of retene-bisulpholic acid with sulphuric
acid, which convert the saturated solution into a pulpy mass.
From
100 parts of retene, 280 parts of these crystals (containing 58.13 p. c.
free sulphuric acid) are obtained. They may therefore be regarded as
a compound of 1 at. of retene-bisulpholic acid with 10 at. of oil of
vitriol. They dissolve easily in water, and are apparently deposited
therefrom in hydrated crystals (Fritzsche).
Retene-bisulpholate of Baryta. Preparation, above. Delicate, colourless
needles, giving off 14.46 p. c. water at 175° (10 at. = 14.53 p. c. HO),
and absorbing it again on exposure to moist air. Submitted to dry
distillation it yields a liquid distillate, which solidifies on cooling, and
combines with picric acid to form yellow needles (Fritzsche).
36 C
16 H
2 Ba
4 S.
12 O
C³¹H¹Ba²,4SO³
Dried.
Fritzsche.
216
40.81
40.78
16
3.02
3:07
137
25.90
25.85
64
12.14
12:16
96
18.13
18.14
......
529
........ 100·00
100.00
-
Retene-bisulpholate of Lead. See p. 10. Dissolves slightly in cold,
and freely in boiling water, separating therefrom on cooling in white
flocks (Knauss).
36 C
16 H
4 S
10 O
2 PbO
C36H16 Pb²,4SO³
Knauss.
216
36.00
35.93
16
2.67
3.17
64
10.67
80
13.33
224
37.33
37.43
600
100.00
The acid dissolves easily in alcohol (Fritzsche).
Primary Nucleus CH24.
Helenene.
C'36 H24 ?
GERHARDT. Ann. Chim. Phys. 72, 181.-N. Ann. Chim. Phys. 12,
190.
When helenin is distilled with anhydrous phosphoric acid, a light
oil passes over, with evolution of carbonic oxide, and a black viscous
14
PRIMARY NUCLEUS C6H24.
residue remains behind. The distillate is treated repeatedly with fuming
sulphuric acid to remove unchanged helenin, precipitated with water,
dried, and rectified.
Properties. Yellow or colourless oil, lighter than water. Boils at
285 to 295 (Traité, 4, 298). Odour faint, resembling that of acetone.
Gerhardt.
:
រ
1
mean.
36 C ...... 216
24 H
90
89.33
38 C ......
228
89.76
21
10
10.22
26 H
26
10.24
CH24....... 240
100
99.55
C381126...... 254
100.00
Gerhardt hesitates between these two formulæ.
Helenene burns with a smoky flame. — In nitric acid it turns red,
then green, and is precipitated by water apparently unaltered; when
heated it is converted into a resin. Cold fuming oil of vitriol is without
action on helenene; the hot liquid carbonises it: if the mixture be
gently heated, the whole dissolves completely with brown-red colour,
and on diluting the solution with water, neutralising with carbonate of
baryta, and evaporating the filtrate, helenene-sulphate of baryta (con-
taining, at 100°, 5.9 p. c. H., and 17·75 BaO) is obtained. The salt is
bitter, easily soluble in water, and non-crystalline.
Carotin.
C3H240² = C36H 24,0²?
WACKENRODER. Mag. Pharm. 33, 148; abstr. Berzel. Jahresber. 12,
277.
ZEISE. J. pr. Chem. 40, 297; Ann. Pharm. C2, 380.
AUG. HUSEMANN. Dissert. über Carotin und Hydrocarotin, Gött. 1860;
Ann. Pharm. 117, 200; abstr. Chem. Centr. 1861, 343; Rép. Chim,
pure 3, 407; Kopp's Jahresb. 1861, 754.
Discovered by Wackenroder in 1832, Vauquelin (Ann. Chim. Phys. 41, 48)
raving previously described a resinous red-yellow colouring matter obtained from
carrots. Especially investigated by Husemann.
Occurrence.
In the roots of the cultivated Daucus Carota.
Preparation. Rasped carrots are subjected to pressure, and the
press-cake is repeatedly agitated with water and again pressed; the
united liquids are precipitated by dilute sulphuric acid, with addition
of a little tincture of galls, and the precipitate of carotin, hydro-
carotin, and other substances (principally vegetable albumin) is pressed
and boiled, in its half-dry state, six or seven times with 5 or 6
times its volume of alcohol of 80 p. c., which takes up hydrocarotin
and manuite. It is then dried and exhausted by boiling six or eight
times in bisulphide of carbon; the greater part of the bisulphide is
distilled off; and the residue is mixed with an equal volume of alcohol
and left at rest, when the carotin crystallises. It is washed with
CAROTIN.
15
boiling alcohol of 80 p. c., and at last with boiling absolute alcohol till
the washings have only a slight yellow colour (Husemann). Zeise
boils the precipitate produced by sulphuric acid in diluted carrot-juice,
after washing, with concentrated solution of caustic potash, and washes
it with dilute sulphuric acid and with weak and strong alcohol, in
succession, to dissolve fat, vegetable albumin, and other substances:
the carotin remaining behind is crystallised from bisulphide of carbon
with the help of absolute alcohol. Wackenroder obtains carotin by
exhausting with ether either the sliced roots washed and dried, or the
coagulum formed by heating the expressed juice. The residue left on
evaporating the ethereal solution is shaken either with cold strong
alcohol, or repeatedly with ammonia, to remove fatty matter; it is then
again dissolved in ether, and, after addition of alcohol, left to
crystallise.
Properties. Carotin forms red cubes, or octahedral crystals, some-
times exhibiting a golden or satiny lustre. At 100° it assumes a
splendid red colour, resembling that of copper reduced by hydrogen.
(Husemann, Zeise). Melts at 168° (Zeise), 167.8° (Husemann), to a
thick dark-red liquid, which solidifies in an amorphous condition on
cooling. See below. Inodorous, tasteless, neutral (Wackenroder); ac-
cording to Zeise, the odour is faint and agreeable; according to Huse-
mann, powerful, especially on warming, like that of orris root. Heavier
than water.
Husemann.
mean.
36 C
24 H
216
84.37
84.06
24
9.37
9-78
20
16
6.26
6.16
C36IT2102
.... 256
100.00
100·00
Zeise proposed the formula CH¹.
Decompositions. 1. In diffused light, and more quickly in sunshine,
it becomes paler and colourless from without inwards, so that on ex-
posure for three weeks the red colour disappears completely. The
resulting colourless product is difficultly soluble in bisulphide of carbon
and benzene, easily soluble in alcohol and ether, and non-crystallisable;
it turns red again when heated (Husemann). This change, supposed by
Wackenroder to be caused by an admixture of fat turning rancid, is suffered also by
pure carotin (Husemann). 2. Carotin dried at 90°, when subjected to a
gradually increasing temperature, loses at 150°, 10 p. c. in weight, and
becomes inodorous and discoloured: when thus altered, or when fused,
it behaves towards solvents in the same manner as bleached carotin
(Husemann, Zeise). Carotin, heated above its melting-point, forms a
limpid liquid; after being heated to 250° it is soft and yellowish-red
on cooling; at a higher temperature (287', Zeise) it carbonises, with
empyreumatic odour, giving off a little gas and a colourless oil (Huse-
mann, Zeise).
3. When heated in the air, carotin takes fire and burns
without leaving a residue (Zeise).
4. Dry chlorine converts carotin into quadrichlorcarotin. Bromine
and iodine also form substitution-products (Husemann). 5. Carotin dissolves
in cold fuming nitric acid with yellow-red colour, and is precipitated by
water as lemon-yellow nitrocarotin, which is insoluble in bisulphide of
16
PRIMARY NUCLEUS CH; CIILORINE-NUCLEUS CCH.
carbon, and difficultly soluble in ether and absolute alcohol.-6. Oil
of vitriol dissolves carotin, forming a fine purple-blue solution, from
which water precipitates amorphous carotin in dark-green flocks.
Carotin which has been altered by heat or exposure to air dissolves in
oil of vitriol with brown colour. - 7. Dry sulphurous acid colours carotin
deep indigo-blue without producing further change. Blue carotin
turns red again at 125°, or when warmed with caustic potash; it does
not contain sulphurous acid. Aqueous sulphurous acid slowly colours
carotin coffee-brown; caustic potash restores the red colour. - 8. Caro-
tin is rendered uncrystallisable by boiling with alcoholic potash. It is
not decomposed by nascent hydrogen, nor by hydrosulphuric acid,
alcoholic hydrosulphate of ammonia, dry hydrochloric acid, dilute
mineral acids, or aqueous alkalis (Husemann).
Combinations, With Water? Solutions of carotin in imperfectly
dehydrated bisulphide of carbon or benzene deposit a white efflorescent
body, which splits up, on the slightest warmth, into water and carotin,
part of the carotin becoming sulphur-yellow and amorphous. More
permanent crystals, perhaps of a second hydrate, are obtained, together
with carotin, from the bisulphide solution to which absolute alcohol has
been added: they form thin colourless laminæ, a solution of which in
benzene deposits distinct six-sided prisms (Husemann).
Carotin is insoluble in water and in aqueous alkalis and acetic acid
(Wackenroder). Its alcoholic solution is not precipitated by metallic
salts, but is coloured darker and greenish by sesquichloride of iron
(Husemann).
Carotin is easily soluble in bisulphide of carbon. It is scarcely soluble
in boiling dilute or absolute alcohol, but more freely so in presence of
hydrocarotin or fat oils. Amorphous carotin is soluble in alcohol.
Difficultly soluble in ether and chloroform, and easily soluble in benzene
and in fired and volatile oils.
Chlorine-nucleus C36 C14H20.
Quadrichlorcarotin.
C36C14H2002
C¹³°C14T20,0²?
HUSEMANN. Diessertation über Carotin, &c. Gött. 1860.
Carotin exposed for some time to the action of dry chlorine, takes up
about 55-86 p. c. of its weight (4 at. Cl 54 p. c.), and becomes whitish-
yellow and almost completely soluble in alcohol. From the alcoholic solu-
tion water precipitates quadrichlorcarotin as a white powder containing
37·06 p. c. chlorine (cale. 3601 Cl). It turns dark-red and soft at 100°,
and melts at 120°. Easily soluble in bisulphide of carbon, ether,
and benzene.
=
ALKANET-RED.
17
26
Primary Nucleus C3II25; Oxygen-nucleus CIIO6.
Alkanet-red.
? C35H2008 = ('361±²º0°,0².
PELLETIER. J. Phys. 79, 278; Bull. Pharm. 6, 445. —- Ann. Chim. Phys.
51, 191; Schw. 67, 87; Ann. Pharm. 6, 27.
JOIN. Chem. Schriften 4, 81.
BOLLEY & WYDLER.
Ann. Pharm. 62, 141.
Acide anchusique (Pelletier). Pseudalkannin (John). Anchusin. -- Preisser's
statements were contradicted by Bolley (Ann. Pharm. 62, 133). The colouring
matter of the roots of Anchusa tinctoria (Handbuch viii, Phytochem. 58).
Preparation. 1. The chopped roots are exhausted in a percolator
with cold water, which takes up a brown substance; they are then
dried and exhausted with alcohol. The alcoholic extract, after addi-
tion of a few drops of hydrochloric acid, to prevent the conversion of
the red into alkanet-green, is first distilled and then evaporated over
a water-bath, till a thick opaque liquid remains, from which the greater
part of the colour is already deposited; the liquid is shaken with
ether, which assumes a dark-red colour, and with water; and after
removing the aqueous layer, the ethereal solution is repeatedly shaken
with fresh water, until it is reduced in bulk and becomes syrupy. On
evaporation the alkanet-red is left behind (Bolley & Wydler).
2. Coarsely powdered alkanet roots are exhausted with bisulphide of
carbon; the extract is freed from the bisulphide, partly by distillation
and completely by evaporation over a water-bath; the residue is
treated with cold water containing 2 p. c. of caustic soda; and the fine
indigo-blue solution is filtered and precipitated with a slight excess of
hydrochloric acid, which throws down the alkanet-red as a red-brown
precipitate. This is washed with water, collected, pressed, and dried.
The mass thus obtained forms a purple-red powder when triturated,
and colours fat very deeply (Lepage, Polyt. Centr. 1859, 751; Chem.
Centr. 1859, 397). — Pelletier either exhausts the roots with boiling
alcohol and evaporates, and dissolves the residue in ether, or exhausts
the root with ether and evaporates the extract.
When
Properties. Dark red-brown, resinous, brittle mass, slightly heavier
than water, melting below 60° without decomposition.
cautiously heated, it volatilises in violet-red vapours resembling those
of iodine, having a penetrating odour, and sublimes in very light
flocks; a part, however, is decomposed (Pelletier). According to Pelletier
it has an acid reaction; according to Bolley & Wydler it has not.
Calculation according to Gmelin.
Pelletier. Bolley & Wydler.
36 C
20 H
80
C36 H2009
216
72.00
69.85
•
71.33
20
6.67
6.93
7:00
64
21.33
23.22
21.67
300
...... 100·00
100.00
100.00
Pelletier's formula is C7II04; that of Bolley & Wydler CIÒ³.
VOL. XVII.
C
18
PRIMARY NUCLEUS C36H26; OXYGEN-NUCLEUS C36H06
Decompositions. 1. Alkanet-red, submitted to dry distillation, yields a
combustible gas and water, together with aromatic and empyreumatic
oils.-2. Chlorine passed into the alcoholic solution colours it dirty
yellow, and throws down yellow flocks soluble in alcohol. - 3. Con-
centrated nitric acid converts it into oxalic acid and a small quantity
of a bitter substance.-4. The alcoholic solution mixed with water
and boiled is quickly coloured blue-green (Pelletier). Pure alkanet-red
dissolved in alcohol remains unchanged after boiling for four hours,
but, on addition of a little ammonia or of the nitrogenous brown
substance of the roots, it is converted into alkanet-green (Bolley &
Wydler).
Alkanet-green is obtained by evaporating the alcoholic tincture of the roots
without addition of hydrochloric acid, the change of colour appearing soon after
boiling commences. The extract is evaporated to dryness over a water-bath; the
black-green residue is washed with water, which becomes coloured by a brown
nitrogenous substance, and then exhausted with ether, which takes up a large quan-
tity of a fine green colouring matter. Alkanet-green contains 70'08 p. c. C., 7·60 H.,
and 22:32 O., corresponding to the formula C3H08 (calc. 7034 p. c. C., 7·64 H.),
and is formed from alkanet-red by the elimination of carbonic acid. According to
Bolley & Wydler thus: C35H2009 + 2HO = C³4H²²O³ + CO².
C34H22O3
The brown nitro-
genous substance is easily soluble in water, especially when hot, but insoluble in
ether and strong alcohol. Its aqueous solution is rendered darker by alkalis, and
precipitates metallic salts. By slow evaporation in the air, it acquires an acid
reaction. It contains 40·05 p. c. C., 4:32 H., 3·12 N., and 52.51 O. (Bolley &
Wydler).
Alkanet-red is insoluble in water. It dissolves in oil of vitriol with
amethyst-red colour (John).
Dissolves in aqueous ammonia and in alkalis with blue colour, and
is precipitated by acids in brown-red flocks. Baryta-, strontia-, and
lime-water also form blue compounds only slightly soluble in water,
but, like the compounds with alkalis and metallic oxides, soluble in
alcohol and ether (Pelletier). Chloride of tin (proto-salt?) throws
down from alcoholic alkanet-red a scarlet-red precipitate (John); bi-
chloride of tin colours it violet without forming a precipitate (Bolley &
Wydler). Alcoholic alkanet-red does not precipitate alcoholic neutral
acetate of lead; but from the alcoholic solution of the basic acetate it
throws down a grey-blue precipitate somewhat soluble in alcohol.
It colours sesquichloride of iron decp olive-green, with slight precipita-
tion (Bolley & Wydler). — Mercuric chloride precipitates the alcoholic
solution flesh-coloured: other metallic salts, alum, for example, pre-
cipitate it only on account of the water they contain, the precipitates
being therefore quite soluble in alcohol (Pelletier).
Alkanet-red dissolves in alcohol, and more easily in ether. It is
soluble in volatile oils and fats, with fine red colour (Pelletier).
Appendix to Alkanet-red.
1. Chica-red.
BOUSSINGAULT. Ann. Chim. Phys. 27, 315; Berzel. Jahresber. 5, 251.
O. L. ERDMANN. J. pr. Chem. 71, 198; Dingl. 147, 467; Chem. Centr.
1857, 753; Chem. Gaz. 1857, 465; Kopp's Jahresb. 1857, 487.
CHICA-RED.
19
The resinous red of Bignonia Chica. The colouring principle of the
dye-stuffs known in commerce as Chica, Carajuru, or Carucru.
Carajuru is obtained by the natives of Guiana and Brazil from the
leaves of Bignonia Chica. The bruised leaves are steeped in water and
set aside till fermentation takes place, during which the red colour is
thrown down. The precipitation is accelerated by the introduction of
a bark into the liquid. The colour is washed, dried in the sun, and
made into balls. Carajuru occurs in the form of blood-red cakes, six
or eight inches in diameter, and three to four inches thick, resembling,
except in point of colour, pieces of indigo. It is a mixture of chica-red,
vegetable cellular matter, and mineral substances. See also Hancock,
(Ed. N. Phil. J. 7, 283), and Virey (N. J. Pharm. 5, 151), on carajuru.
Chica-red is obtained from carajuru by boiling with alcohol and
evaporating the tincture, when it is left as an amorphous, brownish,
shining mass (Boussingault). This mass is digested in ether till it
imparts only a light yellow colour thereto, and the undissolved portion
is dried over oil of vitriol (a); or the colouring matter is extracted with
alcohol containing sulphuric acid; the solution neutralised with car-
bonate of ammonia; and the precipitate washed with boiling water
and dried at 100° (b) (Erdmann).
Chica-red obtained according to a contains 59.62 p. c. carbon, 5·34
hydrogen, and 35-04 oxygen; that prepared according to b contains,
on an average, 63.10 p. c. carbon, 4.94 hydrogen, and 31.96 oxygen;
a corresponds therefore to the formula CH907; b to the formula of
anisic acid, C¹¹ºH80°, with which chica-red is isomeric (Erdmann).
Carajuru exposed to light assumes a brown-red, and at last a cinna-
mon-brown colour (Erdmann). Chica-red is decomposed by heat,
puffing up, evolving yellow fumes, and leaving a difficulty combustible
charcoal. Chlorine turns it brown and decomposes it. Cold oil of
vitriol blackens it without setting free sulphurous acid; water added
thereto dissolves a portion and leaves a black residue, which again
turns red in a few days under water (Boussingault). — Chica-red,
warmed with nitric acid, is pretty quickly converted into anisic acid,
without any considerable evolution of red vapours. The reaction
is attended with the emission of an odour of hydrocyanic acid
(Erdmann). Carajuru treated with nitric (or chromic) acid, also yields
principally anisic acid, together with picric and oxalic acids.
When carajuru is digested with potash, grape-sugar, and water or
alcohol, in a closed flask, according to the method described under
INDIGO (xiii, 39, 7), a violet solution, immediately turning brown in
the air, is produced, from which hydrochloric acid free from air throws
down a red-yellow precipitate (Erdmann).
-
Chica-red is insoluble in water. Carajuru gives up its colouring
matter to hydrochloric acid, forming a dark brown-yellow solution.
With warm dilute sulphuric acid it forms a yellow to orange solution,
which deposits yellow-red, amorphous granules on cooling, and gives,
with ammonia, a dark purple-red precipitate (Erdmann). — Chica-red
is soluble in ammonia, and is precipitated from the solution by hydro-
chloric acid with yellowish-brown colour (Erdmann). It dissolves.
quickly and completely in caustic potash and carbonate of potash, the
solution having the colour of wine-lees, and is again precipitated by
acids (Boussingault). According to Erdmann, carbonate of ammonia
and carbonate of soda extract hardly any colour from carajuru; accord-
ing to Boussingault, carbonate of potash takes up the whole of the
C 2
20
PRIMARY NUCLEUS C; OXYGEN-NUCLEUS C36H2006.
colouring matter. Aqueous, and more especially alcoholic potash,
take up the colouring matter of carajuru in large quantity, the latter
assuming a deep blood-red colour (Erdmann).
Chica-red dissolves easily in alcohol: the ruby-red solution forms
no deposit on cooling, and is precipitated by water only after concen-
tration (Boussingault). It dissolves slightly in ether with yellow colour
(Erdmann). Acetic acid is coloured dark-yellow by it, and deposits a
portion with carmine-red colour on standing. The red dissolves slightly
in oil of turpentine with brown colour, but is insoluble in castor, olive,
and neat's-foot oil, with which, however, it forms a very intimate.
carmine-red mixture (Boussingault).
2. Red colouring matter of the root-bark of Lithospermum arvense.
Extracted from the bark by alcohol containing acetic acid. The greater
part of the alcohol is distilled off, and the remainder is evaporated over
the water-bath; the black mass which separates from the aqueous
residue is collected and treated while still moist, with ether, which dis-
solves nearly the whole; and the ethereal solution is then filtered and
evaporated. The black, resinous colouring matter thus obtained is
not perfectly dried even by prolonged heating in a steam-bath; it
dries better after treatment with a concentrated solution of carbonate
of soda, by which a small portion is dissolved with blue colour, precipi-
table in red flocks by dilute sulphuric acid.-The colouring matter
dissolves in oil of vitriol with fine red colour, and is precipitated from
the solution by water with green coloration. It is quickly decom-
posed by nitric acid. It dissolves in ether with blue colour, and in
alcohol with violet colour, which is turned blue by alkalis (Ludwig &
Kromayer, N. Br. Arch. 96, 271; Chem. Centr. 1859, 87).
3. Resinous red of Spanish pepper. The extract, prepared with
boiling alcohol, is exhausted with water and cold alcohol in succession,
the red colour being thus left behind. It dissolves in hot caustic
potash-solution, and is precipitated blood-red by acids. Not percep-
tibly soluble in cold alcohol; the solution in hot alcohol deposits it in
flocks on cooling (Braconnot, Ann. Chim. Phys. 6, 124).
4. Nucin.
A. VOGEL, Jun., & REISCHAUER. N. Repert. 5, 106.
abstr. N. Jahrb. Pharm. 9, 328; J. pr. Chem. 73, 319.
Further 7, 1;
The (altered) colouring matter of green walnut-shells was examined
by Braconnot (Ann. Chim. 74, 305), and J. A. Buchner (Repert. 79, 355),
the latter of whom distinguished a Juglandic acid and a Walnut-
brown.
Source. In the green shells of walnuts. The nucin occurs ready
formed, but is accompanied by another body, allied to pyrogallic acid,
which readily decomposes the nucin when exposed to the air. The
unripe nuts, shelled about the end of June, become covered, on expo-
sure to the air, with small yellow crystalline needles of nucin, which
may also be detected in the cells of the shell under the microscope.
Most selvents, as ether, alcohol, chloroform, and oil of turpentine,
CETRARIC ACID.
21
:
extract the nucin from the shells, but leave it on evaporation in a
changed state in the form of a dark resin, from which nucin can no
longer be obtained by sublimation Rectified benzene or sulphide of
carbon only, when left for a short time in contact with the shells, yields
on evaporation crystals of nucin, which, however, easily undergo altera-
tion when benzene is the solvent used. But if the substance accom-
panying the nucin be first decomposed by shaking the ethereal extract
with nitrate of silver (or nitrate of copper), whereby metallic silver is
thrown down, the ethereal layer, when afterwards evaporated, yields
nuciu, which does not suffer change. The substance which decom-
poses the nucin may be obtained in the following manner. Walnut-
shells are digested with alcohol, and the tincture is removed, whereupon
it exhibits a yellow colour, before turning green or brown, and imme-
diately precipitated with neutral acetate of lead; the white precipi-
tate, separated by filtration, is then decomposed by hydrosulphuric
acid; and the filtrate is evaporated, an acid gum having a harsh taste,
being left behind. This substance, in contact with nucin, turns it
brown and decomposes it.
Preparation. The separated and somewhat comminuted shells are
digested for two hours in ether, and the decanted tincture is shaken up
with an aqueous solution of nitrate of copper containing a slight excess
of hydrated oxide of copper, until a pure blood-red coloration appears;
the ethereal layer is then removed and allowed to evaporate over oil
of vitriol. (When evaporated in the air, the nucin turns brown and undergoes
decomposition.) Part of the nuciu remains dissolved in the aqueous
nitrate of copper; it may be set free by the cautious addition of nitric
acid till the red colour of the solution is changed to blue-green, and
can then be taken up by ether. The nucin thus obtained is mixed
with quartz-sand and heated to 80° or 90° in a sand-bath placed within
a water-bath, when, on continued heating for a week, an abundant
sublimate is obtained.
Properties. Reddish-yellow, strongly lustrous, very brittle needles,
half an inch long; or small, apparently quadratic prisms, volatile with-
out decomposition, and containing no nitrogen.
Nucin is insoluble in water. It dissolves abundantly in aqueous
ammonia, in aqueous caustic alkalis, in borates and phosphates of the
alkalis, and in basic acetate of lead with splendid purple-red colour, and
is precipitated by acids in brown-red flocks.
It dissolves with difficulty in alcohol, easily in ether.
Oxygen-nucleus C¹³6H16010.
Cetraric Acid.
C36H16016
C3%[[101 = (3I1101,O.
BERZELIUS. Schw. 7, 317.
HERBERGER. Repert. 36, 226; 56, 273; 58, 271. Ann. Pharm. 21,
137.
SCHNEDERMANN. Ann. Pharm. 54, 143,
22
PRIMARY NUCLEUS C6H26; OXYGEN-NUCLEUS C6H10010.
SCHNEDERMANN & KNOP. Ann. Pharm. 55, 144; J. pr. Chem. 36, 107.
Cetrarin. Discovered by Herberger, but first obtained pure by Schnedermann
& Knop.
Sources. In Iceland moss (C'etraria islandica). - Sticta pulmonacea
contains a similar bitter substance, Knop and Schnedermann's stictic
acid, which has not been further investigated (J. pr. Chem. 39, 367).
Preparation. Iceland moss is boiled in alcohol with addition of
carbonate of potash, and the decoction is strained and precipitated
with dilute hydrochloric acid and water. The precipitate, which con-
tains cetraric acid, lichenic acid (xvi, 195), tallochlor and other sub-
stances, is exhausted, first with boiling alcohol of 42 to 45 p. c., and
afterwards with ether holding oil of rosemary or camphor in solution.
From the residual grey-white mixture of cetraric acid and an indif-
ferent white body, the acid is taken up by cold aqueous bicarbonate
of potash, and at once precipitated from the alkaline solution by hydro-
chloric acid. It is purified by crystallisation from the smallest possible.
quantity of alcohol. A portion of the cetraric acid is taken up by
the weak alcohol, and evaporates, together with the lichenic acid, on
cooling. The latter substance is extracted by boiling rock-oil as
described at xvi, 195, and the undissolved cetraric acid is then purified
with bicarbonate of potash. A further portion of the cetraric
acid dissolves in ether containing oil of rosemary, and crystallises
therefrom tolerably pure on partially distilling the solution and cooling
(Schnedermann & Knop). Cetraric acid may also be obtained by
precipitating an alkaline decoction of Iceland moss with hydrochloric
acid, washing the precipitate with a cold mixture of oil of rosemary
and ether, and exhausting the residue with bicarbonate of potash
(Schnedermann & Knop).
Herberger digests Iceland moss for an hour, at a temperature of
60-70°, in 4 pts. of alcohol of sp. gr. 0·83, decants, presses the residue,
and exhausts it twice with cold water. The clear alcoholic liquid, when
added to the aqueous infusion, deposits greenish-white flocks, from which
alcohol takes up a little cetrarin. The filtrate, mixed with sulphuric
acid, throws down cetrarin, which is collected, pressed, and treated, while
still moist, with ether or alcohol of sp. gr. 083, which takes up leaf-
green and a little cetrarin. The remainder, on boiling with 200 pts. of
absolute alcohol, is dissolved (with the exception of some inorganic salts),
and the filtrate, when cooled and concentrated, yields pure cetrarin.
The following substances are also obtained in the preparation of
cetraric acid.
a. Tallochlor. The green colouring matter of Iceland moss. It is
taken up by the ether and oil of rosemary used for washing cetraric acid.
After crystallising out the cetraric acid taken up at the same time, the
solution is evaporated to dryness, and the residue is dissolved in boiling
alcohol, diluted with water till the alcohol is reduced to 42-45 p. c.,
and filtered boiling. By this process, repeated several times, the
lichenic acid is removed, and the residue is then treated with boiling
rock-oil, which dissolves tallochlor and fat, whilst cetraric acid and
brown substances are left behind. The solution, after addition of
water, is submitted to distillation; the residue is dried till the rock-oil
is completely volatilised, and afterwards dissolved in alcohol; and the
CETRARIC ACID.
23
tallochlor is precipitated either by digestion with hydrate of lime, or
better by alcoholic neutral acetate of lead. The green flocks thus pro-
duced are boiled with ether, and freed from oxide of lead by means of
acetic acid,
Brittle, friable, green mass, insoluble in water, and nearly
insoluble in hydrochloric acid, but soluble in strong alcohol, ether, and
volatile and fixed oils (Schnedermann & Knop).
b. A yellowish-white, indifferent body. Remains behind on dissolving
cetraric acid in bicarbonate of potash, and is purified by washing with
water and crystallising from alcohol.-Inodorous, tasteless. After
deducting 0.2 to 0'3 p. c. of ash, it contains 67.39 to 70 p. c. carbon,
10.82 to 11-23 hydrogen, and 0.51 nitrogen. Insoluble in water, acids,
alkalis, ether, and oils, Dissolves with difficulty in boiling alcohol, the
solution becoming turbid and slimy on cooling (Schnedermann &
Knop).
Properties. Cetraric acid forms a snow-white, loose network of
delicate shining crystals, appearing under the microscope as long needles.
It is not volatile, and cannot be melted without decomposition. Very
bitter. Does not lose water at 100° (Schnedermann & Knop). Herberger's
cetrarin forms a white powder resembling magnesia, permanent in the
air, inodorous, and neutral.
36 C
16 H
16 O
C36H16016
Knop & Schnedermann.
mean.
60.05
At 100.
216
60.00
16
128
4.4.4
35.56
4.67
35.28
....
360
100.00
100.00
According to Knop and Schnedermann it is CH16015; according to Hlasiwetz
(Wien. Acad. Ber. 20, 208) C4H¹515.
Decompositions. 1. The solutions of cetraric acid in aqueous am-
monia and in the alkalis absorb oxygen from the air, especially when
heated, acquiring at the same time a brown colour, and losing their
bitter taste. When cetraric acid is boiled in caustic potash, with
access of air, till the bitter taste has completely disappeared, and the
solution is precipitated with hydrochloric acid, the brown precipitate
(lichenulmic acid of Knop & Schnedermann), dried at 80°, contains 60·7
p. c. C., 4·3 H., and 35 O.; it dissolves slightly in water, and combines
with bases: when dissolved in ammonia and dried over oil of vitriol, it
leaves a dark-brown mass, which is soluble in water and precipitates
the salts of the earth-metals and heavy metals (Knop and Schneder-
mann, J. pr. Chem. 40, 393.)
Cetrarin turns brown at 125°, and when more strongly heated gives
off a red-yellow acid oil, which solidifies in the cold: at 160° it blackens
and ultimately leaves a large quantity of porous charcoal. By long
boiling with water it is coloured brown. Concentrated nitric acid con-
verts it into a yellow-brown resin and oxalic acid, with evolution of
nitric oxide. Phosphoric acid gradually converts it into ulmin.
- Oil of
vitriol colours it first yellow, then brown, and dissolves it with red-
brown colour changing to dark blood-red: water throws down ulmin
from the solution. Aqueous hydrochloric acid gently warmed with
cetrarin converts it into cetrarin-blue, which remains behind on evapora-
tion, as a light green-blue bitter mass This last substance is quickly
21
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS C6H160¹º.
:
converted into ulmin by alkalis, and dissolves in oil of vitriol with dark
blood-red colour: it is coloured a fine carmine-red by concentrated
nitric acid, dissolves with yellow colour in a large quantity of the acid,
and is precipitated by water at first unchanged. When hydrochloric
acid gas is passed over cetrarin, there is no absorption in the cold, and
no formation of cetrarin-blue; but on heating, the cetrarin becomes
carbonised, with formation of a yellow-red liquid and a carmine-red,
semi-solid mass (Herberger).
Combinations. Cetraric acid is almost absolutely insoluble in
water; water boiled with it acquires a faintly bitter taste (Knop &
Schnedermann). - Cetrarin dissolves very slightly in bisulphide of carbon
(Herberger).
It dissolves very readily in aqueous alkalis and their carbonates; the
bright yellow solutions have a very bitter taste, and are precipitated by
acids. Respecting their alteration in contact with the air, see above.
cetrarin precipitates most metallic salts (Herberger).
Alcoholic
Cetrarate of Ammonia. Solutions of the acid in aqueous ammonia
turn brown in the air and on evaporation. When cetraric acid is boiled
with alcohol and solid carbonate of ammonia, and the yellow filtrate is
concentrated by rapid boiling in flasks, a small quantity of the ammonia-
salt separates from the red-yellow liquid, on cooling, in the form of a
yellow micro-crystalline powder; most of the salt remains, however, in
the mother-liquor, and undergoes further changes. In dry gaseous
ammonia, free from air, cetraric acid becomes hot, assumes a lemon-
yellow colour, and takes up 10.2 p. c, of its weight of ammonia, forming
the salt 2NII³,C6H16016 (calc. 9:44 p. c. NH³). The salt smells
slightly of ammonia, but loses this smell over oil of vitriol, and then
forms with water a fine yellow neutral solution (Knop & Schneder-
mann).
3
Cetrarate of Lead. Formed by precipitating the neutral ammonia-
salt with neutral acetate of lead. Yellow flocks insoluble in water.
The precipitate produced by alcoholic neutral acetate of lead in an alco-
holic solution of cetraric acid contains varying proportions (38.7 to 44-4
p. c.) of oxide of lead (Schnedermann & Knop).
Schnedermann & Kopp.
36 C........
216
38.19
36.29
14 H
14
2.48
2.78
11. O
112
19.80
21.20
2 Pho
223.6
39.53
39.73
C36H¹4Pb2016
565.6
100.00
100.00
The salts of the alkalis precipitate ferric salts brown-red, or in more
dilute solutions, blood-red. Cetrarate of silver is a yellow precipitate,
quickly turning brown (Schnedermann & Knop).
Cetraric acid dissolves with difficulty in cold, easily in boiling strong
alcohol. It dissolves slightly in ether, but not in fixed or volatile oils
(Schuedermann & Knop). It does not combine with urea (Hlasiwetz).
Alcoholic cetrarin is not precipitated by gallic or tannic acid (Herberger).
:
PELOSINE.
25
Oxyazo-nucleus C36NHI¹ºOº.
Pelosine.
C3NH3C = C3NIFO,II.
WIGGERS. Ann. Pharm. 33, 81; Prelim. Notice, Ann. Pharm. 27, 29.
BÖDEKER. Ann. Pharm. 69, 53; Pharm. Centr. 1849, 150; Chem. Gaz.
1849, 152; Lieb. Kopp's Jahresb. 1849, 385.
GR. WILLIAMS. Chem. Gaz. 1858, 321; J. pr. Chem. 76, 382; Kopp's
Jahresb. 1858, 375.
Cissampeline. Discovered by Wiggers, and specially investigated
by Bödeker. Occurs in Radix Pareira brava, the root of an American
menispermaccous plant, Cissampelas Pareira.
Preparation. The sliced or bruised roots are boiled four times in
water containing sulphuric acid, and the brown decoction is filtered.
When it is quite cold, carbonate of soda, not in excess, is added, and the
bulky grey-brown precipitate thereby produced is washed, dried, dis-
solved in water containing sulphuric acid, and treated with animal
charcoal. The filtered solution is again precipitated with carbonate of
soda; the now dirty-yellow precipitate is washed and dried completely
at 100°, and afterwards powdered and exhausted with ether, which
takes up pelosine. Water in the precipitate, or in the ether, prevents the solu-
tion of pelosine. Alcohol takes up other substances at the same time. The
colourless ethereal solution yields, on evaporation, anhydrous pelosine,
which is coloured yellow by some decomposition-product formed during
concentration (Wiggers). If the ethereal solution is not quite colourless, it
must be evaporated, and the foregoing process of solution in acid, precipitation
with carbonate of soda, and exhaustion of the dried precipitate with ether, repeated
(Wiggers).
Properties. Yellowish, transparent, amorphous varnish, triturable to
a white powder (Wiggers, Bödeker). In the moist state, or in solution,
it turns litmus blue. Has a nauseous, sweetish, bitter taste (Wiggers).
Bödeker.
At 120°.
mean.
36 C
N
216
72.24
71.93
14
4.68
21 H
21
7.02
7.13
60
48
16.06
C36NH2106
299
100.00
Decompositions, 1. Pelosine, when heated, melts easily, turns brown,
puffs up, evolves an odour of burning bread, and burns with a bright,
smoky flame, leaving a light, difficultly combustible charcoal (Wiggers).
2. Moist or dissolved pelosine, but not the perfectly dry substance, is
decomposed by exposure to air and light, with especial rapidity in pre-
sence of alkalis, with formation of a brown decomposition-product,
insoluble in ether, but soluble in alkalis (Wiggers), and of Bödeker's
pelluteine. The decomposition is accompanied by evolution of ammonia
26
PRIMARY NUCLEUS C36H26; OXYAZO-NUCLEUS C36NH906.
(Bödeker). 3. Pelosine dissolves in weak nitric acid without decom-
position. Nitric acid of sp. gr. 1.25, or higher, converts it, on warm-
ing, into a tough, brown-yellow, resinous mass, insoluble in pure water,
or in water containing nitric acid, probably the same body that is
produced on exposing pelosine to the air (Wiggers).—4. Pelosine
distilled with caustic potash yields methylamine, bimethylamine, pyrrhol
(xv, 5), and combustible gases (Gr. Williams).
Combinations.
With Water. Hydrated Pelosine. Pelosine takes
up water or aqueous vapour very rapidly (Bödeker). When the ethereal
solution is poured upon water, and the ether is distilled off, hydrated
pelosine remains floating on the water in the form of a white powder.
On shaking the ethereal solution with water, the hydrate separates at
the surface of contact of the two layers of liquid (Wiggers). Nearly
white, amorphous powder (Wiggers). After drying over oil of vitriol
it loses, at 120°, 8.21 p. c. = 3 at. water (calc. = 8.28 p. c. HO)
(Bödeker).
Pelosine is insoluble, or nearly so, in water cither cold or boiling
(Wiggers).
Pelosine neutralises acids completely. The salts are not crystal-
lisable; the hydrochlorate alone, according to Wiggers, forms small
nodules. From the aqueous solutions of the salts, ammonia, and caustic
alkalis and their carbonates, throw down hydrated pelosine as a bulky
white precipitate, easily soluble in excess of potash, but difficultly
soluble, or insoluble, in excess of the other precipitants. The salts of
pelosine give abundant white precipitates with phosphate of soda, and
with protochloride of tin (Wiggers).
Hydrochlorate of Pelosine. Dry hydrochloric acid gas is passed into
a solution of dry pelosine in ether free from water and alcohol, till the
solution has an acid reaction. The white flocks produced are quickly
thrown on a filter, and washed continuously with absolute ether, so
long as any acid is thereby removed, and the filter is at once placed in
a receiver over oil of vitriol. Snow-white powder, which absorbs
water with avidity, and cakes together to an amber-coloured mass.
Dissolves easily in water and in alcohol without colour, and remains
behind, on evaporation, as an amorphous varnish. The salt, exposed to
moisture, and afterwards dried over oil of vitriol, loses 5.08˚p c. of
water at 110° (2 at. = 5 24 p. c. HO) (Bödeker).
Bödeker.
Dried.
mean.
36 C......
N
216
64.38
63.69
14
4.17
4:08
22 H.......
22
6.55
6.59
60
48
14.32
14.56
Cl..........
35.5
10.58
11.08
CNH2O6, HCI
335.5
100.00
100.00
Pelosine does not combine with perchloric acid (Bödeker, Ann. Pharm. 71, 63).
Chromate of Pelosine. - Hydrochlorate of pelosine is precipitated
by bichromate of potash in bright yellow flocks, which become dirty
yellow-brown when washed, and assume a still darker colour on drying
in a vacuum. At 80° the salt quickly becomes dark-brown, and a
į
:
:
PELLUTEINE.
27
little over 100° evolves an odour of chinoline and carbolic acid, whilst
sesquioxide of chromium and charcoal remain behind (Bödeker). See
also (p. 26) the decomposition of pelosine by caustic potash, according to which
Williams regards the formation of chinoline as improbable.
Bödeker.
Over oil of vitriol.
mean.
36 C
N
216.0
58.81
58.99
14.0
3.81
23 H
23.0
6.26
5-55
80
64.0
17.42
CrO3
50.3
13.70
1454
C36NH2¹06, Cr03 + 2aq.
367.3
100'00
A
Chloride of gold forms with pelosine-salts, a dirty-yellow precipitate,
the supernatant liquid quickly assuming a violet colour and depositing
gold (Wiggers).
Chloroplatinate of Pelosine. Alcoholic hydrochlorate of pelosine is
precipitated by bichloride of platinum, and the pale-yellow precipitate
is washed with alcohol and water, whereby it acquires a brown colour
at the edges. Amorphous, strongly electric powder. After drying
over oil of vitriol, it does not lose weight at 110°. When more strongly
heated, it melts and swells up strongly, emitting a repulsive, pene-
trating odour (Bödeker).
36 C
N
22 H
At 100°.
Bödeker.
216.0
42.79
43.50
14.0
2.77
22.0
4.35
4.88
48.0
9.50
98.7
19.53
19.48
3 Cl
106.5
21.06
C36NH2106, HCl,PtC12
505.2
100.00
60
Pt
The salts of pelosine give an abundant white precipitate with tannic
acid (Wiggers).
Pelosine dissolves very easily in alcohol, and is precipitated from the
solution by water as a hydrate. It dissolves slowly, but abundantly,
in ether. In ether containing water it is converted into the hydrate,
which is insoluble in ether (Wiggers).
Appendix to Pelosine.
BÖDEKER.
Pelluteine.
Ann. Pharm. 69, 59.
Formation (p. 25.)
Hydrated pelosine is exposed to air and light until, after drying, it
is no longer soluble in absolute ether, and to convert the remainder
into pelluteine it is boiled repeatedly with water in a shallow basin.
The dried substance is boiled with absolute alcohol, and the solution
filtered from brown flocks of humus, when, on cooling, the pelluteine is
deposited in pale brown-yellow flocks, which are to be washed with cold
alcohol.
28
PRIMARY NUCLEUS C6H26; OXYAZO-NUCLEUS CNH¹O.
Pelluteine contains, at 110°, 73 88 p. c. C., 3:84 N., 6.18 H., and
16.10 O.; in the platinum double-salt, 17.84 p. c. Pt., whence Bödeker
deduces the formula CNH207; Gerhardt (Traité 4, 230), the formula
C3NH’O6.
Pelluteine behaves towards acids in the same manner as pelo sine.
It forms dark-yellow precipitates with various reagents. It is insoluble
in ether.
Codeine.
C30NII2106 = C36NH¹906, II³.
ROBIQUET. J. Chim. méd. 9, 96; J. Pharm. 19, 87; Ann. Chim. Phys.
51, 259; Ann. Pharm. 5, 106; Schw. 67, 297; abstr. Pogg. 27, 650.
- N. J. Pharm. 31, 10; J. pr. Chem. 72, 271.
GREGORY.
COUERBE.
J. Pharm. 20, 85.
Ann. Chim. Phys. 59, 159.
PELLETIER. J. Pharm. 21, 557; N. Br. Arch. 5, 158; Ann. Pharm. 16,
27. — Ann. Chim. Phys. 63, 185; Ann. Pharm. 22, 132.
REGNAULT. Ann. Pharm. 26, 25; J. pr. Chem. 16, 272.
LIEBIG. Ann. Pharm. 26, 44.
DOLLFUS. Ann. Pharm. 16, 215.
ANDERSON. Trans. Roy. Soc. Edin. 20, 157; Compt. chim. 1850, 321;
Ann. Pharm. 77, 341; Pharm. Centr. 1851, 337; N. Ann. Chim.
Phys. 34, 493.
Discovered by Robiquet in 1832; particularly investigated by Anderson.
Source. In opium. Smyrna opium contains 0.62 to 0.86 per cent.
(Mulder), 0.25 p. c. (Schindler); opium from Constantinople 0-52 p. c.
(Schindler). Couerbe obtained from 40 pounds of opium 14 ounces of
codeine. Merck obtained from Smyrna opiump. c.; from Bengal
opium p. c.
Preparation. By treating opium according to the Robertson-Gregory
method (xvi, 419), a mixture (or double-salt) of hydrochlorate of mor-
phine and hydrochlorate of codeine is obtained, from an aqueous solu-
tion of which ammonia precipitates the greater part of the morphine.
On concentrating the filtrate, hydrochlorate of codeine crystallises
first. It is freed from most of the sal-ammoniac with which it is mixed
by recrystallisation, dissolved in hot water, and decomposed by a con-
centrated solution of caustic potash, whereby a portion of the codeine
is thrown down in the form of an oil, which afterwards solidifies, whilst
another portion crystallises on cooling. The mother-liquor, when con-
centrated, deposits first a little more codeine, and afterwards crystals of
morphine (Robiquet, Anderson). The codeine is purified by washing
with cold water, dissolving in ether, and leaving the solution to evapo-
rate, with addition of water, when hydrated codeine crystallises
(Robiquet); or, the codeine is dissolved in hydrochloric acid, boiled with
animal charcoal, again precipitated with caustic potash, and freed from
morphine by solution in ether containing water (Anderson). — For other
modes of preparation see xvi, 421, 422.
Winckler (Repert. 45, 459) frees the aqueous extract of opium from
morphine by animonia, from meconic acid by chloride of calcium, and
CODEINE.
29
from colouring matter by basic acetate of lead. The filtrate is freed
from lead by sulphuric acid, treated with an excess of caustic potash,
and exposed to the air till the excess of potash is saturated with car-
bonic acid, after which it is agitated with ether. On evaporating the
ethereal solution, there remains a yellowish, non-crystalline residue,
which, after addition of hydrochloric acid, yields crystals of hydrochlorate
of codeine.
Merck (Ann. Pharm. 11, 279) treats the mixture of morphine and
codeine thrown down by caustic potash with cold alcohol, and neutralises
the tincture cautiously with sulphuric acid. He then distils off the
alcohol, dilutes the residue with water so long as cloudiness is produced,
and evaporates the filtrate to a syrup. After cooling, the syrup is
mixed with ether and an excess of caustic potash-solution, and shaken.
The separated ethereal solution yields, after some hours, crystals of
codeine, which are purified from adhering oil by solution in ether.
O. Henry (J. Pharm. 21, 222; abstr. Ann. Pharm. 15, 152) exhausts
3 ounces of opium with lukewarm water; concentrates the filtrate some-
what; precipitates morphine and narcotine 'by ammonia; and evaporates
the filtrate, whereupon the greater part of the meconate of lime is thrown
down. The precipitate produced (after filtering from the lime-salt) by
infusion of galls is dissolved in alcohol, according to vii, 177, 3, and
freed from tannic acid by means of neutral acetate of lead, and from
excess of lead by hydrosulphuric acid. The filtrate is then evaporated,
and the brown tarry residue is exactly neutralised with nitric acid. After
two crystallisations, silky needles are obtained, from which potash throws.
down a white precipitate of codeine.
Solutions containing morphine, codeine, and opianyl, when acidified
with hydrochloric acid, yield to ether only the last-named substance
(Pelletier).
On the detection of codeine in cases of poisoning, sec Stas (in the places men-
tioned, xvi, 424).
Properties. Codeine is obtained from ether in small, colourless,
anhydrous crystals (Regnault, Anderson). Hydrated codeine crystal-
lised from an aqueous solution loses its water of crystallisation at 100°
(Anderson).Codeine melts at 100° (Couerbe); at 150° and solidifies in
the crystalline state on cooling (Robiquet). Hydrated codeine melts.
to an oil in boiling water, losing its water of crystallisation (Couerbe). -
Codeine has a strongly alkaline reaction (Robiquet, Anderson). It is
poisonous (Kunkel). In doses of 0.15 to 0.20 gramme, it produces a heavy, in-
toxicated sleep, with feeling of stupefaction, and sometimes nausea and vomiting on
awaking; in doses of 0.020 to 0·03 grm. it is soothing (Robiquet). Compare Gregory
(J. Pharm. 20, 85). -Lavo-rotatory: [] 118.2°, scarcely altered by
acids (Bouchardet & Boudet, N. J. Pharm. 23, 392; Ann. Pharm. 88,
213), and not affected by difference of temperature. The rotation is
not in proportion to the amount of codeine in solution, and is not constant
for different colours (Robiquet).
36 C
Anhydrous.
216
N
1.1
72.24
4.68
Robiquet.
70.36
Couerbe.
71.85
5.35
5.23
21 H
60
21
48
7.02
16.06
7.59
7:15
16.70
15.77
་
C35NH2¹06
..... 299
100.00
100.00
100.00
1.
30
; OXYAZO-NUCLEUS CNH¹906.
PRIMARY NUCLEUS (H26
Regnault.
OZHO
C......
73.12
Gregory.
73.18
Will.
Anderson.
!
73.28
73.03
N
4.89
4.83
4.50
7.21
7.24
7.25
7.05
14.78
14.75
15.42
100.00
100.00
100.00
……....
According to Regnault, the formula is C35NH2005; according to Dollfus, C34NH19()5.
The above formula was proposed by Gerhardt (Rev. Scient., 10, 202; N. Ann. Chim.
Phys. 7, 253) and shown to be correct by Anderson.- Codeine contains 2 at. CH
more than morphine, and is isomeric with pelosine (p. 25).
Amorphous Codeine. When a solution of codeine in excess of mode-
rately concentrated sulphuric acid is warmed for some time (not how-
ever too long or too strongly), and is afterwards precipitated with
carbonate of soda, a grey precipitate is produced, which, after washing,
is to be dissolved in alcohol and again thrown down by water. It con-
tains 71.92 p. c. carbon and 7.53 hydrogen (after prolonged treatment
with sulphuric acid, 72.53 p. c. carbon, 6·84 hydrogen), and has therefore
the same composition as codeine. It melts at 100° to a black resin, and
is insoluble in water, but easily soluble in acids, forming amorphous
salts, which dry up to a resinous mass on evaporation. Amorphous
codeine dissolves easily in alcohol, and is precipitated from the solution
by ether (Anderson).
Decompositions. 1. Melted codeine, when more strongly heated,
creeps up the sides of the vessel without volatilising; on platinum-foil
it burns with flame and leaves no residue (Robiquet). — 2. For the reaction
with iodine, see below. Chloride of iodine forms biniodocodeine (p. 36)
(Brown).-3. Bromine-water quickly dissolves codeine, and forms hydro-
bromate of bromocodeine having a characteristic red colour; the salt
is converted by excess of bromine into hydrobromate of terbromo-
codeine, the greater part of which is thrown down in the form of powder
(Anderson). 4. Chlorine or chlorine-water forms with aqueous codeine
a dark-brown liquid, from which ammonia precipitates an amorphous,
basic resin (Anderson). — 5. Codeine dissolved in excess of dilute
hydrochloric acid and treated with successive small quantities of chlorate
of potash, at 70°,is converted into chlorocodeine (Anderson). — 6. Codeine
dissolves in cold oil of vitriol without coloration (Riegel, Guy). The
solution in excess of moderately strong sulphuric acid turns brown after
warming for some time, and throws down amorphous codeine on addi-
tion of carbonate of soda (see above): by continued heating a green
powder, corresponding with sulphonarcotide (xvi, 149) is obtained
(Anderson).-7. Strong nitric acid warmed with codeine acts violently
on it, with formation of red vapours and a red solution, leaving on
evaporation a yellow resin, the red solution of which in caustic potash
yields a large quantity of methylamine when heated. — Very dilute
nitric acid, at a temperature below 100°, forms nitro-codeine, which
is decomposed by continued heating, with formation of a yellow resin
(Anderson).
Oil of vitriol containing nitric acid immediately colours codeine pale-
green, then blue-green; with traces of nitric acid, green (Couerbe).
The colourless solution in oil of vitriol is coloured a dirty brown-red by
peroxide of lead, and dark-green, with brisk evolution of gas, by
chromate of potash (Riegel).
CODEINE.
31
8. Codeine, heated with caustic potash solution, solid caustic potash,
or potash-lime, evolves methylamine and propylamine [or trimethyla-
mine? (Hofmann, Ann. Pharm. 79, 29)], these substances being mixed
with ammonia, even when the decomposition is effected at the lowest
possible temperature. During the decomposition, colourless crystals,
resembling benzoic acid and having an alkaline reaction, sublime in the
neck of the retort; the crystals turn brown in the air, dissolve slightly
in water and easily in acids, and are precipitated by chloride of platinum.
If the temperature has not exceeded 175°, the alkaline residue in the
retort is black-brown and decomposible by acids, with separation of
humus-like flocks; it yields at a red-heat a little non-basic oil and a
further quantity of volatile bases, among which ammonia predominates
(Anderson). — 9. Concentrated alcoholic codeine absorbs cyanogen, as-
suming a yellow and brown colour, and deposits crystals of bicyano-
codeine, the odour of cyanogen being at the same time replaced by that
of hydrocyanic acid (Anderson).-10. Iodide of ethyl, heated with alco-
holic codeine, forms iodide of ethyl-codeine (How).
Codeine is not altered by sesquichloride of iron (Robiquet) or by
iodic acid (Riegel).
Combinations.—With Water. A. Bi-hydrated Codeine.-Codeine is
obtained from water, or from ether containing water, in hydrated
crystals (in small white silky scales: Robiquet) which lose 6·50 p. c.
(Robiquet), 5.65 p. c. (Gregory), 5·66 p. c. water (=2 at.) at 100°
(Anderson). Sp. gr. = 1·3 (Hunt, Lieb. Kopp's Jahresb. 1855, 566).
The crystals are right prismatic (trimetric, rhombic). Fig. 53, without a,
p and m. The crystals obtained from solution in water are without the
face t, but have in place of it a dome z, which would truncate the face
between t and u. y: y 92° 20′ (Miller), 92° 30′ (Kopp), 91° 40′
(Sénarmont), 92° 8' (Keferstein); u: t = 140° 23′; z ; t = 157° 25';
z : t = 141° 37' ; y : u = 116° 18′; y : i 116° 45'; u: i = 126° 57'
(Miller); u: u over m =
u : u over m = 78° 30′ (Kopp); u : u above = 99° 55′ (Sénar-
mont) 101° 2' (Keferstein); z: z above 134° 45' (Sénarmont)
134° 39′ (Keferstein); u : z = 163° 20′ (Keferstein, Pogg. 99, 275).
Cleavable parallel to t (Miller, Ann. Pharm. 77, 381), parallel to u (Kopp,
Krystallogr. p. 266).
36 C
Gerhardt.
N
23 H
80
216
68.14
.......
67.82
14
4.41
23
7.25
7.46
....
64
20.20
100.00
C36NH2¹06,2HO ........ 317
B. Codeine dissolves in cold, and more freely in hot water: 1,000
parts of water at 15° dissolve 12.6 parts, at 43°, 37 parts, and at
100°, 51.8 parts of codeine (Robiquet). When an excess of codeine is
boiled with water, the undissolved portion melts to an oil (Robiquet).
With Iodine.-Iodine, triturated with codeine, forms a brown com-
pound little soluble in water; the same body is formed also, together
with iodide of codeine, by alcoholic iodine (Pelletier). Tincture of
iodine throws down a scarlet-brown precipitate from hydrochlorate of
codeine (v. Planta). A solution of equal parts of iodine and codeine
in the smallest possible quantity of alcohol, deposits on standing small
crystals which are ruby-red by transmitted, and deep violet and
31
PRIMARY NUCLEUS C36H; OXYAZO-NUCLEUS CNH¹O.
liquor of hydrochlorate of morphine); another time the hydrated crystals were
rendered anhydrous at 100°
Anderson.
36 C
Anhydrous.
216.0
mean.
64.38
64.62
N
22 H
14.0
4.17
22.0
6.55
6.76
60
48.0
14.32
Cl
35.5
10.58
C36NH2¹06, HCI
335.5
100.00
Anderson.
Hydrated.
mean.
36 C......
216.0
59.58
59.68
N
14.0
3.86
25 H
25.0
6.89
7.08
90
Cl
72.0
19.88
35.5
9.79
C36NH2¹06, HCl + 3aq.
362.5
100.00
....
Anderson (Chem. Soc. Quart. J. 15, 466) did not succeed in obtaining a double-
salt of hydrochlorate of codeine with sal-ammoniac. (Contrary to Robiquet.)
Nitrate of Codeine. - Prepared by gradually adding nitric acid of
sp. gr. 1.06, to powdered codeine, avoiding an excess.--Crystallises from
a solution in boiling water in small prisms. Melts when heated, and
solidifies to a brown resinous mass on cooling: by a stronger heat it is
rapidly decomposed, and leaves a heavy, difficultly combustible char-
coal (Anderson).
36 C........
2 N
at 100°.
Anderson.
216
59.66
59.40
28
7.73
22 H.
22
6.07
6.54
12 O ....
96
26.54
C36NH2106, HO,NO5
362
100.00
Chromate of Codeine forms fine yellow needles (Anderson).
Codeine-salts give bulky brown-yellow precipitates, with phosphomo-
lybdic acid (xiii, 164) (Sonnenschein); and dirty-white precipitates with
phosphantimonic acid (xiv. 277) (Schulze). - Codeine forms, with iodide
and bromide of mercury, crystallisable double salts, corresponding to
those of morphine, and obtained in like manner; they are soluble in
hot water and alcohol (Groves). Iodhydrargyrate of potassium throws
down, from hydrochlorate of codeine, a yellowish-white, pulverulent
precipitate, which is insoluble in hydrochloric acid (v. Planta).
Codeine forms, with mercuric chloride, a white precipitate, which
crystallises from hot water and alcohol (Anderson). Hydrochlorate
of codeine is not precipitated by mercuric chloride (v. Planta).
Terchloride of gold forms, with hydrochlorate of codeine, a brown
precipitate, soluble in hydrochloric acid (v. Planta).
Chloroplatinate of Codeine. - Chloride of platinum, not in excess,
precipitates from moderately concentrated solutions of hydrochlorate of
codeine, a pale-yellow powder, which, on standing beneath the surface
of the liquid, is converted into orange-coloured crystalline granules;
the mother-liquor deposits a further quantity on standing. In more
CODEINE.
35
dilute solutions, the mixture remains clear at first, and afterwards
deposits tufts of delicate needles having a silky lustre (Anderson). -
Crystallises in fine dark-yellow, hard needles (Liebig); from a solution
in hot water, in granules and as powder, with partial decomposition.
By long boiling with excess of chloride of platinum it is completely
decomposed. The air-dried crystals contain 4 at. water, of which
3 at. 5.15 p. c., are given off at 100°, the remaining atom being
expelled at 121°, together with a little acid, whereby the salt is rendered
brown (Anderson). Dissolves in water more easily than the correspond-
ing morphine-salt (Liebig).
36 C
N
23 H
70
Pt
3 Cl
C36NH2¹06, HCl,PtCl² + aq.
Anderson.
at 100°.
mean.
216.0
42.01
41.91
14.0
2.72
23.0
4.47
4.76
56.0
10.89
98.7
19.19
19.11
106.5
20.72
514.2
100.00
Liebig found 19 81 p. c. platinum (in the anhydrous salt ?) calc.
>
19.53 p. c.
Protochloride of palladium produces, with codeine, a yellow precipi-
tate, which is decomposed on boiling, with separation of palladium
(Anderson). — Hydrochlorate of codeine is not precipitated by chloride
of iridium and sodium (v. Planta).
Hydrocyanate of Codeine is non-crystalline (Anderson).
Hydroferrocyanate of Codeine. Alcoholic codeine forms, with alcoholic
hydroferrocyanic acid, a white precipitate which dissolves in excess of
the acid, and crystallises in white needles on long standing. Easily
decomposible, and not susceptible of re-crystallization. In the dry
'state, or in solution, it is decomposed by heat, with evolution of a
large quantity of hydrocyanic acid, and separation of white protocyanide
of iron, which immediately turns blue (Dollfus).
Ferricyanide of potassium throws down from aqueous salts of codeine,
after some time, a crystalline precipitate, a solution of which deposits a
blue powder, even on evaporation in a vacuum (Dollfus).
Hydrosulphocyanate of Codeine. Sulphocyanide of potassium added
to acetate of codeine, occasions no precipitate at first, but in a quarter
of an hour pearly crystals are produced, The crystals disappear quickly
when the liquid is heated, and are again formed on cooling (0. Henry,
J. Pharm. 24, 194). The precipitate contains hydrosulphocyanate of
codeine, together with sulphocyanide of potassium, which last is not
completely removed even by six or eight re-crystallisations; it is better,
therefore, to prepare the salt from hydrosulphocyanic acid and codeine
(Dollfus). Stellate groups of fine transparent needles, which melt at
100° (Dollfus), and lose 2·47 p. c. = 1 at. water (Anderson).
Dollfus,
Anderson.
38 C
2 N
22 H
60
2 S
at 90°.
at 100°.
228
63.68
62.30
63.20
28
7.82
22
6.11
6.13
6.33
4.8
13:43
32
S:93
9.04
........ 100·00
C¹³6NH²¹O¤, C²NHS² ........ 358
D 2
36
OXY-IODO-AZO-NUCLEUS C30NH12O6.
-
The crystals contain 16.68 p. c. of hydrosulphocyanic acid (calc.
16.52 p. c.)
(Dollfus). The salt analysed by Dollfus, dried at 90°, contains at. of water (calc.
62-46 p. c. C., 5.9 H.) (Gerhardt, N. J. Pharm. 13, 308).
Acetate of Codeine is crystallisable and non-deliquescent (0. Henry).
Oxalate of Codeine - Crystallises from a hot solution, on cooling, in
short prisms and scales, which lose 7 p. c. = 3 at. of water (calc. = 7·27
p. c.) at 100°, and tnrn brown at 121°, undergoing decomposition. -
Dissolves in 30 parts of water at 15.5°, and in pt. of water at 100°
(Anderson).
38 C
N
22 H
10 O
C3NH2O,CHO
Anderson.
at 100°.
228
66.28
66.19
14
4:07
22
6.39
6.60
.... ...
80
23.26
344
100.00
Tartrate of Codeine is not crystallisable (Anderson). - Picric acid
throws down, from hydrochlorate of codeine, a sulphur-yellow powder
(v. Planta). Alcoholic picric acid scarcely precipitates an alcoholic
solution of codeine (G. Kemp). — The salts of codeine are abundantly
precipitated by tincture of galls (Robiquet). Tannic acid precipitates a
solution containing th of codeine (O. Henry, J. Pharm. 21, 212).
Hydrochlorate of codeine behaves, towards tincture and infusion of
galls, in the same manner as the morphine-salt (v. Planta).
00
Hydrochlorate of codeine forms, with hydrochlorate of morphine, a
double-salt, which may be obtained according to xvi, 416. The salt
contains 3 parts of codeine to 1 part of morphine (Köne, Bull. de l'Acad.
de Bruxelles, 1837, p. 424).
C. With Alkalis. Codeine dissolves in aqueous ammonia (O. Henry),
in 68.5 parts of moderately strong solution of aminonia at 15.5°, about
as freely, therefore, as in water (Anderson). It does not dissolve in
alkaline liquids (Robiquet). See above. It is not precipitated from a
saturated aqueous solution, by concentrated solution of caustic potash
(Anderson).
Codeine dissolves in alcohol and ether (Henry, Robiquet). The
ethereal solution, when evaporated, yields a few crystals at first, and
afterwards remains [with ether containing alcohol (Anderson)] in the
form of a syrup, which crystallises only after addition of water
(Robiquet).
Oxy-iodo-azo-nucleus C30NH171206.
Biniodocodeine.
C30NH191206=C36NH171206, H2.
J. BROWN. Trans. Roy. Soc. Edin. 21, 1, 49; Phil. Mag. [4] 8, 201;
Ann. Pharm. 92, 325; J. pr. Chem. 63, 370; Pharm. Centr. 1854,
797; Lieb. Kopp's Jahresb. 1854, 510.
Aqueous chloride of iodine (obtained by passing chlorine into water
BROMOCODEine.
37
in which iodine is suspended till nearly the whole is dissolved) throws
down from concentrated aqueous solutions of hydrochlorate of codeine
a yellow crystalline precipitate, which is deposited from a hot, mode-
rately dilute alcoholic solution, on cooling, in stellate crystals.
The crystals contain iodine (hydriodate of biniodocodeine, or biniodo-
codeine? Kr.). They lose a portion of their iodine on re-crystallisation
from alcohol, and separate again from a concentrated alcoholic solution,
in an amorphous mass. They are insoluble in water, but soluble in cold
hydrochloric acid, from which they separate on heating, in the form of
an oil, afterwards solidifying to a flocculent mass. They are precipi-
tated from the solution in hydrochloric acid by potash and ammonia.
Bichloride of platinum, added to the solution in hydrochloric acid, forms
a yellow precipitate containing 12.20 p. c. platinum, and corresponding
to the formula CNH191206, HCl, PtC+2HO (calc. 11.95 p. c. Pt.).
Oxy-bromo-azo-nucleus C36NH¹Br0º.
Bromocodeine.
C36NH20 Br0=C36NH18Br0°, H³.
ANDERSON. Ann. Pharm. 77, 362.
Preparation. Bromine-water is added by small portions to finely
powdered codeine till the whole is dissolved (small crystals of hydro-
bromate of bromocodeine being deposited when saturated bromine-
water is used). The bromocodeine thereby formed is at once precipi-
tated by ammonia as a silver-white powder, and freed from codeine
thrown down at the same time by solution in hydrochloric acid, precipi-
tation by ammonia, and re-crystallisation from alcohol. It is apt to retain
small quantities of codeine.
Properties. The hydrated crystals lose their water at 100°. Melts
to a colourless liquid when heated.
36 C
N
20 H
Br
6 O
C3NH2BrO
at 100°.
Anderson.
216
57.14
57.21
14
3.70
20
5.29
5.44
80
21.16
21.50
48
12.71
378
100.00
Decomposes a little above its melting point. A solution in oil of
vitriol assumes a dark colour on heating. Less easily decomposed than
codeine by nitric acid. An excess of bromine gradually converts it into
hydrobromate of tribromocodeine, which is precipitated.
Crystallised bromocodeine forms prisms with dihedral summits, or
small shining needles containing sometimes 2.32 p. c. (= 1 at.), some
times 6.66 p. c. (= 3 at.) of water.
Hydrobromate of Bromocodeine. Small prisms, slightly soluble in
J
38
OXY-BROMO-AZO-NUCLEUS CNH16B306.
cold, very easily soluble in hot water. Does not lose its water of
crystallisation at 100°.
36 C .....
N..
2 Br
23 H
8 0.
at 100°.
216
Anderson.
45.28
45.18
...
14
160
2.93
33.51
23
4.84
5.25
64
13.41
100.00
C36 NH20 BrO6HBr + 2 aq. 477
Hydrochlorate of Bromocodeine forms star-shaped groups of needles,
resembling those of hydrochlorate of codeine.-Chloro-platinate of
Bromocodeine is a pale-yellow powder, insoluble in water and alcohol,
containing 16.98 p. c. platinum (calc. 16.89 p.c. Pt.).
Bromocodeine dissolves easily in alcohol, especially when hot. It is
nearly insoluble in ether.
Oxy-bromo-azo-nucleus CNH¹Br³0.
Terbromocodeine.
C36NBH1806 = C36NBr³H¹606, H².
ANDERSON. Ann. Pharm. 77, 365.
Codeinc is converted by bromine-water into hydrobromate of bromo-
codeine, and more bromine-water is then added till a fresh addition
no longer produces a bright-yellow precipitate on standing for a
day. The precipitated hydrobromate of terbromocodeine is collected,
washed with water, dissolved in hydrochloric acid, and precipitated by
ammonia. To purify the flocculent precipitate of terbromocodeine thus
obtained, it is washed with water, dissolved in alcohol, and precipitated
by water, then again dissolved in alcohol, and thrown down by ether.
White, heavy, amorphous precipitate, grey after drying.
Anderson.
at 100°.
36 C
N
216
40.27
39.69
14
2.61
3 Br
240
44.77
44.68
18 H
18
3.35
3.66
6 O
48
9.00
C26NH18Br306
536
100.00
......
Turns brown on heating, and undergoes decomposition when melted,
leaving a difficultly combustible charcoal.
Insoluble in water. Behaves as a feeble base, and forms amorphous
sparingly soluble salts.
Hydrobromate of Terbromocodeine.-Bright yellow, amorphous powder,
slightly soluble in cold, and rather more soluble in hot water.
!
!
CHLOROCODEINE.
39
72 C
2 N
9 Br
39 H
12 O
2C36NB3H1806,3HBr
Anderson.
at 100°.
mean.
432
32.84
32.21
28
2.12
720
54.75
55.03
39
2.96
2.85
96
7.33
1315
100.00
Hydrochlorate of Terbromocodeine.-Deposited from a solution of
terbromocodeine in hot dilute hydrochloric acid, on cooling, as an amor-
phous powder.
Chloro-platinate of Tribromocodeine. -- Brown-yellow powder, soluble
in water and alcohol. Contains, at 100°, 13.07 p. c. platinum, agreeing,
therefore, with the formula CNBr³H¹0,HCl,PtCl (calc. 13-29 p. c. Pt.).
Terbromocodeine is easily soluble in alcohol, insoluble in ether.
Oxy-chloro-azo-nucleus CNH18C106.
Chlorocodeine.
C36NH20CIO = C36NH18C10°, H².
ANDERSON. Ann. Pharm. 77, 368.
Finely powdered chlorate of potash is added by degrees to a solution
of codeine in excess of dilute hydrochloric acid, at 60° or 70°, so long as
the precipitate produced by ammonia in a test-portion of the liquid con-
tinues to increase. The liquid is then precipitated with a slight excess
of ammonia, and the silvery, crystalline precipitate is dissolved in hydro-
chloric acid, treated with animal charcoal, again precipitated by am-
monia, and allowed to crystallise from hot alcohol.
If the action of chlorate
of potash were continued too long, decomposition-products would be formed. Some
decomposition always takes place, and hence the filtrate from the chlorocodeine is
coloured dark-red.
The crystals obtained from water are hydrated chlorocodeine.
They are rendered anhydrous by drying at 100°.
Anderson.
at 100°.
mean.
36 C.........
N....
216
64.76
64.81
14
4.19
Cl
35.5
10.64
10.32
...
20 H
20
5.99
6.15
6 0
48
14.42
333.5
100.00
C36NH20C106
Chlorocodeine treated with boiling nitric acid, is less easily decom-
posed than codeine, evolving red vapours and a peculiar gas having
a very penetrating odour. Dissolves in cold, and blackens in hot oil
of vitriol.
Hydrated Chlorocodeine. — Obtained from hot aqueous solutions of
40
OXY-NITRO-AZO-NUCLEUS C3NH18X06.
small prisms, closely resembling, and probably isomorphous with
those of bromocodeine. Loses 7:36 p. c. (= 3 at.) of water at 100°
(calc. 7·48 p. c. HO).
Dissolves very slightly in hot water. The salts of chlorocodeine
resemble those of bromocodeine.
Sulphate of Chlorocodeine. Radiated groups of short prisms, easily
soluble in hot water and alcohol.
C36NIT20C106
SO³,HO
Crystals.
333.5
Anderson.
79.63
49
11.75
11.90
36
8.62
8.76
C36NH20C1O6,SO³,HO + 4aq.
418.5
100.00
....
4 HO
Chloroplatinate of Chlorocodeine. - Hydrochlorate of chlorocodeine
forms, with bichloride of platinum, a pale-yellow precipitate but
slightly soluble in water.
36 C
N......
21 H
6 0
....
Pt.....
4 Cl......
C36NH2C106, HCl,PtCl²
at 100°.
Anderson.
216
40.02
40.30
14
2.59
21
3.89
4.09
48
8.91
98.7
18.28
18.29
142
26.31
539.7
1000.00
Chlorocodeine dissolves easily in strong alcohol, especially when
hot. It is only slightly soluble in ether.
Oxy-nitro-azo-nucleus CNH18X06.
Nitrocodeine.
C35N2H20010 C36NH18X06,H³.
ANDERSON. Ann. Pharm. 77, 358; Prelim. Notice Ann, Pharm. 75, 80.
Preparation. (See p. 30.) Finely powdered codeine is added to
moderately hot (not boiling) nitric acid of sp. gr. 1·06, and the liquid
is heated for a few minutes, or until a small portion gives an abundant
precipitate, on addition of ammonia. The whole is then neutralized
with ammonia, which throws down nitrocodeine in silvery laminæ.
The precipitate is dissolved in hydrochloric acid, boiled with animal
charcoal, precipitated several times by ammonia to remove resin and
unchanged codeine, and crystallised from dilute alcohol or ether-
alcohol. Careful treatment is necessary to prevent the decomposition
of the nitrocodeine by nitric acid. The decomposition is manifested
by the evolution of red vapours, and by the red colour of the liquid
which has been precipitated by ammonia.
Properties. Yellow or fawn-coloured silky, delicate needles ap-
pearing under the microscope as four-sided prisms with dihedral
NITROCODEINE.
41
summits. Melts, when cautiously heated, to a yellow oil, which
solidifies in the crystalline state.
36 C
2 N
20 H
10 O
C35NH20X06
Anderson.
Crystals.
mean.
216
62.79
62.66
....
28
8.11
20
5.81
5.85
80
23.29
344
100.00
Decompositions. Nitrocodeine, when strongly heated, explodes with-
out flame, leaving a heavy charcoal. On warming it with hydrosul-
phate of ammonia, sulphur is precipitated, and a brown filtrate is ob-
tained, from which ammonia throws down a brown, amorphous pre-
cipitate. This precipitate, when dissolved in hydrochloric acid, boiled with animal
charcoal, and precipitated by ammonia, yields a pale-yellow base, easily soluble in
alcohol, from which it is usually deposited in the form of an amorphous powder, but
was obtained on one occasion in brown crystals: probably Azocodeine C36N2H2006.
Combinations. Nitrocodeine dissolves slightly in hot water, crystal-
lising on cooling. — It forms, with acids, neutral soluble salts, from
which ammonia and potash precipitate the nitrocodeine as a crystalline
powder.
Sulphate of Nitrocodeine forms tufts of neutral needles, very soluble
in hot water. The salt, dried at 100°, contains 10-13 p. c. sulphuric
acid, corresponding to the formula CNH20XO,SO³,HO (calc. 10∙17
p. c. SO³).
Hydrochlorate of Nitrocodeine. Nitrocodeine dissolves readily in
hydrochloric acid, and yields this salt in the form of a resinous mass
on evaporation.
Chloroplatinate of Nitrocodeine. - Hydrochlorate of nitrocodeine.
throws down from bichloride of platinum a yellow powder insoluble in
water and in alcohol. The air-dried powder loses 6:56 p. c. of water =
4 at., at 100° (calc. = 6·14 p. c. HO).
36 C .....
2 N.
21 H.....
at 100°.
Anderson.
216
39.25
39.11
28
5:08
21
3.81
4.09
10 ......
80
14.58
Pt
98.7
17.93
17.88
...
....
3 Cl
106.5
19.35
C36NH20XO6, HCl,PtCl²
550.2
100.00
....
The oxalate forms fine yellow short prisms, easily soluble in
water.
Nitrocodeine dissolves freely in hot alcohol, slightly in ether.
42
CONJUGATED COMPOUNDS OF CODEINE.
Conjugated Compounds of Codeine.
Bicyanocodeine.
C40N3H2106 C36Cy2AdH706,H2.
=
ANDERSON. Ann. Pharm. 77, 371.
Cyanogen gas is slowly passed into a saturated solution of codeine
in alcohol, and the crystals thereby formed are collected on a filter.
On again treating the filtrate with cyanogen, a further quantity
of less pure crystals is obtained. The crystals are dissolved in warm
ether-alcohol, through which cyanogen is passed to convert any un-
changed codeine, and the colourless or yellowish crystals which form
on cooling are purified by re-crystallisation from hot alcohol or ether-
alcohol.
Highly-lustrous, thin, six-sided laminæ. Contains no water of
crystallisation.
In vacuo.
Anderson.
40 C.....
240
68.37
68.13
3 N....
42
11.68
11.66
21 H.......
21
5.97
6:05
6 O.....
48
13.97
14.16
C40N3H2106
351
100.00
100.00
Bicyanocodeine dissolves with difficulty in water, more easily on
addition of alcohol. The aqueous solution deposits crystals of codeine
on evaporation. With hydrochloric, sulphuric, and oxalic acids it forms
difficultly soluble crystalline compounds, which, when kept for 24
hours, evolve an odour of hydrocyanic acid, and, even before that,
yield ammonia on addition of potash. Bichloride of platinum added to
the solution in hydrochloric acid produces an immediate evolution of
hydrocyanic acid.
Ethyl-codeine.
C40NH2506 = C26N(C4H6) H1806,H2.
H. How. Chem. Soc. Qu. J. 6, 125; Ann. Pharm. 88, 339.
Tinecodeïn.
A mixture of finely-powdered codeine with iodide of ethyl and a
quantity of absolute alcohol sufficient to dissolve the codeine, heated
in a water-bath for two hours in a sealed tube, solidifies, from forma-
tion of crystals of hydriodate of ethylcodeine. The crystals are
collected, washed with alcohol, and re-crystallised from water.
An aqueous solution of these crystals decomposed by oxide of
silver yields hydrated ethylcodeine having a strong alkaline reaction;
it absorbs carbonic acid on evaporation, and leaves a coloured
translucent residue. This residue is decomposed by heating with
SYCOCERYLIC ALCOHOL.
43
iodide of ethyl, in the same manner as methyl-morphine (xvi., 439) is
decomposed when heated with iodide of methyl, without formation of
biethylcodeine.
Hydriodate of Ethylcodeine forms tufts of white needles. Its aqueous
solution is not precipitated by ammonia or potash, but becomes turbid
on boiling with solution of caustic potash, apparently from decompo-
sition of the ethylcodeine.-Dissolves easily in cold water.
at 100°
How.
40 C .....
N
240
52.73
52.59
14
3.07
26 H
26
5.71
5.87
6 O .....
48
10.57
I
127
27.92
27.91
C36N (C4H³) H200,HI
455
100.00
Primary Nucleus C2H28.
Sycocerylic Alcohol.
C36H30O2 = C6H28,H20².
,
W. DE LA RUE AND H. MÜLLER. Lond. Roy. Soc. Proc. 10, 298;
Phil. Mag. [4] 20, 225; Ann. Pharm. 116, 255; Zeitschr. Ch. Pharm.
3, 743; Rép. Chim. pure, 2, 410;- Phil. Trans. 1860, 43; Chem. Soc.
Qu. J. 15, 62; J. pr. Chem. 89, 221; Chem. Centr. 1862, 705 ; Kopp's
Jahresb. 1861, 637.
Source. Occurs as acetate of sycoceryl, in the resin of Ficus
rubiginosa, from New South Wales.
Preparation. The resin is first treated with cold alcohol to remove
sycoretin, and the residue is exhausted with boiling alcohol; the
solution, on cooling, yields crystals of acetate of sycoceryl, a small
quantity of another flocculent substance being also deposited towards
the end of the crystallisation. When the solution is allowed to cool
only to about 40°, and the crystals then formed are separated, re-
crystallised from alcohol, and afterwards treated, at 30°, with a
quantity of ether insufficient for complete solution, the acetate is
obtained, whilst a neutral crystalline body (containing 75.56 p. c. C, and
12·3 H), insoluble in ether, is left behind.
left behind. The acetate is decomposed
by boiling with sodium-alcohol, and the sycocerylic alcohol thereby
formed is thrown down by addition of water, and crystallised from
alcohol.
Properties. Very thin crystals, resembling caffeine, usually aggre-
gated in masses like Wavellite. Melts at 90° to a liquid heavier than
water, and solidifies in the crystalline state on cooling; after being
strongly heated it solidifies to a transparent glass, which becomes
crystalline in contact with alcohol. Distils partly undecomposed.
44
PRIMARY NUCLEUS CH28.
De la Rue and Müller.
mean.
36 C......... 216
82.44
82.39
30 H
30
11:45
11.38
20
16
6.11
6.23
C36H 3002
262
100.00
100.00
Homologous with benzylic alcohol (xii, 18) and cuminic alcohol (xiv, 14).
Decompositions. 1. Sycoccrylic alcohol is only slowly attacked on
boiling with dilute nitric acid: the dark-yellow resin formed after six
hours, when washed and dried and afterwards dissolved in warm
alcohol, yields white and yellow crystals, easily soluble in aqueous
ammonia and potash, and precipitable by alcoholic neutral acetate of
lead, probably a mixture of sycocerylic acid, C36H1804, and nitrosyco-
ccrylic acid. —2. Moderately dilute aqueous chromic acid, boiled with
sycocerylic alcohol for eight hours, produces no sycocerylic acid: on
one occasion, neutral thin prisms, probably of sycocerylic aldehyde,
C36H280², were produced. 3. The alcohol dissolves easily in oil of
vitriol, forming a brown solution from which water throws down a
viscid resin; no conjugated compound of sulphuric acid remains in
solution. 4. Sycocerylic alcohol is readily attacked by chlorine and
bromine, and forms yellow crystals with iodine.-5. A solution of
sycocerylic alcohol in benzene evolves hydrochloric acid gas when
treated with pentachloride of phosphorus at 60°. If, after the evolution
of gas has ceased, the remaining chloride of phosphorus is removed,
and the benzene solution is washed with water and aqueous alkali and
evaporated, there remains an amorphous, greenish, viscid residue,
easily soluble in ether and chloroform, but difficultly soluble in alcohol.
6. Potassium evolves
On one occasion crystals were also obtained.
hydrogen from melted sycocerylic alcohol, and becomes covered with
a white crust, which, when heated till it melts, blackens and takes fire.
-7. Sycocerylic alcohol, treated with fused caustic potash, evolves
hydrogen without forming sycocerylic acid. 8. With chloride of
acetyl it forms acetate of sycoceryl, and with chloride of benzoyl, ben-
zoate of sycoceryl.
Combinations. Sycocerylic alcohol is insoluble in water, aqueous
ammonia, and alkalis. It dissolves readily in alcohol: a hot saturated
solution forms a semi-solid mass of crystals on cooling; a solution in
very dilute alcohol deposits, on cooling, a jelly, which afterwards
becomes crystalline. Dissolves in ether, benzene, chloroform, and light
mineral oil.
Acetate of Sycoceryl.
C'40H3204 = C6H290, C4H³O³.
WARREN DE LA RUE & MÜLLER.
Sycocerylic Acetate.
Sycoceryl-acetic ether. — Essigsycocerylester. A con-
stituent of the resin of Ficus rubiginosa, from which it is obtained by
the process already described (p. 43).
BENZOATE OF SYCOCERYL.
45
On gently warming sycocerylic alcohol with chloride of acetyl, a
large quantity of hydrochloric acid gas is evolved, and a solution is
obtained which, when boiled with water to remove excess of the
chloride, solidifies to crystals of acetate of sycoceryl. The crystals are
purified by re-crystallisation from alcohol.
Properties. Crystallises from alcohol, in thin laminæ resembling
cholesterin, and from ether in flat six-sided tables. Melts at 118—120°,
and solidifies only below 80° to a mass which is transparent at first,
but afterwards becomes opaque and crystalline. Distils unchanged;
when it is too strongly heated the distillate smells rancid and like
acetic acid. Brittle; strongly electric when rubbed. Neutral.
De la Rue and Müller.
mean.
40 C
32 H
210
78.94
79-09
32
10.52
10.28
•
4 O
32
10.53
10.63
........
C36H-90,C¹H³03
304
100.00
100.00
Hot dilute nitric acid converts it into a resin. The easily pre-
pared solution in fuming nitric acid is precipitated by water in amor-
phous yellow flocks. - Dissolves easily and without coloration in oil
of vitriol; the solution becomes brown on standing, and gives off
traces of sulphurous and acetic acids; water precipitates from the
solution a hard substance, fusible below 100°, difficultly soluble in
alcohol, easily soluble in chloroform and benzene. Acetate of
sycoceryl forms resinous compounds with chlorine, bromine, and iodine;
the last two when added gradually to a warm alcoholic solution of the
acetate, form crystals of a colourless bromine- or iodine-compound,
which are deposited on cooling. Acetate of sycoceryl is not affected
by boiling solution of caustic potash, but is decomposed by the fused
hydrate, with liberation of hydrogen. Sodium-alcohol decomposes it.
even at 30°, forming acetic acid and sycocerylic alcohol.
Acetate of sycoceryl dissolves very easily in hot alcohol, and in
acetic acid, acetone, chloroform, ether, benzene, and oil of turpentine. It
is not precipitated by alcoholic neutral acetate of lead, or by alcoholic
acetate of copper.
Benzoate of Sycoceryl.
C50H3404 = C36H²⁹O,C¹¹H'O³.
WARREN DE LA RUE & MÜLLER. Loc. cit.
Sycocerylic alcohol is dissolved in chloride of benzoyl (no gas being
evolved in the cold), and the solution is heated as long as hydrochloric
acid gas is given off. The crystalline mass formed on cooling is
thrown into a warm aqueous solution of bicarbonate of potash, with
which it is warmed for several hours. The resin thereby separated,
after washing with warm water and boiling alcohol, is dissolved in
boiling ether, from which it is obtained in crystals. Boiling absolute
alcohol dissolves only a trace of the crystalline substance and deposits.
46
PRIMARY NUCLEUS C36H2S..
!
it again, on cooling, in small crystals recognisable under the micro-
scope. It dissolves with difficulty in cold ether, and in all propor-
tions in chloroform and benzene, crystallising in prisms on evaporation.
Sodium-alcohol decomposes it only on long boiling, with formation of
sycocerylic alcohol and benzoate of soda.
Sycoretin.
The resin of Ficus rubiginosa is resolved by treatment with alcohol
into about 73 per cent. of sycoretin, soluble in the cold, 14 p. c. of
acetate of sycoceryl soluble in hot alcohol, and 13 p. c. of residue,
consisting of caoutchouc, sand, and fragments of bark.
On mixing the neutral pale-brown solution in cold alcohol with
water, the sycoretin is precipitated, and may be rendered colourless
by repeated solution and precipitation. A saturated alcoholic solu-
tion deposits, in the cold, a small quantity of a crystalline substance,
sycoretin in a purer state remaining in solution. The latter may be
separated, by fractional precipitation with water, into two portions,
the first of which contains 74.65 p. c. C. and 10:11 H., the second
77·89 p. c. C and 9·94 H.
Sycoretin is amorphous, white, neutral, very brittle and extremely
electric. It melts in boiling water to a thick liquid which floats on
the surface. Melts alone at 100°.
Sycoretin undergoes decomposition a few degrees above its
melting-point, frothing up and giving off water with a wax-like
odour. When further heated it melts quietly, and yields a distillate
containing acetic acid and tar, charcoal being left behind. — It is
attacked by nitric acid and dissolved on boiling therewith; water
precipitates from the yellow solution a slightly acid nitro-compound
which is soluble with dark colour in aqueous alkalis, and forms an
explosive compound with potash. In this reaction a little oxalic acid
is formed, but no picric acid.-Sycoretin dissolves in oil of vitriol
with fine green colour, without forming sugar; water throws down
from the solution a brown precipitate less soluble than sycoretin.
caustic potash acts on sycoretin in the same way as oil of vitriol.
Sycoretin is insoluble in water, dilute acids, ammonia, and aqueous
alkalis. It is not precipitated from its alcoholic solution by neutral
acetate of lead or acetate of copper. Dissolves casily in alcohol, ether,
chloroform, and oil of turpentine (Warren de la Rue & Müller).
Axinic Acid.
? C³³H2804 = (³61128,04.
F. HOPPE. J. pr. Chem., 80, 130.
Source. Occurs as glyceride (triaxin) in the Age or Axin of the
Mexicans (p. 47).
When axin is exhausted with ether, the ether evaporated, and
the residue saponified with alcoholic potash, the alkaline solution, on
cooling, deposits of laurate potash, which must be removed by filtra-
AXINIC ACID.
47
!
tion.
The filtrate mixed with hydrochloric acid and water, deposits
a thick brown oil, which is to be washed with dilute alcohol by decanta-
tion, dissolved in ether, recovered from the solution by distillation,
and dried over a water-bath. It does not solidify at 0°, and is in-
soluble in water but soluble in cold, and more easily in hot, alcohol
and ether. It possesses these properties and the following composition,
however, only when exposure to air has been avoided throughout the
process of preparation.
F. Hoppe.
b.
C.
a.
36 C
28 H
216
....
28
4 O
32
78.25
10.14
11.61
....
77.78
77.48
76.86
....
10.44
10.31
10.25
....
11.78
12.21
12.89
G
C36H2801
276
100.00
100.00
100.00
100.00
....
b and had probably taken up a little oxygen on opening the tube (Hoppe).
с
Decompositions. A drop of axinic acid exposed to the air takes up
oxygen, and becomes covered with a pellicle in one or two minutes.
The acid prepared with partial access of air solidifies above 0°, smells
like linseed-oil varnish, and has the composition of linoleic acid (xvi,
305). Left in contact with oxygen for twelve hours, the acid solidifies
completely; exposed to the air for some days, and frequently moistened
with ether to ensure the contact of air, notwithstanding the crust, it
increases about 13.7 p. c. in weight. By this oxidation, there are
formed 58.8 p. c. of aginin, insoluble in ether, and 54.9 p. c. physetoleic
acid (xvi, 317).
Aginin, purified as far as possible by ether, is a bright-yellow,
amorphous, friable substance, not fusible without decomposition, and very
hygroscopic. It contains, after drying in a vacuum, 58.35 to 60.31 p. c.
C., and 6-70 to 7.51 H.: aginin formed by the action of the air on axin,
exhibits the same composition.- When heated to 80°, it is decomposed,
with evolution of water-vapour and colourless gases, which are absorbed
by caustic potash. Heated to 110° with water in a sealed tube, it
forms a dark-brown solution, with dark flocks. It dissolves in nitric
acid, with evolution of nitric oxide, and water throws down colourless
needles from the solution. Aginin dissolves in caustic alkalis, forming
brown solutions, which are precipitated by acids in flocks.
Age or Axin. Obtained in Mexico by boiling a species of coccus
(Coccus Axin) with water. Dark-yellow, buttery; hardens on exposure
to the air. Has an agreeable odour, like that of arnica flowers. Dissolves
with difficulty in cold, more easily in hot alcohol, and very easily in
ether, leaving a hardened crust of aginin. The ethereal solution leaves,
when evaporated, a brown fat, which melts at 31°, and contains, on
the average, 78.03 p. c. C., 10:34 H., and 11.63 0. It is composed of
laurostearin (with a little palmitin) and triaxin, and on account of this
latter constituent, rapidly absorbs oxygen from the air, forming thereby
aginin, and a glyceride of physetoleic acid (xvi, 317) (Hoppe, J. pr,
Chem. 80, 102).
4.8
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS CH¹¹0.
Oxygen-nucleus C36H18010.
Usnic Acid.
? С3818014 = C6H18010,04.
W. KNOP. Ann. Pharm., 49, 103; J. pr. Chem., 31, 196.
ROCHLEDER & HELDT. Ann. Pharm., 48, 9.
KNOP & SCHNEDERMANN. J. pr. Chem., 39, 363.
STENHOUSE. Phil. Trans., 1848, 88; Ann. Pharm., 68, 97, and 104.
HESSE. Ann. Pharm., 117, 343.
Usnein. Alpha-usninsäure (Hesse). Thomson's Parietin (xvi, 171), which
Gerhardt regarded as usnic acid (Traité, 3, 789), appears to be impure chryso-
phanic acid.
Sources. Usnic acid occurs in the following lichens: Usnea florida,
U. hirta, U. plicata (Knop); Usnea barbata (Rochleder & Heldt); Cla-
donia digitata, Cl. bellidiflora, Cl. maculata, Čl. rangiferina, Cl. uncinata,
Lecidea geographica, Biatora lucida, Parmelia hæmatomma, P. sarmentosa
(Knop); P. furfuracea (Rochleder & Heldt); P. saxatilis (Overbeck,
N. Br. Arch. 82, 150); Lecanora ventosa (Knop); Ramalina calicaris
(Rochleder & Heldt). Evernia prunastri contains usnic and also evernic
acid (Stenhouse).
Preparation. Best from Cladonia rangiferina or Usnea florida (Stenhouse).
1. The comminuted lichen is softened in water, and exhausted with
thin milk of lime: from the dark-yellow solution thus obtained, the usnic
acid is precipitated by hydrochloric or acetic acid, and the precipitate is
dried and purified by crystallisation from alcohol, with aid of animal
charcoal (Stenhouse). Hesse boils the liquid (acidified with hydrochloric
acid) for some time, whereby the usnic acid is thrown down in the
crystalline state: he then washes the precipitate with water, boils it
with alcohol to remove resin, and purifies it by crystallisation from hot
acetic acid, with the aid of charcoal.-2. The chopped lichen ist
digested with ether for several days; the ether is distilled from the
extract, and the residue mixed with alcohol; the usnic acid is then
separated in crystals, which may be purified by washing with hot
alcohol (Knop).-3. Rochleder & Heldt exhaust with ammoniacal
alcohol, precipitate with acetic acid, and purify by re-crystallisation.
Hesse's beta-usnic acid is obtained from Cladonia rangiferina. The lichen is
washed with luke-warm water and exhausted with dilute caustic soda; the alkaline
solution is precipitated by hydrochloric acid, and the precipitate is washed, dried,
and exhausted with ether. After distilling off the ether, the residue is mixed with
alcohol, which takes up resin and leaves beta usnic acid. The latter is purified by
crystallisation from strong boiling alcohol, with the help of animal charcoal. Beta-
usnic acid exhibits the characters of usnic acid, with the exception of its melting-
point, which is 175°. It yields, when heated, a sublimate of white lamine and flat
needles, and contains 62-7 p. c. C., and 5.3 H. (Hesse).
Properties. Pure sulphur-yellow, transparent prisms, triturable to
a paler, strongly electric powder (Knop). Delicate, interlaced, shining,
pale-yellow needles (Rochleder & Heldt). Straw-yellow, shining
USNIC ACID.
49
lamine (Stenhouse). Melts at 203° (Hesse), 200° (Knop), to a yellow
transparent resin, which forms a crystalline solid on cooling. Taste.
less (Rochleder & Heldt).
According to Hesse.
Calculations.
According to Strecker.
31.3
According to Gerhardt.
38 C........
36 C...........
62.42
38 C ......
63.7
....
18 H
5.20
18 H......
5.0
16 H.....
....
....
14 O
32.38
14 0.....
14 0........
....
C36H19014.... 100.00
C38 II 18014
100.0
C3H6O1+
Analyses.
64.04
4:49
31.47
100.00
ს.
C.
Rochleder and Heldt.
Knopp. Stenhouse.
Hesse.
C.... 63.39
63.49
63.72
63.49
....
....
H ....
O....
4.99
4.82
31.62
31.69
4.92
31.36
....
5.08
31.43
62.8
5.0
62.2
...
5.3
32.2
32.5
....
100.00
100.00
100.00
100.00
100.0
100.0
a was obtained from Cladonia rangiferina, b from Usnea florida (Rochleder and
Heldt). Knop investigated an acid from Usnea florida; Hesse an acid from
Ramalina calicaris. — According to Hesse's formula, which, indeed, is rendered
probable by these considerations, usnic acid bears the same relation to everninic
acid as lecanoric to orsellinic acid, whilst evernic acid occupies an intermediate
position between the two :-
C36H18014+ 2HO
Usnic acid.
-
C18H1008+ C18H1008
Everninic acid.
C34H16O14 + 2HO
Evernic acid.
C18H1003 + C16H808
Everninic acid. Orsellinic acid.
C3H4014 + 2HO
Lecanoric acid!
C16H8O8+ C16HSOS
Orsellinic acid.
Decompositions. 1. Usnic acid subjected to dry distillation yields
a sublimate of beta-orcin (xiii, 150), together with a distillate of
brown resinous liquid, whilst a difficultly combustible charcoal remains
behind (Stenhouse). The decomposition is accompanied by the evolu-
tion of an inflammable vapour, which has a peculiar odour and violently
attacks the respiratory organs (Knop).--2. According to Knop, it is
but little altered by chlorine; according to Stenhouse, it is resinized
thereby. Hypochlorite of soda does not colour usnic acid (Hesse). -
3. Decomposed by heating with oil of vitriol (Knop). See below.
4. Dilute nitric acid has but little action on usnic acid: the concen-
trated acid dissolves it to a yellow-brown syrup, from which the
usnic acid may be precipitated by water, unchanged at first. The
solution slowly evolves red vapours in the cold, and afterwards, on
mixing with water, throws down a yellow resin, which, when washed
and dried, forms a red-yellow friable mass, exploding when heated,
dissolving easily in alcohol, and thereby separable from unchanged
usnic acid. Its alcoholic solution is coloured green by agitation with
protosulphate of iron (Knop & Schnedermann).-5. Usnic acid, boiled
with an excess of caustic potash solution, or with baryta or lime-water,
yields acid resins and beta-orcin; the liquid is coloured red from
VOL. XVII.
E
50
PRIMARY NUCLEUS CH23; OXYGEN-NUCLEUS CH18010.
some further change in the beta-orcin (Stenhouse). The formation of
beta-orcin is represented by the equation.
C36H18014 + 2HO 4C02 + 2C16H1004 (Hesse).
―
A solution of usnic acid in excess of ammonia assumes, when
exposed to the air, a wine-red colour from above downwards, the
usnic acid being at last converted, by successive steps, into a
red colouring matter, which colours the liquid dark wine-red, and
remains behind on evaporation. A solution in excess of alkali red-
dens more quickly in the air, especially when heated. From a solution
which has attained a carmine-red colour, acids precipitate golden-
yellow flocks, which dissolve in alcohol with yellow colour, and
remain as an amorphous powder on evaporation. The flocks dissolve
in caustic potash with carmine-red, and in oil of vitriol with dirty
olive-green colour: they melt to a carmine-red mass, and afterwards
form a solution of the same colour with oil of vitriol. By the con-
tinued action of potash, a black tar is at last produced (Knop). —
6. Chromic acid acts violently upon usnic acid (Knop & Schne dermann).
-7. The solution of usnic acid in excess of potash, when heated with
peroxide of lead, quickly assumes a brown-red colour, and, on addition
of an acid, throws down brown flocks, the quantity of which con-
stantly decreases. On continued heating, the liquid becomes lighter-
coloured, and at length nearly colourless, the usnic acid being com-
pletely oxidized to carbonic acid and water (Schnedermann &
Knop).
Usnic acid is not wetted by water, and is not soluble therein
(Knop). It dissolves in oil of vitriol with yellow colour, and is pre-
cipitated from the solution by water, unchanged (Knop).
Usnic acid combines with bases, forming salts. They are not
decomposed by carbonic acid, but other acids precipitate the usnic
acid in the form of a nearly white powder, which, when precipitated
from an aqueous solution, obstinately retains a portion of the base.
The salts of the alkalis are colourless and crystallisable. In the
absence of an excess of alkali, they slowly become coloured in the air.
The salts of the earthy alkalis, earths, and heavy metals are obtained
by precipitation in amorphous flocks, which aggregate in microscopic
granules when heated. In presence of an excess of the precipitant,
they are generally soluble in hot water, and are thrown down in the
amorphous state on cooling. The salts are, for the most part, soluble
in alcohol. Ether takes up usnic acid from the salts of the earths and
heavy metals (Knop).
Usnate of Ammonia. a. Neutral. Usnic acid is suspended in
alcohol, into which ammonia gas is passed till solution is effected.
The liquid is then allowed to evaporate spontaneously. — The salt
crystallises as needles, from which boiling water separates usnic acid
containing ammonia (Knop).
b. Acid. Usnic acid absorbs moist ammonia-gas, and forms
therewith an acid salt. When powdered usnic acid is digested in
an excess of aqueous carborate of ammonia, an acid salt is produced
which, after the carbonate is poured off, dissolves in water, and is
again precipitated by carbonate of ammonia (Knop).
Usnate of Potash. When powdered usnic acid is boiled with
USNIC ACID.
51
excess of aqueous carbonate of potash, this salt crystallises on cool.
ing, and may be purified by re-crystallisation. White crystalline.
laminæ, containing 12-30 p c. of water (6 at. = 12·32 p. c.) (Hesse), a
part of which is given off at ordinary temperatures (Knop). The
aqueous solution froths like soap-water, and deposits flocks of an acid
salt when much diluted (Knop).
36 C ........
at 100° and 130°.
Stenhouse.
Hesse. Knop.
mean.
216
56.22
56.60
17 H......
17
13 O
ΚΟ
104
47.2
4.42
27.08
12.28
4.50
26.92
....
11.98
11.04
11.57
....
C36H17K014
384.2
100.00
100.00
....
....
Usnate of Soda. Obtained in the same manner as the potash-salt.
Silky, radiated needles, more easily decomposed in the air than the
potash-salt. Decomposed by boiling with water, with formation of an
acid salt (Knop).
Usnate of Baryta. A slight excess of chloride of barium is addled
to a hot aqueous solution of the potash-salt, and the whole is heated
to boiling, when a snow-white, silky precipitate of the hydrated salt
is produced, a small portion only being dissolved. The salt loses its
water of crystallisation at ordinary temperatures. By dissolving it in
strong alcohol and evaporating the solution, the anhydrous salt is
obtained in yellowish-white, crystalline crusts, which do not again
dissolve in alcohol (Knop).
Knop.
at 100°.
nean.
C36H17013
337
81.5
BaO
76.5
18.5
17.41
C36H7BaO1
413.5
100.0
The lead-salt is white; the silver-salt white, and easily decomposed
(Knop). The acid is not coloured by ferric chloride (Hesse).
Usnate of Copper. — The potash-salt is decomposed by a slightly
insufficient quantity of nitrate of copper. Grass-green, amorphous
precipitate, which becomes electric when rubbed (Knop).
at 100°.
Knop.
36 C
17 H.
216
57.34
57.15
17
4.51
4.38
13 O......
104
27.74
28.27
CuO
39.8
10.41
10.20
C36H17 CuO¹4 376.8
100.00
100.00
Usnic acid is scarcely soluble in cold, and very slightly soluble in
boiling alcohol. It dissolves difficultly in cold, but more freely in
boiling, ether, also in boiling oil of turpentine, and hot fatty oils (Knop).
E 2
52
PRIMARY NUCLEUS C“H²; OXYAZO-NUCLEUS C¹³N²H~04.
.....
Oxyazo-nucleus CN2H2204.
Menispermine.
? C'²6N²H²404 = C36N2H2204,II².
PELLETIER & COUERBE. Ann. Chim. Phys. 54, 196; Ann. Pharm. 10,
198.
Source. In the husk of Cocculus indicus.
Preparation. The berries, bruised together with the husks, are
exhausted with boiling alcohol of 36°; the extract is filtered; the
alcohol distilled off; and from the residue (first freed from picrotoxine
by treatment with boiling water), the menispermine and paramenis-
permine are taken up by acidulated water, and thrown down from the
solution by ammonia. The precipitate is dissolved in dilute acetic
acid, precipitated by ammonia, and dried; it is then exhausted with
alcohol, and the solution is left to evaporate spontaneously, whereby a
yellow alkaline resin, crystals of menispermine, and a yellowish mucus
are obtained. The crystals are picked out as far as possible and
removed, and the yellow mucus is first freed from resin by means of
cold alcohol, and then washed with cold ether, which takes up the
remaining menispermine and leaves it behind on evaporation. The
whole of the crystals are purified by rinsing with cold alcohol. By
dissolving the yellow mucus in absolute alcohol and evaporating the
solution at 45, paramenispermine is obtained.
Properties. White, semi-transparent, four-sided pointed prisms,
resembling cyanide of mercury and melting at 120°. Tasteless. Not
poisonous.
Pelletier and Couerbe.
mean.
36 C........... 216
72.00
70.45
2 N.
28
9.35
9.45
24 H.....
24
8:00
8.01
4 O.....
32
10.65
12.09
C'36N2H2404
300
100.00
100.00
....
The formula was proposed by Pelletier and Couerbe. According to Liebig (Ann.
Pharm. 10, 208) it is to be regarded as very doubtful.
Decompositions. 1. Menispermine is decomposed by heating in a
glass tube, and leaves charcoal.
verts it into resin and oxalic acid.
2. Concentrated nitric acid con-
Menispermine is insoluble in water.
It dissolves in dilute acids and forms therewith salts, from the
solutions of which alkalis precipitate menispermine.
Sulphate of Menispermine. - Oil of vitriol dissolves menispermine
when warmed, and deposits it again on addition of aqueous ammonia.
With dilute sulphuric acid, needles or prisms are obtained, which
melt to a wax at 105°, redden and evolve hydro-sulphuric acid when
HYDROCAROTIN.
53
!
more strongly heated.
The salt has an alkaline reaction. Contains
15 p. c. of water, 6-87 of sulphuric acid, and 78.13 of menispermine, or,
according to Pelletier & Couerbe, 2 atoms of menispermine and 10
atoms of water to 1 atom of sulphuric acid.
Menispermine dissolves in cold, and more freely in warm alcohol
and ether.
Paramenispermine.
PELLETIER & COUERBE. Ann Chim. Phys. 54, 196; Ann Pharm. 10,
200.
Source. In the husks of Cocculus indicus.
Preparation. See page 52.
Properties. Four-sided prisms with rhombic base, or radiated star-
shaped masses. Melts at 250° and sublimes undecomposed. Has the
same composition as menispermine.
Paramenispermine is insoluble in water. It dissolves in dilute acids,
but does not form salts, and is decomposed by boiling acids.
Soluble in absolute alcohol, nearly insoluble in ether.
Primary Nucleus C361134,
Hydrocarotin.
C³63002
C¹³6 H3º, C³.
30
AUG. HUSEMANN. Dissert. über Carotin und Hydrocarotin. Gött. 1860.
First observed by Bödeker; investigated by Husemann. - Occurs,
together with carotin, in the roots of the cultivated Daucus Carota.
The alcoholic solution of hydrocarotin and mannite, obtained in the
preparation of carotin (p. 14), deposits, on cooling, a red-brown slimy
sediment, which being removed and the liquid set aside for a week, a
mixture of mannite and hydrocarotin crystallises out. The mother-
liquor, when concentrated, yields more hydrocarotin, but of a darker
colour, till at last a thick syrup remains. The mannite is removed by
solution in water, and the hydrocarotin is purified by repeated re-crystal
lisation from the smallest possible quantity of boiling alcohol, and at
last by boiling with water.
Properties. Large, colourless, very thin, soft, flexible laminæ, pos-
sessing a strong silky lustre. Crystallises from ether in flat rhombic
tables. Inodorous, tasteless. Floats on water like a fatty body, with-
out being wetted. At 100° it is hard and brittle; a little above 100°
yellowish and soft; a few degrees below its melting-point, dark-
yellow. Melts at 126.5° without losing weight, and solidifies, on
cooling, to a brittle resin, which cannot be re-crystallised,
54
PRIMARY NUCLEUS CH30; IODINE-NUCLEUS CIH”.
Husemann.
36 C
30 H
20
C39H300
mean.
216
82.44
82.32
30
11:41
11.53
•
16
6.15
6.15
262
100.00
100.00
Decompositions. 1. When heated above its melting-point, it turns
red, and at 280° carbonises, giving off white empyreumatic vapours
and a colourless oil. 2. With iodine, bromine, and chlorine it forms
substitution-products containing 1 at. iodine, 3 at. bromine, and 4 at.
chlorine. 3. It is not altered by concentrated nitric acid; fuming
nitric or nitro-sulphuric acid dissolves it, forming a colourless solution,
from which water precipitates a white amorphous nitro-compound,
casily soluble in ether, alcohol, and benzene, and difficultly soluble in
bisulphide of carbon. 4. Oil of vitriol colours hydrocarotin ruby-red,
dissolves it, on warming, with bright-red colour, and carbonises it on
boiling. From the solution prepared by gently warming, water
throws down the whole of the hydrocarotin in the amorphous state,
nothing remaining in solution. 5. Hydrocarotin is not altered by
boiling solution of caustic potash; when melted with hydrate of potash
it is converted into a yellow amorphous mass, which reddens at 80°,
and melts at 120° to a dark-red viscid liquid.
IIydrocarotin is not altered by dilute or concentrated acids, even
on addition of oxide of manganese, chromate of potash, or peroxide of
lead; nor by ferricyanide of potassium, permanganate of potash, sul-
phurous acid, hydrochloric acid gas, hydrosulphuric acid, or hydrosul-
phate of ammonia.
Combinations.
With Water. - A solution of hydrocarotin in bisul-
phide of carbon containing water yields, at a low temperature,
crystals which lose their water at ordinary temperatures.
Alcoholic hydrocarotin does not precipitate either metallic salts or
tannic acid.
Hydrocarotin dissolves in boiling alcohol, crystallising therefrom
almost entirely on cooling. It dissolves easily in bisulphide of carbon,
ether, choloroform, benzene, and volatile oils; also in fixed oils, even in the
cold.
Iodine-nucleus C36IH29.
Iodo-hydrocarotin.
С36290² = С36IH29,0².
IIUSEMANN. Dissertation über Carotin und Hydrocarotin. Gött. 1860.
Hydrocarotin, exposed to sunshine with vapour of iodine,
assumes a darker colour, becoming black at last, and increases about
49.6 p. c. in weight (calc. 1809 p. c.). The product is thrown down
from its ethereal solution by weak alcohol in the form of a yellow-
QUADRICHLOR-HYDROCAROTIN.
55
white powder, which turns soft and dark-red at 70° to 80°. It dissolves
with difficulty in alcohol, easily in ether, bisulphide of carbon, and
benzene.
Bromine-nucleus C36Br³H27.
Terbromo-hydrocarotin.
C36 Br³H270² = C³6Br³H27,0².
IIUSEMANN. Dissert. über Carotin und Hydrocarotin. Gött. 1860.
Hydrocarotin becomes brown and soft in vapour of bromine,
giving off hydrobromic acid, and in 24 hours is converted into a
brittle, red-brown mass, which is precipitated from its ethereal solution
by alcohol, as a pale-yellow powder.
Contains 47.7 to 48'7 p. c. of bromine (C36Br³H270² 48.09 p. c. Br). –
It assumes a darker colour and softens at 162°, blackens at 170°, and
carbonises without melting. The solution in ether or benzene is
coloured red by boiling with alcoholic potash, and leaves, on evapora-
tion, a yellow-red body, free from bromine, soluble in bisulphide of
carbon with red colour: probably carotin.
Terbromo-hydrocarotin is insoluble in boiling alcohol, and difficultly
soluble in boiling ether. It dissolves easily in bisulphide of carbon and
benzene, and does not crystallise from the solution.
Chlorine-nucleus Cs6C14H26.
Quadrichlor-hydrocarotin.
C36C14H260² = C³6C1¹H²º,0².
HUSEMANN. Dissert. über Carotin und Hydrocarotin. Gött. 1860.
Chlorine gas is passed over pulverulent hydrocarotin for three
days, and the hydrochloric acid formed is expelled at 100° by dry
air, the hydrocarotin then increasing about 55-36 p. c. in weight
(calc. 52.67 p. c.). The product is repeatedly boiled with alcohol, and
afterwards dissolved in ether-alcohol and precipitated by water.-
Or, hydrocarotin suspended in water is subjected to the prolonged
action of chlorine gas.
White powder, containing on an average, 35.17 p. c. of chlorine
(calc. for C36C14H26O² = 35·5 p. c. Cl.). Obtained from its solutions as a
brown-yellow, amorphous, brittle resin. It softens, and turns dark-
red at 80°, melts at 118°, and remains red on cooling.-Alcoholic
potash converts it into a body free from chlorine.
Soluble in ether and absolute alcohol; easily soluble in benzene and
bisulphide of carbon.
56
GLUCOSIDE OF GLYCYRRETIN.
Primary Nucleus C113; Oxygen-nucleus C³H2O.
Glycyrretin.
? C'362608 = C6H260,0².
GORUP-BESANEZ. Ann. Pharm. 118, 241.
On boiling a solution of 1 part of glycyrrhizin in 20 parts of water,
together with the precipitate at first produced, with 1 part of concen-
trated hydrochloric acid for four hours, renewing the water as it evapo-
rates, the precipitate melts to a brown-red mass, which at last becomes
brittle, the liquid remaining of a wine-yellow colour, and containing
sugar in solution. The brown-red mass is glycyrretin; it may be
decolorised by treating its alcoholic solution with animal charcoal,
and is then a yellowish-white, friable substance.
It contains, in various preparations, from 73 to 75 p. c. of carbon,
and 9.53 to 10.39 of hydrogen, not agreeing with the formula CH²ºOº
(calc. 70·5 C. 8.5 H.), which is therefore probable only from the formula
of glycyrrhizin, C4H6O18, and on the supposition that the decom-
position takes place according to the equation:
C49H36018 + 2HO C36H2608 + C12H12012.
Probably the product first formed itself undergoes change.
Brown-yellow glycyrretin has a very bitter taste. It does not
melt in boiling water, but melts easily when heated on platinum-foil,
taking fire, and burning with a very smoky flame, like a resin. It
dissolves in oil of vitriol, forming an amaranth-red solution, which
changes, on standing, to violet, and on dilution with water to purple-
violet, with deposition of a blue-black precipitate. It is precipitated
by acids from its brown-red solution in ammonia or aqueous alkalis.
Dissolves in alcohol, from which it is precipitated by water, and rather
less casily in ether.
Glucoside of Glycyrretin.
Glycyrrhizin.
PFAFF. System. der Mat. med. 1, 187.
ROBIQUET. Ann. Chim. 72, 143.
DÖBEREINER. Elemente der pharm. Chemie, 194.
BERZELIUS. Rogg, 10, 243; Lehrb. 3, 356.
TROMMSDORFF. Taschenbuch, 1827, 1.
L. A. BACKER. Repert. 88, 176.
A. VOGEL. J. pr. Chem. 28, 1; abstr. Ann. Pharm. 48, 347.
LADE. Ann. Pharm. 59, 224; J. pr. Chem. 40, 121.
GORUP-BESANEZ. Ann. Pharm. 118, 236; abstr. J. pr. Chem. 84, 246;
Chem. Centr. 1861, 798; Rép. Chim. pure, 4, 30; Kopp's Jahresb.
1861, 757.
Glycion. Pfaff's Sweet Extractive. Berzelius's Liquorice sugar.
GLYCYRRHIZIN.
57
Source. In the roots of Glycyrrhiza glabra and Gl. echinata.
Monesia bark (Derosne, Henry & Payne, J. Pharm. 27, 25.)
In
Berzelius extracted from the leaves of Abrus præcatorius, a bitter-
sweet substance allied to glycyrrhizin, obtained in the same way, and
exhibiting the same reactions with acids, alkalis, and metallic salts. --
The root of Polypodium vulgare contains a similar, but more easily
decomposed substance. Its aqueous infusion tastes like that of
liquorice; it is precipitated by sulphuric acid after some hours, the
liquid losing, at the same time, its sweet taste. The precipitate
assumes a yellow colour, and when dissolved in alcohol and treated
with carbonate of potash, yields a red, but not sweet substance, easily
soluble in water; neither does the precipitate thrown down from the
infusion by neutral acetate of lead, yield any sweet substance when
decomposed by hydrosulphuric acid (Berzelius).
Sarcocolla, the substance which exudes from Penaen Sarcocolla and
P. mucronata, contains a sweet substance allied to glycyrrhizin (Döbe-
reiner), or to the sweet substance of Polypodium (Desfosses, J. Pharm.
14, 276). According to Pelletier (Bull. Pharm. 5, 5; Ann. Chim. Phys. 51,
198; Berz. Jahresbr. 13, 314), it is resolved, by treatment with ether,
into a resin which dissolves, and a residue of gum and sarcocollin, the
latter of which dissolves in alcohol. Sarcocollin contains 56-48 p. c. C.,
8.34 H., and 35.18 0. It is soluble in water and alcohol, but insoluble
in ether, has a bitter-sweet taste, and is converted into oxalic acid by
nitric acid (Pelletier). See also Thomson (System der Chemie, Wolff's trans., 4,
37); Pfaff (System der Mat. med. 1, 190); Johnston (J. pr. Chem. 23, 397; Ann.
Pharm. 37, 35).
Preparation of glycyrrhizin. From the Russian, not from the Spanish
liquorice root, the latter yielding a coloured glycyrrhizin, difficult to purify (Gorup-
Besanez). 1. An aqueous extract of the roots is boiled down rapidly, and
the green-brown coagulum which forms is removed; the filtrate is then
concentrated and precipitated by dilute sulphuric acid (the deposited
nitrogenous substance being first separated if necessary). The pale-
yellow flocks first thrown down are converted after some hours into a
dark-brown tough mass, which is washed with water by decantation,
till the washings are no longer rendered cloudy by salts of baryta.
The residue is dissolved in alcohol of 82 p. c.; to the solution (not too
concentrated), a small quantity of ether is added; and the brown resin
which is deposited after some time is removed. The ether-alcoholic
solution is evaporated over the water-bath, and the residue is purified
by again dissolving it in alcohol, mixing the solution with ether,
whereby a little more resin is precipitated; filtering, and evapo-
rating to dryness (Gorup-Besanez). A similar process was previously
adopted by Lade, who, however, did not purify his product with ether.
Robiquet uses vinegar to precipitate the aqueous extract. Berzelius
precipitates with sulphuric acid; dissolves the washed precipitate,
which still contains sulphuric acid, in alcohol; precipitates the acid by
careful addition of carbonate of potash, and evaporates the filtrate.
Martin (Pharm. Viertelj. 10, 259; Kopp's Jahresb. 1860, 551), precipi-
tates the extract prepared with cold water, with bitartrate of potash;
digests the dried precipitate with alcohol at a gentle heat; filters the
solution to remove bitartrate of potash and other insoluble salts; and
evaporates to dryness.
2. The roots are exhausted with boiling water, and to the filtered
58
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS CHO6.
liquid basic acetate of lead is cautiously added; the precipitate is
washed and decomposed under water by hydrosulphuric acid, and the
filtrate is boiled and evaporated. The residue is purified by repeated
solution in alcohol and evaporation (Vogel). The product thus obtained
probably still requires to be purified according to 1.
To prepare glycyrrhizin from the Succus Liquiritii of commerce,
C. Rump (N. Repert. 4, 153) exhausts it with weak ammonia-water,
precipitates the glycyrrhizin with hydrochloric or acetic acid; dissolves
the precipitate in ammonia-water; removes magnesia and lime by the
addition of phosphate and oxalate of ammonia; and throws down the
glycyrrhizin by acetic acid. The gelatinous precipitate is dried and
triturated, and afterwards washed with water.
Properties. Amorphous, yellowish-white powder, having an intense
bitter-sweet taste (Gorup-Besanez). According to Vogel, brown-yellow;
according to others, a brown, transparent, brittle, shining mass. Its alcoholic
solution smells like infusion of liquorice-root; the aqueous solution
reddens litmus strongly (Lade). It is without action on polarised
light (Ventzke, J. pr. Chem. 25, 65).
Gorup-
Besanez.
::
61.46
Vogel.
mean.
48 C
288
61.54
61.65
36 H
36
7.69
18 O
111
30.77
7.64
30.71
Lade.
mean, at 100°
61.02
7.25
31.73
mean.
....
....
C48113018
468
100.00
100.00
100.00
...
....
7.71
30.83
100.00
Lade's glycyrrhyzin contained a little nitrogen. Vogel proposed the formula
CHIO, Lade the formula C3H4014: Gorup-Besanez, who recognised glycyrrhizin
as a glucoside, considered the above a probable formula.
Decompositions. 1. Glycyrrhizin heated to 200° melts to a dark-
brown, transparent mass (Lade), takes fire, and burns with a luminous,
smoky flame, frothing up and evolving resinous vapours, which redden.
litmus, and have an odour of burnt sugar (Trommsdorff). When
blown into the flame of a candle, it burns like lycopodium (Berzelius).
2. It reduces sesquioxide of chromium from a mixture of bichromate of
potash and sulphuric acid, and is violently decomposed by peroxide of
lead (Gorup-Besanez). - 3. Decomposed by cold, and more rapidly by
hot nitric acid, a large quantity of nitric oxide gas being liberated,
and a bright-yellow body deposited, whilst oxalic acid and pale-
yellow crystals of a nitro-compound [probably styphnic acid (xi, 228)]
are likewise formed (Gorup-Besanez. Lade).
By boiling with nitric acid, Robiquet obtained a yellow, tough
mass, which was resolved by water into an artificial bitter, and a
white, tasteless residue.
On boiling a concentrated infusion of liquorice with nitric acid till
all frothing has ceased, precipitating the product with water, boiling
the washed precipitate with concentrated nitric acid, and pouring the
solution into water, with constant stirring, there is thrown down a
light, yellow, very bitter powder, which reddens litmus, burns on
platinum-foil like wax, is slightly soluble in water, insoluble in boiling
concentrated nitric acid, but easily soluble in alcohol and in aqueous
alkalis, forming with the last, orange-coloured solutions from which it
is precipitated by acids. This substance has the composition a (Lade).
GLYCYRRHIZIN.
59
Glycyrrhizin, subjected to the same treatment, yields a body having
the composition b. When glycyrrhizin is added to cold nitro-sulphuric
acid, a yellowish-white, amorphous powder (c) is deposited. This
body resembles that obtained by Lade, and is, like it, free from
nitrogen (Gorup-Besanez).
Gorup-
Besanez.
Lade.
a.
C.
48 C.......
34 H
288
57.83
57.23
57.04
34
6.82
6.03
6.66
22 O
176
35.35
36.74
36:30
...
C4H84022 ....... 498
100.00
100.00
100.00
Gorup-
Besanez.
b.
48 C....
288
61.80
60.95
34 H
34
7.29
7.27
18 O
144
30.91
31.78
•
C48H34018
466
100.00
100.00
4. Glycyrrhizin dissolves in oil of vitriol, forming a red-brown
solution (brown according to Lade), from which water precipitates
grey-brown flocks. It is decomposed by boiling with dilute acids,
glycyrretin being deposited and sugar remaining in solution (Gorup-
Besanez). The decomposition may perhaps be expressed thus:
C48H36018 + 2HO = C36:608 + CH12012,
the equation requiring 65.3 p. c. of glycyrretin and 38.4 p. c. of sugar,
whilst 65.4 p. c. of glycyrretin and 17.5 p. c. of sugar are obtained
(Gorup-Besanez).When the decomposition is effected with hydro-
chloric acid, and the solution is filtered from glycyrretin, the acid
being afterwards removed by acetate of silver, and the excess of
silver by hydrosulphuric acid, the sugar is left on evaporation in the
form of a brownish, very sweet syrup, which does not crystallize.
It behaves like grape-sugar with alkaline solutions of copper and
with potash, oxide of bismuth, gallic and sulphuric acids, and yeast
(Gorup-Besanez).
Glycyrrhizin does not reduce potassio-cupric tartrate at tempera-
tures of 75° to 100° (Mathey, N. Br. Arch. 72, 293). It is not sus-
ceptible of fermentation (Lade), and is not decomposed by emulsin
(Gorup-Besanez).
Combinations. Glycyrrhizin dissolves with difficulty in cold, and
more easily in hot water, forming a yellow solution, from which a
small portion is deposited in resinous drops on cooling (Gorup-
Besanez). A hot saturated solution solidifies to a brown jelly on
cooling (Lade).
Mineral and vegetable acids produce, in aqueous solutions of gly-
cyrrhizin, curdy precipitates, which in very dilute solutions appear
only after some time. They dissolve slightly in pure, but not in
acidulated water (Berzelius, Döbereiner). According to Berzelius and
Vogel, these precipitates are to be regarded as combinations of gly-
60
; OXYGEN-NUCLEUS CHOº.
PRIMARY NUCLEUS CH³232
cyrrhizin with acids. That produced by sulphuric acid contains, after
washing, 7:34 p. c. of sulphuric acid and 92.66 p. c. of glycyrrhizin
(Vogel). Backer and Lade, on the contrary, found it perfectly free
from sulphuric acid. The precipitate thrown down by acetic acid.
(Berzelius's acetate of glycyrrhizin) dissolves more freely in boiling water
than the sulphuric precipitate, and forms, when dry, nearly white,
sweet scales containing acetic acid (Berzelius). — Acetic acid precipi-
tates the infusion of liquorice-root, but not aqueous glycyrrhizin. It
dissolves the precipitates produced by other acids (Backer).
Glycyrrhizin combines with bases (Berzelius). Ammonia and
alkalis render it more soluble in water (Lade, Rump). They dissolve
it with deep red-yellow colour, evolving a peculiar odour (Gorup-
Besanez). Glycyrrhizin expels carbonic acid from the carbonates of
potash, baryta, and lime. After filtering and evaporating, there
remains an extract, which has a sweet taste, provided the alkali does
not predominate. The extract is easily soluble in water, less freely in
alcohol (Berzelius).
Chloride of barium throws down from aqueous glycyrrhizin a com-
pound soluble in hydrochloric acid (Vogel). Sulphate of magnesia
(Gorup-Besanez), sesquichloride of iron, protochloride of tin, and sulphate
of copper also produce precipitates. Ferrous and mercurous salts, and
corrosive sublimate, on the contrary, do not (Berzelius, Gorup-Besanez).
Nitrate of silver produces a cloudiness in aqueous glycyrrhizin (Gorup-
Besanez). It throws down a white, easily soluble precipitate (Lade).
The precipitates produced by ferric sulphate and sulphate of cop-
per in infusion of liquorice are soluble in excess of caustic potash
(Lassaigne, J. Chim. méd. 18, 418). The precipitates formed with
salts of the metals give up a little glycyrretin to warm alcohol
(Dübereiner, Berzelius). When they are decomposed under water
by hydrosulphuric acid, the water takes up little or nothing, the
glycyrrhizin remaining in combination with the acid (Berzelius).
Lime-compound. Aqueous glycyrrhizin does not precipitate chloride of cal-
cium (Gorup-Besanez). When an infusion of liquorice prepared with
cold water, is boiled with milk of lime, and the product is collected
and washed, there remains on the filter a dirty yellow residue, which
is difficultly soluble in water, and imparts thereto a sweet taste. This
body is resolved by treatment with carbonic acid under water into
carbonate of lime and the lime-compound of glycyrrhizin, the latter of
which is soluble in water, but insoluble in alcohol (Lade). Aqueous
glycyrrhizin-lime deposits crystals of carbonate of lime when exposed
to the air (Kuhlmann, Ann. Pharm. 27, 22).
Two-thirds. Alcoholic glycyrrhizin is precipitated by alcoholic
chloride of calcium, and the pale-yellow precipitate is washed with
alcohol (Gorup-Besancz).
96 C
76 H.....
Gorup-Besanez.
576
54.54
53.86
76
7.19
7.08
40 O.....
320
30.30
30.77
3 CuO
84
7.97
8.29
2C+SHO¹8,3 CuO,4HO
1056
100.00
100.00
**
Lead-compound. An aqueous solution of glycyrrhizin is rendered
turbid (precipitated according to Berzelius and Vogel) by neutral acetate of
;
ONONIS-GLYCYRRHIZIN,
61
lead, and is precipitated by the basic acetate and by an ammoniacal
solution of the neutral acetate (Gorup-Besanez). On precipitating
alcoholic glycyrrhizin with aqueous neutral acetate of lead, filtering
when the further addition of a small quantity of the acetate no
longer causes a precipitate, and then adding a large quantity of the
aqueous acetate, dark-yellow granules and resinous drops are pre-
cipitated, the latter of which are soluble in alcohol. Basic acetate of
lead, added to the filtrate, throws down a further portion, but not the
whole, of the glycyrrhizin (Gorup-Besanez).
a. With 6 at. of Lead-oxide.—An aqueous solution of neutral acetate
of lead containing a little ammonia, is added to aqueous glycyrrhizin,
while constantly stirring, till the greater part of the glycyrrhizin is
precipitated. The yellowish-white flocks are washed, and dried at
100° Pale-yellow powder, insoluble in water and alcohol (Gorup-
Besanez).
Gorup-Besanez.
48 C
40 H
22 O
6 РЬО
C48H3618,6Pьо,4но
at 100°.
288
24.52
24.07
40
3.46
2.92
176.
14.94
16.13
670.2
57.08
56.88
1174.2
100.00
100.00
b. With 3 atoms of Lead-oxide? -Glycyrrhizin dissolved in weak
alcohol is precipitated by cold aqueous neutral acetate of lead, and
the precipitate is washed with alcohol. - Yellow, amorphous powder
(Lade). Contains 41.59 p. c. of oxide of lead (Vogel).
at 100*.
Lade.
48 C...
288
35.86
37.46
36 H.....
36
4.48
4.37
18 O
144
17.92
18.37
3 Pbo.....
335.1
41.74
39.80
C49H36O18,3PbO
803.1
100.00
100.00
c. The precipitate b, after washing with water and drying, con-
tains 45.98 p. c. C., 5·49 H., 23·89 O., and 24.64 PbO, or about 4 at. of
oxide of lead to 3 at. of glycyrrhizin.
Glycyrrhizin dissolves quickly and abundantly in alcohol, especially
in absolute alcohol (Vogel, Lade). It dissolves completely in warm
ether (Gorup-Besanez). Lade found it insoluble in ether. It is not
precipitated by infusion of galls (Berzelius). It is withdrawn from its
aqueous solution by animal charcoal containing lime (Lade).
Appendix to Glycyrrhizin.
Ononis-glycyrrhizin.
REINSCH. Repert. 76, 27.
HLASIWETZ. Wien. Acad. Ber. 15, 165.
Ononid (Reinsch). Occurs in the dried roots of Ononis spinosa, and
is perhaps produced from true glycyrrhizin contained therein, during
drying Alasiwetz).
62
PRIMARY NUCLEUS C6H3.
Preparation. 1. An aqueous decoction of the roots is precipitated
with dilute sulphuric acid; and the brown flocks are washed with cold
water, dried, and repeatedly treated with absolute alcohol, until the
residue left on evaporation is perfectly soluble in absolute alcohol.
2. When an alcoholic extract of the roots is evaporated to a syrup
(the onocerin being first crystallised out) and allowed to stand for
some days, a deposit of resin is thrown down, after which the clear
liquid is to be separated and precipitated with water and dilute sul-
phuric acid. The precipitate is purified as in 1.-3. If the brown
resin obtained as in 2 is dissolved in alcohol and precipitated by
alcoholic neutral acetate of lead, and the brown precipitate is decom-
posed by hydrosulphuric acid under water, the solution filtered from
sulphide of lead, leaves, when evaporated, a brown, shining extract,
triturable to a light-brown powder which behaves like glycyrrhizin
(Illasiwetz). Reinsch proceeds in the same way as Berzelius in the
preparation of glycyrrhizin (p. 57).
Dark-yellow, amorphous, brittle mass, tasting at first bitter and
afterwards persistently sweet (Reinsch, Hlasiwetz). Cakes together
in the mouth to a resin. Has an acid reaction (IIlasiwetz).
Calculation according to IIlasiwetz.
a.
36 C
216
22 H
22
....
16 O
128
59.01
6.01
34.98
59.1
....
6.2
317
....
C36H 2016
366
100.00
100'0
...
Hlasiwetz.
b.
C.
a.
59.6
57.8
61.5
...
6.0
344
6.4
6.3
....
35.8
32.2
....
100.0
100.0
100.0
....
....
a and were prepared according to 1, c according to 2, and d according to 3.
Ilasiwetz gives for e the formula C36H23017, and for d the formula C36H22O14.
Ononis-glycyrrhizin melts when heated, with strong intumescence,
gives off acid vapours, and burns with a smoky flame, leaving char-
coal (Reinsch).
The aqueous solution gives an abundant white precipitate with
sulphuric acid. Precipitates are also produced by neutral acetate of lead,
acetate of copper, mercurous nitrate, and nitrate of silver, but not by
tartar-emetic or tincture of galls (Reinsch).
Dissolves freely in alcohol.
Primary Nucleus CI134.
Oleic Acid.
C'36II340) = C31134,0.
CHEVREUL. Ann. Chim. 94, 90, and 263.— Ann. Chim. Phys. 2, 358.—
Recherches sur les corps gras, 75.
BRACONNOT. Ann. Chim. 93, 250.
LAURENT. Ann. Chim. Phys. 65, 149; Ann. Pharm. 28, 253.-Ann.
Chim. Phys. 66, 154.
VARRENTRAPP. Ann. Pharm. 35, 196.
C. BROMEIS. Ann. Pharm. 57, 38.
HEINTZ. Pogg. 83, 555; 89, 583; 90, 143.
BERTHELOT. N. Ann. Chim. Phys. 41, 243.
OLEIC ACID.
63
Chevreul's Graisse fluide. Acide oléique. Braconnot's Huile. Elainsäure.
Discovered by Chevreul in 1811, and first prepared pure by Gottlieb, who also
established its formula. Gottlieb and Heintz showed that the oleic acid of butter,
which Bromeis supposed to be a peculiar body, is identical with common oleic acid.
Concerning the moringic acid of Walter and the filixolic acid of Luck, see
Appendix to Oleic acid.
Source. Occurs as triolein in most (non-drying) liquid and solid
fats. (See below.)
In the bile of men, oxen, pigs, and bears (Chevreul). In the
Mineralmoor of Marienbad (Lehmann).- It does not occur in castor-oil
or spermaceti (or only in very small quantity) (Heintz), nor in wax
(Thénard, Redtenbacher), the last substance yielding no sebacic acid
when subjected to dry distillation. Concerning the occurrence of oleomar-
garin, see under olive-oil; concerning oleophosphoric acid (xvi., 483).
Preparation. Almond-oil (olive-oil, goose-fat, butter, or other fat
containing olein) is saponified by boiling with caustic potash, and the
soap is decomposed by dilute hydrochloric acid. The separated fatty
acids are then maintained at a temperature of 100° for several hours
with oxide of lead, and the mixture of lead-salts thus obtained is
treated with cold ether, which takes up the oleate, but leaves the salts
of the solid fatty acids undissolved. The ethereal solution, when
shaken with excess of dilute hydrochloric acid, throws down chloride
of lead, which sinks to the bottom of the watery layer, whilst oleic
acid remains dissolved in the ether. Lastly, the ether is distilled off,
and the acid freed from adhering water by evaporation (Varrentrapp,
Bromlis).
Purification. Oleic acid, prepared as above, still contains oxidized
products and colouring matters, to remove which, its solution in a large
excess of ammonia is precipitated by chloride of barium; the precipitate
is dried and boiled repeatedly with fresh portions of alcohol; and the
salt which is deposited on cooling is re-crystallised once or twice from
alcohol. It is then decomposed by tartaric acid, and the separated
oleic acid is washed with water to remove adhering tartaric acid
(Gottlieb).
Or, the acid obtained from the lead-salt is cooled down, in small
portions, to 6° or 7°, when it solidifies to a crystalline mass, which is
pressed between folds of blotting-paper. The solid and purer acid is
thus separated from the fluid portion, which contains oxidised products.
By repeatedly melting, cooling, and pressing the crystallised portion,
at last with addition of a little alcohol, the impurities are completely
removed (Bromeis).
Inasmuch as oleic acid readily absorbs oxygen, all the operations
should be conducted with the least possible exposure to the air, more
especially when the acid is subjected to a temperature of more than
10° (Bromeis). In digesting the acid separated from the potash-soap
with oxide of lead, the quantity of oxide used should be such as to
saturate only a portion of the oleic acid, as in that case the solid fatty
acids are completely separated, and less ether is afterwards required
to exhaust the lead-salt (Varrentrapp). The baryta-salt is to be
crystallised from moderately-hot strong alcohol; in boiling alcohol it
melts to a tough, dark mass (Saalmüller). Tartaric acid is preferable
64
PRIMARY NUCLEUS CH34.
to hydrochloric acid for decomposing the oleates of the alkalis, since
the latter is apt to colour oleic acid. Moreover, by using tartaric acid
it is easier to remove the whole of the alkali (Varrentrapp).
From the mixture of stearate (margarate) and oleate of potash
obtained by saponification, Chevreul separates the first two acids as bi-
acid salts, in the manner described at page 355, vol. xvi., and after-
wards decomposes the mother-liquor with tartaric acid, the oleic acid.
then rising to the surface in the form of an oil. It is washed with hot
water, cooled, filtered from the margaric acid which crystallises out,
and freed from acetic acid and colouring matter, either by solution in
12 parts of alcohol and precipitation with water, or by converting it
into a baryta-salt. The latter, Chevreul boils with water, which takes
up acetic acid and colouring matter, and re-crystallises from alcohol.
-If the potash-soap obtained by saponifying human fat be digested,
in as dry a state as possible, in alcohol of sp. gr. 0·821, the alcohol is
found, after 24 hours, to have taken up principally oleate of potash,
which may be freed from margaric acid dissolved at the same time by
evaporating the solution, treating the residue with cold absolute
alcohol, evaporating the filtrate, &c. It is afterwards to be purified
as above (Chevreul).
The coloured oleic acid of stearin works is freed from the greater
part of the solid fatty acids by filtration at 0°. After separation
from its lead-salt, it is to be again saponified with an alkali and salted
out with chloride of sodium, with addition of carbonate of soda. In
this way only, and not by treatment with animal charcoal, can the
colouring matters be removed (Varrentrapp). Berthelot filters com-
mercial oleic acid twice at 0°; neutralises with caustic potash; dissolves
in two parts of alcohol; filters the cold solution; precipitates with
chloride of barium; and purifies the baryta-salt as above. When
cantharides' fat is employed, the lime-soap may also be treated with
ether instead of the lead-soap; or the fatty acids of cantharides' fat
are dissolved in 5 or 6 parts of alcohol of 85 p. c.; the solution is pre-
cipitated with alcoholic neutral acetate of lead; and the precipitate is
dissolved in warm acetic acid and allowed to stand for 24 hours, where-
upon, palmitate and stearate of lead crystallise out, whilst the oleate
of lead remains in solution and is thrown down from the filtrate by
ammonia (Gössmann).
The oleate of baryta obtained from butter (and from beef and
mutton suet) by Gottlieb's method, contains a salt richer in baryta, the
presence of which renders the following process necessary. The salt
is exhausted with cold ether, and re-crystallised from a large quantity
of hot alcohol; it is then allowed to digest for several days with a
large quantity of ether, again washed with ether, pressed, and re-crys-
tallised from alcohol. The crystals are shaken with ether and hydro-
chloric acid, and the ethereal layer is agitated with ammonia and
aqueous neutral acetate of lead. The upper of the two layers thus
obtained contains oleate of lead in solution: this is decomposed by
hydrochloric acid, and the oleic acid is converted into baryta-salt
(Heintz).
Properties. Fine, dazzling white needles, which melt at 14° to a
colourless oil. The fused substance solidifies at 4° to a white, hard
crystalline mass, expanding considerably, so that the fluid portion is
driven out. Sp. gr. 0.898 at 19° (Chevreul). Volatilises in a vacuum
OLEIC ACID.
65
without decomposition (Chevreul, Laurent). Inodorous, tasteless.
In the unchanged (not oxidised) condition, and also in alcoholic solu-
tion, its reaction is neutral (Gottlieb).
Chevreul.
Laurent.
mean.
36 C
216
76.59
76.7
75.86
34 H......
34
12.06
114
12.28
4 O...
32
11.35
11.9
11.86
C36H3101
282
100.00
100.0
100.00
Varrentrapp.
Gottlieb.
A. Völcker.
mean.
C ...
74.95
75.77
76.34
76.29
H ....
11.74
12.06
12.14
12.14
O ...
11.52
11.57
100.00
100.00
Gottlieb alone examined pure oleic acid; that of the other chemists was more or
less oxidised and had an acid reaction. Laurent's acid was distilled in a vacuum:
it did not solidify at 0°.. Earlier formula: C35H3003.5 (Chevreul); C70607
(Laurent); CH005 (Varrentrapp). - The oleic acid of butter, of almond oil, and
of olive oil exhibits the same composition (Gottlieb). See also the analyses of the
baryta-salt.
Decompositions. 1. Oleic acid, heated a few degrees above 100°,
assumes a dark-brown colour, and before boiling evolves a large
quantity of hydrocarbons, together with a little carbonic acid and
water: at a comparatively low temperature, it yields a distillate of
colourless oil (afterwards yellow, and at last brown, according to
Chevreul), a little charcoal remaining behind (Bromeis). During the
whole of the distillation, a tolerably regular evolution of carbonic acid
and hydrocarbon gases takes place. The distillate deposits crystals
of sebacic acid (xiv, 493) on cooling, the fluid portion consisting of a
little undecomposed oleic acid and hydrocarbons boiling at 160—280°
and higher. That portion of the distillate which passes over with the
water-vapour contains 84.13 p. c. C., 13.02 II., and 2.85 O. (Varren-
trapp). The distillate contains also acetic (Chevreul), caproic, caprylic,
and probably butyric and valerianic acids. Pure oleic acid yields a
large quantity, the oxidised acid only a small quantity of sebacic acid
(Gottlieb), and hence Bromeis did not obtain any by the distillation of
his butyroleic acid,
2. Oleic acid (which, in the solid state, is unalterable in the air
(Gottlieb), absorbs, in the melted state, at 15°, in 14 days, 20 times its
volume of oxygen without forming any perceptible amount of carbonic
acid or water (Bromeis). After exposure to the air for five hours, at
100°, it is yellow and rancid, and solidifies only partially in the cold:
it then contains, on an average, 73.23 p. c. C., 12·07 II., and 14.70 0.,
or 34 at. carbon, 33 at. hydrogen, and 5 at. oxygen (Gottlieb). An
altered acid of similar composition (containing 72-5 to 73-7 p. c. C., and
and 11.6 to 12.4 p. c. H.) was investigated by Bromeis as butyroleic
acid. By the further action of oxygen, products are formed, which
do not solidify at 14°, and prevent the crystallisation of the yet
unchanged acid (Gottlieb). The oxidation-products are converted
into the silver-salt and the ethyl-compound of oleic acid (see below);
VOL. XVII,
F
66
PRIMARY NUCLEUS C36H31.
1
but in preparing the baryta-salt, they remain in the mother-liquor,
and are separated from it by mineral acids as a red-brown, rancid,
very acid and viscid oil, the baryta-compounds of which contain 14.28
and 15.63 p. c. of baryta (Gottlieb). Concerning the formation of
ozone in this oxidation, see Schönbein (J. pr. Chem. 74, 338).
3. Oleic acid burns when heated in the air (Chevreul).
4. Oleic acid, submitted to dry distillation with sulphur, yields a
red-brown, disagreeably smelling oil [apparently containing odmyl
(x, 97)], in which margaric acid is suspended; the reaction is attended
with violent intumescence, and the evolution of a large quantity of
hydrosulphuric acid. The distillate is free from sebacic acid (Anderson,
Phil. Mag. J. 31, 164; Ann. Pharm. 63, 370). The margaric acid here
spoken of may be palmitic acid (xvi, 356) (Kr.).
5. Bromine and chlorine form with oleic acid, in presence of water,
bromoleic and chloroleic acids; iodine does not act upon it (Lefort).
6. Nitrous acid converts oleic acid into elaidic acid, without
forming a second decomposition-product (Gottlieb). See under Elaidic
acid.
7. In the decomposition of oleic acid by nitric acid, volatile acids of
the general formula C¹¹H"Oʻ, non-volatile acids of the formula C¹H"-208,
azelaic acid, and other less accurately investigated products, are
formed.
a. When oleic acid is cautiously added in small quantities to mode-
rately hot red fuming nitric acid, a violent reaction takes place, and a
large quantity of red vapours charged with volatile acids, is evolved.
If, after the first action has ceased, the mixture is heated more strongly
and then boiled for several days, with addition of more nitric acid if
necessary, and the contents of the retort are at last freed from all
volatile products by adding water and distilling, a distillate is obtained
containing a mixture of the following acids, viz., in greatest quantity,
caproic, valerianic, and acetic acids; in medium quantity, caprylic,
butyric, and propionic acids; in smallest quantity, capric, pelargonic,
and oenanthylic acids (Redtenbacher, Ann. Pharm. 59, 41).
When a weaker (commercial) acid is employed in the oxidation, for the sake of
preparing the non-volatile products, the distillate possesses an irritating odour,
which attacks the respiratory organs, and is not destroyed by neutralising with
carbonate of soda. On distilling the solution (first rendered alkaline), a colourless,
thin, volatile oil is obtained, but in too small quantity for further examination.
(Bromeis, Ann. Pharm. 35, 93). Wirz (Ann. Pharm. 104, 261), who, however, oxi-
dised the non-volatile acids of cocoa-nut oil with nitric acid, also mentions this
volatile body, as well as an (acid?) oil of the distillate which he erroneously re-
garded as Laurent's azoleic acid or oenanthylic acid. The distillate obtained in the
oxidation of fatty oil of almonds by nitric acid is also regarded by Arppe (Ann.
Pharm. 120, 292) as ananthylic acid (as found by experiment ?).
b. Concentrated or weaker nitric acid, heated with oleic acid, in the
proportion of 2 to 7 volumes of the former to 1 volume of the latter,
reacts violently after an hour, so that a part of the liquid is projected
from the vessel containing it; but on further heating, the oleic acid is
quietly oxidised, becoming thinner and clearer, and at length disap-
pearing completely. The residual acid solution contains succinic acid
(x, 108) and, according to Laurent and Bromeis, lipic (x, 434), adipic
(xi, 422), pimelic (xii, 463), suberic (xiii, 204), and azelaic (xvii, 79)
:
OLEIC ACID.
67
acids, and, according to Wirz (in the oxidation of the acids of cocoa-
nut oil) also lepargylic (xiii, 374) acid. Arppe (Ann. Pharm. 95, 242;
115, 143), however, doubts the purity of most of the acids thus
obtained; he considers that the presence of lipric, adipic, and lepar-
gylic acids is not established, and finds, as solid products of the oxida-
tion of oleic acid (and other fats) only succinic, suberic, and azelaic
acids, with perhaps a fourth uncrystallisable acid. Arppe formerly de-
scribed, as a product of the oxidation of oleic acid, another acid, X, which he after-
wards regarded as a secondary product of sublimation, and lately (Ann. Pharm. 124,
98) as pimelic acid. Sebacic acid, which is formed by the oxidation of spermaceti,
is not produced by the action of nitric acid on oleic acid (Arppe).
The following products seem to be formed more especially by the incomplete
oxidation of oleic acid. — I. A solid fatty acid. If, after the first violent action of
nitric acid has ceased, the residue is cooled, it solidifies to a semi-solid mass, from
which alcohol takes up margaric acid melting at 60° (containing 7408 p. c. C.,
12.50 H.). The margaric acid may, in this case, be formed from the impure oleic
acid employed, but the pure acid, treated in the same way, also yields an acid
melting at 80°, solidifying at 70°, and forming with potash a red soap from which
acids precipitate a thick brown oil (Bromeis). II. Nitro-caprylic and Nitro-capric
acids (xiii, 217 and xiv, 500). These were obtained by Wirz in the oxidation of the
acids of cocoa-nut oil, and appear to be mixed with the solid acid (I), since they are
reddened by potash. The following product should also be mentioned here. When
oleic acid is boiled with red fuming nitric acid (see above), not, however, till the
fatty layer completely disappears, there floats upon the surface of the cooled liquid,
an unctuous fat, heavier than water, and having the smell of perspiration; it is
easily soluble in alcohol and ether, and is precipitated from its blood-red alkaline
solutions by acids without alteration. It explodes when heated, with an odour of
cinnamon, evolving nitrous and volatile fatty acids, and leaving a black, tough residue
which contains suberic acid. By boiling with water it is decomposed into fatty acids
which volatilize, and suberic and pimelic acids which remain behind (Redten-
bacher). III. Laurent's Azoleic Acid. It is produced by boiling oleic acid with
nitric acid, according to x, 434, till three-fourths is dissolved, and forms the oily
layer which floats undissolved on the surface of the acid solution. When removed
and distilled alone, it passes over at first undecomposed, then blackens and froths
up, and towards the end of the distillation yields a sublimate consisting of a difficultly
fusible, white powder. Azoleic acid, heated with alcohol and oil of vitriol, yields an
ether, one-fifth of which distils unchanged, the remainder being decomposed in the
same manner as the acid by further heating. When decomposed by alcoholic
potash, with subsequent addition of hydrochloric acid, it yields azoleic acid insoluble
in water, and containing 62 81 p. c. C., 1071 H. (Laurent). According to Bromeis,
(Ann. Pharm. 35, 109; 37, 300), who analysed the ether, this acid has the same
composition as cenanthylic acid, and, according to Tilley (Ann. Pharm. 39, 166), is
probably identical therewith. Enanthylic acid, however, when obtained as the
principal product of the oxidation of castor oil, passes over in the distillate, and,
according to Redtenbacher, is obtained from oleic acid in very small quantity only,
together with many other acids, whilst Laurent's azoleic acid is obtained from the
residue. The formation of oenanthylic acid, here and above (by Arppe), seems to be
merely conjectured and not established by experiment (Kr.).
8. Oleic acid, distilled with bichromate of potash and sulphuric acid,
yields an acid distillate, which smells like tallow and rape-oil
(Arzbächer, Ann. Pharm. 73, 199).
9. The brown mixture of peroxide of lead and oleic acid is discolour-
ised at 120°, and becomes thick and viscid, evolving a large quantity
of water-vapour, but no other gas (Bromeis, Ann. Pharm. 42, 71).
>
10. Oleic acid, mixed with oil of vitriol, forms Frémy's oleo-sul-
phuric acid, an aqueous solution of which soon splits up into metoleic
and hydroleic acids. See further under Olive-oil. A single drop of oil of
F 2
63
PRIMARY NUCLEUS C36H34.
vitriol colours oleic acid brown (Varrentrapp), especially when the acid
is already partially decomposed (Gottlieb).
A solution of oleic acid in oil of vitriol, heated to 100°, evolves
sulphurous acid, and perhaps also hydrosulphuric acid, with coloration,
but without frothing; above 100° it froths up violently and carbonises
(Chevreul). The sulphuric acid solution behaves like ricinoleic acid on
addition of sugar (Neukomm). When 3 drops of oleic acid are shaken
up with 3 cubic centimetres of alcohol, and 1 drop of sugar solution is
added, together with 4 or 5 drops of oil of vitriol, the mixture assumes a
rose-to carmine-red colour from the bottom upwards, and when shaken
after three hours becomes red-brown-violet, while part of the oleic
acid collects on the surface (Benecke, Studien über Gallenbestandtheile,
Giessen, 1862).
11. When melted with hydrate of potash, oleic acid splits up into
palmitate and acetate, with evolution of hydrogen (Varrentrapp).
C32H31KO + C4H³KO4 + 2H.
C36H340 + 2(KO,HO)
From the further action of the hydrate on the acetic acid, a little
oxalic acid is produced (Varrentrapp). In the distillation with excess
of hydrate of potash, an odour of butyrate of amyl is evolved (Al.
Müller, Handwörterbuch, 6, 874).
12. Oleic acid, distilled with 4th of its weight of quick lime, yields a
liquid, neutral, unsaponifiable distillate, which deposits only traces of
a solid body, and probably stands in the same relation to oleic acid
as stearone to stearic acid. The residue contains carbonate of lime
(Bussy, Ann. Pharm. 9, 271).
On distilling a mixture of 1,000 grammes of oleic acid, 300 gr.
hydrate of lime, and 300 gr. soda-lime, and cooling the distillate, a
liquid is obtained amounting to two-thirds of the quantity of the oleic
acid employed. The non-condensable gases, absorbed by an excess
of bromine, form bromine-compounds, from which, by agitation with
caustic soda and washing with water, the bromides of the hydro-
carbons C"II" may be separated. In this way were obtained, from
3 kilogrammes of oleic acid, with the aid of an equal quantity of
bromine, 100 gr. of bibromide of ethylene (viii, 366), 600 gr. of bibro-
mide of propylene, C'H Br², 100 gr. of bibromide of butylene, CH®Br³,
50 gr. of bibromide of amylene, CH"Br², and 200 to 300 gr. of un-
separated volatile bromine-compounds of hydrocarbons of higher atomic
weight (Berthelot, N. Ann. Chim. Phys. 53, 200).
10
13. Oleic acid, heated with an equal quantity of glycerin, yields
triolein, and, with an excess of glycerin, monolein. A mixture of oleic
acid and glycerin, saturated, at 100° with hydrochloric acid gas, yields
a neutral compound corresponding to triolein, but containing also
hydrochloric acid. In the same manner, when oleic acid and glycerin
are heated to 100° for 71 hours with tartaric, phosphoric, or sulphuric
acid, the resulting glyceride contains a portion of the second acid in
combination (Berthelot, N. Ann. Chim. Phys. 41, 248). See also xvi,
358.
Combinations. Oleic acid is insoluble in water.
It dissolves in 10 parts of cold oil of vitriol without decomposition,
with slight evolution of heat, and coloration, which is increased to a
certain extent after some days (Chevreul). Sce above.
OLEATES.
69
Oleates.-Oleic acid decomposes the carbonates of the alkalis when
heated therewith, slowly expelling the carbonic acid (Chevreul, Gottlieb).
According to Unverdorben, it also partially decomposes acetate and
hydrochlorate of lime. The oleates are soft, frequently oily, or easily
fusible to an oil, and more easily soluble in alcohol (and especially so
in ether) than in water (Chevreul). Oleic acid easily forms acid and basic
salts, and when an impure acid is employed, the impurities may be transferred to
the salts in definite proportions (Gottlieb). See Oleate of silver.
Soaps are mixtures of salts, principally oleates, palmitates, and
stearates. They are prepared, in some cases, by heating the base
with a fatty body and water; in other cases (especially when the base
is too feeble to effect saponification) by double decomposition. They
are the harder the more palmitic and stearic acids, the softer the more
oleic acid they contain; almond and olive oils, however, yield harder
soaps than tallow, lard, or butter.
Oleate of Ammonia. Oleic acid instantly combines with aqueous
ammonia, with rise of temperature, forming a jelly which is com
pletely soluble in water at 15°. The solution becomes cloudy on
boiling, from loss of ammonia (Chevreul).
1
Oleate of Potash. a. Mono-salt. Oleic acid combines with caustic
potash, the combination being attended with evolution of heat. A
solution of 47.2 parts of caustic potash dissolves 295 parts, or rather
more than 1 atom, of oleic acid (Chevreul). One part of oleic acid,
heated with one part of caustic potash and five parts of water, forms
a soft salt, which is insoluble in the supernatant liquid, and becomes
harder on cooling. A mixture of 2 parts of oleic acid, 1 part of caustic
potash, and 8 parts of water, yields a pellucid jelly, which separates
from the aqueous liquid when heated with part of caustic potash.
If this be pressed and dissolved in boiling alcohol, and the solution
allowed to evaporate spontaneously, the salt is left in the form of a
transparent jelly. In the voltaic circuit it liberates oleic acid at the
positive, and potash at the negative pole. It is decomposed by acids,
even by carbonic acid, when passed through the solution at a tempera-
ture of 5º. — Exposed to air saturated with moisture, at 12°, it takes
up, in seven days, 162 parts of water, and deliquesces. Swells up to a
transparent jelly in 2 parts of cold water, and dissolves completely in
4 parts to a ropy syrup. The solution in a very large quantity of
water deposits binoleate of potash when kept for some months, potash
and a trace of oleic acid remaining in solution. Oleate of potash dis-
solves in 2-15 parts of alcohol at 10°, and in 1 part of alcohol of sp. gr.
0·821 at 50°. The solution turns cloudy at 40·5°, congeals to a soft
mass at 31°, and solidifies at 12°. A solution in 2 parts of hot alcohol
remains clear down to 12°, and deposits crystals of the mono-acid salt
at 10°. Dissolves in 29·1 parts of boiling ether, the solution remaining
clear at 12°. Insoluble in concentrated solution of caustic potash, and
in various aqueous salts, e.g., chloride of sodium (Chevreul).
Chevreul.
earlier.
later.
C36 H3303
273
85.26
86.35
84.81
ΚΟ
47.2
14.74
13.65
15.19
C36H 33 KO
320.2
100.00
100.00
100.00
70
PRIMARY NUCLEUS C36H34.
b. Bi-acid. — On heating 112 parts of oleic acid with 1 part of
hydrate of potash and 43·4 parts of water, and afterwards diluting the
whole with 108 parts of water, a jelly is obtained, the filtrate from
which contains a small quantity of potash, and probably a trace of acid.
The jelly is insoluble in water, but soluble in hot and cold alcohol.
It reddens litmus, the colour disappearing on washing with water
(Chevreul).
Potash forms softer soaps with the fats than soda; with lard it
yields a soap of the consistence of butter, containing, after pressing,
14.9 p. c. potash, 66.1 p. c. saponified fat, and 19.0 p. c. water, and
after pressing more strongly, 15.85 p. c. potash, 72·4 fat, and 11.75
water (Chevreul). Potash-soap is soluble in water and alcohol. It is
precipitated from its aqueous solution by common salt [not by salts of
potash (Wittstein, Pharm. Viertelj. 1,426)].
Oleate of Soda. Mono-acid salt. The union of oleic acid and moist
hydrate of soda is attended with rise of temperature. Water con-
taining 31-3 pts. of soda dissolves 310 pts. of oleic acid. One part of
oleic acid, heated with part of hydrate of soda, and 5 parts of water,
yields a soft jelly, insoluble in the alkaline liquid, solidifying on cooling
to a tenacious mass. On boiling 1 part of oleic acid with part of
hydrate of soda and 8 parts of water, the salt is deposited in trans-
lucent granules, which are opaque when cold. When boiled with an
additional 4 parts of water, it separates from the alkaline liquid in the
form of a jelly. If this jelly be dried and dissolved in hot alcohol, and
the solution allowed to evaporate spontaneously, there remains a solid,
brittle, transparent mass, having a bitter alkaline taste (Chevreul). The
salt crystallises from absolute alcohol, but not from alcohol containing
water, nor from a solution so concentrated as to be syrupy (Varren-
trapp). Exposed to moist air, 1 part of the salt takes up, in six days,
0.975 pts. of water without deliquescing. Dissolves very easily in
10 pts. of water at 12°, in 20-6 pts. of alcohol of sp. gr. 0·821 at 13°,
in 10 pts. at 32°, and in 100 pts. of boiling ether, a portion being
deposited on cooling (Chevreul).
Chevreul.
earlier.
later.
C36H3303
NaO
273
89.8
90.8
89.39
31
10.2
9.2
10.61
C'36H33NaO+
304
100.0
100.0
100.00
Soda-soap is prepared either from fat and soda, or from potash and fat
with subsequent addition of common salt. In the latter case the chloride
of sodium and the potash-soap are partially converted into chloride of
potassium and soda-soap, the latter rising to the surface of the ley, while
the excess of potash or soda remains in solution, together with other
salts accidentally present and glycerin. The soap is capable of taking
up a large quantity of water without losing its solidity. The soda-soaps
of commerce contain, as a rule, from 14 to 38 p. c. of water, the pro-
portion varying, however, in particular cases, between 8 and 75 p. c.
It dissolves easily in warm water and in alcohol. The solutions
solidify on cooling, the more easily the greater the quantity of stearic
acid present. They are decomposed by nearly all acids, and by salts
of the earths and heavy metals. Soaps are completely separated from
their solutions by common salt and sal-ammoniac.
OLEATES.
71
Oleate of Baryta.
a. Mono-acid salt. — Preparation see above. It may
also be obtained by precipitating the soda-salt with chloride of barium,
or by boiling oleic acid with baryta-water or carbonate of baryta
(Chevreul, Varrentrapp). - Dazzling white, loose, finely crystallised
powder, which cakes together at 100° without melting (Gottlieb). More
easily fusible when impure. Tasteless, insoluble in water, but soluble in
boiling alcohol. One litre of a boiling alcoholic solution deposits 5 grammes of
the salt on cooling (Berthelot).
Varrentrapp. Gottlieb.
Völcker.
mean.
mean.
36 C .......
33 H.....
216
61.79
63.36
61.51
61.59
33
9.44
9.51
9.44
9.46
3 0......
24
6.87
8.79
....
....
BaO
76.5
21.90
18.34
7.13
21.92
7.03
....
21.92
....
....
....
C36H33 BaO4
..
349.5
100.00
100.00
100.00
100.00
....
C
Maskelyne.
61.80
Heintz.
ll.
b.
C.
Gössmann.
61.20
61.65
61.53
61.68
H
9.64
9.45
9.44
9.45
9.46
....
O
6.68
7.45
6.94
7.05
6.40
BaO 2188
21.90
21.97
21.97
22.46
100.00
100.00
100.00
100.00
100.00
Chevreul found in his earlier analyses 21.88 p. c., afterwards 22.97 p.c., BaO.
Varrentrapp's baryta-salt contained impure (oxidised) oleic acid (Gottlieb).
Völcker's acid (Ann. Pharm. 64, 345) was obtained from oil of ben; Maskelyne's
(Chem. Soc. Q. J. 8, 1) from vegetable tallow; Heintz's from (a) beef-suet, (b)
mutton-suet, (c) butter; Gössmann's from cantharides' fat.
b. Bi-acid? The mono-acid salt dissolves abundantly in moderately
warm oleic acid (Chevreul). — A dilute alcoholic solution of a deposits,
on cooling, flocks containing, after drying first in a vacuum, and after-
wards at 60° to 70°, 10-30 p. c. of baryta; the mother-liquor yields.
crystals of the mono-acid salt when concentrated (Gössman, Ann.
Pharm. 86, 322).
C72H6707
BaO.
Gössmann.
555
76.5
87.88
12.12
10.30
631.5 ........ 100.00
Oleate of Strontia. Obtained by boiling oleic acid with carbonate
of strontia. Resembles the baryta-salt. Soluble in alcohol (Chevreul).
C'36H3303
Sro
C36H30 STO
Chevreul.
273
84.
52
16.
15.92 to 16.2
325
100.
Oleate of Lime.
Oleate of potash precipitates from chloride of
calcium a white powder, which melts at a gentle heat and becomes
transparent (Chevreul).
Dissolves in alcohol and ether.
72
PRIMARY NUCLEUS C36H34.
C36H3303
CaO
...
C36H33CaO+
Chevreul.
273
28
90.7
9.3
8.8
301
100.0
***UJA
Oleate of Magnesia. Obtained by precipitating a boiling solution
of sulphate of magnesia with oleate of potash. White, somewhat
translucent granules, softening between the fingers (Chevreul).
C36H3303
MgO
C36H33 Mg04
Chevreul.
273
93.18
20
6.82
7.0
293
100.00
Oleate of Chromium. - Precipitated by oleate of potash from a
solution of chloride of chromium. Violet precipitate, soft in the moist
state, hard when dried (Chevreul).
Oleate of Zinc. - Precipitated from sulphate of zinc by a boiling
solution of oleate of potash. - White. Melts under 100° (Chevreul).
C35H3303
ZnO
C36H33ZnO¹
Chevreul.
273
40.5
.... ...
87.09
12.91
12.91
313.5
100.00
Oleate of Lead. — Aqueous solutions of soap are completely preci-
pitated by oxide of lead, no oleic (or margaric) acid remaining in solu-
tion (Gobley, N. J. Pharm. 21, 248). — Dissolves in ether (Gusserow).
a. Basic. Obtained by boiling oleic acid with an excess of basic
acetate of lead. Soft at 20°; melts completely to a transparent
liquid at 100° (Chevreul).
C36H3303
2 Pho
C36H33PbO¹,PbO
Chevreul.
273
54.93
224
45.07
45.18 to 45.95
497
100.00
....
b. Mono-salt. A cold alcoholic solution of oleate of soda is pre-
cipitated with neutral acetate of lead, and the flocculent precipitate
is washed and dried in a vacuum (Gottlieb). — Light, loose, white
powder, which melts to an oil about 80°, and solidifies on cooling to a
brittle translucent mass (Gottlieb).
Gottlieb.
36 C
33 H
30
РЬО
mean.
216
56.16
55.88
33
8.58
8.69
24
6.25
6.48
112
29.01
28.95
100.00
100.00
C36H33PbO¹....... 385
Ad
Oleate of Iron. Dissolves in all proportions in alcohol, forming
brown solutions. The solution in a small quantity of alcohol is oily
(Unverdorben).
Oleate of Cobalt.-Oleate of potash throws down from hot sulphate
of cobalt a precipitate at first bluish-green, afterwards green, which
settles down slowly (Chevreul).
OLEATES.
73
Oleate of Nickel. Greenish-yellow precipitate, which is very slowly
deposited (Chevreul).
Oleate of Copper. Obtained by precipitating a boiling solution of
sulphate of copper with oleate of potash, or by heating oleic acid with
oxide of copper. - Splendid green salt perfectly fluid at 100°
(Chevreul). Dissolves in alcohol in all proportions, with blue-green
colour; in a small quantity it forms an oily liquid (Unverdorben).
Concerning its action on the organism, see Langenbeck and Städeler
(Ann. Pharm. 97, 155).
C56H3303
CuO
273
40
C36 F33 CuO¹
313
Chevreul.
87.22
...
12.78
100.00
12.23
Oleates of Mercury. a. Mercurous Salt. Oleic acid is digested for
some time with mercurous oxide; or mercurous nitrate is precipitated
with oleate of potash. Whitish-grey flocks, bluish after drying. —
Forms with aminonia a black ammoniacal powder. Insoluble in water
and cold alcohol, but soluble in hot alcohol. Soluble in hot and cold
ether (Harff, N. Br. Arch. 5, 306).
C36H3303
Hg20
C36H33Hg204
Harff.
273
56.76
208
43.24
43.20
481
100.00
Mercuric Salt. Oleate of potash throws down from mercuric
nitrate, white flocks which turn greasy on washing and dry up to a
solid mass.
Contains 30.18 p. c. of oxide of mercury (1 at. = 28.35
p. c. HgO). Dissolves slightly in cold, better in hot alcohol, and with
moderate facility in ether (Harff).
Oleate of Silver. Nitrate of silver forms with the soda-salt a white,
very bulky precipitate, which easily blackens from reduction of silver
(Gottlieb). The precipitate turns brown on exposure to light, and when
dried in a vacuum at a temperature considerably below 100°; it is con-
verted into a soft, pasty mass, which dries with difficulty (Varrentrapp).
Gottlieb added to an alcoholic solution of partially oxidised oleic acid,
first a little ammonia, then an excess of nitrate of silver, and obtained
thereby a precipitate of loose flocks, which afterwards united into a
soft, yellowish-white mass. It contained 66·82 p. c. C., 10·43 H., and
11.71 AgO., corresponding to the formula C108H98 AgO¹5, or the ter-acid
salt of an altered oleic acid (Gottlieb).
Oleic acid mixes with cold and hot alcohol in all proportions: from a
mixture of equal parts of acid and alcohol, water does not take up any
alcohol (Chevreul). It is miscible also with ether (Chevreul). It is
dissolved by bile, forming therewith a soap having a strongly acid
reaction (Marcet, Phil. Mag. J. 17, 145).
Oleic acid mixes with margaric and stearic acids in all proportions.
Cold alcohol takes up from such mixtures a large quantity of oleic,
together with a little stearic and margaric acids. Alcohol at a tem-
perature of 60° dissolves the whole of the mixture, but deposits the
greater part of the stearic and margaric acids on cooling (Chevreul),
74
PRIMARY NUCLEUS C30 F31.
TABLE of the melting-points of mixtures of Oleic and Margaric acids,
according to Chevreul.

Percentage
of oleic acid.
Melting
point.
Percentage
of oleic acid.
Melting
Percentage
Melting
point.
of oleic acid.
point.
95
7°
60
41°
25
49.25°
90
17
55
42.5
20
50.25
85
26.5
50
4.4
15
51.5
80
31.5
45
45.75
10
53
75
35 5
40
46.75
5
54
70
37.5
35
48
1
55
65
39.5
30
48.5
Acids nearly identical with Oleic Acid.
See below.
1. Walter's Moringic Acid. Occurs in oil of ben.
Colourless or yellowish oil of sp. gr. 0.908 at 12.5°. Congeals to a
crystalline mass at 0°. Has a faint odour and an insipid taste. Reddens
litmus. Assumes a blood-red colour with oil of vitriol, and carbonises
when heated therewith. Contains 74.9 p. c. C., 11.8 H., and 13.3 0.,
corresponding to Walter's formula C³°H280¹, and likewise very nearly
with that of oleic acid (Compt. rend. 22, 1143; Ann. Pharm. 60, 271).
2. Filixoleic acid. Occurs, according to Luck, in the roots of Aspi-
dium Filiz mas. When from an ethereal extract of the root, the filicic
acid is removed in the manner already described (xvi, 126), an ethereal
solution of the oil of the root is obtained, and from this the oleic acid is
separated. Purified by Gottlieb's method (p. 63), it forms a bright-
yellow, inodorous oil, which has a faint taste and strongly acid reaction,
and does not solidify at 8°. It contains 75-06 p. c. Č., 12·58 H., and
12.36 O., and has therefore the composition of oleic acid. It yields the
same products as oleic acid when submitted to dry distillation, and
forms a baryta-salt containing 62.51 p. c. C., 9.96 H., 8-35 O., and
19.18 Ba0. Luck proposed the formula C2Hª¹O (Jahrb. pr. Pharm.
22, 153).
Elaïdic Acid.
C36H3404 = C'36H34,04.
Literature, History, and Formation also of Elaïdin.
POUTET. J. Pharm. 5, 337; 6, 77; Ann. Chim. Phys. 12, 58.
F. BOUDET. J. Chim. méd. 8, 641; Ann. Chim. Phys. 50, 391; J. Pharm.
18, 469; Ann. Pharm. 4, 1; Schw. 66, 186.
LAURENT. Ann. Chim. Phys. 65, 152; J. pr. Chem. 12, 411.- Rev.
scient. 14, 569.
II. MEYER. Ann. Pharm. 35, 174.
GOTTLIEB.
Ann. Pharm. 57, 52.
Poutet discovered that olive oil has the property of solidifying with
{
:
ELAÏDIC ACID.
75
mercurous nitrate. This property was more accurately investigated
by Boudet, and especially by Gottlieb, the former of whom discovered
elaïdic acid. The statement of Pelouze and Boudet that cocoa-nut oil contains
claïdin, and that of Boudet that margarin may be converted into elaïdin, have
been found to be erroneous.
Formation. The non-drying fatty oils, in contact with hyponitric
acid, solidify to elaïdin (Boudet). Oleic acid, under the same circum-
stances, is converted into elaïdic acid (Pelouze & Boudet; Meyer), no
second product being formed when pure oleic acid is used (Gottlieb).
1 2
Olive oil with th of a solution of 6 parts of mercury in 7 parts of
nitric acid of sp. gr. 1.35 forms a mixture which solidifies in two hours
in winter and in eight hours in summer, whilst poppy oil, treated in the
same way, remains quite fluid, throwing down only a slight precipitate
(Poutet). In this reaction hyponitric acid is the only active agent, a very
small quantity of it sufficing to effect the conversion. Olive oil placed
in contact with 200 vols. of nitric acid and 100 vols. of oxygen absorbs
the gases completely, turning green and becoming nearly solid within
two hours (Boudet). Oleic acid behaves in the same manner
(Gottlieb).
5
400
33
100
200
5 0
Olive oil solidifies with rd of hyponitric acid (dissolved in 3 times.
its weight of nitric acid of sp. gr. 1·35) in 70 minutes, with th in
78, with th in 84, with th in 130 minutes, and with th in 7
hours; th does not cause it to solidify. The product has the same
properties whatever quantity of hyponitric acid has been employed.
Other fatty oils (but not the drying oils of hemp, linseed, walnut,
poppy, and beech-nut) are rendered thick by hyponitric acid. One
hundred parts of the undermentioned fatty oils at 17, added to a
solution of 3 pts. of hyponitric acid in 9 pts. of nitric acid solidify in
the following times :-
Oil of cashew-nut in 43 minutes, to a sulphur-yellow mass.
Olive oil
73
""
""
""
blue-green
""
Hazel-nut oil
103
""
""
blue-green
وو
Sweet almond oil
160
""
""
dirty-white
">
Bitter almond oil
160
""
>>
dark-green
Rape oil
2400
""
""
19
brown-yellow
Olive oil, mixed with 4th or more of hyponitric acid, froths up and
becomes heated, turning green and ropy; it does not solidify but is
capable, when mixed with 5 or 6 times the quantity of olive oil, of
converting the whole into elaïdin (Boudet). When elaïdic acid is
melted with dilute nitric acid and copper turnings, with access of air,
the nitrous acid formed is taken up by the fluid elaïdic acid, which is
thereby converted into a colourless, heavy, viscid oil. This oil, after
being completely freed from nitric acid by washing with water, pos-
sesses the property of converting 20 times its volume of oleic acid into
elaïdic acid in eight or ten days (Gottlieb). Impure elaïdin, formed by
the action of mercurous or hyponitric acid on olive oil, gives off no
gas in the cold; at a temperature of 100° it evolves a volume of
nitrogen equal to that of the oil employed, and when heated for
several hours, also carbonic acid (Boudet). Oleic acid also forms im-
pure elaïdic acid, which, after absorbing 20 or 30 volumes of hyponitric
acid, evolves only a small quantity of nitrogen, and no other gas, when
76
PRIMARY NUCLEUS C35H3.
heated, the mass nevertheless containing nitrate of ammonia. The
newly-formed product, heated with hydrate of lime, yields ammonia
and a small quantity of neutral, odorous oil, insoluble in water
(Gottlieb).
When olive oil, or oleic acid which has been changed by exposure
to the air, is used in the preparation of elaïdic acid, there remains in
the mother-liquor a red oil, which dissolves with red colour in alkalis,
and is separated again by acids (Meyer). With pure oleic acid this
body is not formed (Gottlieb). The addition of poppy oil, even of
1 per cent. only, to olive oil retards the formation of elaïdin (Boudet).
Almond oil mixed with drying fat no longer solidifies with nitrous acid
(Schlippe, Ann. Pharm. 105, 19).
Preparation. Nitrous acid is passed into oleic acid for five minutes, and
the liquid is cooled, whereupon it solidifies in half an hour to a yellow
foliated mass. This mass is washed repeatedly with boiling water
and afterwards dissolved in an equal weight of alcohol, and the crystals
which form on standing are purified by re-crystallisation (Meyer). The
acid obtained by saponifying elaïdin and decomposing the soap, cannot
be purified by crystallisation from alcohol (Meyer).
Properties. Fine pearly lamine, resembling boracic or benzoic acid
(Boudet, Meyer), attaining a length of 2 inches, and a breadth of half
an inch with angles of 112° and 68° (Laurent). Melts at 44° (Boudet),
44° to 45° (Meyer), and solidifies at 42° (Laurent), expanding con-
siderably (Gottlieb). By partial solidification, pearly, translucent lamina
are obtained (Laurent). Distils almost unaltered. Has a strongly acid
reaction.
Laurent.
mean.
earlier. later.
12.07
11.45
36 C .......
31 H .....
40
216 ..
34
76.59
75.00 .... 76.48
12.06
12.27
32
11.35
12.73
....
C36 H3404
282
....
....
....
100.00 100.00 100.00
....
....
...
Meyer.
mean.
76.51
12.25
11.24
Gottlieb.
mean.
76.50
....
12.18
11.32
DOLO
****
100'00
....
100.00
The above formula is according to Laurent (Rev. Scient., 14, 569) and Gottlieb. —
Isomeric with oleic acid (Gottlieb, Gerhardt, Compt. rend. 23, 1115). Earlier
formula: C70680s (Laurent), C72H68O7 (Meyer.)
Decompositions. 1. When elaïdic acid is subjected to dry distillation
a portion is decomposed, with formation of hydrocarbons (Meyer).
From impure claïdic acid Meyer obtained also sebacic acid, the production of which
by the dry distillation of the pure acid remained doubtful. No caprylic or capric
acid is formed, as in the dry distillation of oleic acid (Gottlieb). 2. Melted
elaïdic acid absorbs oxygen. After exposure to the air for some hours,
at 100°, it solidifies only partially on cooling, so that an oil may be
expressed from the solid portion. When it is maintained at a tempe-
rature of 65° for 14 days, the melting-point gradually sinks; the acid
evaporates partially in oily drops, turns rancid, and is at last converted
into a yellow viscid mass, having the smell of poppy oil, no longer
solidifying with nitrous acid, and drying up on glass plates. It then
and
contains 69.22 p. c. C., 10.58 H., and 20-20 O., or 36 at. C., 33 at. H.,
8 at. O. (Gottlieb). 3. Elaïdic acid melted with hydrate of potash, splits
up like oleic acid into palmitic and acetic acids (Varrentrapp, Meyer).
ELAÏDIC ACID.
77
Combinations. Elaïdic acid is insoluble in water. The acid expels
carbonic acid from alkaline carbonates, and forms transparent, very
thick soaps (Boudet, Meyer).
Ammonia-salt. Soluble in water and alcohol.
Potash-salt. Light, shining needles, soluble in water and alcohol
(Boudet).
Soda-salt. A. Mono-acid. Elaïdic acid is boiled with water and an
excess of carbonate of soda; the solution is evaporated, and the
residue exhausted with alcohol (Boudet). Light, silvery lamine,
easily soluble in warm water and alcohol, less soluble in warın ether
(Boudet, Meyer).
Meyer.
C36H3303
NaO
mean.
273
89.8
31
10.2
10.41
100.0
C36H33NaO¹........ 304
B. Bi-acid. — A dilute aqueous solution of A becomes alkaline
and turbid on standing, from separation of crystalline scales of a
bi-acid salt (Boudet). Contains 5.17 p. c. Na0, and solidifies to a
crystalline mass after melting (Laurent).
Laurent.
C72HG707
NaO
C36H33 NaO+, C36H³¹04
555
94.71
31
5.29
5.17
2.
586
100.00
Baryta-salt. -White precipitate, containing 21.52 p. c. baryta
(Meyer).
C36H3303
BaO
C26 H33 BaO+
Meyer.
273
78.10
76.5
21.90
21.52
349.5
100.00
The magnesia-salt dissolves very slightly in water and alcohol
(Boudet).
Lead-salt. The acid loses 3:36 p. c. of water when heated with oxide of lead
(Laurent) (1 at. 3.19 p. c.). White, bulky precipitate, thrown down.
from the soda-salt by neutral acetate of lead acidified with acetic
acid (Meyer). Dissolves slightly in alcohol.
C36H3303
PbO
C36133 Pb 04
Meyer.
mean.
273
70.99
112
29.01
29.04
385
100.00
Silver-salt. Obtained by precipitating an alcoholic solution of the
soda-salt with nitrate of silver. White, bulky precipitate, difficultly
soluble, after drying, in water, alcohol, and ether; more easily soluble
in the moist state. Crystallizes from a solution in ammonia in small,
white prisms (Meyer).
78
PRIMARY NUCLEUS C36H34.
Meyer.
Gottlieb.
mean.
mean.
36 C
33 H
30
216
55.51
55.34
55.34
33
8.49
8.65
8.51
•
24.
6.16
6.13
6.46
AgO
116
29.84
29.88
29.69
C36 H33 AgO¹
389
100.00
100.00
100.00
....
Boudet found 29.81 p. c. AgO.
Elaïdic acid is very easily soluble in alcohol. Boiling alcohol dis-
solves it in all proportions: one part of alcohol of sp. gr. 0.92 at 36°
dissolves 5 parts of the acid (Boudet). It is soluble in all proportions
in alcohol, less freely soluble in ether (Meyer). A mixture of equal
parts of elaïdic and margaric acids solidifies to a porcelain-like, trans-
lucent mass after melting; a mixture of 2 parts of elaïdic acid and
1 part of margaric acid melts at 42°, and solidifies in the crystalline
state, like pure elaïdic acid (Gottlieb).
OUDEMANNS.
Stearidic Acid.
C3[[34O4 = (36T13404.
J. pr. Chem. 89, 193.
Not named by Oudemanns.
Formation. By heating bromo-stearate of silver with water.
C36 BrH³+ AgO+
C3H3O+ + AgBr.
Bromostearate of silver is boiled with water for several hours; the
mixture of bromide of silver and stearidic acid, which separates, is
treated with alcohol; and the solution is filtered from bromide of silver
and evaporated, with the addition of water. The lard-like residue,
when submitted to distillation, yields colourless stearidic acid, whilst
bromostearidic acid (formed from admixed bibromostearate of silver)
remains behind, and is decomposed at a stronger heat.
Properties. Amorphous mass, resembling the soft animal fats.
Melts at 35°, and has a peculiar faint odour. Distils unchanged.
Oudemanns.
at 100°
mean.
36 C
216
76.60
76.16
34 H
34
12.06
11.99
40
32
11.34
11.85
C36IT40¹.. ....... 282
100.00
100.00
Isomeric with oleic and elaïdic acids.
With the alkalis it forms soaps, an alcoholic solution of which pre-
cipitates salts of the metals. Dissolves in alcohol more easily than
elaïdic acid, and does not crystallise from the solution.
AZELAIC ACID.
79
ぎ
​!
Appendix to Oleic Acid and Supplement to xiii, 374.
Azelaic Acid,
LAURENT. Ann. Chim. Phys. 66, 156.
WIRZ.
ARPPE.
Ann. Pharm. 104, 270.
Ann. Pharm. 115, 143; 120, 288; 124, 86.
Apelaic acid (Berzelius). Azelic acid (Arppe).
Discovered by Laurent, and prepared pure by Arppe. Bromeis
(Ann. Pharm. 35, 103) doubted the peculiarity of the acid. The acid
described at xiii, 374, as anchoic or lepargylic acid is to be regarded as
impure azealic acid (Arppe).
Formation. Produced, together with other acids, by the oxidation.
of oleic acid by nitric acid (p. 66) (Laurent).
Obtained in small quantity from oleic acid, in greater quantity from
almond oil, and most abundantly from ricinoleic acid, but not from
spermaceti, bees'-wax, or stearic acid (Arppe). Also from the fatty
acids of cocoa-nut oil, and from Chinese wax, since these substances
serve for the preparation of lepargylic acid.
Preparation. 1. Oleic acid is oxidised with nitric acid, according
to x, 434, and the mixture of suberic and azelaic acids, which crystallises
on cooling, is separated, according to xiii, 205, by treatment with
ether, which takes up the azelaic and, at the same time, a portion of
the suberic acid. The residue which remains on evaporation of the
ether is again digested with so much cold ether that only one-half is
dissolved, and the first half of the acid deposited from this solution is
removed, only the half remaining in solution being considered purc
(Laurent).
2. One or two pounds of castor oil are heated in a capacious retort
with a little nitric acid of sp. gr. 1·25, aud when the frothing which
first takes place has subsided, more acid is added to the amount of
2 parts of acid to 1 part of oil. The whole is then boiled for a day,
the acid solution is separated from the oil, and the latter is again boiled
with fresh acid. In this way is obtained a distillate containing œnan-
thylic acid, and an acid solution with an oil floating on the surface;
this last is removed by means of a tap-funnel.
a. The floating oil just mentioned, as well as that separated at a
later stage of the process, is boiled with water, when azelaic acid is
taken up by the water, and cenanthylic acid is volatilised with the
aqucous vapour.
b. The acid solution is concentrated, with frequent addition of
water, to drive off nitric acid, until it solidifies almost completely to a
white granular mass, the oil which separates being removed. The
granular mass, when washed on a filter with cold water, is resolved
into an easily soluble portion, containing principally oxalic acid, and a
more difficultly soluble mixture of acids, which, for the more complete
separation of oxalic acid and oil, is once crystallised from warm
water. The crystals are washed with cold water, dried, and melted,
80
APPENDIX TO OLEIC ACID,
and the mass, after solidifying, is triturated, and again washed with
water, to remove more completely the easily soluble acids. The
undissolved portion, again dried, melted, and rubbed to a fine powder,
is repeatedly treated with twice its volume of ether, by which it is
separated into azelaic acid which dissolves, and insoluble suberic acid.
The ethereal solution is evaporated; the azelaic acid, which remains in
the form of an oil, is dissolved in boiling water; and the crystals
formed are removed before the mother-liquor is quite cold. The liquid
afterwards throws down a granular deposit, consisting of a mixture of
suberic and azelaic acids, from which ether takes up the latter acid.
Azelaic acid thus obtained still contains an admixture of oil, from
which it is freed by treating it with a quantity of ether insufficient for
complete solution, dissolving the acid taken up in water, and removing
the oily drops which separate by filtration. The acid is to be considered
pure only when its melting-point is constant, and when its solution in
warm water does not become turbid on cooling (Arppe).
Properties. Large, dazzling-white, pearly lamine, or transparent
flattened needles, having a glassy lustre. The faces are frequently
curved. The crystals are distinctly cleavable in two directions at
right angles to each other. From very dilute solutions they are depo-
sited on cooling in lamine, which appear under the microscope of the
three following forms: a. very oblique rhombic tables with acute angles
of about 22°; b. apparently quadratic tables; c. flattened thin prisms,
acuminated at the ends with faces forming an angle of 127° with each
other, and angles of 117° with the prismatic faces. The angle of 127°
is frequently replaced by a face. Melts at 106°, and solidifies on
cooling to a laminated crystalline mass. Volatile the vapour is irri-
tating and suffocating. Has a faint taste and a distinctly acid
reaction (Arppe). Laurent's acid was an easily fusible body, forming a dull mass
after melting. Wirz obtained an acid in fine white granules, melting at 98°.
Laurent.
Wirz.
Arppe.
18 C............ 108
16 H
57.45
54.91
55.9
57.51
16
8.51
8.11
8.2
8.67
8 O......... 64
34.04
36.98
35.9
33.82
C18H1608 188
100.00
100'00
100.0
100.00
Laurent proposed the formula C20H180¹º, but had some doubts as to the purity of
his acid.
When the acid is submitted to distillation in a retort, a portion only
passes over undecomposed, the greater part being converted into a
brown humus-like substance, besides which a little oil is formed.
Burns with a luminous flame (Arppe).
Combinations. Azelaic acid dissolves in 700 parts of water at 15°,
and easily in hot water, from which it crystallises. When it is heated
with a quantity of water insufficient for solution, the undissolved
portion melts to an oil (Arppe).
Azelaic acid is bibasic, and forms especially di-acid salts, C18M²H¹408.
It expels carbonic acid from its combinations. The salts of the alkalis
and alkaline earths are soluble, the lime-salt least so; those of the
heavy metals are insoluble. A moderately dilute aqueous solution of
AZELAIC ACID.
81
the salts is not precipitated by chloride of barium; chloride of calcium
throws down an abundant precipitate, or deposits crystals in more
dilute solutions; sesquichloride of iron forms a brick-red, sulphate of
copper a blue-green precipitate. The salts are decomposed by dilute
hydrochloric or nitric acid, with separation of crystalline azelaic acid.-
The di-acid ammonia-salt cannot be obtained in solid form (Arppe).
Potash-salt. — Di-acid. Crystallises from a syrupy solution in
delicate, soft needles, C¹KH¹¹0 + 4aq., which effloresce, and at 100°
become anhydrous (Arppe).
Soda-salt. — The di-acid salt, C¹8Na²H¹¹08 + 2aq., forms large, trans-
parent laminæ, having a glassy lustre; when the acid is incompletely
neutralised, granules of a 3-acid salt, CNa H¹08, C¹8NaI¹508, are
obtained (Arppe).
A. Half and two-thirds.
18
Baryta-salt.
A warm aqueous solution
of the acid, neutralised with warm baryta-water, deposits granules of a 3-
acid salt, C¹Ba²H¹408,C¹8BaH150, which crystallises from water in
transparent crystals, and when washed with hot water, leaves a di-
acid salt (Arppe).
B. Mono-acid.-Obtained as a heavy powder by boiling the aqueous
acid with carbonate ¡of baryta.
Strontia-salt. Di-acid. The salt with 4 atoms of water is a heavy
powder, easily soluble in warm water, from which it is not again depo-
sited. By concentrating the solution, thin crystalline crusts, and a
light powder are obtained; on spontaneous evaporation, white granules
containing 2 atoms of water are deposited (Arppe).
Magnesia-salt. The salt with 6 atoms of water effloresces from the
loss of 4 atoms. It resembles the strontia-salt, and dissolves in
nearly equal quantity in hot and cold water: a solution evaporated in
a vacuum yields a fine crystalline powder; when it is concentrated by
heat, crystalline crusts are obtained (Arppe).
,
Alumina-salt. C'18H 1608, A120³. Obtained by decomposing the
ammonia-salt with a solution of alum. Amorphous powder, insoluble
in water and in aqueous azelaic acid (Arppe).
Manganese-salt. Di-acid. -- Anhydrous, reddish, difficultly soluble,
crystalline powder (Arppe).
Zinc-salt. Di-acid.
―
White, insoluble powder which melts and
puffs up when heated. Anhydrous. —The di-acid lead salt, C¹ºÐ¸²Î¹¹Oª,
is a white powder (Arppe).
16
Iron-salt. Brick-coloured powder containing, after strongly dry-
ing, 27-19 p. c. sesquioxide of iron. Probably Û¹¹Ò³‚F¸³Ù³‚3HO
(calc. 27.15 p.c. Fe2O3) (Arppe).
Fe²0³)
Nickel-salt. A solution of hydrated oxide of nickel in the acid is
evaporated, and the excess of acid is removed from the residue by
means of alcohol. The salt remains as an apple-green crystalline
powder (Arppe).
Copper-salt. -- Di-acid. - Anhydrous; blue-green. Insoluble in
water (Arppe).
VOL. XVII.
G
82 CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS C3H4.
Silver-salt. Precipitated from the ammonia-salt by nitrate of silver
as a fine white powder, which, after washing and drying, does not
blacken. Crystallises from a solution in warm dilute nitric acid in
small granules (Arppe).
Arppe.
mean.
18 C
108
26.86
27.31
14 H
14
3.48
3.51
80
64
15.93
15.52
2 Ag
216
53.73
53.66
C18 A&HOS
402
100.00
100.00
Azelaic acid dissolves easily in ether, and more easily in alcohol
(Arppe).
Conjugated Compounds of the Primary Nucleus C36H34.
Oleate of Methyl.
56
C38H3604 C2H³O,C6H330³.
Obtained in the same way as oleate of ethyl and resembles that
compound. Sp. gr. 0.879 at 18°.
Sp. gr. 0·879 at 18°. With mercurous nitrate it forms
elaïdate of methyl (Laurent, Ann. Chim. Phys. 65, 299).
Elaïdate of Methyl.
C38H3604 C2H³O,C6H330³.
A. LAURENT. Ann. Chim. Phys. 65, 294.
Methyl-elaïdic ether. Elaïdate de Méthylène. Elaïdinformester.
Prepared from wood-spirit, oil of vitriol, and elaïdic acid or elaïdate.
of soda, and purified by washing with caustic potash-solution, drying
over chloride of calcium, and distilling. Mercurous nitrate converts
oleate of methyl into elaïdate of methyl.
Thin colourless oil of sp. gr. 0.872 at 18°, volatile without decomposi-
tion. Burns with a white, almost smokeless flame. It is not acted on
by a boiling aqueous solution of potash, but is rapidly decomposed by
a boiling alcoholic solution.
Laurent.
38 C
228
77.02
75.44
36 H
36
12.16
12.40
40
32
10.82
12.16
C²H³0, C36H330³........ 296
100.00
100.00
OLEATE OF ETHYL.
83
Oleate of Ethyl.
C'40H3804 =
C4H50, C36H3303.
LAURENT. Ann. Chim. Phys. 65, 298.
H. MEYER. Ann. Pharm. 35, 188.
VARRENTRAPI. Ann. Pharm. 35, 206.
BROMEIS. Ann. Pharm. 42, 62.
BERTHELOT. Chimie organique 2, 83; N. Ann. Chim. Phys. 41, 245.
Oleic ether. Oel-Naphtha. Ether oléique. Oëlsäurevinester.
Formation and Preparation. 1. Oleic acid is heated with part of
oil of vitriol and 2 parts of alcohol for some hours, and the oily layer is
washed successively with hot water and hot weak caustic potash, then
dried and distilled (Laurent). 2. Hydrochloric acid gas is passed into
a solution of oleic acid in three times its volume of alcohol, when in a few
minutes, and before the solution is saturated with the gas, the ether
separates. It is removed, freed from admixed oleic acid by shaking
with weak alcohol, and from alcohol by shaking with water, and dried
(Varrentrapp).-3. Alcoholic hydrochloric acid decomposes triolein
almost completely, forming glycerin and oleate of ethyl, the latter of
which retains small quantities of olein (Berthelot).
Properties. Thin, colourless oil, of sp. gr. 0.871 at 18° (Laurent).
According to Laurent, it distils undecomposed, but according to
Varrentrapp and Bromeis, it is decomposed thereby, with formation of
alcohol and hydrocarbons, and separation of charcoal. — Nearly in-
odorous and tasteless (Bromeis). Neutral.
Varrentrapp.
Bromeis.
40 C
38 H
4 O
C+H5O,C36H3303
mean.
mean.
240
77.42
76.50
74.17
38
12.26
11.94
11.75
32
10.32
11.56
14.08
310
100.00
100.00
100.00
Concerning the oleic acid of Bromeis see vii, 1485.
Decompositions. 1. Oleate of ethyl in contact with oxygen absorbs
1 per cent. in 24 months, and a little more when in contact with brass
filings (Berthelot).-2. Burns with white, nearly smokeless flame
(Laurent). Water partially decomposes oleate of ethyl in 106 hours.
at a temperature of 100°; on the addition of one volume of acetic
acid and two to three volumes of water, a considerable amount of decom-
position takes place in 106 hours at 100°; no acetate of ethyl is formed
thereby (Bertliclot). 4. Oleate of ethyl is converted, by contact with
mercurous nitrate, into elaïdate of ethyl, without altering in appearance
(Laurent).5. Decomposed by alcoholic potash, but not by a boiling
aqueous solution (Laurent). —6. When heated to 100° for 200 hours
with hydrochloric acid and a large excess of glycerin, it is converted into
olein. Traces of olein are likewise obtained (Berthelot) by heating with
glycerin alone.
Oleate of ethyl is difficultly soluble in alcohol, and soluble in all
proportions in ether.
G 2
8
CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS CH3.
Elaïdate of Ethyl.
C40H304 C4H50,030H303.
=
LAURENT. Ann. Chim. Phys. 65, 294.
H. MEYER. Ann. Pharm. 35, 184.
Ether elaïdique. Elaidinnaphtha. Elaidinvinester.
Two parts of elaïdic acid are heated for some hours with 1 part
of oil of vitriol and 4 parts of alcohol; or hydrochloric acid gas is
passed into an alcoholic solution of elaïdic acid till the elaïdate of ethyl
separates. Purification is effected by washing with water and dilute
caustic potash (Laurent), or by shaking with water and alcohol, and
then again with water to remove the alcohol taken up (Meyer).
Oleate of ethyl is converted into elaïdate by mercurous nitrate
(Laurent).
Thin, colourless oil, inodorous in the cold, but having a faint smell
when heated. Sp. gr. 0·868 at 18° (Laurent). Boils at a little above
370° according to Laurent; but according to Meyer it is decomposed
by distillation.
Meyer.
40 C
38 H
40
C+H5O,C36H3303.
Laurent.
distilled.
in vacuo.
240
77.42
76.02
77.50
....
38
12.25
12.33
12.12
32
10.33
11.65
10 38
310
100.00
100.00
100.00
Burns in the manner of a fatty oil, with white, nearly smokeless
flame. It is not acted on by aqueous potash, even when heated there-
with, but is rapidly and completely decomposed by boiling alcoholic
potash (Laurent).
Insoluble in water. Soluble in oil of vitriol (Laurent). Dissolves
easily in absolute alcohol (Meyer), in about 8 parts of ordinary alcohol,
and in all proportions in ether (Laurent).
BERTHELOT.
Monolein.
C42H4008 = C6H70³,C³Ħ³³O³.
Chim. organ. 2, 79; N. Ann. Chim. Phys. 41, 243.
A mixture of oleic acid and excess of glycerin is heated to 100° for
118 hours, or better to 200° for 18 hours, in a sealed tube which has
been previously filled with carbonic acid. The upper layer, which
separates on cooling, contains the olein formed in the reaction, together
with excess of oleic acid; it is mixed first with a little water, then
with ether and slaked lime, and shaken. After some minutes more
ether and animal charcoal are added, and the whole is again shaken.
The ethereal layer which forms on standing contains the olein with a
little oleate of line. The residue is again treated several times with
:
TRIOLEIN.
85
ether, and the united extracts are then concentrated in a vacuum,
filtered from the oleate of lime which is precipitated, and further
evaporated in a stream of dry carbonic acid. The last traces of cther
are removed by a gentle heat.
Neutral, yellowish oil, of sp. gr. 0.947 at 21°. Inodorous and nearly
tasteless. Solidifies slowly, between 15° and 20°, to a white mass in-
terspersed with crystalline granules. When cooled rapidly to 0°, it
becomes solid, and afterwards melts below 10°; but again congeals if
kept long at that temperature. Distils undecomposed in a vacuum.
Bethelot.
42 C
40 H
80
CH705,C36H33033
mean.
252
70.8
71.4
40
11.3
11.5
64
17.9
17.1
356
100.0
100.0
Monolein becomes acid in the course of a few weeks when exposed
to the air. Decomposes on heating, with disagrecable smell, burns,
and leaves a residue of charcoal. It is very slowly saponified by
moist oxide of lead at 100°, and is not decomposed in 107 hours by
alcoholic acetic acid at 100°.
BERTHELOT.
Diolein.
C78H74012 = C6H806,2C6H330³.
Chim. organ. 2, 81; N. Ann. Chim. Phys. 41, 250.
Monolein is heated to 280° for some hours with 5 or 6 times its
weight of oleic acid, or triolein is heated to 200° with glycerin for 22
hours.
15°.
Neutral oil of sp. gr. 0·921 at 21°. Begins to crystallise at 10° to
Berthelot.
mean.
78 C
74 H
468
73.35
73.5
74
11.59
11.8
12 O
96
15.06
14.7
CH³06,2C36H³30³
638
100.00
100.00
BERTHELOT.
Triolein.
C114H10412 = C6H5O3,3C3H3303.
Chim. organ. 2, 81; N. Ann. Chim. Phys. 41, 251,
Relating to Oil-fat:-
BRANDIS. Comment. de ol, unguin. nat. Gött. 1785,
DEHNE. Crell. chem. J. 3, 32.
SCHEELE. Opusc. 2, 175.
CHEVREUL Recherches, 185 and 244,
86
CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS CH³¹.
---
BRACONNOT. Ann. Chim. 93, 225.
SAUSSURE.
112.
Ann Chim. Phys. 13, 338; Schw. 28, 389; N. Tr. 5, 2,
URE. Kastn. Arch. 1, 385; Schw. 39, 335; Repert. 16, 349.
LIEBIG & PELOUZE. Ann. Pharm. 19, 268.
In an impure state it forms Huile grasse non siccative, Braconnot's Huile absolue,
Chevreul's elain, afterwards olein, as well the Oelfett of the third edition of this
work. When freed from foreign substances, this body is, according to Berthelot,
identical with triolein.
Source. Triolein forms the principal constituent of the greasy fat
oils, and occurs in smaller quantity in the solid fat.
See below.
Preparation. A. From Oleic acid and Glycerin. Glycerin is heated
to 200°, in a sealed tube, with an equal quantity of oleic acid, and the
fatty layer which forms is mixed with 15 or 20 times its weight of oleic
acid and again heated to 240° for four hours. The triolein, extracted with
the help of lime, ether, and animal charcoal (somewhat in the manner
described at xvi, 359), is precipitated from its ethereal solution by the
addition of 8 or 10 volumes of alcohol, collected on a filter, and dried
in a vacuum (Berthelot).
B. From Fatty oils. 1. A fatty vegetable oil is cooled to 5°.
when the stearin solidifies and the oil is expressed; it deposits a little
more stearin at -10° (Braconnot). 2. Lard or tallow is dissolved in
boiling absolute alcohol and cooled, whereupon the whole of the olcin
and only a little of the stearin remain in solution. The solution is dis-
tilled with water, which often takes up odorous or colouring sub-
stances. The residual oil-fat, after repeatedly washing with water,
still deposits a little stearin in the cold (Chevreul).-3. When olive
oil is left in contact with cold caustic soda-solution for 24 hours, the
triolein alone remains unsaponified (Kerwyck, Berth. Chim. organ.
2, 82).
The product obtained according to 1 and 2 [still containing margarin (Saussure,
Pelouze, and Boudet)] is hereinafter distinguished as oil-fat.
Properties. Neutral oil remaining fluid below
undecomposed in a vacuum and partially at
(Berthelot).
:
10° it volatilises
ordinary pressures
Berthelot.
mean.
114 C
104 H
684
77.37
77.4
104
11.76
11.8
12 O
96
10.87
10.3
C6H5O3,3 C36H3303 884
100.00
100.0
....
Oil-fat is colourless, yellow or brown-yellow, and of rather lower specific gravity
than the fat of drying oils; its specific gravity when obtained from olive oil, is 0.915
(Saussure), 0·913 to 0916 (Chevreul), from goose-fat, 0·929 at 15° (Chevreul). The
sp. gr. of natural triolein is 0.914 (Berthelot). For the expansion by heat see
Kopp (Ann. Pharm. 93, 161). The oil-fat obtained from almond oil does not
congeal in the greatest cold; that from olive oil not at 10° (Braconnot) but
according to Saussure it solidifies at 4° the oil-fat from human fat solidifies below
4°, that from hog's lard at + 7° (Chevreul), at + 9° (Saussure). In the solid
-
:
DECOMPOSITION OF OLIVE OIL BY OIL OF VITRIOL.
u. I
85
state it is buttery or crystallises in needles. It distils unaltered in a vacuum
(Chevreul), and partially so over an open fire (Berthelot). After heating to 216° it
is not solid at ordinary temperatures (Berthelot). Inodorous, of mild taste, neutral.
Prepared from human fat it contains 77.5 p. c. C., 11.5 H., and 110 O.; from hog's
lard, 779 p. c. C., 114 H., and 107 O.; from mutton suet, 782 p. c. C., 111 H.,
and 107 O. (Chevreul). See Saussure (Ann. Chim. Phys. 13, 338). Ure (Schw.
39, 335). See also vol. vii, p. 237, of this work.
Decompositions. See vii, 240. 1. Triolein becomes acid in the air
(Berthelot). It absorbs in 2 months, in the dark, 6 per cent. of
oxygen, and, if exposed to the light in contact with oxide of lead or
brass filings, 8 per cent. (Berthelot). Oil-fat turns rancid in the air,
and in thin layers becomes more viscid, but does not, dry. — Triolein is
not perceptibly altered by ozone, but in presence of aqueous caustic
alkalis or their carbonates, it absorbs ozone rapidly and continuously,
and becomes thick and soapy, evolving an odour of cnanthol. On dis-
tilling with water, the product yields a milky distillate, smelling strongly
of oenanthol and acrolein, and slightly reducing nitrate of silver; when
distilled with phosphoric acid, it yields also formic and propionic acids,
whilst palmitic and oleic acids remain in the residue (Gorup-Besanez,
Ann. Pharm. 125, 213). 2. Moist bromine and chlorine convert oil-fat
into viscid products which contain 4 atoms of bromine or chlorine to
76 atoms of carbon. Iodine does not act upon it (Lefort, Compt. rend.
37, 29).—3. Oil-fat is more easily saponified by alkalis than tallow or the
fat of drying oils (see xvi, 313). When heated with oxide of lead and water,
it forms a firmer plaster than drying oil with separation of glycerin.-
The decomposition (of triolein and oil-fat) into oleic acid and glycerin ist
effected (1) by water at 220°, part of the fat, however, remaining un-
changed after six hours; (2) by moist oxide of lead at 100°, slowly and
with difficulty; (3) incompletely by fuming hydrochloric acid when
heated therewith to 100° for 96 hours. Alcoholic hydrochloric acid
decomposes triolein almost completely into glycerin and oleate of ethyl;
alcoholic acetic acid does not act upon it at 100° (Berthelot). —4. With
mercurous nitrate (Poutet), or nitrous acid (Boudet), oil-fat solidifies to
elaïdin. For the decomposition with oil of vitriol see below.
Triolein dissolves very slightly in alcohol, but abundantly in ether
(Berthelot).
Appendix to Triolein.
I. Decomposition of Olive Oil by Oil of Vitriol.
FRÉMY. Ann. Chim. Phys. 65, 121; Ann. Pharm. 19, 296; 20, 50.
When two parts of olive oil are gradually mixed with one part of oil
of vitriol, so that no heating takes place, the slightly coloured mixture
becomes thick and viscous after some minutes without evolving sul-
phurous acid. When allowed to stand for 24 hours, the products first
formed undergo further change, the mixture then containing margaro-
sulphuric, oleosulphuric, and glycerosulphuric acids. On diluting with
water, an oily mixture of margarosulphuric and oleosulphuric acids rises.
to the surface, whilst sulphuric and glycerosulphuric acids remain in
solution.
The oily mixture of acids, which cannot be separated into its consti-
tuents, dissolves in alcohol and in pure water, but not in water contain-
88
APPENDIX TO TRIOLEIN.
ing sulphuric acid. Its aqueous solution tastes oily, and afterwards
bitter. With the alkalis and ammonia it forms salts soluble in water
and alcohol, and with the other bases, salts insoluble in these liquids.
Its aqueous solution deposits, at ordinary temperatures, a mixture of
metamargaric and metoleic acids, after the removal of which the
filtrate, heated to 100°, throws down hydromargaritic and hydroleic
acids. Lastly, by heating a fresh aqueous solution of the mixture,
hydromargaric acid, formed by the union of the metamargaric and
hydromargaritic acids, may be obtained.
a. Oleosulphuric acid. On mixing oleic (metoleic or hydroleic) acid
with oil of vitriol, a compound is formed which is soluble in water but
insoluble in dilute sulphuric acid. Its aqueous solution decomposes
slowly in the cold and immediately on boiling, the oleic acid employed
being set free. These conjugated sulphuric acids form soluble salts
with the alkalis, and insoluble salts with the other bases. The baryta-
compound of metoleosulphuric acid contains 2 at. metoleic to 1 at.
sulphuric acid.
b. Margarosulphuric acid. Margaric acid is precipitated from its
solution in oil of vitriol by water unaltered, but when dissolved in oil
of vitriol, together with oleic acid, it forms a compound soluble in
water.
c. Metamargaric acid. From the mixture of metamargaric and met-
oleic acids formed by cold water (see above) the greater part of the met-
oleic acid may be separated by pressure. The solid residue, treated
with warm alcohol of 36°, gives up principally metamargaric acid, a
small quantity only of the metoleic acid dissolving. The metamargaric
acid is allowed to crystallise from the solution, and is purified by re-
crystallisation. It is also obtained by the dry distillation of hydro-
margaric acid. Nodules, or less frequently, shining lamina, solidifying
at 50° to a nearly transparent mass of soft needles. Contains, on an
average, 74.07 p. c. C., 12.62 H., and 13.21 O.; when obtained from
hydromargaric acid 75.00 p. c. C., 12·53 H.; the lead-salt contains
59·09 p. c. C., 9.94 H., and 23.81 PbO; the silver-salt 55·34 p. c. C.,
9.54 H., and 28-53 AgO. The remaining salts behave like those of
palmitic acid metamargaric acid also forms acid salts. According to
Frémy, metamargaric acid is represented by the formula C35H350) 4'5,
and loses 1 at. of water on combining with oxide of lead or other
bases. See Gerhardt (Traité, 2, 837).
d. Metoleic acid. The metoleic acid obtained as above (c) is freed
from metamargaric acid by repeated boiling with alcohol and at last by
cooling. Yellowish oil containing 74-77 p. c. C. and 11.90 H. By distilla-
tion it is decomposed, in the same manner as hydroleic acid, into car-
bonic acid which is evolved during the whole of the process, a little
water, followed by a mixture of caproene or oleene (xi, 411) pelargonene
or elaene (xiii, 367), and a small quantity of empyreumatic oil. It is
insoluble in water, but slightly soluble in alcohol, and easily in ether:
it forms easily alterable and generally acid salts, of which those of the
alkalis only are soluble in water. The silver-salt contains 60·10 p. c. C.,
2.7 H. and 24.73 AgO. Frémy's formula for the acid is C35H3245, and
for the silver-salt CH³¹Ag045 + ½ aq.
31
e. Hydromargaritic acid. This acid is thrown down, together with
FATTY OILS OCCURRING IN NATURE.
89
hydroleic acid, when the cold aqueous solution from which the whole of
the metamargaric and metoleic acids have been deposited on standing
is heated to the boiling-point. The solidified mixture is repeatedly
triturated with alcohol of 36°, which dissolves the hydroleic and leaves
the sparingly soluble hydromargaritic acid undissolved: the latter is
then crystallised from hot alcohol. It crystallises in hard, rhombic
prisms which melt at 68°, and are insoluble in water, difficultly soluble
in alcohol, but easily in ether. When submitted to dry distillation, it is
resolved into water and metamargaric acid. The difficultly soluble
salts exhibit the characters of the metaoleates. The acid contains 71:0
p.c. C., and 12·26 H.; the silver-salt 52.66 p. c. C., 8.84 H., and 27·59 AgO:
from these numbers Frémy deduces the formula C35H36·50º and C35H35·5 AgОº.
Gerhardt (Traité, 2, 837) considers the formula CHO probable.
f. Hydroleic acid. The alcoholic solution obtained in the preparation
of hydromargaritic acid is precipitated with water and the acid is cooled
to a few degrees below 0° for some time in order to crystallise out the
remainder of the hydromargaritic acid. Slightly coloured oil, easily
soluble in alcohol and ether. It is decomposed by dry distillatiou in the
same way as metoleic acid. Contains 73.14 p. c. C. and 11·86 H. in
the syrupy lead-salt, 66.20 p. c. C., 10·57 H., and 11:02 PbO; in the
silver-salt, 59-52 p. c. C., 10.00 H., and 20-09 AgO. Frémy gives for the
acid the formula C35H3505, and supposes that the salts retain half an
atom of water. On heating the acid with oxide of lead, 1 atom of water
is eliminated.
g. Hydromargaric acid. When metamargaritic and hydromargaritic
acids are mixed in equivalent proportions, or when margaro-sulphuric
acid is decomposed by boiling water, and the acid which separates is
crystallised from alcohol, hydromargaric acid is obtained in nodules or
occasionally small, slightly lustrous needles, melting at 60° and after-
wards solidifying to an opaque mass. The acid dissolves in alcohol
much more easily than either of those employed in its formation. It
contains, on an average, 72.74 p. c. C. and 12.52 H. (Frémy's formula
C¹³5H$5·50³); in the lead-salt, 56.90 p. c. C., 9·85 II., and 23·45 PbO; in the
silver-salt, 60.76 p. c. C., 10.51 H., and 18·03 AgO. In both these salts,
according to Frémy, 1 atom of base takes the place of atom of water;
by heating with excess of oxide of lead, a 2-acid salt is obtained, in
which 1 at. PbO replace 1 at. water. The acid forms a neutral and an
acid potash-salt, the latter of which is decomposed by a large quantity
of weak alcohol, with separation of free acid.
II. Fatty Oils occurring in Nature.
Under this head are included the more fully investigated fatty oils
which appear to contain ordinary oleic acid. The following memoirs
may also be referred to.
On the behaviour of the fatty oils with oxygen (Saussure, Ann. Chim.
Phys. 49, 225; Pogg. 25, 364); with phosphorus (Nieper, Jahrb. pr.
Pharm. 7, 300); with sulphur (Radig, N. Br. Arch. 2, 19); with phos-
phorus, sulphur, arsenic, and chlorine (Reinsch, J. pr. Chem. 13, 136;
14, 259); with chloride of sulphur (Roussin, Compt. rend. 17, 877). On
the solubility of arsenious and arsenic acids in fatty oils (Grundner,
Repert. 61, 289; Heimpel, Repert. 62, 1 and 19; Blondlot, Compt. rend.
90
APPENDIX TO TRIOLEIN.
50, 165). On solubility in alcohol, ether, and acetate of ethyl (Planche,
Bull. Pharm. 1, 298; Boullay, Bull. Pharm. 2, 260). On the saponifi-
cation of oils by anhydrous oxides (Pelouze, N. Ann. Chim. Phys. 47,
371); by chloride of zinc (L. Kraft & du Mottay, Compt. rend. 48, 410,
Rép. Chim. pure 1, 269); by soaps (Pelouze, Compt.rend. 41, 973). On
the decomposition of oils by vegetable matters occurring in the seeds
(Pelouze, N. Ann. Chim. Phys. 45, 319). Concerning the distinction
between the several fatty oils and the detection of their adulterations,
see Lipowitz (N. Br. Arch. 20, 215; 24, 107); Seyfried (J. pr. Pharm.
3, 216); Buchner (Repert. 69, 264), Heidenreich (Repert. 84, 392), Laurot
(N. J. Pharm. 2, 397), Soubeiran & Blondeau (J. Pharm. 27, 65),
Fauré (Dingl. 77, 350), Gobley (Dingl. 91, 384), E. Marchand (N. J.
Pharm. 24, 267), Mauméné, Calvert, Fehling, and Van Kerckhoff
(loc. cit.), Cailletet (Rép. Chim. appliquée 2, 86 and 293), and par-
ticularly Chateau (Mulh. Soc. Bull. 31, 405, 441, 479, 567; — 32, 211,
261, 317, and 353).
A M
1. Olive oil. Baumöl. Obtained from the pulp of the fruit of Olea
europea (Handbuch, viii, [1], 47). Concerning the formation of the
oil in the olives, see de Luca (Compt. rend. 53, 380; 55, 470, and 506).
Colourless, or greenish-yellow. Sp. gr. 0.913 (Muschenbroek); 0.9153
(Brisson); 0-915 at 10.5°, 0.9178 at 15°, 0.91635 at 17.5°, the sp. gr.
of water at 17.5° being unity (Pohl); 0.9192 at 12°, 0·9109 at 25°,
0·8932 at 50°, 0·8625 at 949, the sp. gr. of water at 15° being 1
(Saussure). The cold-pressed oil contains 77-36 p. c. C., 11-45 H., and
11.29 0. (Lefort).
Olive oil is resolved by saponification into glycerin and fatty acids.
According to the older statements of Chevreul, and of Pelouze &
Boudet, these acids are margaric and oleic; according to Collett
(J. pr. Chem. 64, 108) palmitic and oleic; according to Heintz and
Kreig (J. pr. Chem. 70, 367), oleic, palmitic, butic, and perhaps also
stearic. See further Heintz and Hetzer (J. pr. Chem. 64, 111). — Olive
oil contains cholesterin (Benecke, Studien, p. 108).
Olive oil congeals above 0°, frequently even at 10°, from the
crystallisation of small granules. It may be separated, by cooling
and pressing, into a fluid and a solid portion. At a temperature
of
6° the solid portion amounts to 28 p. c. (Braconnot) at + 6° to 8°
to 33 p. c. (Gusserow). It forms the stearin of olive oil or the oleo-
margarin of Pelouze and Boudet, and, according to these chemists, is
to be regarded as a definite compound of olein and margarin. - The
portion of olive oil which remains fluid on cooling forms the oil-fat of
the older chemists, but after more complete separation of the solid
portion it is identical with triolein (p. 86).
The stearin of olive oil melts at 20° (Pelouze and Boudet); that
obtained by expression at -2° to 3°, still containing a little oil
at 22° (Saussure), 28° (Lecanu). According to Berthelot (N. Ann.
Chim. Phys. 41, 242), the melting-point never rises above 28°. It dis-
solves easily in ether, and yields by saponification a mixture of acids
which melts at 45° (59° Lecanu), and contains about an equal number
of atoms of oleic and margaric acids (Berthelot), the melting-point of
which cannot be raised by re-crystallisation (Lecann). Gusserow
(Kastn. Arch. 19, 77) obtained, by expressing olive oil at a temperature
between 6° and 8°, 3rd of stearin, melting at 20° to 25°, which, on
standing for a long time at a temperature of 15° or 16°, separated into
FATTY OILS OCCURRING IN NATURE,
91
ڈ
a fluid and a solid portion. The latter, when saponified with oxide of
lead, yielded acids melting at 64°, and forming lead-salts, from 100
parts of which ether took up 63 parts of oleate of lead.
Olive oil boils at 315° (Saussure). It becomes paler at 120°;
nearly colourless at 200°; smells and tastes rancid after cooling; boils
at a temperature rising from 328° to 394° with decomposition, and
after boiling for some time appears dark golden-yellow and syrupy,
and deposits sebacic acid (Pohl, Wien. Acad. Ber. 12, 80; J. pr. Chem.
63, 400). — Olive oil, submitted to dry distillation, behaves like poppy
oil (Bussy and Lecanu). By slow boiling an unctuous distillate is
obtained, from which, by pressing and crystallising from hot alcohol,
Varrentrapp's margaric acid, melting at 55° to 56°, may be obtained.
It is still, however, contaminated with margarin (xvi, 351), which
may be removed from the potash-salt by ether, after which the acid
melts at 60°, and contains 74.82 p. c. C. and 12.42 H. (Varrentrapp,
Ann. Pharm. 35, 65). Probably palmitic acid (xvi, 351) (? Kr.). - Olive
oil yields, besides water and gas, a distillate, which is the more limpid
the more quickly the distillation is conducted, and which does not
solidify when the oil is made to boil from the commencement. By dis-
tilling at a temperature at which boiling does not take place, and
heating more strongly when nothing more passes over, it yields at
first an unctuous, and afterwards a fluid, acid, yellow distillate.
The former distillate is thinner and yellowish at the beginning, then
more solid and white, and at last, when the distillation below the
boiling point is nearly at an end, again yellowish. The whole of this
distillate is of the consistence of lard, solidifies at 20°, and has a dis-
agreeable smell and an acid reaction. It gives up to water a non-acid,
odorous principle, sebacic acid, an acid resembling butyric acid, and a
brown substance, whilst oleic and margaric (or stearic) acids and a
non-acid fatty oil remain behind (Dupuy, Ann. Chim. Phys. 29, 319;
32, 53).- -Cotton-wool soaked in olive oil takes up 2.8 p. c. of oxygen
when exposed to the air for two months (Vogel, Dingl. 156, 147).
The oil mixed with platinum-black in a stream of oxygen, and
heated to 80° or 90°, yields carbonic acid (Reiset & Millon).
With 4th of its weight of flowers of sulphur it forms, when mo-
derately heated, a dark-brown, tenacious ointment, which dissolves
in all proportions in ether, and is precipitated by alcohol. This
body forms, with ammonia-water, a yellow liniment, which is not
blackened by salts of lead; with caustic potash-solution it becomes
thick, and on boiling swells up, and is converted into a jelly
(Brandes, Br. Arch. 39, 77). Treated with moist bromine, ac-
cording to xvi, 316, olive oil forms a pale-yellow viscid product of
sp. gr. 1.276 at 9.5°, containing 36-42 p. c. of bromine, and forming
Lefort's brominated olive oil, for which he gave the formula C³Br²H³°Oª.
See also Knop (Pharm. Centr. 1854, 321, 403, 498). Chlorinated olive
oil, C3 C12H3004, obtained by the action of moist chlorine, is colourless,
of sp. gr. 1.078, and contains 20.74 p. c. of chlorine (Lefort, N. J.
Pharm. 23, 345). Concerning the behaviour of olive oil with chloride.
of lime, see Lipowitz (N. Br. Arch. 20, 215).- Chlorochromic acid pro-
duces a violent reaction, the oil becoming heated and frothing up
(Thomson, Pogg. 31, 607). Chloride of sulphur dropped into olive oil
causes it to solidify to a yellow, translucent, caoutchouc-like jelly,
which is not altered by water, alcohol, or ether (Rochleder, Dingl.
111, 159). — Olive oil is coloured light-green by agitation with th its
92
APPENDIX TO TRIOLEIN.
volume of syrupy phosphoric acid, and also, in 15 minutes, when shaken
with an equal volume of sulphuric acid of sp. gr. 1·475 to 1·635, or in
five minutes with nitric acid of sp. gr. 1.18 to 1.33. Shaken with th its
volume of nitrosulphuric acid it is coloured bright orange-yellow in
two minutes (Calvert, J. pr. Chem. 61, 354).
When 10 cub. cent. of oil
of vitriol are cautiously poured into 50 grammes of olive oil, the tem-
perature rises to 42° in two minutes without liberation of sulphurous
acid (Maumené, Compt. rend. 35, 572). See Fehling (Dingl. 129, 53).
Olive oil solidifies with hyponitric acid and mercurous nitrate, elaidin
(p. 98) being formed. With alcoholic ammonia it forms a large
quantity of an amide, solidifying at 97° (Carlet). It is coloured yellow
when heated to boiling with th its volume of solution of caustic
potash of sp. gr. 1.34 (Calvert). Concerning the products of saponification
see above. It is also saponified by heating 40 parts of the oil with 100
parts of lime-soap and an equal quantity of water to 155°—165°,
whereas water alone does not act upon it at this temperature (Pelouze,
Compt. rend. 41, 973; J. pr. Chem. 68, 141). - Sodium and potassium
become oxidised in olive oil, and form soaps (Gay-Lussac & Thenard).
Olive oil, heated with oxide of manganese, forms a manganese-soap,
with evolution of carbonic acid (Scheele). See vii, 243.
Phosphorus dissolves in 36 parts of olive oil at 15°, and in 25 parts
at 100° (Buchholz). — A solution of selenium in olive oil, in a fluid state,
is orange-yellow and clear by transmitted, pale-red and cloudy by
reflected, light; at ordinary temperatures it is unctuous, and loses its
colour on becoming solid, but regains it when melted (Berzelius).
Olive oil dissolves very slightly in wood-spirit and alcohol, and in
13 parts (Lecanu), 2.7 parts (Brande) of cold ether. From a mixture of
3 parts of olive oil and 2 parts of ether, alcohol does not take up any
ether (Planche). Olive oil dissolves in 5 parts of acetic ether (Planche).
2. Almond oil.From the kernels of Amygdalus communis (Handbuch,
viii, [1] 14). Sweet and bitter almonds yield oils of the same nature.
Colourless or yellowish; sp. gr. 0-911 (Brandis), 0.917 (Brisson),
0.918 at 15° (Schübler), 0-92 at 12°, that of water at 15° being in unity
(Saussure). Expands on heating in precisely the same way as olive
oil (J. Chim. méd. 20, 65). Almond oil is thicker than poppy oil,
thinner than olive oil; it becomes thick at 10°, cloudy at 16°, and
solidifies at 21° to a white butter (Schübler). It solidifies at +6°
(Fourcroy), at 10 to 11° (Braconnot), not at 11°, but slowly at
at
—
p
-
18° (Brandis). Braconnot (Ann. Chim. 93, 241) separated it, by
pressing at 10°, into 76 parts of an oil which did not solidify in the
most intense cold, and 24 parts of stearin melting at 6°. According to
Gusserow (Kashtn. Arch. 19, 79) it solidifies at 10 to 12° to a homo-
geneous mass, which remains solid at 5 to 6º, but gradually liquefies
2 to 3º, and does not admit of separation into portions of different
melting-points. From the lead-salts of the fatty acids of almond oil,
ether takes up about 77 p. c. of oleate of lead (Gusserow). Ether
dissolves the lead-plaster formed from almond oil almost completely,
leaving only traces of the lead-salts of solid fatty acids (Kr.).—The
oil expressed from bitter almonds contains, on an average, 70-53 p. c.
C., 10-61 H., and 18.66 0.; that from sweet almonds 70-48p. c. C., 10.64 H.,
and 18.88 0. (Lefort).
Almond oil turns rancid in the air. It does not yield margaric
acid by distillation (Anderson). See xvi, 351, — Phosphorus dissolves in
FATTY OILS OCCURRING IN NATURE.
93
36 parts of almond oil at 15°, and in 31 parts at 100° (Buchholz).
Almond oil, heated with phosphorus, behaves in the same way as poppy
oil (Jonas). - Sulphur, warmed in almond oil, melts to an oily layer
beneath the surface, and when further heated, dissolves to a dark red,
thick, glutinous liquid which swells up at the temperature of decomposi-
tion of the oil, with abundant and continuous evolution of hydrosulphuric
acid, and yields a distillate of dark-brown, repulsive-smelling oil, from
which margaric acid is deposited on cooling, the portion remaining
fluid containing odmyl (x, 97). In this reaction neither acrolein nor
sebacic acid is produced (Anderson, Ann. Pharm. 63, 370). See also
xvi, 351. On boiling 3 parts of iodine with 1 part of almond oil and
6 parts of water, most of the iodine distils unchanged, the oil becoming
heavy, brown, and viscid (Reinsch, J. pr. Chem. 14, 263). -Bromine and
chlorine form with the oil of bitter and sweet almonds products of
similar composition; they are colourless, of the consistence of castor
oil, and contain 17.55 p. c. chlorine and 32:56 p. c. bromine. Sp. gr. of
the bromine-compound, for which Lefort proposed the formula
C20BrH¹704, = 1·252 at 19.2°, that of the chlorine-compound, C³CIH¹Oª
=1.057 at 18.5° (Lefort, N. J. Pharm. 23, 282). Concerning the behaviour
of almond oil with bromine, see also Knop (Pharm. Centr. 1854, 321, 403 and 498);
with chloride of lime: Lipowitz (N. Br. Arch. 20, 215). — Almond-oil is
coloured yellow-brown by oil of vitriol. When 15 grammes of the oil
are mixed with 5 grammes of oil of vitriol, the temperature of the
mixture rises to 40.3 (Fehling). Mercurous nitrate converts almond oil
into a mass which is softer than that formed with olive oil (Davidson,
Ed. N. Phil. J. 28, 250).
The oil expressed from bitter almonds is oxidised by nitric acid, with
the same phenomena which occur in the oxidation of castor oil, yielding
œnanthylic acid and a non-volatile fatty oil, together with oxalic, suc-
cinic, suberic, and azelaic acids (Arppe, Ann. Pharm. 120, 292).
Almond oil takes fire with chlorate of potash and oil of vitriol (A. Vogel,
Ann. Pharm. 74, 115). It forms with alcoholic ammonia an amide melting
at 92° (Carlet, Par. Soc. Bull. 1, 73). — When heated with chloride of
mercury it becomes black, and evolves acid vapours (E. Davy).—
Almond oil yields a very hard soap.
Almond oil dissolves in about 25 parts of cold, and 6 parts of hot,
alcohol, and mixes with ether and chloride of ethyl (Pfaff). According to
Brande, it dissolves very slightly in alcohol of sp. gr. 0-82, and in 3.2
parts of ether, and according to Planche, in 4 parts of acetate of ethyl.
3. Fatty Ant-oil. Obtained by expressing the residue which
remains in the distillation of ants with water. Saffron-yellow; tastes
mild at first, afterwards irritating (Göbel). Reddish-brown, trans-
parent; floats on water and solidifies at a moderately low temperature.
Forms soap and plaster (Margraf).
4. The almonds of Anacardium orientale contain a little sweet oil.
The pericarp contains rd of a blistering oil of sp. gr. 0.991, easily
soluble in ether, and turning black in the air (Lepine, N. J. Pharm.
40, 16).
5. Oil of the seeds of Argemone mexicana. Orange-yellow, mild.
Remains fluid at 8° (J. Lepine).
6. Oil of Aspidium Filix mas. On treating the ethereal extract of
the root with water containing ammonia, filicic acid is taken up
94
APPENDIX TO TRIOLEIN.
thereby, whilst the oil remains dissolved in the ether.
Dark grass-
green, thicker than olive oil, tastes first mild and afterwards harsh,
and smells like the root. Deposits no solid fat even in winter. Saponi-
fies with some difficulty, and yields a green, soft, friable soda-soap.
Contains Luck's filixoleic acid (p. 74) (Luck, Jahrb. pr. Pharm. 22,
153). See also Winckler (Mag. Pharm. 22, 48).
7. Oil of the almonds of Azadirachta indica. Yellow, of sp. gr.
0-921. Tastes bitter; smells like garlic; congeals at + 7°. Yields by
saponification 35 p. c. of fatty acids melting at 30°, and 65 p. c. melting
at 44° (Lepine).
8. Oil of Barley-meal. - Obtained by exhausting the meal first with
water, and afterwards with hot alcohol. Greenish-brown, thick oil,
which becomes granular in the cold like olive oil, and smells and tastes
like fusel oil. Saponifiable. Dissolves slightly in alcohol, and is pre-
cipitated from the solution by water (Fourcroy & Vauquelin, N. Gehl.
2, 383).
9. Oil of Beech-nuts. From the kernels of Fagus sylvatica.
Yellow; has a mild and agreeable taste, and a faint odour. Sp. gr.
0·9207 (Lefebvre), 0·9225 at 15° (Schübler), 0·923 (Fabbroni). Thickens
and becomes turbid at 15°, and solidifies at 17.5° to a yellowish-
white mass (Schübler). Contains, on the average, 75.11 p. c. C., 11·06 HI.,
and 13.83 0. (Lefort). —With moist chlorine it forms Lefort's chlorinated
beech oil of sp. gr. 1·084 at 105°, of the consistence of castor oil, and
containing 22.72 p. c. chlorine; with moist bromine, brominated beech oil of
sp. gr. 1353 at 6-5, containing 40.57 p. c. bromine. Lefort (N. J.
Pharm. 23, 342) proposes the formulæ C³°H2804 (for beech-nut oil),
C30 II26C120, and CH2Br20. The oil yields a soft soap (Pelletier).
It forms, with alcoholic ammonia, a very small quantity of an amide
melting at 70° (Carlet). - Dissolves in 2 parts of acetate of ethyl at
12-5° (Planche).
26
10. Oil of the seeds of Butea frondosa. Yellow; of sp. gr. 0.917;
nearly tasteless. Solidifies at 10° (Lepine).
11. Oil of the seeds of Calophyllum inophyllum. - Green-yellow;
bitter and aromatic; of sp. gr. 0-942. Solidifies at +5° (Lepine).
12. Oil from the nut of Canarium commune. Moderately mobile ;
colourless. Tastes sweetish. Assumes the consistence of honey in
the cold, from crystallisation of stearin. Contains 47 parts of
stearin to 53 parts of oil-fat. Turns rancid in a year. The fresh oil
deposits stearin at a temperature of 15°, but after keeping for eight
months, the stearin is deposited only at 2.5° (Bizio, Bibliot. ital.
1823, No. 91, p. 60).
13. Oil of the almonds of Cassuvium pomiferum (the cashew-nut).
Sweet, pale yellow oil of sp. gr. 0·916. The pericarp of the nut con-
tains a thick viscid blistering oil of sp. gr. 1·014, which reddens litmus
and turns darker in the air. Dissolves in alcohol and ether with the
exerption of some white flocks. Dyes linen a permanent yellow-red
(Lepine).
14. Oil of Cotton-seeds. Contains palmitin and a large quantity of
olein (Slessor, N. Edin. Phil. Journ. 9, 11; Chem. Centr. 1859, 140.
See also Williams (Dingl. 43, 239), who appears to regard it as a
drying oil. — Sp. gr. 0·9306 at 15° (Lefebvre).
FATTY OILS OCCURRING IN NATURE.
95
15. Croton oil. From the fruit of Croton Tiglium (Handbuch, viii
[1], 23). — Thick brown oil, having a strong rancid odour. Acts as a
violent purgative. When rubbed upon the skin, it produces inflamma-
tion, the oil obtained from the press-cake by displacement with alcohol
being more active in this respect than the expressed oil. Becomes
cloudy on slight cooling, from separation of solid fatty acids. Croton
oil dissolves in 23 parts of alcohol of 85 p. c. The neutral, bright-
yellow oil which has been freed from admixed resin and free fatty
acids by shaking with alcoholic potash, requires 35 parts of alcohol for
solution (Schlippe). According to earlier statements it is easily soluble
in alcohol. - Croton oil is not solidified by nitrous acid.
On exposure
to the air, it forms a thick viscid mass, differing from that formed with
poppy oil, and probably resulting only from the liberation of fatty acids,
and not from the decomposition of drying oil acids (Schlippe). A mix-
ture of croton oil and alcoholic ammonia deposits crystals of an amide
which, after re-crystallisation from alcohol, melts at 100°, and has the
composition of margaramide CNH3502 (Rowney, J. pr. Chem. 67,
160). Croton oil yields, when saponified, a brown soap and a black
mother-liquor, which is decolorised by acids (Schlippe).
Croton oil contains crotonol (xiii, 376), together with a decomposi-
tion-product thereof, to which it owes its smell; also stearic, palmitic,
myristic, lauric (this acid passes over together with a decomposition-
product of croton oil on boiling the seeds with water), angelic (x, 413),
and crotonic (CH°O¹) acids in the form of glycerides. A mixture of the
last two acids appears to form the jatrophic acid of Pelletier & Caventou,
and the crotonic acid of the older chemists. Croton oil contains two
other members of the oleic acid (CnHn - 20¹) series, probably C4H³204 and
C20H1804 (Schlippe, Ann. Pharm. 105, 1).
31
The lime-soap obtained from croton oil dissolves partially in ether
with yellow-brown colour. On distilling off the ether, decomposing the
residue with carbonate of potash, and precipitating the resulting solu-
tion of the potash-soap with chloride of barium, a baryta-soap is obtained,
which, after washing and drying, exhibits the following behaviour. It
gives up to boiling alcohol a portion which crystallises from the filtrate,
melts easily to a clear oil, and contains 22.9 p. c. baryta (? C³¹II³¹Ba0¹=
22 84 p. c. BaO). From the portion remaining undissolved after twice boil-
ing
with alcohol, ether takes up a baryta-salt containing 32.12 p. c. baryta
(? C20H180432-2 p. c. BaO). The baryta-salts obtained by four times.
repeated boiling with alcohol contain 247, 23.02, 23.1 and 29.2 p. c.
baryta. Hence Schlippe supposes croton oil to contain two or more liquid
acids belonging to the same series as oleic acid, but differing therefrom.
16. Oil of the seeds of Daphne Mezercum. Oleum Seminum Coccognidii.
Extracted from the bruised seeds by boiling alcohol. Greenish-yellow
or yellow. Sp. gr. 0.914, of that obtained from very old seeds 0.921.
Acts as an irritant and vesicant. When the alcohol which has been
used for its extraction is cooled to 12.5°, the oil floating on the sur-
face being first removed, it deposits fatty granules which do not
possess blistering properties after purification (Martius, N. Br. Arch.
110, 39).
17. Oil of Earth-almond. - From the roots of Cyperus esculentus.
Sp. gr. 0.918. Smells like hazel-nuts, and has a slightly camphory,
not disagreeable taste. Deposits stearin. Yields a good soap with
96
APPENDIX TO TRIOLEIN.
.......
soda. Dissolves with difficulty in alcohol, but very easily in ether, and
in 30 parts of acetate of ethyl (Lesant, J. Pharm. 8, 509).
300
18. Oil of Eggs. Obtained by expressing hard-boiled and warmed
yolks of eggs, or by exhausting them with ether, the two processes,
however, yielding different products. The oil obtained by expression
is reddish-yellow, thick, tasteless or of mild taste, and neutral. On
long standing it deposits stearin, and at 4° to 6° solidifies to a granular
mass, which leaves on the filter more stearin, melting at 56°. The oil
freed from stearin is thicker than linseed oil, thinner than olive oil, and
congeals at 0° to a non-crystalline mass (Planche, J. Pharm. 1, 438).
Egg oil contains th of cholesterin, which is deposited in lamina when
the oil is kept at a temperature of 12--15° (Lecanu, J. Pharm. 15, 1).
It contains volatile acid (Redtenbacher). Dissolves in 22.5 parts of
alcohol of 90 p. c. on digesting for 24 hours, with partial separation of
stearin. Egg oil extracted by ether is of a fine yellow colour, not red
(Mialhe & Walmé, J. Pharm. 16, 128). It is sharp, smells disagreeable,
absorbs oxygen, and contains besides egg oil proper, the viscous sub-
stance (xvi, 484) which is left behind on filtration, and remains in
the press-cake, when the oil is obtained by expression. The ex-
pressed oil, as well as that extracted by ether and freed from the
viscous matter, congeals at - 6° to a crumbly mass in which many
laminæ of cholesterin are discernible. Both oils deposit in the cold a
mixture of oil-fat, margarin-fat, cholesterin, and colouring matter;
they are free from phosphorus and sulphur, and differ from other
oils only in containing cholesterin and colouring matter (Gobley,
N. J. Pharm. 9, 12; Compt. rend. 21, 989). The blackening of silver by
eggs is owing to sulphur in the albumin, and not to an oil contain-
ing sulphur (Gobley). That portion of the oil extracted by ether which
is insoluble in alcohol (and thereby separated from the viscous matter)
is a slightly coloured, mild, semi-solid fat, difficult to saponify, yielding
by Gusserow's method oleic acid, and in addition stearic acid (contrary
to Gobley, who found only margaric), margaric acid, and perhaps also
a third acid richer in oxygen (Kodweiss, Ann. Pharm. 59, 261). — The
oil extracted by ether from ducks' eggs is of a darker golden-yellow
colour, and less viscid than that of hens' eggs, and does not possess
the peculiar odour of the latter oil (Geissler, N. Br. Arch. 11, 168).
19. Fatty oil of Ergot-of-rye.
A hot alcoholic solution of the brown
fat extracted by ether deposits the greater part in a colourless state on
cooling. It forms a thick, somewhat rancid oil of sp. gr. 0·922 at 7·5°.
Solidifies partially at 0°, and completely at 37°.
37°. When boiled in a
glass tube it is converted into very acid vapours which smell like those
of other fatty oils, leaving a very little charcoal. It is not saponified,
or only to a slight extent, by boiling with potash. Insoluble in cold,
and soluble only in a large quantity of boiling alcohol, but easily
soluble in ether (Wiggers, Schw. 64, 164). See Wrigt (Pharm. Centr.
1840, 524) who obtained a saponifiable fat soluble in alcohol.
―
11.25°.
20. Oil of Euphorbia Lathyris (Handbuch, viii [2], 24. - Pale-yellow
oil of sp. gr. 0.9201, congealing at
The oil extracted by
alcohol or ether contains a white crystalline body, a brown oil, a resin,
and other substances (Soubeiran, J. Pharm. 21, 259; Br. Arch. 33,
227). The oil extracted by ether (Fleurot) and the expressed oil
(Chevallier) deposit white ncedles on keeping (J. Chim. méd. 5, 356).
TNT
:
FATTY OILS OCCURRING IN NATURE.
97
21. Hazel-nut Oil. — From the shelled nuts of Corylus Avellana.
Thick, pale-yellow or nearly colourless, inodorous oil having a mild,
agreeable taste. Sp. gr. 0.9242 at 15°. Becomes very thick at 15°
to 16°, and congeals at 19° to a yellow-white mass (Schübler).
Contains 77.4 p. c. C., 11.6 H., and 11.0 0. The colourless chlorinated
oil of sp. gr. 1.081 at 3.5°, contains 20.65 p. c. of chlorine: the yellowish
brominated oil is of sp. gr. 1·28 at 2·3°, and contains 36·47 p. c. of
bromine (Lefort). Lefort's formulæ are CH3204, C³6Cl²H³°Ò¹, and
C³ B₁·³Ï³°³. — With alcoholic ammonia it forms oleamide (Carlet).
B12H300¹.
Dissolves in 7 parts of acetate of ethyl at 12.5° (Planche).
30
22. Oil of Horse-chestnuts. From Aesculus Hippocastanum. Golden-
yellow; of sp. gr. 0.927; solidifies at 1.25°; smells and tastes like
beet. Easily saponifiable. - Vauquelin extracted from the scales of
Aesculus Hippocastanum, with hot alcohol, an inodorous, green-yellow,
rancid oil which yielded a moderately firm soap with soda.
23. Oil of the fruit of Mesua ferrea. - Chestnut-brown oil of sp. gr.
0.954, solidifying at 5° (Lepine).
24. Oil of Morels. — From Helvella Mitra. Thick oil lighter than
water, having the smell and taste of morels. Forms a hard soap with
soda. Dissolves in alcohol and ether (Schrader). Morels contain also
a white, crystalline, pearly, and tolerably hard fat resembling spermaceti.
It melts on platinum to a clear oil, burns with a somewhat fatty odour,
and leaves charcoal. Dissolves easily in cold alcohol and ether, slowly
in olive-oil (Schrader, Schw. 33, 593).
25. Oil of the seeds of Nigella sativa. - Orange-yellow; of sp. gr.
0.92; congeals at 2°. Smells aromatic and camphory (Lepine).
26. Fatty oil of the root and seeds of Paris quadrifolia. - Extracted
by ether from the roots and seeds which have been previously exhausted
with water and alcohol, and freed from paridin and resin by treatment
with cold alcohol of sp. gr. 0.85.- Green-yellow, non-drying oil of
sp. gr. 0.935. Dissolves with difficulty in alcohol, but easily in ether.
The acid separated from the soap solidifies easily (Walz, J. pr. Pharm.
6, 10).
27. Oil of Parsley. From the seeds of parsley. The powdered
seeds are exhausted with alcohol and the tincture is decolorised by
animal charcoal and ths of the alcohol are distilled off; the residue is
then exhausted with ether or chloroform; the extract is again sub-
mitted to distillation, and the last traces of ether or chloroform are
allowed to evaporate spontaneously in a basin. The residual liquid is
triturated with 4th of its weight of litharge, left to stand for 48 hours,
and lastly filtered through charcoal. Colourless oil of sp. gr. 1.078
at 12°, becoming cloudy at 12° without solidifying. Tastes sharp
and biting, smells strongly of parsley seeds, and has a faintly acid
reaction. Deflects a ray of polarised light slightly to the left. Free
from nitrogen. Febrifuge. Evolves a few bubbles at 150 to 175°,
and becomes coloured at 220°, without losing weight or being essentially
altered. Combustible. Assumes a splendid red colour with oil of vitriol
and solidifies, losing its taste and smell. Parsley oil is converted into
a resin by nitric acid, but is not altered by hydrochloric acid. Potassium
evolves gas-bubbles, and dissolves. Parsley oil forms an emulsion.
VOL. XVII.
H
DorM
98
APPENDIX TO TRIOLEIN.
with alkalis without undergoing further change; after agitation with
ammonia it remains unaltered. The oil is insoluble in water, but easily
soluble in alcohol of 50 to 60 p. c.; alcoholic neutral acetate of lead
produces in the solution a strong cloudiness which disappears on
warming and appears again in the cold. Parsley-oil dissolves in
acetic acid and in all proportions in ether and chloroform (Homolle and
Joret, N. J. Pharm. 28, 212; Pharm. Viertelj, 5, 253). It is doubtful
whether this body must be considered as belonging to the fatty oils
(Kr.).
-
28. Oil of Plum-kernels. From Prunus domestica. Yellow-brown
oil, of sp. gr. 0·9127 at 15°, thinner than oil of brassica, thicker than
hemp oil. Becomes cloudy at 6° from separation of white flocks, and
solidifies at — 8.7° to a yellowish mass. Has an agreeable taste and
smell of almonds. Easily turns rancid, and remains greasy when ex-
posed to the air (Schübler).
29. Oil of the seeds of Pongamia glabra. - Dark-yellow oil of sp. gr.
0-945, having a poisonous odour and bitter taste. Solidifies at 8°
(Lepine).
-
30. Sesame oil. From the fruit of Sesamum orientale. Golden-
yellow, somewhat darker than almond oil. Inodorous, and having a
slight taste of hemp. Sp. gr. 0.9143 at 11° (Lefort); 0.9235 at 15°
(Lefebvre); 0.923 at 15°, 0.921 at 17.5, 0.9183 at 21.3°, water at 17·5°
being 1 (Pohl). Contains on an average, 70-44 p. c. C., 10·74 H., and
18.82 0. (Lefort). Remains clear at 4°, and solidifies at 5° to a
yellow-white, homogeneous mass (Pohl). Becomes rancid on standing
in the air. The oil is decolorised by heating to 150-215°, evolving
white vapours at the latter temperature, and appearing, after cooling,
brighter than at first; it becomes darker and yellowish-brown at 300°,
and boils at 335-390° with decomposition (Pohl). Sesame oil forms.
with chlorine a viscid yellow compound, darker than the oil, of sp. gr.
1·065 at 6º, and containing 17.24 p. c. of chlorine. The bromine-com-
pound contains 32 61 p. c. of bromine; its sp. gr. at 18° is 1.251. Lefort
proposes the formulæ, C20H1804, C20CIH1704, and C20BrH1704 (Lefort, N.
J. Pharm. 23, 285). - Sesame oil is not coloured by shaking with th
its volume of syrupy phosphoric acid. When shaken with an equal
volume of sulphuric acid of sp. gr. 1.475 to 1.53, it appears greenish
after 15 minutes; treated in the same way with nitric acid of sp. gr.,
it is coloured in five minutes orange-yellow, and with an acid of sp. gr.
1.22 or 1.33, red (Calvert, J. pr. Chem. 61, 354). Oil of vitriol forms
with sesame oil a red-brown jelly, which evolves sulphurous acid when
heated; water throws down therefrom a curdy, white and purple pre-
cipitate (Pohl, Wien. Akad. Ber. 12, 80 ; J. pr. Chem. 63, 400.)
•
31. Fatty oil of Silkworms. Obtained by extracting with alcohol,
and washing the extract with hot water. Brown-green oil, remaining
fluid at 0°. Lighter than water. Neutral. Dissolves easily in cold
alcohol and ether. Easily saponifiable by caustic potash; less easily
by oxide of lead, yielding stearic acid, and a liquid acid, probably oleic
(Lassaigne, J. Chim. méd. 20. 471).
32. Spindle-tree oil. From the seeds of Euonymus Europaeus (Hand-
buch. viii., [2] 22). According to Schübler, a red-brown oil of repul-
sive odour and taste; according to Schweizer, bright-yellow, smelling
ELAÏDIN.
99
like rape-oil, and having a bitter, afterwards harsh taste. Sp. gr.
0.938 at 15°, being the heaviest oil after castor-oil (Schübler). Viscid
oil, becoming thicker at 16°, with deposition of stearin, and solidi-
fying at 20° to a red-brown mass (Schübler). Solidifies at
G
12
to 15°, and deposits colouring matter (Schweizer). Non-drying
(Riederer). Gives up to warm water a bitter substance, but no free
acid. Dissolves with difficulty in alcohol, the solution having an acid
reaction. Not precipitated from its ether-alcoholic solution by alcoholic
neutral acetate of lead. The yellow potash-soap is decomposed by
acids, oleic and margaric acids being separated, whilst benzoic and
acetic acids remain in solution. The benzoic acid is present in the oil
in the free state, the acetic acid as glyceride (Schweizer, J. pr. Chem.
53, 437; Ann. Pharm. 80, 288; Lieb. Kopp's Jahresb. 1851, 444). See
also Riederer (Kastn. Arch. 6, 413; Ann. Pharm. 8, 209). His euonymin
was obtained by evaporating an ether-alcoholic solution of the oil with
magnesia, exhausting the residue with alcohol, evaporating and exhaust-
ing with ether.
33. Oil of the seeds of Sterculia fætida. — Bright-yellow, of sp. gr.
0.923, not congealing at 3° (Lepine).
34. Oil of various species of Thea or Camelia. Used in China as
olive oil. Inodorous, and of straw-yellow colour. Does not solidify at
5.5°, but resembles an emulsion at 4.5°. Sp. gr. 0.927. Contains 25
parts of stearin and 75 of olein. Insoluble in alcohol, and very
slightly soluble in ether (Thomson, J. Chim. méd. 13, 409; Dingl. 66,
240).
35. Fatty Oil of Truffles. The oil extracted by ether is greenish-
brown, rancid; tastes sharp and harsh; reddens litmus, and is heavier
than water. It deposits stearin on standing, and yields traces of
volatile oil when distilled. Saponifiable; soluble in hot alcohol (Riegel,
Jahrb. pr. Pharm., 7, 225).
Elaïdin.
C114H104012 C6H503,3C3H3303.
Literature, History, and Formation (p. 74).
The product of the action of mercurous nitrate or hyponitric acid
on olive oil is dissolved in a small quantity of ether, and the filtered
solution is cooled to 0°, whereupon the elaïdin crystallises in nodules.
It is freed from the red mother-liquor, by washing with cold ether
(Meyer). Boudet boils the impure elaïdin with alcohol, but Meyer did
not succeed in decolorising and purifying it by this method.
White mass resembling stearin and melting at 32° (Meyer), 36°
(Boudet). Like stearin it has two different melting-points, the first of
which is 23.7°, the second 28° (Duffy). See further under Tristearin.
UorM
II 2
100
APPENDIX TO TRIOLEIN.
Meyer.
mean.
114 C........
684
77.37
76.96
104 II
104
11.76
12.03
•
12 O.....
96
10.87
11.01
C6H5O3,3C3H3303
881
100.00
100.00
The elaidin investigated by Meyer still contained margaric acid, which he was
unable to separate by recrystallization: hence the above formula and the view of
Gerhardt (Précis 1, 179), who regarded elaidin as isomeric with olein (triolein), are
rendered doubtful. Elaidin may possibly be a compound of glycerin with two
different acids, corresponding to the oleomargarin of olive oil (Kr.).
Decompositions. Elaïdin submitted to dry distillation, emits a strong
penetrating odour, evolves gases, and yields a fluid distillate which is
buttery on cooling, and contains water, acetic acid, elaïdic acid, and
volatile and empyreumatic oil. Towards the end of the distillation
sebacic acid is obtained, a small quantity of charcoal remaining behind
(Boudet). Meyer, by the dry distillation of elaïdin, obtained acrolein,
elaïdic acid, hydrocarbons, and perhaps sebacic acid. — Elaïdin yields by
saponification, elaïdic acid (Boudet); a mixture of elaïdic and margaric
acids, melting at 38-5°, which cannot be separated into the pure acids
re-crystallisation (Meyer). -- Hyponitric acid forms with elaïdin a fluid
compound containing an acid richer in oxygen and the elements of
ammonia (Pelouze and Boudet, Ann. Pharm. 29,47).
-
Elaïdin dissolves in 200 parts of boiling alcohol of sp. gr. 0·898,
and also to a slight extent in stronger alcohol, and in all proportions
in ether.
BERTHELOT.
Mannitic Bioleate.
(194][76()14 = ('¹¹ºOº,2C36H330³.
N. Ann. Chim. Phys. 47, 326; Chim. organ. 2, 192; Lieb.
Kopp. Jahresb. 1856, 660.
Mannite oléique. Bioleinmannitanester (p. xv, 362).
Obtained in the same manner as the corresponding palmitic com-
pound (xvi, 380). The ether employed in its extractionl ikewise takes
up oleate of lime, which is deposited when the ethereal solution is
made to boil in a vacuum.
Nearly colourless, neutral, waxy mass, becoming soft and tenacious
at a gentle heat, and afterwards melting to a yellowish liquid. On
evaporating its solution in a vacuum, it remains as a spongy, distended
elastic mass. When heated with hydrate of lime, it is resolved into
mannitan and oleic acid. - Dissolves in ether.
84 C
76 H
140
CIIO,2CH3Q3
After deducting 3 p. c. of ash.
Mou
Berthelot.
504
72.82
72.3
76
10.98
11.4
112
16.20
16.3
692
100.00
100.0
;
OLEAMIDE.
101
Bromine-nucleus C Br2H32.
Bromoleic Acid.
C96B1²H³20¹ = C36 Br²H³2,04.
LEFORT. Compt. rend. 37, 28; J. pr. Chem. 60, 179; Pharm. Centr.
1853, 491; in detail N. J. Pharm. 24, 113.
Oleic acid treated with bromine and water, according to xvi, 316,
is converted into a brown oil of sp. gr. 1·272 at 7·5°, which boils at 200°,
and reddens litmus. Contains, on an average, 36.45 p. c. of bromine
(calc. 36.36 p. c. Br).
Chlorine-nucleus C6C12H32.
Chloroleic Acid.
C36C1²H³204 = C¹³6Cl²H³²,0¹.
32
!
LEFORT. N. J. Pharm. 24, 113.
Obtained from chlorine and oleic acid in presence of water, accord-
ing to xvi, 316.
Brown oil of sp. gr. 1·082 at 8°, thicker than oleic acid. Reddens
litmus. Boils at 190°. Coutains on an average 20·61 p. c. of chlorine
(calc. = 20·23 p. c. Cl).
Amidogen-nucleus C36 AdH33
Oleamide.
C30NH3502C36AdH33,02.
BOULLAY. N. J. Pharm. 5, 329; abstr. J. pr. Chem. 32, 223; Compt. rend.
17, 1346.
ROWNEY. Trans. Roy. Soc. Edin. 21, part 2; Chem. Gaz. 1855, 361;
J. pr. Chem. 67, 157; abstr. Lieb. Kopp's Jahresb. 1855, 531; Prelim.
notice: Chem. Soc. Qu. J. 7, 200; Lieb. Kopp. Jahresb. 1854, 465.
CARLET. Par. Soc. Bull. (1859) 1,73; abstr. Lieb. Kopp. Jahresb.
1859, 366.
The transformation of fats by ammonia was investigated in 1844
by Boullay, who, however, did not prepare the amides in a pure state,
and regarded them, even when obtained from different fats, as one and
the same product, margaramide.
Formation. From almond oil (Rowney) or hazel-nut oil (Carlet) and
alcoholic ammonia. Seal oil yields, with alcoholic ammonia, all
102 PRIMARY NUCLEUS CH; AMIDOGEN-NUCLEUS CAαH33.
amide melting at 82° and having the composition of oleamide (Rowney).
The oils are also converted into amides by long standing with
aqueous ammonia, or by prolonged treatment with ammonia-gas and
subsequent standing (Boullay). On boiling the product (from olive
oil) with water, a milky frothing liquid is obtained, on the surface of
which the amide collects in a solid form on cooling. The acid mother-
liquor contains glycerin, colouring matter, an acid compound of a non-
fatty acid with ammonia, and a little margarate and stearate of ammonia
(Boullay).
Preparation. A mixture of 1 volume almond oil, 2 volumes alcohol,
and 4 volumes concentrated ammonia, is allowed to stand in a closed
vessel, with occasional shaking, for several months, or until it solidifies;
the mass is then collected, pressed, and purified by washing and re-
crystallisation. -Carlet employs 1 volume of hazel-nut oil and 1 to 2
volumes of a saturated alcoholic solution of ammonia, and allows the
mixture to stand until the solid mass is soluble in all proportions in
hot alcohol. It is then purified by re-crystallisation from alcohol till
the melting-point remains constant.
Crystalline nodules, which begin to melt at 79°, become per-
fectly fluid at 81°, and solidify to a semi-transparent mass at 78°
(Rowney). After melting, it solidifies to a very crystalline mass at 75°
(Carlet).
Rowney.
Carlet.
mean.
mcan.
36 C
N
216
76.86
76.48
76.43
14
4.98
4.59
5:07
35 H......
35
12.45
12.27
12.63
20
16
5.71
6.66
5.87
C36 NH3502
281
100.00
100.00
100.00
་་་……
Bouillay's margaramide, obtained from olive oil and melting at 60°, contained
75-72 p. c. C., 5·32 N., 12.96 H., and 6·00 O.
Oleamide acquires a yellow colour and a rancid odour in the air.
When heated with alcoholic potash in a sealed tube, it is decomposed
with formation of oleate (Carlet). It is not attacked by boiling
solution of caustic potash, but is decomposed by the fused hydrate
(Rowney).
Insoluble in water; easily soluble in warm alcohol (Rowney).
Elaïdamide.
C36NH350² = C¹³Adͳ⁹,О³.
TH. ROWNEY. Trans. Roy. Soc. Edin. 21, part 2; Chem. Gaz. 1855,
361, J. pr. Chem. 67, 157; abstr. Lieb. Kopp. Jahresb. 1854, 465;
1855, 531; Prelim. notice: Chem. Soc. Qu. J. 7, 200.
Elaïdin, obtained by the action of hyponitric acid on almond oil, is
allowed to stand in a close vessel with 4 times its volume of ammonia-
water and twice its volume of alcohol; and the amide, which is formed in
abundance, is collected, pressed, and purified by washing and recrystal-
lisation,
!
STEARIC ACID.
103
Shining, colourless needles, which melt partially at 92° and com-
pletely at 94°, and solidify to an opaque mass at 91°.
Rowney.
36 C .....
N
216
76.86
mean.
76.44
......
14
35 H......
35
4.98
12.45
....
4.88
12.70
2 0....
16
5.71
5.98
C36NH3502
281
100.00
100.00
Isomeric with oleamide.
30
Primary Nucleus, C361136.
Stethal.
C³6H³⁹O² = C¹³6Hª³‚H²O².
36
,
Not obtained in the pure state. Occurs in spermaceti. See xvi, 344.
Stearic Acid.
C¹36H960¹ = ('36H$6,0¹.
CHEVREUL. Ann. Chim. 88, 225; Schw. 14, 420; Ann. Chim. Phys. 2,
354. Ann. Chim. Phys. 23, 19; Schw. 39, 175. -- Recherches sur les
corps gras.
BRACONNOT. Ann. Chim. 93, 250.
REDTENBACHER. Ann. Pharm. 35, 46.
BROMEIS. Ann. Pharm. 35, 86; 37, 303.
STENHOUSE. Ann. Pharm. 36, 57.
ERDMANN. J. pr. Chem. 25, 497.
FRANCIS. Ann. Pharm. 42, 256; Phil. Mag. 21, 161.
GOTTLIEB. Ann. Pharm. 57, 35.
LAURENT & GERHARDT. Compt. rend. 28, 400; Compt. chim. 1849,
337; Ann. Pharm. 72, 272.
HARDWICK. Chem. Soc. Qu. J. 2, 232; Ann. Pharm. 72, 268.
CROWDER. Phil. Mag. [4] 4, 21; J. pr. Chem. 57, 292; Pharm. Centr.
1853, 2.
HEINTZ. See references xvi, 343.
BERTHELOT. See references xvi, 350.
PEBAL. Wien. Akad. Ber. 13, 285; Ann. Pharm. 91, 138; J. pr. Chem.
63, 385; Chem. Centr. 1854, 810.
J
Talgsäure. Acide stéarique.
History, xvi, 350.
See the other synonyms, xvi., 365, 366 -
Occurrence. As tristearin, more especially in the solid fats. (See
xvi, 385.)
The following sources of stearic acid must also be noticed. In
spermaceti combined with ethal or similar compounds (xvi, 347). — In
104
PRIMARY NUCLEUS (136H36.
the Mineral-moor of Marienbad (Lehmann, J. pr. Chem. 65, 481). In
sweat (Schottin, Pharm. Viertelj. 2, 57). See also Cerotic acid.
Formation. 1. By the saponification of tristearin.-2. By heating
stethal (xvi, 347) with potash-lime (Heintz). According to Lewy
(Compt. rend. 16, 677) and Gerhardt by heating cerin with potash-
lime, but according to Brodie not. (Sce under Cerotic acid.)
Preparation. According to Chevreul (xvi, 355); Heintz (xvi, 354).
Its preparation in the pure state is more difficult by Chevreul's method;
in Heintz's process, on the other hand, ethers of the fatty acids are
apt to be formed (Berthelot, N. Ann. Chim. Phys. 41, 220). Pebal
proceeds in the same way as Heintz, but employs neutral acetate of
lead for the fractional precipitation; precipitates at the boiling heat;
and boils the precipitates with the liquid for ten minutes; even thus,
however, pure stearic acid is obtained only after very often repeated
fractional precipitation. Stearic acid is most casily obtained pure from
mutton suet. The suet is saponified with th to rd its weight of
caustic potash; the soap is decomposed with boiling hydrochloric
acid; and the fatty acids are washed, dissolved in a little hot alcohol,
and allowed to crystallise, then pressed, and repeatedly recrystallised
from a relatively large quantity of alcohol till the melting-point
reaches 69·1 to 69.2° (Heintz). The expressed fat of Cocculus indicus,
treated in the same way, yields pure stearic acid (Crowder). — Shea-
butter (xvi, 386) is the material best adapted for the preparation of
stearic acid (II. L. Buff, Oudemanns). It contains about 70 p. c. of
stearic to 30 p. c. of oleic, but no other solid fatty acid (Oudemanns,
J. pr. Chem, 89, 215).
Properties. Stearic acid crystallises from alcohol in nacreous
needles and laminæ (Chevreul); in lamina (Heintz). It melts at 69.1°
to 69.2° to a colourless oil, which on cooling solidifies to a white, fine,
scaly crystalline mass, lamino-crystalline on the recently fractured
surface (Heintz). The impure acid solidifies in masses of acicular or
wavellitic structure. The melting point was found by Chevreul at 75°
(so idifying point 70°); by Duffy, at 68° (solidifying point 65.8°);
by Stenhouse, at 69°; by Redtenbacher, Kopp, and others at 70°; by
Hardwick, at 70.5°; Pebal found that the purest acid melted at 69.2°.
After fusion it is friable and greasy to the touch (Chevreul). It
expands very strongly when heated, especially at the moment of fusion.
(about 11 p. c.), and contracts so strongly in solidifying that cast
lumps appear porous. Its volume, that at 0° being taken for unity, is
1.038 at 50°, 1.054 at 60°, 1.079 at 70°, and by fusion the volume at 70°
increases to 1·198. Between 9° and 11° its specific gravity is equal to
that of water (II. Kopp, Ann. Pharm., 93, 184). It boils and distils
in a vacuum (Chevreul), and in quantities of 15 to 20 grammes under
the ordinary atmospheric pressure, for the most part without alteration
(Laurent and Gerhardt, Hardwick, Heintz). When heated to 300
330° in a sealed tube for several hours, it does not alter either its
appearance or its melting-point, or give off either gas or water
(Berthelot). It is tasteless and inodorous, reddens litmus when warm,
and even when cold if it be dissolved in strong alcohol, but on adding
water, which precipitates the acid, the blue colour is restored
(Chevreul). It has a distinct acid reaction (Heintz).
STEARIC ACID.
105
Redten- Sten-
Chevreul. bacher. house.
Erd-
Hard-
mann.
wick. Francis.
36 C......
36 H......
40
36
32
216 76.06 76.30 75.51 75.75 76.50 76.13 74-73
12.68 12:43 12.86 12.78 12.81 12.86 12.46
11.26 11.27 11.63 11:47 10.69 11.01 12.81
C36H 3601
284 100.00 100.00 100.00 100.00
100.00 100.00 100.00 100.00
Laurent and Gerhardt.
Crowder. Gottlieb.
α.
b.
C
75.91
76.29
75.41
75.60
Heintz.
75.57 to 75.88
Pebal.
75.84 to 76.15
****
H
13.01
12.83
12.53
12.61
12.59 12.85
12.83 12.71
...
O
11.08
10.88
12.06
11.79
A
100.00 100.00
100.00
4.
The formula C35H3503.5 (Chevreul), CSH6807 (Redtenbacher, Erdmann),
C(8H6607 (Stenhouse), CH3O+ (Gerhardt) have been successively proposed for
stearic acid. Laurent and Gerhardt gave the formula C34H3404, according to which
stearic acid would be isomeric with margaric acid. The above formula first proposed
by Hardwick for stearic acid separated from bassia-oil (bassic acid), then adopted
by Crowder for the stearophanic acid of Francis, has been recognised by Heintz as
the true formula of stearic acid.
Decompositions. 1. When 90 grms. of stearic acid are subjected to
dry distillation, the greater part passes over unchanged, but a smaller
portion is resolved, into carbonic acid, water, and stearone; the dis-
tillate likewise contains acetic acid, butyric acid, a fatty acid of lower
melting point than stearic acid, also hydrocarbons of the formula
CnHn, and ketones richer in oxygen than stearone,-these, as well as the
hydrocarbons, probably resulting from further decomposition of the
stearone. The black-brown residue in the retort still contains stearone,
but scarcely any fatty acids (Heintz).
Chevreul found in the distillate 96 p. c. of unaltered stearic acid,
small quantities of volatile acid, and brown empyreumatic oil, with
traces of acetic and sebacic acids; carbonic acid and hydrocarbons
were likewise given off during the distillation. According to
Redtenbacher, no sebacic acid is produced, the formation of that acid
taking place only when oleic acid is present; but, in addition to a
fatty acid melting at 60-61° (regarded by Redtenbacher as margaric
acid) there are likewise obtained margarone (see under Stearone) and an
empyreumatic oil. If the fatty acid be combined with lime, the lime-
salt exhausted with ether, the margarone allowed to crystallise out as
much as possible, and the ether evaporated, the empyreumatic oil
remains behind. This oil, when purified by rectification, contains on
the average 83·96 p. c. C. and 14:19 H. It must, therefore, be regarded
as a hydrocarbon, but mixed with the ketone of an acid of lower
atomic weight than stearic acid (Heintz). The solid distillate was
mixed with hydrate of lime to a soap, and this was washed with ether,
which left stearate of lime together with a small quantity of the lime-
salt of a more fusible acid. The ether, when distilled, deposited
stearone, then a soft, greasy mixture, and ultimately there remained
an oil which solidified a little above 0°. Of this oil, one portion (a)
passes off in distillation between 273° and 293°, a second portion (b)
between 293° and 309°, and the residue in the retort is solid at medium
temperatures. The portion a deposits a few lamina at 0°, ba con-
siderable quantity; the latter contains on the average 84.94 p. e. C.,
106
PRIMARY NUCLEUS C36 H36.
14-20 H., and 0-86 O., and is therefore a mixture of hydrocarbons
C¹Нº, and ketones (Heintz).
2. Stearic acid mixed with platinum-black, and heated to 100° in
oxygen gas, forms carbonic acid, and at 200° is completely converted
into carbonic acid and water (Reiset and Millon, N. Ann. Chim. Phys.
8, 285; Ann. Pharm. 48, 199). Ileated in oxygen to 180°, it burns
with a dazzling light (Reiset and Millon). It burns in the air like wax
(Chevreul). With ozone it behaves like palmitic acid (xvi, 357).
3. Heated with chromic acid, sulphuric acid, and water, it yields
chromic oxide, and an acid melting at 64-65°, the alcoholic solu-
tion of which first deposits unaltered stearic acid, then an acid
(Redtenbacher's margaric acid) melting between 59° and 60°
(Redtenbacher). — 4. Permanganate of potash converts stearic acid into
stearate and carbonate of potash (Cloez and Guignet, Compt. rend.
46, 1110).
5. Nitric acid forms from stearic acid small portions of volatile acids,
which mix with the unaltered stearic acid, and lower its melting-point
(Heintz). When stearic acid is heated with 2 or 3 pts. nitric acid,
violent action takes place after half-an-hour, nitric acid and pungent
gases being given off, and the fused acid being converted into a
tenacious frothy mass, then becoming clear and mobile, and finally
solidifying as it cools to a tallowy mass which melts at 35° to 45°.
According to Bromeis, this mass contains margaric acid, C³¹³¹04
melting-point 60-5°; 7405 C., 12:58; silver-salt 53.48 C., 8.80 H., 28-22 Ag),
and if crude stearic acid has been used, an oil formed from oleic
acid, and coloured blood-red by potash (Bromeis, Ann. Pharm. 35,
86). After several days' treatment with nitric acid, the stearic acid
disappears completely, being converted into suberic and succinic acids
(Bromeis). In later experiments Bromeis (Ann. Pharm. 37, 303)
obtained also azoleic acid (see Oleic acid, p. 67). Azelaic acid (p. 80)
is not formed from stearic acid.
6. Stearic acid fused with anhydrous phosphoric acid forms a
yellow mass similar to that obtained in like manner from margaric
acid (p. xvi, 357), but less coloured. This body, when freed from
the unaltered stearic acid, melts at 54-60°, and contains, on the
average, 80·4 p. c. C., 12.9 H., and 6.7 O (C36H3402
81.2 p. c. C., 12.77 H.
and 6·03 0), and is converted by hot nitric acid into a brittle waxy mass
containing 77.25 p. c. C., 12-22 H. and 10.53 0. (Erdmann, J. pr. Chem.
25, 500).
=
7. Dry chlorine gas at 100° converts stearic into chlorostearic acid
(IIardwick).
8. Bromine heated with stearic acid and water in a
sealed tube, forms a dark brown liquid, which does not alter perceptibly
at 100°, but between 130° and 140° is slowly converted into a yellow
oily mixture of bromo- and bibromo-stearic acids, mixed with unaltered
stearic acid. Formation of bromo-stearic acid:-
C36H360+ + Br C36H35 BrO + HBr.
When more than 2 at. bromine is used to 1 at. stearic acid, a
large quantity of bibromo-stearic acid is produced, but even then a part
of the stearic acid remains unaltered. If the heat is raised above 140°
the mass remains brown, or charcoal separates from it (Oudemanns,
STEARIC ACID.
107
J. pr. Chem. 89,193). 9. Pentachloride of phosphorus brought in con-
tact with stearic acid at a moderate heat forms a colourless mass, which
soon becomes heated to 150°, turning brown and black. When dis-
tilled it gives off hydrochloric acid, a small quantity of water, a
hydrocarbon, stearic acid, and a solid product less soluble in alcohol
than stearic acid (Chiozza, Gerhardt's Traite, 2, 851).11. Stearate
of potash, in contact with oxychloride of phosphorus, becomes slightly
heated, and at 150° swells up to a dark jelly, perhaps forming
chloride of stearyl, inasmuch as the product treated with alcohol yields
stearate of ethyl (Pebal).· 12. When stearic acid is heated with an
equal weight of sulphur, a trace of hydrosulphuric acid is given off,
and the same products are formed as when stearic acid is heated by
itself (Anderson, Ann. Pharm. 63, 373). 13. The acid heated with oil
of vitriol to 100°, for several hours, is decomposed, with evolution of
sulphurous acid, and carbonises at a higher temperature (Chevreul).
14. Stearate of lime subjected to dry distillation, gives off marsh-gas
and olefiant gas (or gases having the same composition as the latter),
and yields a distillate containing a large quantity of stearone, with
small quantities of other ketones, while carbonate of lime remains
behind. The distillate does not contain any fatty acid (Heintz). See
Stearone.
15. Stearic acid distilled with excess of aniline, yields phenyl-stear-
amide (Pebal). On the other hand, stearic acid crystallises unaltered from its
alcoholic solution mixed with aniline (Pebal).
16. Stearic acid heated with methylic, ethylic, and the homologous
alcohols, with quercite, pinite, and other carbohydrates, with glycerin,
orcin, opianyl (meconin) erythroglucin and cholesterin, yields ethereal com-
pounds formed from the acid and the other body, with elimination of
water. (For details see the several compounds; on the formation of glycerides,
also xvi, 358.) When heated for thirty-six hours with pyrogallic acid
(xi, 398) to 200°, it forms a crystalline compound (Rösing, Compt.
rend. 14, 1149; J. pr. Chem. 71, 325).
Combinations. Stearic acid is insoluble in water.
It dissolves partially and without coloration in 10 parts oil of
vitriol at 20°, the undissolved portion, if left at rest, being converted
into needle-shaped crystals; water added to the solution throws down
the stearic acid in white flocks. On heating the liquid, two yellowish
layers are formed, the upper containing the larger proportion of stearic
acid, and solidifying to a soft mass at 44°, while the lower, when cooled
to 12°, slowly deposits the stearic acid in spherules composed of
needles; water also precipitates but a small portion of the stearic acid
from it (Chevreul).
Stearates. Stearic acid dissolves in a cold aqueous solution of alka-
line carbonate, probably from formation of bicarbonate, and does not
expel the carbonic and form a mono-acid salt till heated to about 100°.
On the other hand, the stearates are decomposed by most other acids,
the separated stearic acid rising to the surface as an oil when the liquid
is warm. The stearates have the consistence of hard soaps and
plasters, and are mostly insoluble in water.
Stearate of Ammonia. Stearic acid, either in the fused or the solid
108
PRIMARY NUCLEUS CH36.
state, al sorbs ammonia gas without elimination of water, the quantity
absorbed amounting, after a month, when the absorption ceases, to
6-68 parts ammonia for every 100 parts of acid (1 at NH³=5′9 parts).
The compound is solid, white, inodorous, has an alkaline taste, may be
sublimed in a vacuum, and then gives off ammonia, but takes it up
again on cooling. When heated in a vessel containing air, it gives off
ammonia and water, and yields a sublimate of acid salt, mixed with
empyreumatic oil. The neutral salt, when protected from the air, dis-
solves in hot water, especially in ammoniacal water, and the solution
on cooling deposits the acid salt in nacreous lamina (Chevreul). The
solution of stearic acid in hot dilute aqueous ammonia deposits small
needles on cooling. When heated for some time, it becomes turbid,
and is then not clarified by further addition of ammonia. The needles
dissolve in alcohol and in ether (Crowder).
Stearate of Potash. A. Mono-acid.
Mono-acid. Separates on cooling from a
solution of 1 part stearic acid and 1 part hydrate of potash in 10 parts
water, in white opaque granules, and may be purified by pressure,
solution in 18 parts alcohol of sp. gr. 0.821, and washing the needles
which then separate, with cold alcohol (Chevreul). —- Obtained also from
carbonate of potash and stearic acid in the same manner as myristate of potash
(xvi, 212) (Crowder). — Shining, delicate needles, scales, and laminæ,
which, when aggregated, form a hard soap; has a faint alkaline taste
(Chevreul).
10
In air saturated with moisture it takes up th of its weight of
water. One part of the salt forms, with 10 parts of cold water, an
opaque gum, which melts at 99° and solidifies to a pearly gum on
cooling. One part of the salt dissolves completely in 25 parts of boiling
water, forming a liquid which is still limpid at 92°, and solidifies to a
pearly mass on cooling.
The solution of 1 part of the salt in 100 parts of hot water deposits
on cooling a mixture of mono- and bi-stearate of potash, while one-
fourth of the entire quantity of potash remains dissolved.
When the
solution of the salt in alcoliol, or in 20 parts of boiling water, is mixed
with 1,000 parts of boiling water, or 5,000 parts of cold water, it
deposits all the stearic acid as bi-acid salt, whilst half the potash
remains dissolved in the water. In like manner the mono-acid salt,
when drenched with 5,000 parts of cold water, gives up half its potash
and is converted into a bi-acid salt without forming a gum. In these
cases the alkaline water contains a trace of stearic acid in solution
(Chevreul). It dissolves at 10° in 231 parts alcohol of sp. gr. 0·794,
in 10 parts at 66°, the latter solution becoming turbid at 55°, and
solidifying at 38°. It dissolves in 67 parts of boiling alcohol of sp. gr.
0794, forming a liquid which gelatinises on cooling. It dissolves in
ether-alcohol, and crystallises therefrom (Crowder, Hardwick). Boiling
ether withdraws from the mono-acid salt a certain quantity of stearic
acid, leaving a compound richer in potash (Chevreul).
Chevreul.
:
mean.
CH3O+
KO
275.0
47.2
85.35
A
14.65
15.19
CHOKO¹
322.2
100·00
B. Bi-acid.
Chevreul's matière nacrée. Formation, supra; Preparation
STEARIC ACID.
109
(xvi, 355.) Delicate, white, pearly lamine, tasteless, softening at 100°.
The solution in absolute alcohol reddens litmus on the addition of a
little water, while a larger quantity of water restores the blue colour
by precipitating the bi-acid salt. Cold water dissolves in a month a
very small quantity of potash, and a trace of stearic acid. The salt
dissolves at 245° in 318 parts alcohol (of sp. gr. 0-834, in 278 parts of
alcohol of sp. gr. 0.794, and in 3-7 parts at the boiling heat. The
solution crystallises on cooling, and is precipitated by water, with
separation of tri-acid salt. It dissolves partially in boiling ether, the
solution on cooling depositing the mono-acid salt, while stearic acid
remains dissolved (Chevreul).
C72H7107
ΚΟ
Chevreul.
559.0
47.2
92.22
7.78
8.57
C36H35 KO+, C36H360±
606.2
100.00
....
C. Triacid and Quadracid? Bistearate of potash forms with 1,000
parts of boiling water a solution of mono-acid salt, rendered turbid and
gummy by suspended triacid salt:
2(C36H35 KO¹‚C¹³6Ħ³6O¹)
=
C36H35 KO¹,2C36H3604 + C36H3³KO¹.
This solution becomes clearer and more fluid at 75°, deposits a few
flocks on cooling to 67°, and from 59° to 26° pearly lamina of the
bi-acid salt resulting from decomposition of the mono-acid salt formed
at the higher temperature, and mixing with the ter-acid salt. This
mixed precipitate contains 6.18 parts potash to 100 parts stearic acid
(5 at. stearic acid, 2 at. potash = 6·73 parts); it melts below 100°, and
solidifies to a translucent wax at 75° to 71°. Its solution in hot
alcohol deposits bi-acid salt on cooling; on the other hand, when
boiled with 1,000 parts of water, it gives up more potash, and is con-
verted into quadrostearate of potash containing 4-47 parts potash to
100 parts acid (calc. 3·9 parts KO), melting to an oil when warmed, and
solidifying on cooling to a white mass, which swells up in water
(Chevreul).
Stearate of Soda. Stearic acid agitated and warmed with disodic phosphate,
forms an emulsion which clarifies on cooling from formation of stearate of soda
(Marcet, N. Arch. Ph. nat. 1, 192; Kopp's Jahresb. 1858, p. 396).
A. Mono-acid. 20 parts stearic acid are heated with 13 parts
soda and 300 water; and the granular mass which forms on cooling is
pressed, dried in the sun, and crystallised from 25 parts of boiling
alcohol (Chevreul). Obtained like myristate of soda (xvi, 212). - Shining
laminæ or translucent very hard soap (Chevreul). Crystalline network
formed of long prisms having a strong pearly lustre (Francis). Melts
above 100°; tasteless at first, afterwards tastes alkaline (Chevreul).
From air saturated with moisture it absorbs at 6°, in 12 days, 7·5 p. c.
water, afterwards not any perceptible quantity. When covered with
600 parts of cold water, it becomes more opaque in 14 days by taking
up water, and gives up to the water a trace of potash. With 10 parts
water at 90°, it forms a thick, nearly transparent solution, which soli-
difies to a white mass at 62°; and this, when heated with 40 parts
more water, forms a solution which is still filtrable below 100°; and
when mixed with 2,000 parts more water, deposits the biacid salt ou
cooling, while half the soda and a trace of stearic acid remain in solu-
110
PRIMARY NUCLEUS C6H36.
tion. It dissolves at 10° in 499 parts alcohol of sp. gr. 0.821, and in
20 parts at the boiling heat; the latter solution becomes turbid at 70°,
and solidifies on cooling to a transparent jelly, which afterwards be-
comes opaque and contracts, from formation of numerous shining
crystals. Boiling ether withdraws from the salt a small quantity of
stearic acid, together with a trace of soda, and yields a slight deposit
on cooling (Chevreul).
Chevreul.
mean.
Redten- Crowder. Heintz.
bacher.
mean.
mean.
36 C
216
....
35 H
35
70.58
11:43
68.50
....
11.24
30
24
NaO
31
7.86
10.13
9.78
•
10.98
10.48
....
10.15
10.08
•
....
C36H35 NaO4
306
100.00
....
100.00
SE P
B. Biacid.
The soap prepared from 5 parts hog's-lard and 3 parts soda
swells up when heated with a large quantity of water, and on cooling deposits bi-
stearate of soda as a translucent jelly. The solution of the monostearate in
2,000 parts of boiling water is left to cool, and the precipitate is col-
lected, washed with cold water, dried, and crystallised from boiling
alcohol. It dries on the filter to a somewhat pearly, white, translucent,
tasteless film, more fusible than the monostearate. It is insoluble in
water, easily soluble in hot alcohol; the solution reddens litmus, but
on adding water, which precipitates the salt, the colour is restored
(Chevreul).
NaO
Chevreul.
559
94.75
31
5.25
5.67
……..
590
100.00
C³H³NaO¹,C³H36O4
Stearate of Baryta. - 1. Stearic acid is digested for two hours in a
closed vessel with an excess of boiling filtered baryta-water; and the pre-
cipitated soap is freed from excess of baryta by decanting the liquid and
boiling with water, then by boiling with alcohol, from any stearic acid
that may have remained uncombined (Chevreul). 2. Stearate of soda
is precipitated with acetate of baryta, and the precipitate is washed suc-
cessively with alcohol, water, dilute acetic acid, and hot alcohol
(Heintz). Prepared by 1, it is a white fusible tasteless powder; by 2,
a micro-crystalline pearly precipitate, not fusible without decomposi-
tion. Insoluble in boiling water and in boiling alcohol (Chevreul), and
in ether (Crowder).
Heintz.
61.02
Hardwick.
36 C
35 H
216.0
61.45
35.0
9.96
61.03
9.90
....
30
24.0
6.83
....
BaO
C36H3BaO+
76.5
21.76
6.93
22.14
Crowder.
61.68
10.31
6.27
21.74
9.90
....
7.52
...
21.56
351.5
100.00
100.00
100.00
....
100.00
...
Chevreul found 22:41 p. c. baryta, afterwards 22:31.
Stearate of Strontia.
fusible tastless powder.
alcohol (Chevreul).
Prepared like the baryta-salt (1). White
Insoluble in water, slightly soluble in boiling
STEARIC ACID.
111
Chevreul.
C36H3503
275
84.1
Sro..
52
15.9
16.34
327
100.0
C36H35 SrO4
Stearate of Lime.
Obtained by precipitating chloride of calcium
stearate of potash, and washing the precipi-
White fusible, tasteless powder.
with a boiling solution of
tate with boiling water.
C36H3503
CaO
C36H 35 Ca04
Chevreul.
mean.
275
28
90.76
9.24
9.96
303
100.00
Stearate of Magnesia. - Prepared like the myristate (xvi, 213).
After recrystallisation from alcohol it forms dazzling white flocks made
up of microscopic lamina, which dry up to a light fusible powder
(Heintz).
Heintz.
36 C ......
216
73.20
73.00
35 H....
3 0......
35
11.87
11.99
24
8.14
8.46
MgO.....
20
6.79
6.55
C36H 35 MgO4
295
100.00
100.00
....
Stearate of Lead.
Stearic acid heated with 9 parts lead-oxide loses
3.4 p. c. water (Chevreul). 1 at. = 3.17 p. c.
A. Biplumbic. Stearic acid is boiled in a close vessel with terplumbic
acetate, and the resulting white, transparent, friable soap, which is
liquid at 100°, is boiled first with water, then with alcohol
(Chevreul).
C36H3503
2РЬО
C36H35 Pbo, Pbo
Chevreul.
275
55.11
224
499
44.89
45.58
46.0
...
100.00
B. Monoplumbic.-Obtained by precipitating nitrate of lead with
a boiling solution of monopotassic stearate (Chevreul). Heintz proceeds
as in the preparation of the myristate (xvi, 313). Redtenbacher precipitates neutral
lead-acetate mixed with acetic acid, with an alcoholic solution of the soda-salt.
Fine, amorphous, white powder, melting at about 125° to a colour-
less liquid, which solidifies to an opaque, amorphous mass (Heintz).
Insoluble in ether (Gusserow).
216.0
35.0
55.87
9.05
Redtenbacher.
55.15
8.96
Heintz.
mean.
55.61
9.03
8.41
26.95
LUIT!
32.0
36 C
35
4
Pb
C36H35PbO4
386.8
....
103.8
8.28
26.80
100.00
8.46
27.43
100.00
Chevreul found 29.47 p. c. lead oxide (calc. 28.91 p. c. PbO).
100.00
112
PRIMARY NUCLEUS C36H36.
Stearate of Copper. — Light-blue bulky amorphous powder. Melts
when heated to a green liquid, easily decomposing at the same time
(Heintz).
Heintz.
36 C
35 H
216
68.64
68.15
35
11.12
11.20
30
24
7.63
7.79
CuO
40
12.61
12.56
CH3 CuO
315
100.00
100.00
Mercurous Stearate. Obtained by heating mercurous oxide with
stearic acid. From mercurous nitrate stearate of potash throws down
a white precipitate, which turns grey when dry, and contains 42.52
p. c. mercurous oxide (1 at. = 43·06 p. c. H2O). Melts when heated
and then decomposes. Insoluble in water; insoluble also in cold
alcohol, sparingly soluble in boiling alcohol, easily in ether whether
cold or at the boiling heat (Harff).
Mercuric Stearate. Obtained by heating mercuric oxide with
stearic acid to 100°, with agitation, or by mixing mercuric nitrate with
stearate of potash, in which case it is precipitated in flocks. White,
softening between the teeth. Contains 29.19 p. c. mercuric oxide (1 at.
28.2 p. c. IIg0). Insoluble in water, sparingly soluble in boiling
alcohol, soluble in ether whether cold or boiling (Harff).
Stearate of Silver. - Obtained by adding a solution of 20 grms. of
the soda-salt in 5 or 6 oz. of strong alcohol to a solution of 12 to 13
grms. silver-nitrate in an equal quantity of alcohol (Crowder). Amor-
phous, white precipitate, very loose and strongly electric when dry.
Assumes a purple colour when exposed to light in the moist state; not
altered by light when dry. Insoluble in water, alcohol and ether,
easily soluble in aqueous ammonia.
8.95
Redten- Hard-
bacher. wick.
54.30
51.82
9.08
Francis. Crowder. Heintz.
53.72
8.83
55.53
valim
36 C........
35 H
216... 55.24
35
9.01
4 O.......
Ag
32
108
8.19
27.62
8:08
8.49
28.61
8.60
28.85
CIAgO
391
100.00
100.00
100.00
100.00
....
....
27.61
****
54.90
9.15
9.03
8.45
27.62
7.76
27.56
100.00
Contains 28-64 p. c. silver (Laurent and Gerhardt); 27.51 p. c. (Pebal).
....
100.00
Stearic acid dissolves in liquid carbonic acid (Gore, Chem. Soc. Qu.
J., 15, 163).
Stearic acid dissolves in 40 parts of cold alcohol of sp. gr. 0·794,
and in any quantity of boiling alcohol of the same strength (Chevreul,
Braconnot). The hot solution of 1 part stearic acid in 1 part alcohol of
sp. gr. 0794, becomes turbid at 50°, depositing nacreous scales, and
solidifies at 45° (Chevreul).
It dissolves in 83 parts cold ether, and in all proportions of hot ether
(Braconnot); in 34 parts bisulphide of carbon, and in 4·55 parts of benzene
of sp. gr. 0·887, at 23° (A. Vogel, Dingl. pol. J., 164, 221).
Stearic Acid with Lauric, Myristic, Palmitic and Margaric Acids.
Mixtures of these acids, as shown by Gottlieb for mixtures of stearic and
STEARIC ACID.
113
Chevreul's margaric acid (comp. Ann. Pharm. 57, 37), exhibit the rela-
tions indicated at page 214, vol. xvi., and the melting points given in
the following tables :-
ACCORDING TO HEINTZ.
1. Stearic and Lauric Acids (xv, 43).
A mixture of :-
:-

Stearic Lauric
acid.
acid.
Melts
at
10
90
41 ·5°
20
80
38.5
30
70
43 4
40
60
50.8
50
50
55.8
90
18 288
60
40
59.0
70
30
62 '0
80
20
6-17
10
67.0
Mode of Solidifying.
Non-crystalline.
Non-crystalline, warty.
Small shining crystalline facets on the surface.
Warty, non-crystalline.
Scarcely crystalline, slightly granular.
More distinctly granular; commencement of
scaly crystallisation.
Somewhat more distinctly granulo-scaly.
Distinctly scaly-crystalline.
The same.
2. Stearic and Myristic Acids. (xvi. 209).
A mixture of :-
Stearic Myristic
Melts
acid.
acid.
at
Mode of Solidifying.
10
90
51.7°
Non-crystalline, opaque.
20
80
47.8
Indistinctly crystalline.
30
70
48.2
Lamino-crystalline.
40
60
50.4
Beautifully broad-laminar.
50
50
54.5
60
40
59.8
70
30
62.8
80
20
65 '0
90
10
67.1
Non-crystalline, opaque.
Neither needles nor lamina; commencement of
scaly crystallisation.
More distinctly scaly.
Still more distinctly scaly.
Scaly crystalline.
3. Stearic and Palmitic Acids (xvi. 350.)
A mixture of :-
Stearic Palmitic Melts Solidifies
acid.
acid.
at
at
90
10
67.2°
62.5°
80
20
65.3
60.3
70
30
62.9
59.3
The same.
60
40
60·3
56.5
50
50
56.6
55.0
4.0
60
56 ·3
54.5
The same.
35
65
55.6
54.3
32.5
30
70
20
80
10
90
5288
67.5
55.2
54.0
The same.
55.1
54.0
57.5
538
Scarcely acicular.
60.1
54.5
Mode of Solidifying.
Scaly-crystalline.
Finely aciculo-crystalline.
Rough, non-crystalline.
Broad, lamino-crystalline.

Non-crystalline, wavy, shining.
Non-crystalline, wavy, dull.
Beautifully acicular.
VOL. XVI.
I
114 CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS CH36.
4. Stearic, Palmitic, and Myristic acids.
The melting point of a mixture of 32.5 p.c. palmitic acid with 67.5
p.c. myristic acid, which is situated at 46·2°, sinks lower when to 20 parts
of this mixture there are added from 1 to 7 parts of stearic acid. "The
melting points of the several mixtures are as follows:
With 1 part stearic acid the melting point is 45.2°
2
3
,,
>>
>>
44.5
44.0
4
43.8
5
44.6
>>
6
45'4
""
7
46.0
>>
8
46.5
These mixtures solidify to non-crystalline masses (Heintz).
5. Stearic and Margaric acids (xvi, 472). Mixtures of these two
acids melt more easily than stearic acid, but only a few of them less
casily than margaric acid. They solidify almost in the same manner
as unmixed fatty acids, differing, therefore, in this respect from mix-
tures of stearic with palmitic acid (IIeintz).
A mixture of :-

Stearic Margaric
Melts
acid.
acid.
at
Mode of Solidifying.
10
90
59.5°
Scaly crystalline.
20
80
59.8
The same, but less distinctly.
30
70
60·8
Like the last.
40
60
61 .2
The same.
50
50
62.0
The same, but less pearly.
60
40
63.1
The same.
70
30
64.7
The same.
80
20
66.2
The same.
90
10
67.6
Scaly crystalline.
Conjugated Compounds of the Primary Nucleus C136 H36.
Stearate of Methyl.
C38H380 = C²H³O,C6H5O³.
LASSAIGNE. Ann. Pharm. 23, 169.
HANHART. Compt. rend. 47, 230; J. pr. Chem. 77, 5.
Methylic Stearate. Methyl-stearic ether.
holzäther. Stearinformester.
Stearinsäure-Methyläther. Talg.
1. Obtained by heating 1 part of wood-spirit with 1 part oil of
vitriol and part stearic acid. 2. By heating stearic acid with wood-
spirit to 2007, in a sealed tube for a day. Purified like the glycerides
(xvi, 358). Melts at 38. Neutral (Hanhart).
STEARATE OF ETHYL.
115
Stearate of Ethyl.
C40H4004
CH*O* = C*HO,C3H35O®.
LASSAIGNE. J. Chim. méd. 13, 369; Ann. Pharm. 23, 168.
REDTENBACHER. Ann. Pharm. 35, 51.
STENHOUSE. Ann. Pharm. 36, 58.
FRANCIS. Ann. Pharm. 42, 261.
CROWDER. Phil. Mag. [4], 21; J. pr. Chem. 57, 292.
HEINTZ. See memoirs cited, xvi., 343.
DUFFY. Chem. Soc. Qu. J., 5, 197; Ann. Pharm. 88, 291.
PEBAL. Ann. Pharm. 91, 153.
BERTHELOT. See memoirs cited, xvi., 350.
HANHART. Compt. rend. 47, 230; Chem. Centr. 1858, 676; J.pr. Chem.
77, 5.
BERTHELOT and FLEURIEN. N. Ann. Chim. Phys. 67, 79; Compt. rend.
51, 1020; Ann. Pharm. Suppl. 1, 271; Chem. Centr. 1861, 230.
Ethylic Stearate. Ethyl-stearic ether. Talgäther. Stearinsaures Aethyloxyd.
Stearin-säurevinester. Stearophansaure-äther.
Formation. 1. By heating stearic acid with alcohol to 200°, small
quantities are produced also heating the materials together to 100° for
102 hours (Berthelot); or by boiling stearic acid with alcohol (Lassaigne).
-2. By passing hydrochloric acid gas into an alcoholic solution of stearic
acid (Redtenbacher); by heating alcoholic stearic acid with acetic acid
to 100°, the whole of the stearic acid then entering into combination in
102 hours (Berthelot). By the action of alcohol on the product formed
by heating stearic acid with pentachloride of phosphorus (Pebal).
4. By boiling tristearin with a solution of sodium in absolute alcohol
(Duffy), or by heating tristearin with small quantities of alcoholic potash
(Bouis, Compt. rend., 45, 35).
Preparation. Hydrochloric acid gas is passed into alcoholic stearic
acid; the mass which solidifies on cooling is dissolved in boiling alcohol;
the solution poured into a boiling dilute aqueous solution of carbonate
of soda; and the stearic ether which separates on cooling is purified by
repeated solution in boiling alcohol, and precipitation with a small
quantity of water (Heintz). The ether produced by heating stearic acid with
alcohol to 200° in a sealed tube for several days, may be purified like palmitin (xvi.,
337) (Hanhart).
Properties. Crystalline mass, semi-transparent, and resembling white
wax. Melts at 33.7° (Duffy, Heintz); at 27" (Lassaigne); 30°-31° (Redten-
bacher); 31° (Hanhart); 32° (Francis); 32.9° (Pebal); 33·3 (Crowder). Solidifies
to a translucent mass (Duffy); to a crystalline mass, soft at first, after-
wards becoming hard and brittle (Heintz). Volatilises a little at the
heat of the water-bath (Crowder); boils at 224° with partial decompo-
sition, leaving a residue of charcoal (Duffy). Tasteless; melts on the
tongue, producing a sensation of cold (Crowder); has a buttery taste
(Francis). Inodorous in the cold; smells faintly when heated (Francis).
1
NO
116 CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS C6H36.
Redtenbacher.
Stenhouse.
40 C ....
40 H
240
76.92
76.13
76.30
40
12.82
12.85
12.92
4 O.....
C4H5O,C36H35(3
32
10.26
11.02
10-78
312
100.00
100.00
100.00
Francis.
Crowder.
Duffy.
Pebal.
Heintz.
76.20
76.90
76.53
76.79
76.59
12.77
13.23
12.50
12.91
12.84
11.03
9.87
10.97
10.30
10.57
100.00
100.00
100.00
100.00
100.00
DELISED
Decompositions. 1. For the decomposition by heat, see above.
2. By
water at 100° it is partially resolved in 102 hours into alcohol and
stearic acid, more abundantly by a mixture of 1 vol. acetic acid and 2
to 3 water, the latter reaction taking place without any formation of
acetic ether (Berthelot).3. Fuming hydrochloric acid at 100°; con-
verts it in 106 hours into chloride of ethyl and stearic acid (Berthelot).
4. Decomposed by alcoholic, but not by aqueous potash (Duffy).
5. Anhydrous baryta heated with the ether to 200° in a sealed tube,
decomposes it completely, and the product heated with water yields
alcoholate and stearate of baryta :
C40H4001 + 2BaO : C36H35 BaO4 + C¹H'BaО².
These are the only products; no ethylic ether is formed (Berthelot and Fleurien).
6. Heated to 100° with glycerin, it does not yield stearin, not even in
presence of hydrochloric acid (Berthelot).
Stearate of ethyl dissolves very easily in alcohol and in ether, and
crystallises from alcohol, but not from ether (Duffy).
Bistearate of Ethylene.
C767408 CH 02, 206H3503.
=
WURTZ. N. Ann. Chim. Phys. 55, 436.
Ethylenic or Glycolic Bistearate. Glycol distéarique. Distearinglycolester.
Obtained by the action of bromide of ethylene (viii, 366) on stearate
of silver. The product is exhausted with ether, the ethereal solution
treated with potash-hydrate, and the filtrate left to evaporate.
Light, shining lamina, melting at 76°, and resembling tristearin.
Wurtz.
76 C.....
456
76.76
76.25
74 I
74
12.46
12.69
80
64
10.78
11.06
C'H'O2,2C36H3503
594
100.00
100.00
DISTEARIN,
117
Monostearin.
C'42H4208 =
C6H705, C6H350)3.
BERTHELOT.
Chim. organ. 2, 65; Ann. Chim. Phys. 41, 221.
A mixture of equal parts of stearic acid and glycerin is heated to
200° in a sealed tube for 36 hours, then left to cool. On opening the
tube there is found floating on the excess of glycerin, a solid layer, con-
taining monostearin and uncombined stearic acid. This layer is melted,
mixed with a small quantity of ether, then with slaked lime, and heated
to 130° for a quarter of an hour, whereby the stearic acid is made to
unite with lime. The monostearin is obtained by exhaustion with ether
and spontaneous evaporation. A mixture of stearic acid and glycerin enclosed
in a sealed tube and left to itself for three months at ordinary temperatures, likewise
yields very small quantities of glycerin.
Properties. Very small white needles, aggregated in roundish
grains, melting at 610, and solidifying at 60° to a hard, friable, waxy
mass. Neutral in alcoholic solution. Volatilises without decomposi-
tion in a vacuum.
Berthelot.
mean.
42 C........
4.2 H
252
70.4
70.4
4.2
11.7
12.3
80
64
17.9
17.3
C6H7O5,C36H3503
358
100.0
100.0
Decompositions. Monostearin decomposes when heated in a tube,
with formation of acrolein. When it is heated on platinum-foil, a
portion evaporates, while the rest turns yellow, and burns with a white,
very luminous flame. Heated with fuming hydrochloric acid to 100°
in a sealed tube for 110 hours, it is almost wholly resolved into glycerin
and stearic acid. A trace of a neutral chlorinated liquid is formed at the same
time. Monostearin is decomposed by heating for some hours to 100°,
with moist protoxide of lead, yielding nearly 25 p.c. glycerin (calc. 25.56
p.c., CH8O6). It is not decomposed by heating to 100° for 26 hours
with alcoholic acetic acid.
Very slightly soluble in cold ether.
Distearin.
C76H78012 C8H806,2036H3503.
BERTHELOT. Chim. organ. 2, 67; N. Ann. Chim. Phys. 41, 226.
Formation and Preparation. 1. One part of monostearin is heated
with 3 parts of stearic acid to 260° for three hours. 2. Stearic acid is
heated with an equal quantity of glycerin to 100° for 114 hours, or to
118
CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS C36H36.
275° for seven hours. 3. The stearin of natural fats is heated with
excess of glycerin to 200° for 22 hours. Separated like monostearin (p. 117).
White microscopic lamina, which melt at 58°, and solidify like
monostearin, at 55°. Obtained in needles by spontaneous evaporation
from ether. Neutral.
Decomposible by moist oxide of lead, at 100°.
Berthelot.
78 C
468
72.9
78 H
78
12.1
72.0 to 73.8
12.2,, 12.5
12 O
96
15.0
C6H8O6,2C35H3503
612
100.0
CHEVREUL.
BRACONNOT.
Tristearin.
CH110012 = C6H5O³,3C6H3503.
Recherches sur les corps gras.
Ann. Chim. 93, 225.
A. VOGEL. Ann. Chim. 58, 154.
LECANU. Ann. Chim. Phys. 55, 192; J. Pharm. 20, 323; Ann. Pharm.
12, 25; abstr. Pogg. 31, 638.
LIEBIG & PELOUZE. Ann. Pharm. 19, 264.
REDTENBACHER. Ann. Pharm. 35, 195.
FRANCIS. Ann. Pharm. 42, 254; Phil. Ann. 21, 161.
ARZBÄCHER. Ann. Pharm. 70, 239; Pharm. C'entr. 1849, 585.
Chem. 57, 335; abstr. Ann.
HEINTZ. See memoirs already cited (xvi, 343, 344, Nos. 1, 2, 5, and 9).
DUFFY. Chem. Soc. Qu. J., 5, 197; J. pr.
Pharm. 84, 291; Lieb. Kopp. Jahresb. 1852, p. 507.-— Chem. Soc.
Qu. J., 5, 303; J. pr. Chem. 58, 358; Lieb. Kopp. Jahresb. 1852,
P. 511.
BERTHELOT. See memoirs already cited.
seq.
Chim. organ. 2, 52, et
H. KOPP. Ann. Pharm. 93, 194; Lieb. Kopp. Jahresb. 1855; p. 43.
BOUIS. Compt. rend. 45, 35; J. pr. Chem. 72, 308; Kopp's Jahresb. 1857,
p. 357.
BOUIS AND PIMENTEL. Compt. rend. 44, 1355; J. pr. Chem. 73, 176;
Kopp's Jahresb. 1857, p. 356.
Talafett. Stéarine or Substance grasse of Chevreul. Suif absolu of Braconnot.
First prepared, though in an impure state, by Chevreul; purer by Braconnot.
Berthelot's researches have demonstrated the identity of the stearin of natural fats
with tristearin.
Occurrence. In many fats, especially in the solid tallows and lards of
the animal kingdom (xvi, 385–400). The stearophanin of Francis is also
resolved by saponification into stearic acid and glycerin, but differs widely from tri-
stearin in its melting point (p. 366).
Preparation. Monostearin is heated for three hours with 15 to 20
times its weight of stearic acid to 270° in a sealed tube, and the
product is purified in the same manner as monostearin (Berthelot);
Heintz (Ann. Pharm. 92, 300) heats stearic acid with glycerin to 200°
for 24 hours in a sealed tube filled with carbonic acid gas; the tube is
TRISTEARIN.
119
then opened; the glycerin decanted; the free stearic acid removed
by treatment with ether and lime; and the mass of glycerides dissolved
out by boiling ether. The mixture thus obtained already contains
monostearin, and may be converted into tristearin by heating to 270°
for eight hours with a large excess of stearic acid; the uncombined
stearic acid may then be removed as before, and the tristearin dissolved
out by hot ether.
Chevreul's stearin is obtained by dissolving mutton-suet in boiling
alcohol, and recrystallising the fat which separates out, till the melting
point becomes constant. Purer than this is Braconnot's stearin, obtained
by repeatedly melting mutton-suet with oil of turpentine; still purer is
that of Lecanu, who melts mutton-suet in the water-bath, adds an
equal quantity of ether, stirring all the while; presses the fat when
cold, and re-crystallises it till the melting point rises to 62°. Above this
temperature the melting point does not appear to be raised by repeated
crystallisation from small quantities of ether; but it may still be raised
by repeated crystallisation from 10 to 100 times its volume of ether.
After 32 crystallisations thus performed, the melting point rises to 69-7°
(Duffy); but the fat thus treated is still a mixture of tristearin and tri-
palmitin (Heintz), as shown by its melting point, and by that of the acids
(= 66.5°), separated from it by saponification. The melting points of
the fatty acids obtained by saponifying different varieties of stearin,
are as follows:
Chevreul's stearin solidifying at 44° yields fatty acids melting at 53°
Braconnot's
Lecanu's
Liebig & Pelouze's
Heintz's
>>
61°
62°
>>
60-62°
62°
>>
>>
>>
2)
وو
62.3°
64-65°
66°
61°
A stearin prepared by Redtenbacher, according to Lecanu's method,
still contained olein, inasmuch as it yielded sebacic acid by dry dis-
tillation, and an acid melting at 65° by saponification. From Brin-
donia tallow, according to Bouis and Pimentel, pure tristearin may be
separated by recrystallisation, yielding by saponification an acid having
the melting point of stearic acid.
Properties. White, pearly, shining nodules, with very fine needles
(Bouis & Pimentel). Small pearly laminæ, resembling spermaceti or
stearic acid (Lecanu). Inodorous; tasteless; neutral. Volatile
without decomposition in a vacuum (Chevreul). A non-conductor of
electricity (Rousseau, J. Pharm. 9, 587).
The stearin of the natural fats, as well as that artificially prepared,
exhibits two (or three) different melting points, since when heated it
first becomes fluid and transparent, afterwards, when further heated,
again solid and opaque, and lastly, a second time fluid (Heintz, Duffy,
Kopp). It expands when heated, but on first melting undergoes a
contraction of about 24 per cent.; near its second melting point it
again expands, and at the moment of melting increases about 5 p. c. in
volume (Kopp).The first melting point of tristearin is 55°, the
second 71.6°. Tallow-stearin melts first at 51-52°, and the second
time at 62°; at 58° it is quite opaque (Heintz). With purer or less
pure tallow-stearin, somewhat different temperatures are observed.
This phenomenon is not produced by the splitting up of tristearin
i nto distearin and free acid, inasmuch as alcohol of 56° takes up no
120
CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS C6H6.
stearic acid therefrom (Heintz). According to Duffy, it is to be ex-
plained by the hypothesis of three modifications of stearin.
a.
First modification. Produced when stearin melting at 69.7° is
heated to 73-7° or higher, and then cooled, when it solidifies only at
51.7°. It is solid below 52°, but melts at that temperature, passing
into the second modification. Shining nodules of sp. gr. 0.9867 at 15º,
0·9600 at 51·5° (Duffy), 0·987 at 10° (II. Kopp).
b. Second modification. Produced by heating stearin of the first
modification to 52° or a few degrees higher for some time, until the
fused mass has again become solid. Lamellar, melting at 64.2°.
Sp. gr. 1.0101 at 15° (Duffy).
C. Third modification. Forms the crystals of stearin which sepa-
rate from ether. It is also formed when stearin is heated to 65° or
66°, after which it solidifies slowly at 62-63° to an opaque, friable,
highly crystalline mass, and melts again only at 69.7°. Sp. gr. at
15° = 1·0179; at 51·5° = 1·009; at 65·5°
1.009; at 65·5° = 0·9931; at 68.2° = 0·9746
(Duffy).
The sp. gr. of melted stearin at 65.5° is 0.9245 (Duffy). — Duffy's
second modification is not obtained from pure stearin, which, however,
contains the first and third modifications, even after several recrystal-
lisations; it is, therefore, not to be regarded as pure stearin (Heintz).
-Tallow-stearin, melting at 60°, possesses at 50°, in the first modifi-
cation, a volume = 1·031, and after passing into the second modifica-
tion a volume = 1·008, the volume at 0° being = 1; its volume in-
creases to 1.076 at the melting-point, and on melting to 1·127 (H.
Kopp).
Melted stearin solidifies on cooling to a very indistinctly crystalline
mass (Heintz), to a blistered mass, which exhibits transparent and
dead-white portions (Bouis & Pimentel). The temperature of melted
stearin falls several degrees below the solidifying point before the mass
becomes solid, but rises again during solidification to 44° (Chevreul),
54° (Lecanu); it forms a semi-transparent mass, having an even
surface, the central point of which ultimately solidifies in radiated
crystals (Chevrcul).
114 C .......
110 H
12 O
Chevreul. Lecanu. Liebig & Pelouze.
77.7
11.8
10.5
100.0
....
....
....
....
76.91.. 74.52 to 76-09
12.39 12:39,,
10.70
100.00
12.32
684
110
76.85
....
12.36
96
10.79
...
CH503,3C363503
890
100.00
***
Arzbacher.
a.
Duffy.
b.
Heintz.
Berthelot.
C.
a.
b.
C
H
O
76.51
12.28
11.21
....
77.12
76·32 .... 76·87 ..
76.74
76.50
75.8
...
....
12.30
10.58
12.32
11.36
12.20
10.93
12.42
10.84
....
12.41
11.09
12.4
11.8
....
....
100.00 100.00
A
100.00 100.00
100.00
100.00
100.0
....
Berthelot analysed artificially prepared tristearin. The stearin of beef-suet
contains, according to Arzbächer, 78-74 p. c. C; but Heintz (b) and Duffy (c) found it
to have the same composition as that from mutton suet. Duffy examined stearin melt-
ing (a) at 62·5° and (b) at 69-7°. The formula of tristearin was deduced by Berthelot
from the combining proportions of glycerin with acids (ix, 491; xvi, 351), Duffy
TRISTEARIN.
121
having previously shown that in the formation of 1 at. of stearic acid from stearin
2 at. of carbon are eliminated. Berthelot's formula alone (none of those previously
proposed for tallow-fat, vii. 235) explains how, in the saponification of stearin, the
under-mentioned amounts of glycerin and acid can be produced.
Decompositions. 1. Stearin when submitted to dry distillation boils
without becoming much coloured, partly volatilising unaltered, and
being partly decomposed, with formation of carbonic acid, gaseous and
liquid hydrocarbons, acrolein (ix, 365), acetic acid, stearic acid, water,
and carbon, which remains behind. Chevreul found also sebacic acid,
though only in the case of stearin containing olein. The hydrocarbons
boil between 190° and 245°, and are polymeric with olefiant gas (Ger-
hardt, Rev. scient. 19, 11). Bussy and Lecanu obtained from tallow-fat
the same products as from drying fat (xvi, 308), but with a much
larger proportion of solid fatty acids; even on rapid distillation, the
distillate solidified, almost up to the end of the process.
See
also Dupuy (J. Chim. méd. 1, 378; Ann. Chim. Phys. 29, 319), and
Lecanu (J. Chim. méd. 1, 458).—2. Pure stearin does not undergo
alteration in the air, and in an impure state probably turns rancid only
when it contains olein or drying fat, and less quickly than those sub-
stances (Chevreul). Hog's lard spread upon the sides of a vessel filled
with oxygen, and left to stand for three years, without exposure to
sunlight, absorbs the greater part of the oxygen, and does not form
carbonic acid, or only a very small quantity. It appears white, smells
rancid and sour, and gives up to water caproic or similar acids, oleic
acid, a non-volatile acid soluble in water, and yellow colouring matter.
The portion insoluble in water contains free oleic acid, margaric, and
stearic acids, yellow colouring matter, and unchanged fats (Chevreul,
Recherches, 453). — 3. Stearin burns with a more luminous flame than
drying- or oil-fat. 4. It is not altered by digestion with 100 parts of
nitric acid of sp. gr. 1.28 in the cold; when boiled therewith for an
hour it evolves a little nitric oxide. By repeatedly distilling and
pouring back the distillate till the residue dissolves therein, and after-
wards evaporating the solution, succinic acid and a yellow acid oil
having a bitter and harsh taste, are obtained (Chevreul). — 5. Bromine
and chlorine readily act upon stearin, forming products more fusible
than stearin, heavier than water, and having, according to Lefort, the
formulæ C76C14H6608 and C76Br4H6O8 (Lefort, Compt. rend. 37, 28).
Iodine does not act upon stearin (Lefort). 6. Hydrochloric acid pro-
duces from beef-suet oleic acid and a little stearic acid, leaving the rest
unaltered (Braconnot).-7. When melted stearin is mixed with half
its weight of oil of vitriol, and the reddish compound formed is imme-
diately washed with a large quantity of boiling water, stearic acid and
oleic acid are produced (Braconnot). Stearin with 10 parts of oil of
vitriol becomes immediately yellow, and after 24 hours, of a darker
colour, which it imparts to the oil of vitriol; it softens and evolves
sulphurous acid, and when heated to 100° after standing for eight days,
it dissolves to a roseate, transparent, thickish liquid, with liberation of
sulphurous acid. Above 100° it carbonises and froths up, from evolu-
tion of sulphurous acid (Chevreul). A mixture of hog's lard and an
equal quantity of oil of vitriol, heated to 100° for a few minutes, and
diluted with water after eight days, yields glycerin-sulphuric or sul-
phoglyceric acid (ix, 491) (Chevreul). Stearin behaves towards oil
of vitriol and sugar-water in the same manner as stearic acid
(Benecke).
122
CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS CH³6.
8. By the saponification of stearin, which is effected with greater
difficulty than that of olein (p. 87), 95.5 p. c. of stearic acid and 10-22
p. c. of glycerin are produced (Heintz),
C114H110012 + 6HQ CH8O6 + 3C36H360¹;
(by calculation 10:34 p. c. glycerin, and 95.73 p. c. stearic acid). (See vii, 235).
Duffy obtained from tallow-stearin, 95.59 to 95.76 p. c. (Bouis &
Pimentel); from Brindonia-stearin, 95.72 p. c. of stearic acid. Stearin
resists the action of hydrate of lime at 100° for some ininutes (Ber-
thelot). When heated in a water-bath for four hours with oxide of
lead and absolute alcohol it does not form lead-plaster (Duffy). Stearin,
saponified with small quantities of aqueous alkali, yields neither mono-
stearin nor distearin on decomposition (Bouis). If alcoholic potash be
added to an ethereal solution of stearin till a precipitate is produced,
and the liquid be heated, the precipitate disappears. The solution
then contains stearic ether and stearate of potash, and is decomposed
by acids, a mixture of stearic ether, stearic acid, and tristearin being
precipitated. The ether is always formed when the alcoholic potash
employed is not sufficient to take up the whole of the stearic acid, and
the mixture is allowed to react for a minute or two (Bouis). –
9. Stearin is apparently not altered by boiling with alcoholic ammonia
(Duffy). — 10. It forms stearate of ethyl when boiled with absolute
alcohol and 3 at., but not with 6 at., of sodium. With fusel-oil it
yields stearate of amyl (Duffy). 11. Stearin is not decomposed by
heating to 100° for 106 hours with alcoholic acetic acid (Berthelot).
12. Mixed with pancreatic juice, it yields an emulsion, in which the
whole of the stearin is converted into acid and glycerin on standing
for a day or two at a temperature of 30° or 40° (Bernard, Berthelot).
Stearin is not perceptibly soluble in alcohol of 36° B., nor even in
alcohol of 97 p.c., in the cold; it dissolves abundantly in hot alcohol,
and separates in flocks on cooling (Lecanu). 100 parts of boiling
alcohol of sp. gr. 0.795 dissolve 15.04 to 16.07 parts of Chevreul's
tallow-fat from mutton suet; 15 48 parts of that from beef suet; 18.25
from hog's lard; and 36 from goose-fat. 100 parts of boiling alcohol
of sp. gr. 0·805 dissolve 6·63 parts of tallow-fat; 100 parts of sp. gr.
0·822 dissolve 145 of the tallow-fat of butter, which is deposited
almost entirely on cooling (Chevreul). Stearin precipitated from an
alcoholic solution retains alcohol even after prolonged fusion (Saussure).
2 2 5
Stearin dissolves very freely in boiling ether which retains th on
cooling (Lecanu). It dissolves in hot acetone more freely than in cold,
and is precipitated on cooling, or by the addition of water (Chenevix).
It is easily soluble in volatile oils, and mixes with melted camphor and
with drying and oil-fut. A solution of 1 part of stearin in 160 parts
of almond oil deposits white flocks of stearin when mixed with 170
parts of ether; it is therefore not rendered more soluble in ether by
admixture with a fatty oil (Lecanu).
Stearochlorhydrin.
C42H4C106 CH6CIO³, C36H9503.
BERTHELOT. N. Ann. Chim. Phys. 41, 304.
BENZOSTEARIC ANHYDRIDE.
123
When a mixture of stearic acid and glycerin, heated to 100°, is
saturated with hydrochloric acid gas, maintained at that temperature
for some hours, and afterwards left to stand for several days or weeks
at ordinary temperatures, a compound of the two acids with glycerin
is formed, with elimination of water:
C36H360 + CH³О6 + HCI C42H4C106 + 4HO.
On neutralising with soda, the new body separates in the form of an
oily layer. It is crystallisable, and after repeated solution in ether
melts at 28°.
Berthelot.
42 C
252·0
66.93
65.0
41 H
Cl
60
41.0
10.89
11.9
35.5
9.43
11.1
48.0
12.75
12.0
CHCIO³,C36H35()3
376.5
100.00
100.0
•
Stearate of Amyl.
C46H4604 C10H110, C36H3503.
=
DUFFY. Chem Soc. Qu. J. 5, 197; J. pr. Chem. 58, 363.
HANHART. Compt. rend. 47, 230;
1858, p. 301.
Stearinmylester.
J. pr. Chem. 77, 5; Kopp's Jahresb.
Obtained by heating stearic acid with amyl-alcohol to 200° in a
sealed tube for a day. The uncombined acid is removed as in the pre-
paration of palmitin (xvi. 353), and the uncombined amyl-alcohol by
treatment with alcohol, which dissolves only a little of the ether
(Hanhart).— Stearate of amyl is also formed by boiling tristearin with
à solution of sodium in amyl-alcohol (Duffy).
Neutral, transparent, soft, and viscous mass, melting at 25.5°
(Duffy), 25° (Hanhart). It is decomposed by alcoholic, but not by
aqueous potash. Dissolves (slightly according to Hanhart) in alcohol,
the solution solidifying to a jelly. The ethereal solution also does
not yield crystals (Duffy).
Benzostearic Anhydride.
C¹50H4006 = C¹¹H5O³,С'³H³50³.
CHIOZZA. Ann. Pharm. 91, 104; J. pr. Chem. 64, 33; Pharm. Centr..
1854, 794.
Benzoyl-stearat.
A mixture of stearate of potash and chloride of benzoyl is heated
in a water-bath till the smell of the latter disappears, and the product
is extracted with ether.
Shining lamine, melting at 70°.
124
CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS C35H36.
Chiozza.
50 C
40 H
60
C¹H503,C36H3503
300
77.32
77.1
40
10.31
10.3
48
12:37
12.6
388
100.00
100.0
......
Chiozza gives for this compound the forniula of benzomargaric anhydride, but
designates it by the above name.
Stearate of Orcin.
C50H4206 = C¹4H70³, C¹³6H3503.
BERTHELOT. N. Ann. Chim. Phys. 56, 74; Lieb. Kopp. Jahresber. 1855,
677.
Orcine stéarique.
When orciu (xiv. 353) is heated with stearic acid to 200° in a
sealed tube for some hours, a mixture is obtained from which water
extracts the uncombined orcin. On separating the excess of stearic
acid from the residue by means of ether and hydrate of lime, according
to xv. 353, the stearate of orcin remains dissolved in the ether, and is
purified by evaporation and solution in bisulphide of carbon.
Slightly coloured, tasteless, neutral wax, which, when heated,
evolves an odour of orcin and stearic acid, and volatilises. - Combus-
tible. Assumes a red colour with ammonia. - Heated to 100° for some
days with moist hydrate of lime, it yields stearate of lime and a sub-
stance soluble in water and alcohol; the latter body becomes coloured
with ammonia, like orcin, but does not form crystals.
Stearate of orcin is insoluble in water, but easily soluble in ether
and bisulphide of carbon.
Stearate of Capryl.
C525204 = C¹¹6170,C6H3503.
IIANHART. Compt. rend. 47, 230; J. pr. Chem. 77, 5.
Stearincaprylester.
Obtained from stearic acid and capryl-alcohol in the same manner
as stearate of amyl. Melts at-4.5°.
4.5°. Colourless, inodorous, taste-
less, and neutral.
Stearate of Opianyl.
92H78012 C20H806,2C36H3503.
=
BERTHELOT. N. Ann. Chim. Phys. 56, 75.
Meconine stéarique.
Formed by heating opianyl (meconin) with stearic acid to 200° for
BISTEARATE OF PINITYL.
125
several hours; boiling the product with water, which takes up uncom-
bined opianyl; and removing the excess of stearic acid by means of
lime and ether, as with palmitin (xvi. 353).
Neutral, white, solid mass, which melts easily and solidifies very
slowly.
Berthelot.
92 C
78 H
552
76.03
75.3
78
10.74
11.2
12 O
96
13-23
13.5
C20H8O6,2C36H3503
726
100'00
100.0
Stearate of Camphyl.
C58H5204 = C20H170,C36H3503.
BERTHELOT. N. Ann. Chim. Phys. 56, 89; Chimie organ. 1, 151.
Camphol stéarique. Stearinsaures Borneol. Stearinbornester.
Obtained by heating stearic acid with borneol (xiv. 332) to 200° for
eight or ten hours in a sealed tube; water is then eliminated and a
mass is formed from which the uncombined stearic acid is removed by
cautious and rapid treatment with ether and hydrate of lime, and the
free borneol by heating the evaporated ethereal solution to 150° in an
air-bath for half a day or longer.
Thick, colourless and inodorous oil, which solidifies to a crystalline
mass after some days or months. Neutral when freshly prepared.
Volatile (without decomposition?). Decomposed by alkalis into stearic
acid and borneol. — Dissolves slightly in cold, and easily in boiling
alcohol and in ether.
Berthelot.
56 C
52 H
4 O
C20H¹70,C36H3503
mean.
336
80.00
79.8
52
12.38
12.5
32
7.62
7.7
4.20
100.00
100.0
BERTHELOT.
Bistearate of Pinityl.
C8H80014C12H1008,2C36H³5(³.
Compt. rend. 41, 454; Chim. organ. 216; Lieb. Kopp.
Jahresber. 1855, 677.
Pinite monostéarique. Bistearinpinitester.
Pinite is heated with stearic acid to 200-250° in a sealed tube for
some hours, and the product is purified as in the case of palmitin (xvi,
353).
Solid, white, neutral mass, resembling stearin. When decomposed
with hydrate of lime, it yields 21 p. c. of pinite (cale. 23 p. c. CIT2010).
126
CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS C36H36.
BERTHELOT.
Quadristearate of Pinityl.
C156H152022 C12H12010,4C36H3503.
Chim. organ. 2, 216.
Pinite distéarique.
Quadristearinpinitester.
Obtained by heating bistearate of pinityl with stearic acid to 220°.
Solid waxy mass, possessing externally all the characters of stearin.
Neutral.
BERTHELOT.
Bistearate of Quercityl.
C84II80014C12H1008,2C36H350³.
Chim. organ. 2, 219.
Quercile stéarique.
Bistearinquercitester.
Obtained by heating quercite with stearic acid to 200° for some
hours in a sealed tube. Solid white mass, resembling stearin.
Soluble in ether, but insoluble in water. Yields quercite and stearic
acid by decomposition with hydrate of baryta.
Bistearoglucose.
C84H78014 C12H806,2CH3503.
BERTHELOT. N. Ann. Chim. Phys. 60, 95; Chim. organ. 2, 289.
Glucose stéarique. A monosaccharide of the 2nd class. See xv, 318.
A mixture of stearin and anhydrous glucose is heated to 120° for
fifty or sixty hours, and the product is purified according to xvi, 353.
Cane-sugar and trehalose (xv, 299) also yield the same compound;
when trehalose is employed the mixture may be heated to 180°. Small
quantities are obtained likewise from stearin and starch at 180°, and
from steariu and woody fibre at 200°.
Microscopic, fine granules, or white fusible mass resembling stearin.
Neutral.
Berthelot.
84 C
78 H
504
72.62
72.4
78
11.24
11.0
14 O
112
16.14
16.6
...
CHSO6,2C36H 35 (3
694
100.00
100.0
...
Assumes with oil of vitriol a reddish colour, quickly changing to
violet and black.-Reduces potassio-cupric tartrate-Decomposed by
treatment with warm alcoholic hydrochloric acid, with formation of
glucose, humus-substances, and stearate of ethyl.
SEXSTEARATE OF MANNITYL.
127
Bistearoglucose is insoluble in water, but forms an emulsion when
shaken therewith. It dissolves in absolute alcohol and in ether.
Quadristearate of Mannityl.
C156H152022 = C12H12O10,4C36Н35(³.
BERTHELOT. N. Ann. Chim. Phys. 47, 324; Chim. organ. 2, 191; Lieb.
Kopp. Jahresber. 1856, 659.
Mannite distéarique. - Quadristearinmanitanester (see xvi, 362).
Mannite, or mannitan, is heated with stearic acid to 200° or 250°
for 15 or 20 hours, and the product is purified according to xvi, 353.
Microscopic, white crystals, or solid, white, fusible mass, resembling
stearin. Neutral.
Heated on platinum foil it gives off vapours, having at last an odour
of caramel, then carbonises and burns.
Decomposed by baryta and oxide of lead at 100°, and in a few
hours by water at 240°. - It is not altered by heating for 8 or 10 hours
with mannite. In the decomposition with baryta 13.2 p. c. of mannitan
is obtained (by calc. 13 p. c. C¹²H¹²O¹º).
Berthelot.
156 C.......
152 H
22 O......
C12H12O10,4C36H3503
mean.
936
74.05
73.93
152
12.03
12.03
176
13.92
14.04
1264
100.00
100.00
Sexstearate of Mannityl.
C228 H216022 C12H*O*, 6C38 H]3503.
Berthelot. N. Ann. Chim. Phys. 47, 324; Chim. organ. 2, 192; Lieb.
Kopp. Jahresber. 1856, 659.
Mannite tristéarique. Hexastearinmannitanester (xv, 362).
Quadristearate of mannityl is heated with a large excess of stearic.
acid to 200-250° for 20 or 30 hours, and the neutral mass thus
obtained is separated, and again treated in the same way with an
excess of stearic acid. Neutral mass, resembling tristearin (p. 119).
228 C
216 H
22 O
C12H6O¹,6C36353
Berthelot.
1368
77.73
77.9
216
12.27
12.6
....
176
10.00
9.5
1760
100.00
100.0
....
128
CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS C6H33.
Bistearate of Dulcityl.
C4H80014C12H1008,2C6H3503.
BERTHELOT. Compt. rend. 41, 454; Chim. organ. 2, 210; Lieb.
Kopp. Jahresber. 1855, 676.
Dulcite monostearique.
Bistearindulcitanester (see xv, 386).
Obtained by heating stearic acid with dulcite to 200°, and purifying
the product according to xvi, 353.
White, solid, crystallisable mass, resembling stearin.- Very slowly
decomposed by hydrate of lime at 100°, yielding 25.4 p. c. of dulcitan,
with an admixture of dulcite (calc. 23'6 p. c. C¹¹2010).
Quadristearate of Dulcityl.
Clō6148018 = C¹²H³06,4C36H³O³.
BERTHELOT. Compt. rend. 41, 454; Chim. organ. 2, 211; Kopp's Jahresber.
1858, 677.
Dulcite distéarique. See xvi, 386.
Obtained as a neutral mass by heating dulcite to 200° with a large
excess of stearic acid. It is purified in the same manner as palmitin
(xvi, 353), which it resembles.
Stearate of Cetyl.
C68680 = C321330, C36H35()³.
Berthelot. N. Ann. Chim. Phys. 56, 70.
Elhal stéarique.
A mixture of 1 part of ethal with 4 or 5 parts of stearic acid is
heated to 200° in a sealed tube, for 8 or 10 hours. The product is
mixed first with a little ether and then with hydrate of lime, which
takes up the uncombined stearic acid, and the whole is heated to 100°
for some minutes, and afterwards boiled with ether, when the ethal and
stearate of cetyl are dissolved, and remain behind on evaporating the
solution. From the mixture thus obtained, the free ethal is removed
by boiling five or six times with 6 to 10 parts of alcohol, and the undis-
solved cetyl-compound is then allowed to crystallise from ether.
Broad shining lamina, resembling spermaceti, melting at 55° to 60°,
and cooling to a crystalline solid. Volatilises with formation of a little
free acid.
Neutral.
68 C
68 II
40
C2H30,CII508
Berthelot.
408
80.31
80.0
68
13·38
13.6
32
6.31
6.4
508
100.00
100·0
AR
STEARONE.
129
Stearate of cetyl burns on platinum foil with a white flame. -- It is
decomposed by hydrate of lime, at 100°, only after 8 or 10 days.
Nearly insoluble in boiling alcohol. Dissolves slightly in cold, and
freely in boiling ether.
Stearone.
C70H7002C36H3602, C3434.
=
Bussr. Ann. Chim. Phys. 53, 410; J. Pharm. 19, 642; Ann. Pharm.
9, 269; J. pr. Chem. 1, 179.
REDTENBACHER. Ann. Pharm. 35, 57.
VARRENTRAPP. Ann. Pharm. 35, 80.
ROWNEY. Chem. Soc. Qu. J. 6, 97; abstr. Ann. Pharm. 88, 285; J.
pr. Chem. 59, 493; N. Ann. Chim. Phys. 39, 490.
HEINTZ. Pogg. 94, 272; 96, 65.
Margarone. Stearene. Discovered by Bussy.
Bussy distinguished stearone and margarone, the former from stearic acid, the
latter from margaric acid, melting at 56°, obtained by the distillation of hog's lard.
His margarone may, therefore, be regarded as a mixture of stearone and palmitone
(xvi, 382). Redtenbacher, supposing that stearic acid is converted by distillation
into margaric acid, described as margarone, stearone obtained from distilled, from
commercial, and from pure stearic acid, and considered the existence of stearone as
impossible. Varrentrapp's margarone was obtained from a mixture of fatty acids
melting at 55-56° (Varrentrapp's margaric acid, xvi, 351), and is doubtless, like
Bussy's, to be regarded as a mixture of palmitone and stearone.
Formation. By the dry distillation of stearic acid in the free state,
or more abundantly, in combination with lime or oxide of lead.
Preparation.—1. Stearate of lime, or a mixture of melted stearic
acid and hydrate of lime, is subjected to dry distillation, and the solid
distillate is boiled for some time with water. The residue is finely
powdered, heated with ether to boiling, and after cooling, collected on
a filter and again treated with ether, when pure stearone remains undis-
solved (Heintz). Bussy purifies it by re-crystallisation from hot alcohol.
2. Stearate of lead is distilled in a current of super-heated steam, and
the nearly colourless distillate is purified as in the first method (II. L.
Buff).
Properties. Delicate, pearly, microscopic laminae, very strongly
electric. Melting-point 87.8° (Heintz), 86° (Bussy), 82° from pure,
77° from commercial or distilled stearic acid (Redtenbacher), 76°
(Varrentrapp; Rowney). Solidifies at 72° (Rowney). Bussy's mar-
garone distils partially undecomposed,
Bussy.
a.
b.
70 C ......
70 H
420
83.00
83.22
81.81
70
13.84
13.77
13.50
20
C70H7002
16
3.16
3.01
4.69
....
506
100'00
100.00
100·00
VOL. XVII,
K
130 CONJUGATED COMPOUNDS OF THE PRIMARY NUCLEUS C36H36.
Heintz.
Redtenbacher.
Varrentrapp.
Rowney.
a.
b.
C
82.59
81.18
82.12
82.98
82.91
H
0
13.81
13.79
13.74
13.91
13.92
3.60
5.03
4·14
3.11
3.17
100·00
100.00
100.00
100.00
100.00
a is Bussy's stearone, b his margarone. Heintz analysed stearone from stearic
acid (a), and from stearate of lime (b). The formulæ proposed for stearone have
varied with that of stearic acid. Rowney gave the formula C28H2O; Heintz, the
one above given.
Decompositions. 1. Margarone burns with a bright smokeless
flame (Bussy). — 2. Melted stearone is converted by bromine into bromo-
stearone, with evolution of hydrobromic acid (Heintz). In other ex-
periments, Heintz obtained, by the action of a great excess of bromine
at high temperatures, only a little bromostearone, but a large quantity
of an easily fusible product, readily soluble in ether. Rowney
obtained, by the action of bromine on his stearene (melting at 72°),
tufts of feathery crystals, melting at 43-45°, and containing, on the
average, 59.86 p. c. C., 9.76 H., and 27.93 Br., corresponding to the
formula C28 BrH2O. Iodine is without action on stearone (Rowney).
-3. Chlorine forms with margarone, at a gentle heat, a colourless,
transparent, viscid liquid (Bussy).-4. Stearone becomes coloured
with oil of vitriol, and carbonises, with evolution of sulphurous acid
(Bussy. Rowney).-5. Stearone is not acted upon by hot nitric acid,
but is decomposed by nitro-sulphuric acid, with formation of an acid
volatile oil (Rowney). - 6. Potassium acts upon margarone, evolving a
little combustible gas (Bussy).—7. Margarone, distilled with quick
lime, yields carbonate of lime and a distillate melting at 60° (Bussy).-
8. Margarone is not decomposed by a boiling strong solution of caustic
potash (Bussy).
Stearone dissolves very slightly in boiling alcohol, and is deposited
almost entirely on cooling (Heintz). Bussy's margarone, melting at
77°, dissolves in 50 parts of boiling alcohol of 36°. Stearone is nearly
insoluble in cold, and very difficultly soluble in boiling ether (Heintz).
Margarone dissolves in 5 parts of boiling ether, acetate of ethyl, or oil of
turpentine (Bussy).
Bromostearone.
C70Br²H680² = C¹³°H³O²,C¾Br²H³² ?
HEINTZ. Pogg. 96, 75.
When an excess of bromine is added to melted stearone, a red oil
separates, which solidifies when shaken with water. This is to be
washed, first with water containing ammonia, and afterwards with cold
alcohol and re-crystallised from ether till the melting-point rises to 72°.
It dissolves with moderate facility in cold ether.
•
RICINOLEIC ACID.
131
Lamina.
Heintz.
70 C..........
420
63.26
63.03
曲​.
2 Br
160
24.09
24-38
68 H
68
10.24
10.35
20
16
2.41
2.24
C70B2H6O2
664
100.00
100'00
****
Stearic Anhydride.
C72H7006 C36H3503, C36H3603.
CHIOZZA. Ann. Pharm. 91, 104; J. pr. Chem. 64, 33; Pharm. Centr.
1854, 794.
Anhydrous stearic acid. Wasserfreie Stearinsäure.
Obtained in the same manner as benzoic anhydride, but difficult to
free from adhering stearic acid.
Chiozza.
72 C
4.32
78.54
77.7
70 H
70
12.72
12.5
60
48
8.74
9.8
C72H7006
550
100.00
100·0
Chiozza calls this body stearic anhydride, but assigns to it the formula of
margaric anhydride, C68H66O6.
Oxygen-nucleus C6H3402.
Ricinoleic Acid.
C36H9406 = C6H³¹0²,0¹.
BUSSY & LECANU. J. Pharm. 13, 70; Mag. Pharm. 18, 47; Berz.
Jahrb. 29, 1, 256.
SAALMÜLLER. Ann. Pharm. 64, 108.
SVANBERG & KOLMODIN. J. pr. Chem. 45, 431.
BOUIS. See xiii, 183. Complete: N. Ann. Chim. Phys. 44, 103, and
48, 99.
PETERSEN. Ann. Pharm. 118, 69.
Sources. In castor oil (see below). In the oil of Jatropha Curcas
(Bouis).
Preparation. Castor oil is saponified with potash or soda-ley, and
the soap is salted out and decomposed by hydrochloric acid. The oily
mixture of ricinoleic acid with a small quantity of solid fatty acids is
then cooled to 10° or
12° with 3rd its volume of alcohol, when the
solid acids crystallise out, and are removed. After driving off the alcohol,
the ricinoleic acid is digested with excess of oxide of lead, and the lead-
salt formed is dissolved in ether, and decomposed with hydrochloric
K 2
132
PRIMARY NUCLEUS CH³; OXYGEN-NUCLEUS C6H³40².
acid and water. The ricinoleic acid, which is left on evaporating the
ethereal layer, is purified by dissolving it in aqueous ammonia, precipi-
tating with chloride of barium, and crystallising the baryta-salt from
alcohol, as with oleic acid (p. 64). From the baryta-salt the acid is
obtained by decomposition with aqueous hydrochloric acid (Saalmüller,
Svanberg, and Kolmodin). In the decomposition of the baryta-salt the
presence of alcohol is to be avoided, as its subsequent removal is
attended with difficulty (Saalmüller).
Properties. Pale wine-yellow oil, colourless in thin layers, of the
consistence of syrup. Sp. gr. 0.94 at 15°. Solidifies completely at
— 6° to -10°, to a granular mass. Inodorous. Has a very dis-
greeable, persistent, harsh taste. An alcoholic solution reddens litmus
(Saalmüller).
In vacuo over
oil of vitriol.
Saalmüller.
Bouis.
mean.
86 C .....
216
72.48
73.23
71.99
AS
31 H.....
31
11.41
11.59
11.51
6 0 ....
4.8
16.11
15.18
16.50
C36H3406
298
100.00
100.00
100.00
....
Bouis' acid was prepared from the amide. Saalmüller gives the formula
C'39H360º, which agrees with his analyses better than the above formula of Svanberg
and Kolmodin. Later analyses, however, as well as the decomposition-products of
the substance appear to support the formula with 36 at. C., which is now generally
adopted.
Decompositions. 1. Ricinoleic acid, subjected to distillation, yields
at first a limpid, and afterwards a thick and repulsive-smelling distillate,
free from sebacic acid (Saalmüller). 2. It does not absorb oxygen
from the air, nor even on long exposure to the gas, and does not form
carbonic acid (Saalmüller). The acid appears to undergo alteration in the air
(Svanberg & Kolmodin).—3. It absorbs a little sulphurous acid gas, with-
out becoming solid or otherwise altered (Saalmüller). See also the decom-
positious of castor oil.
4. By the dry distillation of ricinoleates of the alkalis, various
products are obtained, according as the neutral salt is distilled alone,
or with an excess of alkali. (Sec xiii, 183, 187, 189, and xiv, 494.)
a. By cautiously distilling the neutral soda-salt, until the residue
begins to froth up, a distillate of oenanthol (xii, 446) is obtained, the
residue containing the soda-salt of the same acid that is formed by
the dry distillation of castor-oil (see below). The soda-salt and the
glyceride of ricinoleic acid are, therefore, decomposed in the same
manner by distillation (Städeler). According to Bouis, the neutral
ricinoleates of the alkalis yield, by dry distillation, caprylic aldehyde
(xiii, 187), and a peculiar acid:
C363406 = C6H1602 + 20H180+ (Bouis).
The residue froths up only when more strongly heated, and yields a
brown fetid distillate, containing only a little cenanthol, and no other
aldehyde (Städeler).
b. A mixture of ricinoleate of potash or soda, with excess of hydrate
of potash or soda, froths up when heated, evolves an odour of mush-
rooms, and thickens; at about 250° it ceases frothing, and gives off a
RICINOLEIC ACID.
133
large quantity of hydrogen (no carbonic acid), and a volatile oil,
leaving a light spongy residue, which is inflammable while hot. By
further heating, this residue is also decomposed, with formation of
white vapours having a repulsive odour (Bouis). A mixture of castor-
oil and excess of hydrate of soda behaves in the same manner when
heated.
From the residues, acids separate a white mass which gives up
sebacic acid (xiv, 493) to hot water. The remainder consists of a
dark, viscid oil (amounting to half the volume of the oil when castor-
oil instead of ricinoleic acid is employed), which is saponifiable to a
white, hard soap, deposits crystals of palmitic acid in the cold, and
solidifies only partially with nitrous acid (Bouis). According to Bouis,
sebacic acid is produced more especially by very rapid, and to a less
extent by slow heating.
The volatile oil contains two constituents, one only of which com-
bines with bisulphites of the alkalis in the manner of an aldehyde
(Limpricht). According to Limpricht's earlier views, which were
adopted by Bouis, this aldehyde-like body is to be regarded as caprylic
aldehyde (xiii, 187); but according to the statements of Städeler, which
were confirmed by Dachauer & Petersen, and are now accepted by
Limpricht, it must be regarded as methyl-onanthol (xiv, 189). The
second body, which does not combine with bisulphites of the alkalis, is,
according to Bouis, Moschnin, Squire, Cahours, Limpricht, Malaguti,
and Dachauer (Ann. Pharm. 106, 269), caprylic alcohol (xiii, 183); but,
according to Railton, Wills, Städeler, and Petersen, it is oenanthylic
alcohol; according to E. T. Chapman (N. Chem. Soc. J., 3, 290), some-
times the one, sometimes the other alcohol is produced.
The alcohol is produced more especially, together with a salt of
sebacic acid, by heating rapidly, so that the alkali fuses; the aldehyde,
by heating slowly to 225° or 230°, in which case less sebacic acid is
formed (Bouis). These statements are not in accordance with the
results obtained by Malaguti and Limpricht (xiv, 494). The de-
composition may be represented by the following equations: a. when
methyl-œnanthol or capryl-aldehyde is formed:
C36H3406 + 4HO = C6H1602 + C20H1808 + 4H.
b. When caprylic alcohol is produced:
C36H3406 + 4H0 = C16H1802 + C20H18OS + 2H.
c. When oenanthylic alcohol is formed :
C36H3+06 + 4H0 C14H1602 + C20H¹808 + CH¹.
In this last reaction marsh-gas (or a secondary product) must be
formed, unless the oenanthylic alcohol results from the further decom-
position of the sebate (Städeler).
Ricinoleates. The alcoholic solution of the acid expels carbonic
acid from alkaline carbonates. The salts are all soluble in alcohol,
and some also in ether. They do not become oxidised on keeping
(Saalmüller).
Ricinoleate of Baryta. - Preparation (p. 132). On treating with
warm alcohol, a portion generally remains undissolved in the form of a
tough yellow mass (Saalmüller). — White laminæ, very soft to the
134
PRIMARY NUCLEUS C6H36; OXYGEN-NUCLEUS C6H³40².
touch, or crystalline crusts (Saalmüller). Melts at 100°, without loss of
weight, to a tenacious mass, which may be drawn out in threads like
boracic acid, and becomes translucent and brittle on cooling (Bouis).
Dissolves slightly in cold water, in 300 parts of cold alcohol of 95 p. c.,
and easily in hot alcohol, crystallising on cooling (Svanberg &
Kolmodin).
In vacuo, over oil of vitriol.
36 C
33 H
50
BaO
C36H3BaO6
Saalmüller
Svanberg &
mean.
Kolmodin.
216
59.10
59.81
58.69
33
9.03
9.38
8.96
40
10.94
10.54
11.57
........
76.5
20.93
20.27
20.78
365.5
100.00
100'00
100.00
Bouis found 20.45, Petersen 20·99 p. c. baryta.
Strontia-salt. Precipitated from the ammonia-salt by chloride of
strontium. Crystallises from alcohol in small white granules (Saal-
müller).
Saalmüller.
C'36H3305
SPO
289
84.75
41
52
15.25
14.6
....
341
100.00
Lime-salt.
C36H33Sr06
Obtained from the ammonia-salt by precipitation with
chloride of calcium. Crystallises from alcohol in small white scales,
which lose water when melted, even after long drying in a vacuum
over oil of vitriol. Melts at 80° to a pale-yellow transparent mass,
which is brittle and friable when cold (Saalmüller).
Saalmüller.
At 100°
mean.
36 C........
33 H
216
68.14
66.38
33
10.41
10.59
5 0.....
40
12.61
14:57
......
CaO
28
8.84
8.46
C36H33 CaO6
317
100.00
100'00
Saalmüller supposes the salt to contain 1 at. of water, the presence of which has
not, however, been demonstrated.
Magnesia-salt.
soluble in alcohol.
MgO. (Saalmüller).
Very fine needles, insoluble in water but easily
Contains, after drying over oil of vitriol, 5.69 p. c.
Petersen.
36 C........
216
69.90
70·08
33 H
33
10.68
10.53
5 0.
MgO.
CH*MgO®
40
12.95
13:34
20
6.47
6:05
309
100.00
100.00
Zinc-salt. Crystallises from alcohol in small white granules
(Saalmüller).
C36305
289
87.79
ZnO
40.2
12.21
11.85
C36H33ZnO6
329.2
100.00
RICINELAÏDIC ACID.
135
Lead-salt. The acid, when heated with excess of lead-oxide, loses
2.9 to 3.6 p. c. of water (1 at. = 3·02 p. c.), and forms a solid compound,
the ethereal solution of which, on evaporation over oil of vitriol, leaves
the lead-salt as a transparent crystalline mass. Melts at 100° to a
light brown viscid liquid, and solidifies to an easily pulverisable mass.
Dissolves very easily in ether (Saalmüller). Dissolves in cold, and not
much more freely in hot alcohol (Svanberg & Kolmodin). By precipitat-
ing ammoniacal ricinoleic acid with neutral acetate of lead, a curdy precipitate of
variable composition is obtained (Saalmüller).
At 100°, over oil of vitriol.
36 C.......
33 H
5 0....
Pbo.......
C36H33PbO6
Saalmüller.
mean.
216
53.87
54.58
33
8.23
8.61
40
9.97
9.69
112
27.93
27.12
401
100.00
100.00
....
Silver-salt. Nitrate of silver throws down from the ammonia-salt
a curdy precipitate, which, when treated with alcohol or ether, partially
dissolves, but for the most part blackens and remains undissolved
(Saalmüller). It softens at 100°, melts at higher temperatures to a
black mass, and burns with evolution of disagreeably smelling vapours.
Dissolves easily in hot alcohol, and slightly in cold alcohol and ether
(Bouis).
Saalmüller.
Bouis.
Over oil of vitriol.
mean.
36 C ....
33 H......
216
53.33
54.03
33
8.14
8.27
60
48
11.85
14.18
Ag
C36H33 AgO6
108
26.68
23.52
26.6
#
405
100.00
100.00
Saalmüller precipitates the salt from a strongly ammoniacal solution.
Ricinoleic acid dissolves in all proportions in alcohol and ether
(Saalmüller).
Ricinelaïdic Acid.
C36H3406 = C'Y6E3402, 04.
F. BOUDET. J. Chim. méd. 8, 646; J. Pharm. 18, 497; Ann. Chim.
Phys. 50, 414; Ann. Pharm. 4, 16.
L. PLAYFAIR. Phil. Mag. 29, 475; Mem. Chem. Soc. 3, 222; Ann.
Pharm. 60, 322; J. pr. Chem. 40, 173.
BOUIS. N. Ann. Chim. Phys. 44, 82.
Palminsäure.
Formation. Ricinoleic acid (the mixture of fatty acids obtained by
saponifying castor oil with caustic soda and decomposing the soap) is
mixed with nitric acid, and nitrous acid is passed into the mixture,
whereupon the oil solidifies. Purification is effected by washing with
hot water, crystallising repeatedly from alcohol, and pressing, till the
136 PRIMARY NUCLEUS C3H6; OXYGEN-NUCLEUS C36H340².
melting point becomes constant (Playfair).-2. Ricinelaïdin is saponi-
fied with caustic potash, and the soap is salted out, decomposed by
hydrochloric acid, and purified according to the first method (Boudet.
Playfair).
Properties. Tufts of white silky needles, melting at 50° (Boudet.
Bouis). When prepared according to the first method, it melts at 45-46';
according to the second, at 44.20 (Playfair). Solidifies at 48.5° (Bouis)
to a crystalline mass (Playfair). Reddens litmus strongly (Boudet).
Playfair.
Bouis.
mean.
36 C
34 II
60
216
72.18
73.75
71.53
72.59
34
11.41
11.85
11.50
11.50
48
16.11
14.40
16.97
15.91
C36113406
298
100'00
100'00
100.00
100.00
a was prepared according to 1; b by saponifying a and decomposing the soap.
Playfair gave for a the formula C3H3205; for b, C34H3306. — Isomeric with
ricinoleic acid (Gerhardt. Bouis).
Ricinclaïdic acid, subjected to rapid distillation, yields a buttery
distillate, containing a large quantity of undecomposed acid and the
same volatile oil which is produced by the dry distillation of castor oil:
towards the end of the distillation, a yellow empyreumatic oil passes
over, whilst a little charcoal remains behind (Boudet). When heated
with hydrate of soda, it yields the same products as ricinoleic acid
(Koch, Ann. Pharm. 119, 173; Kopp's Jahresber. 1861, 359).
Ricinelaïdic acid decomposes alkaline carbonates. The ammonia-salt
is not crystallisable (Boudet).
Potash-salt. Obtained by boiling the acid with a concentrated
aqueous solution of carbonate of potash, dissolving the soap which
separates on cooling, in alcohol, filtering from carbonate of potash,
and evaporating (Playfair).
Soda-salt. Formed by neutralising the acid with carbonate of
soda. The alcoholic solution forms a jelly on cooling, A dilute
aqueous solution deposits a bi-acid salt, which crystallises from alcohol
in needles, and reddens litmus (Boudet).
Barytu-salt. Obtained by precipitating the potash-salt with
chloride of barium, and washing the precipitate with water and
alcohol. White powder, unctuous to the touch (Playfair).
36 C
33 II
50
BaO
C35 H33 BaOG
Playfair.
216
59.10
58.04
33
9.03
9.09
40
10.94
11.42
76.5
20.93
21.45
365.5
100.00
100.00
The lime-salt is soluble in boiling alcohol. The magnesia-salt,
obtained by dissolving magnesia in (alcoholic?) ricinelaïdic acid, has an
alkaline reaction, and crystallises from the easily formed solution in
warm alcohol in small lamina, which melt below 100° (Boudet).
CASTOR OIL.
137
Lead-salt. Oxide of lead forms with the acid a salt which is
soluble in boiling alcohol, and separates from a concentrated solution in
the form of a jelly, and from a dilute solution in needles (Boudet).
Neutral acetate of lead precipitates from the soda-salt a basic salt of
varying composition (Playfair).
Copper-salt. Obtained by double decomposition as a fine green
precipitate. It is less soluble in alcohol than the lime-salt, and separates
from the solution in flocks on cooling. The salt is decomposed by pro-
longed boiling with alcohol, with separation of oxide of copper
(Boudet).
Silver-salt. Light, white powder, soluble in ammonia but insoluble
in water, alcohol and ether (Playfair. Boudet).
36 C .......
33 H......
6 O......
Ag...
C6H33 AgO6
216
53.33
Playfair.
51.64 to 52.66
Bouis.
52.66
33
8.14
8.12
8.52
7.86
48
11.85
12:48
108
26.68
27.36
27.69
27.00
405
100.00
100.00
The acid dissolves easily in alcohol and in ether.
Appendix to Ricinoleic and Ricinelaïdic Acids.
Ricinusöl. Dünnes Palmöl.
buch viii, Phytochem. 24).
1, 241.)
1. Castor Oil.
From the seeds of Ricinus communis (Hand-
Concerning its preparation, see Planche (Bull. Pharm.
Transparent, colourless or greenish-yellow, viscid oil. Sp. gr. at
19° 0.96, constant in different samples (Bouis); 0.954 (Brandis);
0.9612 (Brisson); 0.9748 (Brandes & Reiche); 0.9699 at 12°, 0.9575 at
25°, 0·9081 at 94°, the sp. gr. of water at 15° being 1 (Saussure).
Sp. gr. after separation of the stearin, 0·9369 at 21° (Scharling). Has
a faint smell, and a mild, afterwards somewhat sharp taste. Acts as
a purgative. Without action on polarised light (Bouis & Silber-
mann). Does not solidify at 15° (Bouis). Solidifies at
18° to a
transparent yellow mass (Brandis). The oil obtained by expression,
but not that obtained by boiling, deposits stearin in the cold (Boutron-
Charlard, J. Pharm. 8, 392). See below. Dissolves in all proportions
in absolute alcohol (V. Rose, Bouis); in 13 parts of alcohol of 36° (Bouis).
Mixes with ether (Brande) and with chloride of ethyl (Pfaff).
-
2
S
Lefort.
Saussure.
Ure.
mean.
C
H
74.18
74.00
74.46
11.03
10.29
11:41
...
14.79
15.71
14.13
100.00
100.00
100.00
The formula, C6H5O³, proposed by Lefort, expresses the percentage composition,
but not the decompositions of the oil. Castor oil, according to Tuson, contains
small quantities of ricinino (p. 143),
The
138
PRIMARY NUCLEUS C36H36; OXYGEN-NUCLEUS C36H34()².
When exposed to the air, castor oil becomes thicker and dries up,
without turning opaque (Saussure, Bouis).
Dry distillation. Castor oil begins to boil about 265°, and yields a
distillate consisting at first chiefly of a more volatile, afterwards of a
less volatile, oil, without any great evolution of gas. After 3rd of
the oil has passed over, the evolution of gas becomes more abundant,
and the residue thickens without becoming coloured, and suddenly
swells up to a spongy, elastic, caoutchouc-like mass, which fills the
retort. 100 parts of the oil thus treated, yield 3 or 4 parts of a com-
bustible gas (free from carbonic acid), 33 or 34 parts of distillate, and
62 to 64 parts of spongy residue (Bussy & Lecanu).
The formation of the spongy mass (see below) may be prevented by
heating the oil very slowly from the beginning (Bouis). The distillate
consists of water, oenanthol (xii, 446) (Bussy), acetic, ricinic, and
ricinoleic (p. 131) acids (Bussy & Lecanu). It contains, besides
œnanthol, a little acrolein, oenanthylic acid (Bussy), and hydrocarbons,
the last more particularly when the spongy mass is not formed (Bouis).
When distilled with water, it yields oenanthol containing acrolein, from
which crystals [of hydrate of oenanthol (xii, 448)?] separate on cool-
ing to -18° (Bussy).
According to Stanek, the decomposition of castor oil takes place
by two stages: a. Formation of (acrolein and) oenanthol. Probably
thus:-
C36H3406 + 2HO 2014H1402 + 2C4H¹0².
Ricinoleic acid.
In this reaction aldehyde must be formed, from which Bussy and
Lecanu's acetic acid may have been produced. b. Formation of the
spongy residue.
C36H3406
=
C36H3104+2HO + H (Stanek).
Pyroricinic
acid.
This explanation appears to me to be incorrect (Kr).
The vapours produced by heating castor oil are inflammable, and
burn with a very bright flame. If the flame be extinguished, the same
spongy mass remains which is formed by dry distillation. See Jonas
(N. Br. Arch. 46, 168). Castor oil is decomposed by the action of
superheated steam at 160°, solid and liquid fatty acids being produced
(Scharling, J. pr. Chem. 50, 377).
By the action of moist chlorine and bromine, chlorinated and bro-
minated castor oil are formed. (See xvi, 316). Brominated castor oil is
colourless when freshly prepared, but turns brown on heating; it is a
very thick liquid of sp. gr. 1-258 at 13.5°, containing 350 p. c. of
bromine (C56H Br308, according to Lefort). Chlorinated castor oil is
light-yellow, viscid, of sp. gr. 1.071 at 17.5°, and contains 19.65 p. c.
of chlorine (C56H49C1³08) (Lefort, N. J. Pharm. 23, 349).
49
Castor oil gradually absorbs sulphurous acid gas on long exposure
thereto; the oil becomes thinner and after some time solidifies, from
the formation of ricinelaïdin (Boudet). Saalmüller and Bouis were
unable to obtain ricinelaïdin in this way; oil saturated with sulphurous
acid remained unchanged even after keeping for eight years (Bouis).
Over mercury, castor oil absorbs 10 or 12 times its volume of sulphu-
rous acid gas, which it gives up again completely to water (Saalmüller).
CASTOR OIL.
139
Castor oil dissolves in oil of vitriol, forming a yellow to yellowish-
brown solution, which on addition of sugar [or acetic acid (A. Vogel)]
and gentle warming, assumes a fine purple-violet colour, resembling
that produced by gallic acid under similar conditions (Neukomm, Ann.
Pharm. 116, 41; A. Vogel, N. Jahrb. Pharm. 3, 150). The oil is not
coloured by shaking with th of its volume of sulphuric acid of sp. gr.
1.635 or less (Calvert). Its solution in absolute alcohol is decom-
posed by hydrochloric acid gas, with formation of glycerin and the vinic.
ethers of the fatty acids (Rochleder, Ann. Pharm. 59, 260). See vii,
239.
Castor oil in contact with hyponitric acid, solidifies more slowly than
the (non-drying) fatty oils, but more quickly than rape oil, to a golden-
yellow mass of ricinelaïdin (Boudet). The conversion is effected even
byth or less of hyponitric acid; it is brought about also by mer-
curous nitrate (Boudet), but more slowly, being complete only after
some days (Davidson, Ed. N. Phil. J. 250; J. pr. Chem. 20, 235). After
solidification a slow and regular evolution of nitrogen takes place, conti-
nuing for a month when a quantity of hyponitric acid equal toth of the
volume of the oil has been employed, and yielding a volume of nitrogen
nearly equal to that of the oil (Boudet). When mixed with one-third
or half its volume of hyponitric acid, castor oil becomes hot, froths up,
and turns opaque and viscid (Boudet). The oil is not coloured by
agitation with th of its volume of nitric acid of sp. gr. 1·33 or less;
on the further addition of 10 volumes of caustic soda solution, (it
forms a ropy mass.
When shaken with th of its volume of nitro-
sulphuric acid (composed of equal volumes of sulphuric acid of sp. gr.
1·845 and nitric acid) it assumes a brown-red colour in two minutes
(Calvert, J. pr. Chem. 61, 354). When heated with dilute nitric
acid, it froths up strongly, and on continued distillation yields œnan-
thylic acid (xii, 451), whilst a thick fatty oil still containing oenan-
thylic acid, remains in the retort, together with nitric acid holding
suberic and oxalic acids in solution (Tilley, Ann. Pharm. 39, 160).
Besides these, azelaic acid is produced, but no sebacic acid (Arppe, Ann.
Pharm. 120, 288; 124, 98). When the oil is very slowly heated with
dilute nitric acid, a large quantity of hydrocyanic acid is given off, and,
on cooling the mixture before the formation of suberic acid takes place,
it deposits hard, fern-like crystals of an acid soluble in water and
alcohol. This body melts when heated, giving off acid vapours, and
forms a baryta-salt soluble in a large quantity of water, and a silver-
salt which explodes when heated. It contains, on an average, 20-92
p. c. C., 10.34 N., 4.39 H., and 64-35 O., corresponding to the formula
C¹4X H¹7020 (21·05 C., 10·52 N., 4·26 H., and 64·17 0.) (Bouis).
By the action of chloride of lime on castor oil, chloroform is obtained
(Chautard). The oil, heated with bichromate of potash and dilute sul-
phuric acid, yields oenanthylic acid and a neutral volatile oil having the
composition of valeric aldehyde (xi, 17) (Arzbächer, Ann. Pharm. 73,
200). When it is digested or heated with alcoholic ammonia, ricino-
lamide (p. 147) is produced (Boullay; Bouis).
Castor oil is easily saponified by heating with aqueous alkalis; it
yields 8 p. c. of glycerin and (on decomposing the soap) 94 p. c. of oily
fatty acids, the latter consisting of ricinoleic acid with a small quantity
of solid fatty acids (Bussy & Lecanu). See the decomposition with excess of
alkali, under Řicinoleic acid (p. 133).
Concerning the solid fatty acids of castor oil, varying statements have
140 PRIMARY NUCLEUS C6H36; OXYGEN-NUCLEUS C6H3402.
been made: a. According to Bussy & Lecanu, the oily mixture of
fatty acids deposits, at 15° to 18°, 4th at most of an acid melting at
130° (Bussy & Lecanu's margaritic acid), and afterwards, at 10° to 12°,
ricinic acid melting at 22°. Margaritic acid, after re-crystallising and
pressing, forms pearly laminæ containing 70-5 p. c. C., 10-9 H., and
18.6 0.; it distils partly undecomposed, is more difficultly soluble in
alcohol than margaric acid, and forms a magnesia-salt insoluble in
alcohol. Ricinic acid, which is obtained also by the distillation of
castor oil, is white and pearly; it solidifies in a crystalline mass after
fusion, and distils almost without decomposition. It contains 73.56
p. c. C., 9·86 H., and 16.58 O., and dissolves very easily in alcohol and
ether. The magnesia-salt prepared with one part of magnesia and
two parts of the acid, when dissolved in alcohol, turns reddened litmus
blue; it is not perceptibly soluble in water, but dissolves easily in
alcohol, and crystallises therefrom in white, shining needles. The
lead-salt, which has an alkaline reaction, is very easily soluble in
alcohol. This behaviour of the salts distinguishes ricinic acid from
other fatty acids (Bussy & Lecanu).-b. According to Saalmüller, the
solid acids are separated with difficulty by exposing crude ricinoleic
acid to a temperature of 10° or 12, but more easily and com-
pletely after the addition of 3rd of the volume of alcohol. The lamina
which separate exhibit the melting-point of margaric acid only when
they are contaminated with alkali. After purification they melted on
one occasion at 74°, solidifying again at 68° to 70°, and contained
76.85 p. c. C., 12.74 H., and 10-41 O., and might therefore be regarded
as stearic acid. On a second occasion they had, with the same melting-
point (74°), the composition of palmitic acid (mean: 74-66 p. c. C., 12.65
H., and 12.69 0.). "On a third occasion white granules and tables,
melting at 51° (after distillation at 54°), were obtained from the spon-
taneously formed deposit in castor oil, their composition, according to
analyses which were not concordant, being represented by the formula
C6H5905, and that of the potash- and silver-salts by CH57M205. Saal-
müller invariably found only one acid, not susceptible of further decom-
position (Ann. Pharm. 64, 108. — Sill. Am. J. [2] 8, 263; Kopp's
Jahresber. 1850, 403). c. Castor oil, when kept in large quantities,
deposits a solid fat, which, after repeated treatment with alcohol, melts
at 44°, and solidifies to a waxy mass. By saponifying this body, and
decomposing the soap, an acid is obtained which melts at 72°, and
cannot be decomposed by re-crystallisation from alcohol. The acid may
be obtained of the same melting-point by converting the expressed oil
into lead-salts and removing the portion soluble in ether. Its solution
in 50 parts of boiling alcohol solidifies almost completely at 12°. It
contains 74-05 p. c. C., 13·18 H., and 12.77 O.; in the silver-salt 52.39
p. c. C., 9.35 H., 29.40 Ag., and 8.86 0.; and has, therefore, with the
melting-point of stearic acid, the composition of palmitic acid; it is,
however, more volatile than stearic acid, and must be regarded as a
peculiar acid (Scharling, J. pr. Chem. 45, 434),
2. Oil of Jatropha Curcas (Handbuch viii [2], 24.)
9
Oleum Ricinum. Colourless oil of sp. gr. 0.91 at 19°. Inodorous,
and of mild taste. Solidifies to a buttery mass at 8°. Absorbs
oxygen slowly from the air. When heated it yields acrolein, sebacic
SPONGY RESIDUE FROM CASTOR OIL.
141
acid, and other products. When saturated with sulphurous acid gas,
and set aside for three months, it deposits crystalline nodules of an
acid, which, after crystallisation from alcohol, melts at 58° and has the
composition of isocetic acid (xvi, 365). The oil carbonises with oil of
vitriol at 110°. Hyponitric acid renders it pasty, but not quite solid.
Nitric acid evolves nitric oxide and hydrocyanic acid, sets free solid
fatty acids, and ultimately forms suberic acid. With alcoholic ammonia
the oil forms isocetamide (xvi, 365). It is nearly insoluble in alcohol.
-Saponifies slowly with caustic potash, and quickly with caustic soda,
forming a white hard soap, containing isocetic acid and a fluid oleic acid
of the formula C36H340°, which does not solidify at 10°, and forms
two lead-salts soluble in ether, C36H33Pb06, and 2C36H2305, (Pb0,HO)
(Bouis, Compt. rend. 39, 923; Pharm. Centr. 1854, 913; Chem. Gaz.
1854, 469). Since, according to Arnaudon & Ubaldini (Kopp's Jahresber.
1858, 536), the oil yields caprylic alcohol when heated with hydrate of
potash, the fluid oleic acid may doubtless be regarded as ricinoleic
acid.
3. Oil of the fruit of Jatropha glauca and J. glandulifera.-Yellow,
of sp. gr. 0.963; solidifying at 5° (Lepine).
4. Spongy Residue from the dry distillation of Castor Oil.
BUSSY & LECANU. J. Pharm. 13, 57.
STANEK. J. pr. Chem. 63, 138.
Bouis. N. Ann. Chim. Phys. 44, 80.
When the residue left in the distillation of castor oil (according to
p. 138), is freed from acrolein and residual oil, by means of alcohol
(Bussy & Lecanu), alcohol and ether (Stanek), or water and alcohol.
(Bouis), there remains an elastic, pale-yellow, inodorous and tasteless
mass, which is somewhat friable after drying (Bussy & Lecanu).
This mass dried at 100° contains on an average, 77.15 p. c. C.,
10.77 II., and 12.08 O., corresponding to the formula C42H3405 (by calc.
77.30 p. c. C., 10:42 H., and 12.28 0.), and from its behaviour with
caustic potash, is to be regarded as pyroricinate of acryl (Stanek). It
contains 73.2 p. c. C., 10.9 H., and 15.9 0., agreeing with the formula
C36H3206 (by calc. 72.97 p. c. C., 10.81 H., and 16.22 0.); it is saponifiable,
and forms a silver-salt soluble in ammonia, and a baryta-salt, C36H³¹BaOʻ,
containing 21 p. c. baryta, insoluble in water, alcohol, and ether (Bouis).
The spongy mass decomposes when heated, without softening [with
formation of acrolein (Stanek)], and with access of air burns slowly,
with a bright, slightly smoky flame. It is not perceptibly acted on
by nitric acid, oil of vitriol, or hydrochloric acid (Bussy & Lecanu).
By saponification with strong caustic potash it is resolved into pyro-
ricinic acid and a brown resin, evolving at the same time an odour of
aldehyde-resin. Stanek regards the body formed in this reaction, as a
compound of acrolein (CH3406 C6H3003, CH40²). It is not acted upon
C¹³¢H³°³,CH¹0²).
by dilute caustic potash (Bussy & Lecanu).
Insoluble in alcohol, ether, and volatile and fatty oils, even when
boiling (Bussy & Lecanu).
142
PRIMARY NUCLEUS C6H36; OXYGEN-NUCLEUS C36H³¹O².
5. Pyroricinic Acid.
STANEK. Wien. Akad. Ber. 12, 588; J. pr. Chem. 63, 138; Pharm. Centr.
1854, 613; Chem. Gaz. 1854, 381.
Aporicinic acid (Berzelius). Previously observed by Bussy and Lecanu.
Formation. (P. 138.)
Preparation. Castor oil is distilled in a retort over an open fire,
till the residue swells up, with evolution of gas; and the residue, after
cooling, is treated with alcohol and with ether and alcohol in succes-
sion, to remove substances soluble in those menstrua. The undissolved
portion, Stanek's pyroricinate of acryl (p. 141), is saponified with
caustic potash, salted out, and converted into a lime-salt by dissolving
the soap in water and precipitating with chloride of calcium. The
lime-salt is extracted by ether, and decomposed by hydrochloric
acid; the precipitate is again dissolved in caustic potash, and precipi-
tated with neutral acetate of lead; the lead-salt is decomposed under
alcohol by hydrosulphuric acid; and the solution, filtered from sulphide
of lead, is mixed with water, and the alcohol driven off.
After several hours' drying at 100°, it forms a semi-fluid, amber-
yellow, or brownish mass, of peculiar odour. On further drying it loses
more water, and after three days' exposure to a temperature of 100°,
contains 82.5 p. c. C., corresponding to the formula C¹³Î²⁹O² (Stanek).
Dried at 100° for several hours.
36 C...........
216
34 H
34
7 0......
56
C36H3407
306
Stanek.
70.59
70.4
11.11
11.0
18.30
18.6
100.00
100.0
Stanek's formula. From the analysis of the lead-salt he considers the acid to be
C36H3104.
Decompositions. By drying (see above). The freshly prepared lime-
soap, when heated to 260° with excess of soda-lime, leaves a residue
(free from sebacic acid) from which sulphuric acid sets free caprylic acid.
Pyroricinic acid is insoluble in water. It forms with magnesia a
salt insoluble in water and alcohol (Bussy and Lecanu).
Perfectly insoluble in alcohol and
Lead-salt. Preparation, see above.
ether.
At 100°.
Stanek.
36 C......
216
56.58
56.65
30 H...
30
7.86
7.66
30
24
6.29
7.05
РЬО
111.8
29.27
28.64
С36Н30РЬО4
381.8
100.00
100.00
Pyroricinic acid dissolves in weak alcohol less freely than oleic acid
(Bussy & Lecanu, J. Pharm. 13, 57).
RICINOLEATE OF ETHYL.
143
6. Ricinine.
TUSON. Chem. Soc. J. 17, 195; Chem. News, 9, 209; Zeitschr. Ch.
Pharm. 7, 309.
An alkaloid contained in castor-seeds.
similar base, perhaps the same.
Croton seeds contain a
Preparation. The bruised seeds are exhausted by repeated boiling
with water; the decoction is strained; and after separating the oil as
completely as possible, it is evaporated to an extract, which is boiled
with alcohol and filtered. After standing for 24 hours, the tincture is
separated from the deposited resin," and the alcohol is distilled off. The
residue, on standing, deposits crystals of ricinine, which are purified
by re-crystallisation from alcohol, with the help of charcoal.
Properties. Colourless, rectangular prisms and laminæ, having a
slight taste of bitter almonds. When heated it melts to a colourless
liquid, which solidifies in crystalline needles. Sublimes unchanged
between two watch-glasses. Contains nitrogen.
Burns when strongly heated on platinum foil with a luminous
smoky flame. Dissolves in oil of vitriol without coloration; the solu-
tion is coloured green by chromate of potash. - Dissolves in nitric acid
without evolving red fumes, and on evaporation leaves colourless
needles, which turn white in water.
Ricinine is insoluble in water. It forms with hydrochloric acid, a
compound which is decomposed by evaporating the solution. Its
solution, mixed with mercuric chloride, solidifies after some minutes
to a crystalline mass of fine needles. The hydrochloric acid solution,
when evaporated with chloride of platinum, yields orange-coloured
octahedra of the double-salt.
Ricinine is soluble in alcohol, and nearly insoluble in ether and
benzene.
Ricinoleate of Ethyl.
C40H3806- C4H50, C36H330".
SAALMÜLLER. Ann. Pharm. 64, 123.
Ricinölvinester.
Formed by passing hydrochloric acid gas into an alcoholic solution
of ricinoleic acid [into alcoholic castor oil (Rochleder, Ann. Pharm. 59,
260)], and purified by precipitating with water, and washing with
alkaline and pure water.
Wine-yellow oil, not volatile without decomposition.
40 C..............
38 H
60
C¹Ã³О,С36H3305
Saalmüller.
240
73.62
73.87
38
11.66
11.76
48
14.72
14.37
326
100.00
100.00
****
144
PRIMARY NUCLEUS C6H35; OXYGEN-NUCLEUS C3H30.
Ricinelaïdate of Ethyl.
C40H3806 C'H³O,C6H305.
PLAYFAIR. Phil. Mag. 29, 479.
Formed by the action of hydrochloric acid gas on alcoholic ricine-
laïdic acid.
Melts at 16 °(Playfair. Bouis). -Dissolves slightly in cold, and very
freely in hot alcohol.
Playfair.
mean.
40 C.......
38 H
240
73.62
72.43
38
11.66
12.13
6 O......
48
14.72
15.44
C+H5O,C36H3305
326
100.00
100.00
Ricinelaïdin.
C78H72014 = C6H604,2C36H3306.
Literature; see under Ricinelaïdic acid (p. 135).
Palmin. Discovered by Boudet.
Formation. 1. From castor oil and hyponitric acid (p. 139). -
2. From castor oil and sulphurous acid (p. 138).
Preparation. Hyponitric acid gas is passed into castor oil; or the
oil is shaken with 3 p. c. of its weight of nitric acid saturated with
nitrous acid, whereupon the oil is coloured reddish and converted into a
solid mass, sometimes yellow, brittle, and waxy, sometimes translucent
and glassy. It is purified by washing with water and crystallising
from alcohol (Bouis), or ether (Playfair).
Small white nodules (Bouis). Opaque, amorphous granules (Play-
fair). Melts at 43° (Playfair), 45° (Bouis), 62° to 66° (Boudet). Soli-
difies slowly, remaining pasty for a long time.
Bouis.
78 C
72 H....
14 O ...
....
C6H604,2C36H3305
Playfair.
mean.
mean.
168
71.78
72.95
71.45
72
11.04
11.49
11.07
112
17.18
15.56
17.48
652
100.00
100.00
100.00
....
Playfair proposed the formula C37H340°; Bouis, the one above.
Decompositions. Impure ricinelaïdin turns brown in the air (Bouis).
-When submitted to dry distillation it behaves like castor oil, yield-
ing a dark, brown-red spongy residue, a distillate containing oenanthol
(Bertagnini, Ann. Pharm. 85, 282), and an oily acid, fluid at 0°, but no
ricinelaïdic acid (Boudet). If the oenanthol be driven off from the dis-
BROMOSTEARIC ACID.
145
tillate by means of steam there remains a solid acid, containing 73.82
p. c. C., and 11.21 H. (Bouis). With care the distillation may be con-
tinued to the end without the formation of the spongy residue, in which
case a large quantity of acrolein and solid hydrocarbons pass over,
whilst a little carbon remains behind (Bouis). Ricinelaïdin is saponi-
fiable, though less easily than castor oil; it diffuses thereupon an
odour of volatile oil (Boudet). By distillation with excess of hydrate
of potash it yields caprylic alcohol, sebate of potash, and two other
acids (Bouis). See page 133.
Ricinelaïdin dissolves slightly in cold alcohol (Playfair); in 2 parts
of alcohol of 36 gr. at 30°, and still more freely in boiling alcohol
(Boudet). It is easily soluble in ether (Boudet).
Bromine-nucleus C36BrH35.
Bromostearic Acid.
CBr H350 = ('36 BrH5,04.
A. C. OUDEMANNS, Jun. J. pr. Chem. 89, 193.
See page 106.
Stearic acid (7 parts) is heated with water and bromine (4 parts),
in a sealed tube, to 130° or 140° at most, till the brown colour of the
bromine disappears, and the mixture assumes the appearance of a
yellow oil, cooling to a crystalline solid. After washing away the
hydrobromic acid, the contents of the tube are dissolved in 20 times
their weight of warm alcohol of 80 p. c., and the unchanged stearic
acid is separated by cooling to -10°. The liquid is then mixed with an
equal volume of water and an excess of crystallised carbonate of soda,
and evaporated to dryness over the water-bath. The tough saline mass
thus obtained is boiled with 10 volumes of alcohol of 80 p. c., and filtered
as hot as possible; and the crystals of bromostearate of soda which
form in the filtrate (and of which more may be obtained by evaporating
the solution), are collected and purified by repeated crystallisation from
alcohol. The mother-liquor contains bibromostearate of soda.
From the soda-salt the bromostearic acid is separated by dilute sul-
phuric acid.
Properties. Yellow, indistinctly crystalline mass, melting at 41°, and
of sp. gr. 1·0653 at 20°.
Bromostearic acid is very slowly decomposed by heating with
excess of caustic potash. Bromostearate of silver, heated with water,
forms bromide of silver and stearidic acid CH³404 (p. 78).
136
The acid is insoluble in water. It forms with the alkalis soap-like
compounds, which crystallise from alcohol.
Bromostearate of Potash is more soluble than the soda-salt.
Bromostearate of Soda. Preparation described above.
VOL. XVII.
L
146
PRIMARY NUCLEUS C36H36; CHLORINE-NUCLEUS C36C110H26.
Oudemanns.
mean.
36 C..........
Br
216
56.10
55.90
80
20.78
21.08
34 H
34
8.83
8.87
245
3 O.....
24
6.24
6.22
NaO
31
8.05
7.93
C36 BrH34NaO¹
385
. 100.00
!
100.00
The bromostearates of the alkalis precipitate metallic salts.
The acid dissolves easily in alcohol and ether.
Bromine-nucleus C36 Br2H94.
Bibromostearic Acid.
C36Вr²H³¹0¹ = C³6Br²H³4,0ʻ.
OUDEMANNS. J. pr. Chem. 89, 193.
Formed, in the preparation of bromostearic acid, by heating bromine
with stearic acid (p. 145), and obtained in the form of an uncrystal-
lisable soda-salt. The salt is brown, tenacious, very hygroscopic,
dissolves easily in alcohol, and forms with water an opaque, soapy
solution. After drying at 130° it contains 32.5 p. c. of bromine, and
6.59 of soda, approximating to the formula C³Br³ÑaH³O¹ (calc. 347 p. c.
Br. 6·68 NaO).
33
Chlorine-nucleus C36C110H26.
Chlorostearic Acid.
C38C110H2604C36C110H26,04.
HARDWICK. Chem. Soc. Qu. J. 2, 232; Ann. Pharm. 72, 270.
Chlorbassinsaüre. See xvi, 365.
Stearic acid at 100° is treated with dry chlorine, whereupon it
first becomes thicker, and is ultimately converted into a solid resin.
Hardwick.
mean.
36 C........
216
34.06
34.37
10 Cl
355
56.78
57.16
26 H
26
4.10
4.37
4 O
32
5.06
4.10
C36C10H2004
629
100.00
100.00
Forms with potash an amorphous soap, which does not crystallise
from alcohol. The baryta- and lead-salts are insoluble in water.
RICINOLAMIDE.
147
Amidogen-nucleus C36 AdH35.
Stearamide.
C36NH3702 = C36Adн35,0².
H. CARLET. Par. Soc. Bull. (1859) 1, 76.
Obtained in the same manner as palmitamide (xvi, 382). After
melting it solidifies at 107.5°, but is probably still impure. The acid
separated from the amide by alcoholic potash melts at 69.5°.
Carlet.
36 C
216
76.33
74.92
75.74
N
14
4.94
5:00
37 H
37
13.07
11.87
13.90
20
16
5.66
C36NH3702
283
100.00
Stearanilide.
C49NH410² =
C¹³6(NH.C¹²H³)H¾,0².
35
PEBAL. Ann. Pharm. 91, 151.
When an excess of aniline is distilled over stearic acid heated to
230° in an oil-bath, the whole of the stearin is converted into anilide.
The product is purified by repeated crystallisation from alcohol.
C363604 + C¹²NH7 C48NH4102 + 2HO.
=
White, delicate, shining needles, melting at 93.6°, and solidifying to
a mass of radiated crystals. An alcoholic solution does not precipi-
tate nitrate of silver.
Pebal.
mean.
48 C
288
80.22
80.00
N
14
3.90
41 H
20
41
11.42
11.57
16
4.46
C48NH4102
359
....
100.00
Oxy-amidogen-nucleus C3 AdH330².
Ricinolamide.
C36NH350 = С¹³6AdH³³0²,0².
BOULLAY. N. J. Pharm. 5, 329; abstr. Compt. rend. 32, 223.
BOUIS. Compt. rend. 33, 144; Ann. Pharm. 80, 304; J. pr. Chem. 54,
46; Pharm. Centr. 1851, 796; Complete: N. Ann. Chim. Phys. 44, 96.
i
L 2
148
OXY-AMIDOGEN-NUCLEUS C36AdH³30².
Discovered by Boullay in 1843.
Formation and Preparation. An alcoholic solution of castor oil
saturated with ammoniacal gas, is allowed to stand for three or four
months, or heated for three to four days in a bath of chloride of
sodium. The product obtained by expressing and evaporating the
alcoholic mother-liquor is purified by crystallising from alcohol, pre-
cipitating the alcoholic solution with water, and again crystallising
from alcohol.
Properties. White crystalline nodules, melting to a transparent
liquid at 66°. Solidifies to an opaque, brittle mass.
36 C .......
N
216
72.72
Bouis.
69.51 to 73.36
14
471
4:00
>>
35 H
35
11.78
11.40
4.74
12.09
4 O
32
10.79
C3NH35O*
297
100.00
Decompositions. 1. Burns with a smoky flame. - 2. Dissolves in
oil of vitriol with red colour.-3. Decomposed by dilute acids, without
coloration, into ammonia-salt and ricinoleic acid. With hot strong
solution of caustic potash, it evolves ammonia, and forms ricinoleate of
potash, which at higher temperatures is decomposed into a salt of
sebacic and caprylic alcohol (p. 133).
Combinations.
alcohol and ether.
Ricinolamide is insoluble in water, but soluble in
:
ROWNEY.
Ricinelaïdamide.
C³6NH350¹ = C¹²AdH³³O²,0².
Chem. Gaz. 1855, 361; J. pr. Chem. 67, 157.
Obtained by the action of ricinelaïdin on alcoholic ammonia.
Closely resembles elaïdamide. Melts at 91-93°, and solidifies at 89°.
Rowney.
mean.
36 C......
216
72.72
72.78
N
14
4.71
4.79
35 H
35
11.78
11.91
40
32
10.79
10.52
C3NH3501
297
100.00
100.00
VULPIC ACID.
149
COMPOUNDS CONTAINING 38 ATOMS OF CARBON.
Primary Nucleus C38H20; Oxygen-nucleus C8H140º.
Vulpic Acid.
C38H14010 C8H1406,04.
F. MÖLLER & A. STRECKER. Ann. Pharm. 113, 56; abstr. Chem. Centr.
1860, 225; J. pr. Chem. 79, 468; N. Ann. Chim. Phys. 58, 486.
W. STEIN. Zeitschr. Ch. Pharm. 7, 97; N. Br. Arch. 118, 230; Zeitschr.
Ch. Pharm. 8, 47; J. pr. Chem. 93, 366.
BOLLEY & KINKELIN. Zürich. Mitth. 1865, 1; J. pr. Chem. 93, 354.
Vulpulin. Discovered by Bebert (J. Pharm. 17, 696) in Cetraria vulpina, but
imperfectly described by him, so that it was regarded by Berzelius and Gerhardt as
identical with chrysopbanic acid (xvi, 171): investigated by Möller and Strecker.
Stein found in Parmelia parietina [growing, not on trees, like that of Rochleder and
Heldt (xvi, 172), but on a sandstone rock], instead of chrysophanic acid, his
chrysopicrin, which was afterwards recognised by Bolley, Strecker, and Stein him-
self, as vulpic acid: the resinous wall-lichen yellow of Schrader, and the Parmelia
yellow of Herberger may, therefore, also be identical with rulpic acid. See xvi, 171.
Preparation. 1. Extracted from the wall-lichen by sulphide of
carbon in a nearly pure state (Stein). 2. One part of Cetraria vulpina
is digested with 20 parts of luke-warm water and a little milk of lime.
After standing six hours the liquid is strained, and the residue treated
afresh with the same quantity of water and milk of lime. The mixed
extracts are then supersaturated with hydrochloric acid, and the
precipitated flocks are washed with cold water, and purified by
crystallisation from boiling water or alcohol (Möller & Strecker).
Boiling water acts prejudicially in the extraction. - Chloroform also
(Möller & Strecker) and alcohol (Bebert) extract the vulpic acid from
the cetraria.
Properties. Large sulphur-yellow, transparent, pyramids or needles.
belonging to the oblique prismatic system (Möller & Strecker;
Bolley). When crystallised from sulphide of carbon, it possesses the
colour of bichromate of potash; from alcohol it is less red. Acids
precipitate it of a yellow colour from alkaline solutions (Stein). Melts
above 100° (Möller & Strecker), at 110° (Bolley), 140° (Stein), and
solidifies in a crystalline mass. Sublimes at 120° in small yellow
laminæ (Bolley), in long needles having an odour of benzoin. Taste-
less alone, but very bitter in alcoholic solution (Stein).
Möller and Strecker.
mean.
Bolley.
Stein.
38 C
228
70.81
70.63
70-74
70.69
14 H
14
4.35
4.33
4.56
4.41
10 0
80
24.84
25.04
24-70
24.90
C38H14O10
322
100.00
100.00
100 00
...
100.00
Former C30H1003, according to Stein.
Decompositions. 1. Vulpic acid decomposes when heated, evolving
150
PRIMARY NUCLEUS CH20; OXYGEN-NUCLEUS CH1406.
yellow fumes which condense in powder and in drops, and leaving a
large quantity of charcoal. - 2. When boiled with excess of caustic
potash, it takes up 6 atoms of water, and is converted into oxatolylic
acid, carbonic acid, and methylic alcohol:
C38H14010 + 6Hо C32H1606 + 4CO2 + C2H402.
=
3. By boiling with baryta-water it is resolved into oxalic acid,
methylic alcohol, and alphatoluic acid:
C3H14O10 + 8HO 2C¹6H8O4 + C4H²O8 + C²H¹O² (Möller and Strecker).
Bolley obtained oxalic acid, but instead of methylic alcohol, oily
drops having an odour of bitter almonds.-4. Sodium-amalgam de-
colorises the alkaline solution, whereupon hydrochloric acid throws
down a green-yellow body, resembling tannic acid in its behaviour with
tartar emetic and sesquichloride of iron.-5. Solution of chloride of
lime forms with it a red amorphous resin, and a volatile oil having an
odour of bitter almonds, apples, and cinnamon. A similar effect is
produced by heating it to 160° for 12 hours with water containing
sulphuric acid.-6. The acid does not reduce potassio-cupric tartrate
even on boiling with acids or alkalis (Stein).
Combinations. Vulpic acid is nearly insoluble in water, even when
boiling. It assumes a deep-red colour with oil of vitriol, and forms a
brown-red solution, which is changed to pale-yellow by the addition of
water (Bolley).
The acid combines with bases to form salts having the formula
C38MH13010. The vulpates of the alkalis and alkaline earths are crystal-
lisable; those of the heavy metals insoluble in water. The acid
expels carbonic acid from alkaline carbonates (Möller & Strecker).
Ammonia-salt. The solution of the acid in warm aqueous ammonia
deposits, on cooling, yellow needles, which give off water and ammonia
when heated, and afterwards are not completely soluble in water
(Möller & Strecker).
38 C........
N
19 H
Air-dried.
Möller and Strecker.
228
63.84
64.38
14
3.92
4.13
19
5.32
5.11
12 O.......
96
26.92
26.38
C3(NH*)H!3O1 + 2 aq.
357
100.00
100.00
Potash-salt. The acid is dissolved in aqueous carbonate of potash,
or its alcoholic solution is shaken with the dry carbonate (Möller &
Strecker). Stein adds vulpic acid to boiling alcoholic potash till it
ceases to dissolve. Bright-yellow needles, losing 4.8 p. c. (Möller &
Strecker), 4.74 p. c. (Stein) of water at 100° (2 at. = 4.8 p. c.). Diffi-
cultly soluble in water and alcohol.
Möller and Strecker. Stein.
Dried.
38 C
13 H
228
63.30
13
3.61
63.64
3.61
90
72
19.99
20.11
ΚΟ
47.2
13.10
12.64
12.9
CKH13010
360.2
100.00
100.00
t
ALPHATOLUIC ACID.
151
Baryta-salt. When vulpic acid is boiled with moist carbonate of
baryta, pale-yellow needles are obtained on cooling. By re-crystallisa-
tion from boiling alcohol they are converted into orange-coloured
crystals, or a mixture of lighter and darker crystals, containing variable
proportions of water. The paler crystals lose 14.1 p. c. of water at
100° (7 at. = 13·9 p. c. HO) (Möller & Strecker). Similar observations
were made also by Stein.
Möller and Strecker.
Dried.
38 C......
228
58.52
58.40
13 H
13
3.33
3.52
90
72
18.49
18.68
BaO
76.6
19.66
19.40
C38 BaĤ13010
389.6
100.00
100.00
....
Bolley found 20-05 p.c. of baryta; Stein 18.56 p.c. of baryta and 14:06 p.c. of
water.
Alcoholic solution of vulpic acid does not precipitate neutral acetate
of lead; it renders the basic acetate cloudy, and produces a sulphur-
yellow precipitate. The acid colours sesquichloride of iron a deeper
yellow (Stein; Bolley).
Silver-salt. Nitrate of silver throws down from the soda-salt a
yellow precipitate, which, after washing with cold water, loses but
little at 100°, becoming black. It is soluble in aqueous ammonia.
Dissolves in boiling water with partial decomposition.
Möller and Strecker.
38 C
13 H....
228
53.15
54.10
13
3.03
2.99
10 O......
80
18.65
17.75
Ag
108
25.17
25.16
C¹36 AgH¹3010
4.29
100.00
100.00
-
Vulpic acid is easily soluble in bisulphide of carbon (Stein). - It
dissolves in 200 parts of boiling, and 376 parts of cold alcohol of
80 p. c. (Stein); in 588 parts of alcohol of 90 p. c. at 17°, and in 88-3
parts of boiling alcohol. More easily soluble in ether, and especially in
chloroform (Möller & Strecker).
Addenda to vol. xiii, p. 8.
1. Alphatoluic Acid.
C16H804 C16H8,04.
CANNIZARO. N. Ann. Chim. Phys. 45, 468; Ann. Pharm. 96, 246; Chem.
Gaz. 1855, 428; Lieb. Kopp. Jahresber. 1855, 622; Par. Soc. Bull.
1861, 68; Ann Pharm. 119, 253; Kopp's Jahresber. 1861, 421.
Compt. rend. 54, 1225; Ann. Pharm. 124, 252; Kopp's Jahresber.
1862, 267.
MÖLLER & STRECKER. Ann. Pharm. 113, 64.
Formation. 1. By boiling monochlortoluol C¹H7C16 [obtained either
152
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS CH1406.
by the action of chlorine on toluol (according to xii, 291) or of hydro-
chloric acid on benzyl-alcohol (xii, 18)], with alcohol and cyanide of
potassium, cyanide of benzyl, CH'Cy, is produced. This body, when
subjected to prolonged boiling with strong solution of caustic potash,
yields alphatoluic acid, with simultaneous evolution of ammonia.
C16NH7+ 4HO =
C16H8O4 + NH³ (Cannizaro).
2. By boiling vulpic acid (p. 150) with baryta-water (Möller &
Strecker).
Preparation. Vulpic acid is boiled with hot saturated baryta-water
for several hours, or until the solution is completely decolorised, by
which methylic alcohol is volatilised, and oxalate of baryta thrown
down as a crystalline powder. The excess of baryta is precipitated
from the filtrate by carbonic acid; the solution is filtered hot, concen-
trated by evaporation, and super-saturated with hydrochloric acid;
and the crystals which form on cooling are purified by washing with
cold water and re-crystallisation.
Properties. Colourless, broad, crystalline laminæ, greatly resembling
benzoic acid. Melts at 76.5°, solidifying afterwards to a crystalline
blistered mass, and volatilises below 100° in irritating vapours. Boils
at 265.5° (corrected), and distils unchanged (Möller & Strecker). An
acid formed as in (1) was found by Cannizaro to have the same melting-
point as that of Möller and Strecker, but a boiling-point of 261-
262°. The solid acid has a sp. gr. of about 1·3. It expands very
much on melting, and at 83° has a density 1.0778, at 135° = 1·0334,
that of water at 4° being = 1. The expansion between 83° and 135°
amounts to 0·0429 of the volume of the acid at 83°, and consequently
to 0.000825 for 1° (Möller & Strecker).
Möller and Strecker.
mean.
16 C............
8 H
96
70.59
70.50
8
5.88
5.97
4 O.........
32
23.53
23.53
C6H8O4
136
100.00
100.00
Isomeric with toluic acid (xiii, 8), but belongs to the benzoic series, as is shown
by decompositions 2 and 4 (Cannizaro).
Decompositions. 1. Dissolves in hot fuming nitric acid with tran-
sient red colour. The solution deposits, on cooling, colourless needles
of nitroalphatoluic acid, which forms yellowish salts with alkalis.
2. Oxidised by boiling with sulphuric acid and oxide of manganese or
chromate of potash, but with difficulty, and only when the acid em-
ployed consists of oil of vitriol diluted with not more than an equal
weight of water. The products of the oxidation are carbonic acid,
formic acid, oil of bitter almonds, and benzoic acid. —3. Forms with
pentachloride of phosphorus bydrochloric acid, phosphoric oxychloride, and
a colourless, heavy, fuming liquid, chloride of alphatoluyl. This last body
is converted by aqueous ammonia into alphatoluylamide, CNI1902, which
is easily soluble in boiling water (Möller and Strecker). 4. A mixture
of the lime-salt and formate of lime yields by distillation an oil,
C¹¹II®O², which combines with bisulphite of soda to form a crystallisable
OXATOLYLIC ACID.
153
compound. The oil is decomposed by distillation, and when heated
with nitric acid yields benzoic and nitrobenzoic acids (Cannizaro).
Alphatoluic acid is slightly soluble in cold, easily in boiling water;
an excess of the acid melts to an oil in the latter.
With ammonia, alkalis, and alkaline earths it forms easily soluble
salts, difficult to crystallise. Sulphate of copper throws down from
the ammonia salt a pale-green, amorphous precipitate (Möller &
Strecker).
Silver-salt.
Precipitated from the ammonia-salt by nitrate of
silver. Delicate, colourless laminæ, which crystallise from a boiling
aqueous solution (Möller & Strecker).
Mar
Möller and Strecker.
C16H704
Ag
135
108
55.56
44-44
44.4
C¹6AgH704
243
100.00
***
......
The acid dissolves very easily in alcohol and ether, and is withdrawn
from its aqueous solution by those liquids when shaken therewith.
2. Oxatolylic Acid.
16
C32H1606 = C32H¹6,0º.
MÖLLER & STRECKER. Ann. Pharm. 113, 69.
Formation. By boiling vulpic acid with caustic potash (p. 150).
Preparation. Vulpic acid is boiled with an excess of caustic potash
of sp. gr. 105 to 1.15 till the precipitate produced by hydrochloric
acid in a test-portion of the liquid is no longer yellow, but of a some-
what dirty colour; and the oxatoluic acid formed is precipitated by an
excess of hydrochloric acid, and purified crystallisation from alcohol.
By prolonged boiling the alkaline liquid becomes paler, though not
quite colourless, and gives off methylic alcohol and a little toluol.
Properties. Colourless, four-sided, right rhombic prisms, hard and
brittle. Melts at 154°. Strongly acid. Does not lose weight at
100°.
Möller and Strecker.
mean.
Air-dried.
32 C..........
16 H
192
75.00
74.80
16
6.25
6.15
6 O...
48
18.75
19.05
C32H1606
256
100.00
100.00
.....
Decompositions. 1. Oxatolylic acid volatilises, with decomposition,
at elevated temperatures, leaving a little charcoal. 2. Dissolves in
fuming nitric acid with red colour, which disappears on heating. Water
precipitates from the solution a yellow resin, which is resolved into
nitrotoluol and oxalic acid by boiling with caustic potash, probably
154
PRIMARY NUCLEUS CH20; OXYGEN-NUCLEUS C8H1406.
nitroxatolylic acid.-3. It is resolved, by prolonged boiling with
caustic potash of sp. gr. 1.2 to 13, into oxalic acid and toluol :
C32H1606 + 2HO
=
C4H208 + 2014H8.
Combinations. The acid dissolves slightly in boiling water, and is
deposited almost entirely on cooling.
It forms with alkalis easily soluble, and with the alkaline earths
difficultly soluble salts.
Baryta-salt. Obtained as a crystalline precipitate by mixing con-
centrated solutions of the ammonia-salt and chloride of barium. By
re-crystallisation from dilute alcohol it is converted into warts and
shining lamine, which lose 9.9 p. c. of water at 100° (4 at. 10 p. c.
HO).
32 C ....
15 H
Dried.
192
Möller and Strecker.
59.33
59.25
15
4.64
4.61
....
5 0
40
12.36
12.39
BaO
76.6
23.67
23.75
.... ...
C32H15 Ba06
323.6
100.00
100.00
Lead-salt. — A solution of neutral acetate of lead precipitates from
the dilute aqueous ammonia-salt, delicate colourless needles, nearly
insoluble in water. Loses 3.1 p. c. of water at 100°, and a little more
at 120°.
32 C
19 H
90
РЬО
At 100°.
Möller and Strecker.
192
48.63
48.16
19
4.81
4.90
72
18.24
19.49
112
28.32
27.45
395
100.00
100.00
....
C32PbH¹506 + 4aq
Silver-salt. Crystalline precipitate thrown down from the am-
monia-salt by nitrate of silver.
At 100°.
Möller and Strecker.
32 C...........
192
52.89
52.87
15 H......
15
4.13
4.15
6 O......
48
13.22
13.38
Ag
108
29.76
29.60-
C32 AgH1506
363
100.00
100.00
Oxatolylate of Ethyl.
C36H2006 = C4H50,C32H¹505.
Formed by passing hydrochloric acid gas into the alcoholic acid, or
by treating the silver-salt with iodide of ethyl.
Colourless prisms melting at 45·5°. — Însoluble in aqueous am-
monia, but easily soluble in alcohol.
36 C...........
20 H
60
C4H50, C2H5O5
Möller and Strecker.
216
76.06
75.46
20
7.04
7:00
48
19.90
17.54
284
100.00
100.00
....
GUAIACONIC ACID.
155
Primary Nucleus C38H24; Oxygen-nucleus C38H2004.
Guaiaconic Acid.
C38H20010 = C'98 H2004,06.
HADELICH. Dissertation über Bestandth. des Guajakharzes. Göttingen,
1862; J. pr. Chem. 87, 321; Kopp's Jahresber. 1862, 466.
Occurs in guaiac-resin to the amount of about 70 per cent.
The alcoholic mother-liquor from which the guaiacic acid has been
precipitated by alcoholic potash, in the preparation of guaiacic acid, is
evaporated, at 30°, to a thick syrup, and mixed with absolute alcohol,
whereby a little of the potash-salt of guaiacic acid is thrown down.
This last body is removed; carbonic acid is passed into the filtrate;
the liquid, separated from carbonate of potash and mixed with water
and a little hydrochloric acid, is heated to drive off the alcohol; and
the resin thereby separated is washed with warm water. On cooling,
the resin forms a brittle, brown mass, which is resolved, by treatment
with ether, into guaiaconic acid soluble in ether, and guaiac beta-
resin insoluble in that menstruum. The acid is precipitated from the
ethereal solution by caustic potash; the supernatant ether is poured off,
and the alkaline solution diluted with water and precipitated with
neutral acetate of lead. The green-grey precipitate thus obtained is
decomposed under water by hydrosulphuric acid, dried, and exhausted
with alcohol, which takes up the guaiaconic acid. It still contains
colouring matter, which cannot be entirely removed.
Properties. Light-brown, brittle mass, having a conchoïdal fracture,
pulverisable to a paler, inodorous, and tasteless powder. Melts between
95° and 100°. Neutral. Rotates a ray of polarised light to the left.
Hadelich.
At 100°
mean.
38 C............
20 H
228
69.51
68.95
20
6.09
6.53
10 O....
80
24-40
24.52
C38H20010
328
100.00
100.00
....
Contains also 0.8 p.c. of nitrogen.
Burns with lumi-
Yields an oily distillate when heated in a tube.
nous flame. Dissolves in oil of vitriol, forming a fine cherry-red solu-
tion, from which water precipitates violet flocks containing sulphur.-
Forms with fuming nitric acid a deep orange-yellow solution, which is
miscible with water, and yields oxalic acid on boiling. Coloured a
transient blue by oxidising agents. The alcoholic solution reduces
nitrate of silver.
Insoluble in water. The melted acid expels carbonic acid from
alkaline carbonates and forms non-crystallisable compounds, which
are easily soluble in water and alcohol and decomposible by carbonic
acid. The acetates of baryta, strontia, and lime form pale precipitates
with the alcoholic acid.
156
PRIMARY NUCLEUS CH24; OXYAZO-NUCLEUS CNH1508.
Lead-salt. The alcoholic acid is precipitated by neutral and basic
acetate of lead. The precipitate produced by pouring the acid into
excess of neutral acetate contains 37 p. c. of lead; while that produced
by adding it to a boiling alcoholic solution of the basic acetate contains
47.26 p. c. of lead.
Hadelich.
At 100-130°.
mean.
38 C........
228
41.37
41.84
20 H
20
3.63
3.63
12 O......
96
17.42
17.48
2Pb
207
37.56
37.05
C38H18 Pb2010,2HO
551
100.00
D
........
100.00
Hadelich regards the fused acid as anhydrous, and the lead-salt, consequently,
as C3SH20Pb2012.
Guaiaconic acid is easily soluble in alcohol, ether, acetate of ethyl,
chloroform, and acetic acid, but nearly insoluble in benzene and bisulphide
of carbon.
Oxyazo-nucleus C38NH1508.
Chelerythrine.
C38NH1708 = C38NH¹50°,H².
DANA. Annals of the Lyceum of New York, 2, 245; Mag. Pharm. 23,
125.
PROBST. Ann. Pharm. 29, 120; 31, 350.
POLEX. N. Br. Arch. 16, 77.
J. SCHIEL. Ann. Pharm. 43, 233. Sill. Am. J. (2), 20, 220; J. pr.
Chem. 67, 61; abstr. N. J. Pharm. 31, 317: Lieb. Kopp. Jahresber.
1855, 566.
Discovered as Sanguinarine by Dana in the roots of Sanguinaria
canadensis; as Chelerythrine by Probst, and as Pyrrhopine by Polex, in
Chelidonium majus. Probst & Schiel demonstrated the identity of the
two bodies.
Occurrence. In Chelidonium majus (Handbuch, viii [2], 41): more
abundantly in the roots and unripe fruit than in the herb, together
with chelidonine (Probst; Polex). In the roots of Glaucium luteum
(Handbuch, viii [2], 41), together with glaucopicrine, but not in the
herb, which contains glaucine (Probst). In the roots of Sanguinaria
canadensis (Handbuch, viii [2], 41) [and in the leaves, and doubtless also
in the seeds (Gibb)] (Dana), together with one or two other alkaloïds
(Probst; Riegel; Wayne). See below.
The roots (and herb collected in autumn) of Eschholtzia californica (Hand-
buch, viii [2], 41) contain chelerythrine, or a very similar alkaloid, which may be pre-
cipitated from an acetic extract of the plant by ammonia, and extracted from the
precipitate by ether. From the ethereal extract it may be thrown down as hydro-
chlorate, and afterwards purified in the same manner as chelerythrine. It forms a
grey-white powder and produces with acids deep-red, neutral, crystallisable salts;
from which it is precipitated by ammonia and the alkalis (Walz, Jahrb. pr. Pharm.
8, 223).
GUAIACONIC ACID.
157
Preparation. From the roots of Sanguinaria canadensis. 1. The
dried and powdered roots are exhausted with absolute alcohol; the
tincture thus obtained is mixed with water, freed from alcohol by dis-
tillation, filtered, and precipitated by ammonia; and the grey precipi-
tate is collected and boiled with water and charcoal. After filtering
and washing with cold water, the carbonaceous mixture is extracted
with alcohol, which leaves the chelerythrine on evaporation (Dana).
Or, the hot infusion of the powdered root is precipitated with a little
ammonia, potash, or lime, and the precipitate is purified as above.
The powdered root may also be digested with water containing hydro-
chloric or acetic acid; the infusion precipitated with ammonia or potash;
and the dark precipitate dissolved in absolute alcohol and mixed with
cold water, whereby a white precipitate is formed, which is to be puri-
fied with charcoal as before (Dana). - 2. The dried and powdered root is
exhausted with ether, and hydrochloric acid gas is passed into the
filtrate, when impure hydrochlorate of chelerythrine is thrown down,
and is collected and dried. In the ether there remains a brown greasy
resin, together with a little chelerythrine, which is recovered by evapo-
rating, exhausting the residue with water containing sulphuric acid,
and precipitating with ammonia. The precipitated hydrochlorate is
dissolved in water; the solution is precipitated with ammonia; the
precipitate is washed, dried, and dissolved in ether; and the solution is
shaken with animal charcoal till the supernatant liquid appears colour-
less. The precipitate again thrown down from the filtrate by hydro-
chloric acid gas is decomposed by ammonia-water, and afterwards
washed and dried (Probst; Schiel). Schiel purifies chelerythrine extracted
by other methods, by precipitating its ethereal solution with hydrochloric
acid gas or sulphuric acid.
From the roots of Chelidonium majus. 1. The fresh or dried root
(or the residue which remains after treatment with aqueous carbonate
of soda in the preparation of chelidonic acid, according to xii, 413)
is exhausted with water containing sulphuric acid; the liquid is preci-
pitated by ammonia; and the precipitate is washed, freed from water
as far as possible by pressing, and dissolved, while still moist, in
alcohol containing sulphuric acid. The alcoholic solution, diluted with
water, is submitted to distillation, and after the alcohol is driven off,
precipitated with ammonia. The precipitate is dried between blotting-
paper as quickly as possible, at a very gentle heat, powdered, and treated
with ether, which dissolves chiefly chelerythrine. On expelling the
ether, there remains a viscid turpentine-like mass, which is to be dissolved
in as small a quantity as possible of water containing hydrochloric acid,
resin then remaining behind. On evaporating the solution to dryness,
and washing the residue with ether, hydrochlorate of chelerythrine
remains undissolved. This is dissolved in a little cold water, which
leaves most of the hydrochlorate of chelidonine undissolved; the solution
is evaporated; and the residue again treated with water so long as hydro-
chlorate of chelidonine continues to separate. From the last aqueous
solution the chelerythrine is thrown down by ammonia, and is purified by
washing and drying, and subsequently dissolving in ether and evaporat-
ing (Probst). —2. The dried and coarsely powdered roots, collected in
spring, are exhausted by twice boiling with alcohol; water is then
added and the alcohol distilled off; and when the residue is perfectly
cold, the resin which has separated is removed, and the chelerythrine
and chelidonine are thrown down from the filtrate by carbonate of soda.
158
PRIMARY NUCLEUS CH24; OXYAZO-NUCLEUS CNH150º.
The washed and dried precipitate treated with boiling alcohol, yields
a solution which when filtered, cooled, and concentrated, deposits
first chelidonine, and afterwards, on further slow evaporation of the
mother-liquor, yellowish warts and black plates of chelerythrine,
which is purified by pouring off the mother-liquor at the proper point,
picking out the crystals, and re-crystallising from alcohol (Polex).
From Glaucium luteum. The dried and powdered roots of plants of
one to two year's growth are exhausted with water containing acetic
acid; the extract is precipitated by excess of ammonia; and the pre-
cipitate is washed, dried, and exhausted with ether, which leaves nearly
pure chelerythrine on evaporation. The product is dissolved in the
smallest possible quantity of water acidulated with hydrochloric acid;
the water and excess of acid are evaporated; and the remaining hydro-
chlorate of chelerythrine is freed from leaf-green by washing with
ether, after which it is dissolved in a little water and mixed with an
equal volume of strong hydrochloric acid, which precipitates it almost
completely, the supernatant liquid retaining only a small quantity,
precipitable by ammonia. The precipitated salt may be obtained in the
crystalline form by dissolving it in water and evaporating the solution.
By decomposition with ammonia it yields chelerythrine, which is
allowed to crystallise from ether, with addition of water (Probst).
With the first year's roots, Probst employs also the following
method, which yields glaucotine at the same time. The precipitate
produced by ammonia in the acetic extract is dissolved in dilute
sulphuric acid and again precipitated by ammonia; it is then dissolved
in alcohol and ether in succession, and recovered from these solutions,
on evaporation, in the form of a turpentine-like mass, which is dissolved
in dilute sulphuric acid and mixed with concentrated hydrochloric acid,
whereupon the colour of the liquid changes to a dirty brown-red, whilst
hydrochlorate of chelerythrine separates.
After separation of the hydrochlorate of chelerythrine by filtration,
ammonia throws down from the filtrate a red-blue precipitate, which,
after drying, dissolves in absolute alcohol, and remains, on evaporating
the solution, as a brittle mass but little soluble in ether. This mass,
the glaucotine of Probst, is red-blue, soluble in alcohol, but insoluble in
ether, and is taken up by acids, with green colour. The neutral hydro-
chloric acid compound retains the acid when evaporated and further
heated, and also dissolves subsequently in water with green colour,
but not in ether.
Glaucotine is probably a decomposition-product of chelerythrine
(Probst).
Properties. Chelerythrine is obtained from absolute alcohol by
spontaneous evaporation in groups of crystalline nodules (Probst).
White, pearly, fine grains (Dana). Star-shaped groups of transparent
needles, and white nodules (Polex). Its ethereal solution leaves, on
evaporation, a turpentine-like body, which gradually hardens to a
shining friable mass (Probst). The crystals become opaque and
brown on drying (Polex). Softens at 65° like a resin (Probst). Taste-
less (Schiel); in the mouth it slowly creates a very faint taste (Dana);
in alcoholic solution it has a burning sharp taste (Probst); very bitter
(Schiel). Acts as a powerful narcotic poison. The dust excites
violent sneezing (Probst). According to Dana and Schiel, it has an
A
GUAIACONIC ACID.
159
alkaline reaction, but according to Probst and Polex, not. On exposure
to the air, it gradually assumes a yellowish-white colour (Dana), and in
presence of small quantities of acid vapours becomes immediately red
(Polex; Schiel).
Schiel.
at 100-105°.
a. mean.
b.
38 C
228
70.59
69.66
70.34
N
14
4.33
5.23
5:07
17 H
17
5.26
5.16
5.21
80
64
19.82
19.95
19.38
C3NH1708
323
100.00
100.00
100.00
a is sanguinarine, b chelerythrine.-The above is Limpricht's formula (Lehrbuch,
1197). Schiel proposed C38NH1608; Gorup-Besanez (Handwörterb., 2nd ed. 2, 2,
945), C38NH1508; Gerhardt (Traité, 4, 232), C36NH¹70s.
Melts easily when heated, and burns completely, with evolution of
ammoniacal vapours (Polex). — Is not decomposed by nitric acid.
It is insoluble in water.
Chelerythrine unites with acids, which it colours a fine orange-red,
forming neutral salts, partly crystallisable, having a burning sharp
taste, a narcotic action, and dissolving, for the most part, in water.
From the solutions, ammonia, alkalis, or magnesia, precipitate chelery-
thrine in the form of a grey-white, curdy precipitate (Probst).
Concentrated acids have but little action on chelerythrine, in the cold
(Polex). Acetate of chelerythrine forms yellowish-white precipitates
with tartar emetic, sesquichloride of iron, mercurous nitrate, mercuric
chloride, and nitrate of silver. Iodine precipitates the solution of a
crimson, chromate of potash of a yellow, and chloride of gold of a
dark red-yellow colour. Basic acetate of lead and tincture of galls (see
below) do not produce precipitates (Polex).
Phosphate of Chelerythrine. - Permanent in the air, and more easily
crystallisable than the sulphate. Easily soluble in water and dilute
alcohol, difficultly soluble in absolute alcohol, and insoluble in ether
(Probst).
Sulphate of Chelerythrine. Obtained by evaporating a solution of
chelerythrine in dilute sulphuric acid at a gentle heat, washing the
residue with ether, dissolving in alcohol, and allowing the solution to
evaporate spontaneously. Crystallises with difficulty. Permanent in
the air. Melts to a wax when heated, without decomposition. — Easily
soluble in water and dilute alcohol, difficultly soluble in absolute
alcohol, insoluble in ether (Probst).
Hydrochlorate of Chelerythrine. Red, crystalline, neutral mass,
soluble in water and alcohol, but insoluble in ether. Precipitated from
the aqueous solution by strong hydrochloric acid (Probst; Schiel).
Bichloride of Platinum precipitates the salts of chelerythrine orange-
red. Schiel found in the precipitate in his earlier analyses 18.7, 21-7,
and 17·7, and afterwards 18.06 p. c. of platinum (CNH¹708, HCl,PtCl³
requires 18-32 p. c. Pt).
-
Acetate of Chelerythrine. Easily soluble in water and alcohol, even
after evaporation to dryness (Probst). Chelidonate of chelerythrine
dissolves in water and alcohol (Probst).
160 PRIMARY NUCLEUS C38H24; OXYAZO-NUCLEUS CNH1508.
Tincture of galls produces in salts of chelerythrine a [yellow-red
(Schiel)] precipitate, soluble in alcohol (Probst).
Chelerythrine dissolves very easily in alcohol, forming a solution
from which it is precipitated by water, and in ether (Dana). It is
readily soluble in volatile and fixed oils (Polex).
с
Appendix to Chelerythrine.
1. Glaucopicrine.
PROBST. Ann. Pharm. 31, 254.
Occurs in the roots of Glaucium luteum (p. 158).
When from an acetic extract of the roots the chelery thrine is pre-
cipitated by ammonia, a filtrate is obtained, which, after neutralisation
with acetic acid, yields with decoction of oak-bark a precipitate of
tannate of glaucopicrine. The washed precipitate is triturated with
hydrate of lime and alcohol, and heated; the filtrate is treated with
carbonic acid, the alcohol distilled off, and the residue filtered, evaporated,
and exhausted with ether. The residue left on evaporating the
ethereal solution is separated by treating it with a small quantity of
ether into two portions, a purer, which remains undissolved and is
subsequently crystallised from hot water, and a less pure, which
dissolves and is recovered from the solution by evaporation. The latter
portion is dissolved in water containing acetic acid, mixed with basic
acetate of lead, and treated with hydrosulphuric acid. The sulphide of
lead is separated by filtration, and the glaucopicrine thrown down with
it is extracted by oft-repeated boiling with water containing acetic acid.
This solution, together with the filtrate from the sulphide of lead, is
then saturated with sulphate of soda and precipitated by ammonia.
The precipitate is purified, though with difficulty, by dissolving in
ether. The purer portion of the glaucopicrine contains small quantities
of a second alkaloïd, precipitated at the same time by tannic acid.
This second body forms, with hydrochloric acid, a salt which crystallises
in needles and easily deliquesces.
Properties. Dazzling white granules, permanent in the air, and of
a bitter taste.
Glaucopicrine assumes a dark grass-green colour when heated with
excess of oil of vitriol, and is converted into a tough green pellicle,
which is insoluble in water, acids, and ammonia.
Dissolves in water, especially when hot: the concentrated solution
becomes covered on cooling, with a pellicle, which is afterwards pre-
cipitated in the crystalline form. It forms neutral white salts, having a
bitter, extremely nauseous taste.
Hydrochlorate of Glaucopicrine.-Obtained by evaporating a solution
of glaucopicrine in hydrochloric acid, washing the residue with ether,
and crystallising from water. - Rhombic tables with truncated edges,
or tufts of prisms, having a glassy lustre, permanent in the air.
Glaucopicrine dissolves in alcohol, and less easily in ether. It is
withdrawn from its solutions by animal charcoal.
GLAUCINE.
161
2. Glaucine.
PROBST. Ann. Pharm. 31, 242.
Occurs in the herb of Glaucium luteum, but not in the root.
The first year's plants are freed from roots and flowers, ground
with acetic acid, and pressed. The expressed liquid is heated to pre-
cipitate leaf-green, acidified with a little nitric acid, and mixed while
still warm with nitrate of lead. After cooling, the fumarate of lead
which has separated is collected; the excess of lead is thrown down
by hydrosulphuric acid; and the filtrate is neutralised, and precipitated
by decoction of oak-bark. This precipitate, when washed and pressed,
is triturated in the moist state with hydrate of lime, and the mixture is
exhausted with warm alcohol. Carbonic acid is then passed into the
alcoholic liquid; the filtrate is evaporated; and the residue washed
with a little cold water, which removes colouring matter. The remain-
ing glaucine is crystallised from hot water.
White crusts, made up of small pearly scales. It is deposited from
ether as a turpentine-like mass, almost oily at first, but becoming
harder on standing. Melts to an oil under water. Tastes bitter and
very acrid. Has an alkaline reaction. Turns red in the air, especially
in sunshine.
Glaucine is decomposed by heat, without subliming. When heated
with oil of vitriol till the acid begins to evaporate, it assumes a fine blue-
violet colour, without liberation of charcoal or sulphurous acid: on the
addition of water, a liquid of a dark cherry-blossom colour is produced,
from which ammonia throws down an indigo-blue precipitate. This
precipitate dissolves with red colour in acids, and is precipitated
unaltered by ammonia; it dissolves in alcohol with blue colour, but is
insoluble in water and ether. — Hydrochloric acid acts on glaucine in
the same manner as oil of vitriol, but less powerfully. Nitric acid
decomposes it.
Glaucine is soluble in water, especially when hot.
It neutralises acids, and forms therewith white salts, having a
burning acrid taste. It is precipitated from its salts by ammonia in
the form of a white curdy precipitate, which speedily cakes together
into an elastic mass, and afterwards hardens.
Phosphate of Glaucine is not crystallisable.
Sulphate of Glaucine. The dirty-red solution of glaucine in dilute
sulphuric acid leaves, on evaporation, shining crystals, which are freed
from excess of acid by washing with ether, from red colouring matter
by rinsing with absolute alcohol, and further purified by re-crystallisa-
tion from alcohol. Groups of white needles. Dissolves easily in
water and absolute alcohol, but not in ether.
Hydrochlorate of Glaucine. A concentrated solution of glaucine in
hydrochloric acid solidifies on cooling to a soft mass of fine needles,
having a blood-red colour when impure glaucine is used. White
needles and crusts, turning red on exposure to light, and red and dark-
blue on spontaneous evaporation of their solution. The salt dissolves
easily in water, but is insoluble in alcohol and ether.
VOL. XVII.
AL
162
PRIMARY NUCLEUS C33H24; OXYAZO-NUCLEUS C38NH1508.
The salts of glaucine are precipitated by tincture of galls.
Glaucine dissolves very easily in alcohol and ether. It is precipitated
from its solutions by animal charcoal, and is extracted from the char-
coal with difficulty by alcohol.
3. Second alkaloid of Sanguinaria. The name porphyroxine given to this
body by Gibb (Pharm. Viertelj. 10, 56), supposes its identity with the porphyroxine
of opium, which, however, is not indicated by the description.
The root is exhausted with water containing acetic acid; the
chelerythrine is thrown down by the addition of ammonia; and the
filtrate is exactly neutralised with acetic acid, and precipitated with
infusion of galls. The precipitate is collected, washed, dried, triturated
with hydrate of lime [alcoholic potash (Gibb)], and exhausted with
alcohol. The alkaline tincture thus obtained is treated with carbonic
acid, the alcohol is distilled off, and the residue evaporated to dryness,
and exhausted with boiling water. The aqueous solution is again
evaporated, and the residue dissolved in ether. On evaporating the
ethereal solution there remains a dirty-white crystalline mass, which is
purified by re-crystallisation from alcohol, with the help of animal
charcoal.
Small tables, inodorous, tasteless, and very difficultly soluble in
water. Forms with acids colourless, neutral, crystallisable salts,
which are bitter and soluble in water. Dissolves in alcohol and ether
(Riegel, Jahrb. pr. Pharm. 11, 102).
4. Third alkaloid of Sanguinaria. Gibb's Puccine. - Wayne (Pharm.
Viertelj. 6, 254) in preparing sanguinarine by the Probst-Schiel method,
excepting that he precipitated the ethereal solution with sulphuric
acid, found that a second base remained in solution, and was obtained
as a dark-red, amorphous residue by evaporating the ether.
This residue was dissolved in ether, again treated with dilute sul-
phuric acid to precipitate any remaining sanguinarine, then filtered and
evaporated to dryness. The residue, when dissolved in alcohol and
mixed with water, yielded a precipitate of puccine (or sulphate ? Kr.).
This substance, after drying, forms a red, tasteless powder, insoluble
in cold water, and melting to a resin in boiling water. An alcoholic solu-
tion is rendered pale-yellow by treatment with animal charcoal, and
the filtrate leaves on evaporation a pale-red residue, which is coloured
dark-red by hydrochloric acid, and afterwards forms bright-red needles.
With sulphuric acid red nodules are obtained, a solution of which
yields a pale-yellow precipitate with ammonia.
5. Acrid alkaloïd of Eschholtzia. Occurs in the root and herb,
together with a bitter alkaloïd, and in autumn accompanied also by
chelerythrine. This body is precipitated by ammonia from the extract
made with water containing acetic acid, while the bitter alkaloïd
remains dissolved in the liquid. The precipitate is to be washed with
pure weak ammonia, dried, and dissolved in ether. The colouring
matter is removed by evaporating the ethereal solution, dissolving the
residue in water containing acetic acid, precipitating with ammonia,
&c.; or by digestion with animal charcoal. White powder, tasteless
in itself, but very bitter in alcoholic or ethereal solution. Has an
alkaline reaction. Does not assume a violet colour with oil of vitriol.
-Insoluble in water, but easily soluble in acids, forming neutral
CHELIDOXANTHINE.
163
colourless salts, which are completely precipitated by caustic alkalis
and their carbonates in white flocks. The salts are precipitated also
by infusion of galls. The alkaloïd dissolves easily in alcohol and ether
(Walz, Jahrb.pr. Pharm. 8, 223; ¡N. Br. Arch. 42, 133).
6. Bitter alkaloid of Eschholtzia. After throwing down the che-
lerythrine and acrid alkaloïd by ammonia from the acetic extract of the
plant, the filtrate is neutralised with acetic acid and precipitated by
infusion of galls. From this precipitate the bitter alkaloïd is obtained
in the same way as the second alkaloïd of sanguinaria from the cor-
responding precipitate.-Crystalline, easily fusible mass, which has a
nauseous, bitter taste, and turns litmus blue. It colours oil of vitriol
a fine violet, even on the addition of one drop of a solution containing
Tth of the alkaloïd (Walz, Jahrb. pr. Pharm. 8, 224).
1
7. Colouring matter of the petals of Glaucium luteum (Handbuch viii. [2],
41). The petals are exhausted with alcohol, acetic acid, and moderately
concentrated caustic potash in succession, and the residue is dried and
exhausted with ether, which takes up the colouring matter. By
evaporating the ethereal solution, washing the residue successively
with absolute alcohol, warm caustic potash, and acidulated water, and
taking up the colouring matter remaining undissolved by ether, a solu-
tion is obtained which, when evaporated, leaves the colour in the form
of a deep-yellow, fatty mass. It melts when heated, and is decom-
posed at a high temperature. It is bleached by exposure to light. By
treatment with strong caustic potash, it appears to yield a substance
insoluble in water, but soluble in alcohol; for after treatment with
potash it communicates a yellow colour to absolute alcohol, though not
if first washed with acids. It is precipitated from its ethereal solu-
tion by alcohol (Probst, Ann. Pharm. 31, 257).
8. Chelidoxanthine.
PROBST. Ann. Pharm. 29, 128.
In the root, herb, and flowers of Chelidonium majus (Handbuch viii
[2], 41).
The root is first treated with dilute sulphuric acid to remove che-
lerythrine and chelidonine, as described on page 157; the residue is then
exhausted with hot water, and the extract is mixed with neutral
acetate of lead, and afterwards treated with hydrosulphuric acid. The
precipitated sulphide of lead, after washing with cold water, gives up
to boiling water, chelidoxanthine, which is obtained in the form of a
friable mass on evaporating the solution. This mass is washed succes-
sively with ammonia-water and ether, which remove foreign substances,
and the residue is exhausted with absolute alcohol. The solution thus
obtained is filtered and evaporated, and the chelidoxanthine which
remains is washed with cold dilute sulphuric acid, ammonia-water, and
ether. It is lastly dissolved in boiling water, and crystallised by
slow evaporation.
Yellow, friable mass, or short yellow needles and crusts. Has a
very bitter taste.
Chelidoxanthine dissolves in oil of vitriol, with evolution of gas,
M 2
164
PRIMARY NUCLEUS CH²; OXYAŽO-NUCLEUS C³Ñ³H1506.
forming a yellowish-brown solution, which is not precipitated by
water, and only slightly by ammonia.
It dissolves very slightly in cold, but more freely in hot water,
which it colours a deep yellow. It is not altered by acids or alkalis.
-Difficultly soluble in alcohol; insoluble in ether. Precipitated from
its aqueous solution by tincture of galls.
Oxyazo-nucleus C38N3H1506.
Chelidonine.
? C138N³H¹706=C38N3H1506, H².
PROBST. Ann. Pharm. 29, 123.
REULING. Ann. Pharm. 29, 131.
POLEX. N. Br. Arch. 16, 77.
WILL. Ann. Pharm. 35, 113.
Observed by Godefroy (J. Pharm. 10, 635): obtained pure and investigated by
Probst. — Reuling's chelidonine appears to contain chelerythrine.
Occurrence. In the root, herb, and unripe seed-capsules of Cheli-
donium majus; most abundantly in the root, together with chelerythrine
(p. 156).
Preparation. 1. In the preparation of chelerythrine, according to
page 157, after precipitating the sulphuric acid extract of the roots
with ammonia, and extracting the chelerythrine from the precipitate
by ether, there remains a residue which is to be dissolved in the
smallest possible quantity of water acidulated with sulphuric acid, and
mixed with twice the quantity of strong hydrochloric acid, which throws
down hydrochlorate of chelidonine. The salt is decomposed by
ammonia-water, and purified by repeatedly dissolving it in a little
acidulated water, precipitating with hydrochloric acid, decomposing
with ammonia, and lastly by crystallising from boiling alcohol. Or
the base may be dissolved in acetic acid and the solution evaporated,
when crystals free from acetic acid will be formed. The mother-
liquors and wash-waters are precipitated by ammonia, and the preci-
pitate is purified as above (Probst).-2. The expressed juice of celan-
dine yields, with ammonia, a precipitate containing chelidonine,
chelerythrine, a little chelidoxanthine, salts of chelidonic acid, and
other substances. The precipitate (which decomposes on standing) is
exhausted as quickly as possible with alcohol containing sulphuric
acid; the solution is mixed with water; the alcohol distilled off; and
the residue, after filtering from the resin which deposits on cooling,
is precipitated by ammonia, of which an excess is added to dissolve a
brown substance thrown down at first. From this precipitate the
chelerythrine is extracted by ether, and the remainder is dissolved in
water containing sulphuric acid, and precipitated by strong hydrochloric
acid as hydrochlorate of chelidonine. Purification is effected as above
(Probst). See the method of Polex (p. 158).
CHELIDONINE.
165
Properties. Crystallised chelidonine contains water, which is ex-
pelled at 100°. See below. Inodorous. Tastes acrid, not bitter
(Polex); bitter, like sulphate of quinine, and afterwards harsh, pro-
bably from impurities (Reuling). Melts at 130° to a colourless oil (Will).
Volatilises with aqueous vapour (Reuling). Not poisonous (Probst;
Reuling.)
Will.
at 100°
mean.
38 C..........
3 N
228
68.06
67.75
42
12.54
12.19
17 H....
17
5:08
5.62
6 O......
48
14.32
14.44
C'38N3H¹706
335
100.00
100.00
>
The above is Limpricht's formula (Lehrb. 1197). The following formulæ have
also been proposed: C40N3H2006 (Will); CON³H¹ºO6 (Gerhardt); C42N³H¹9O6
(Gmelin).
Decompositions. 1. Chelidonine when heated above its melting point,
turns brown, takes fire, and burns with a bright smoky flame.
2. Submitted to dry distillation it yields empyreumatic vapours.-3. It
is decomposed by strong nitric acid; when boiled therewith it turns
yellow (Polex), dark orange-yellow (Reuling).-4. Carbonises with hot
oil of vitriol (Polex). Dissolves in oil of vitriol with carmine-red colour,
changing to black (Reuling).-5. It is not decomposed by chlorine, or
by aqueous alkalis (Reuling). When melted with fragments of caustic
potash, it evolves a large quantity of ammonia: if the operation be
suspended during the evolution of ammonia, the residue still contains
unchanged chelidonine (Will).
Combinations. With Water. Hydrated Chelidonine. Colourless
tables, having a vitreous lustre (Probst). Transparent tables and cubes
(Polex). — Air-dried chelidonine contains 4.89 p. c. of water (2 at. =
5.09 p. c. HO) (Will).
Chelidonine is insoluble in water (Probst; Will). A solution pre-
pared with hot water becomes cloudy on cooling, without forming a
deposit (Reuling).
The salts of chelidonine are colourless when the acid is itself free from
colour (Probst; Polex). Reuling obtained orange-coloured salts, probably from
his base containing chelerythrine. They are crystallisable, of an acid re-
action, for the most part soluble in water, and have an intensely but
pure bitter taste. From solutions of the salts alkalis precipitate cheli-
donine in the form of a voluminous, curdy precipitate, which becomes.
granular under the liquid. Solutions of chelidonine-salts containing weak
volatile acids lose acid on evaporation (Probst). Acetate of chelidonine
yields with tincture of iodine a carmine-coloured, with chromate of
potash a yellow, with basic acetate of lead a white, and with solution
of gold a dark reddish-yellow precipitate (Polex).
Phosphate of Chelidonine. More easily crystallisable than the sul-
phate. Fusible, and easily soluble in water and absolute alcohol
(Probst).
Sulphate of Chelidonine. - Obtained by dissolving chelidonine in
dilute sulphuric acid, evaporating, washing away excess of acid by
ether, and crystallising from absolute alcohol by spontaneous evapora-
166
PRIMARY NUCLEUS CH6; OXYGEN-NUCLEUS CHO'.
tion of the solution. In warm air the solution dries up to a brittle
gum. Permanent in the air. Melts at 50 to 60° to a viscid mass.
Dissolves easily in water and absolute alcohol (Probst).
Hydrochlorate of Chelidonine. Obtained from hot water in delicate
crystals. Has an acid reaction and a bitter taste. Dissolves in 325
parts of water at 18°, and is precipitated from the solution by strong
hydrochloric acid (Probst).
Nitrate of Chelidonine. - Crystals of considerable size, difficultly
soluble in water, so that nitric acid throws down a crystalline precipi-
tate from the sulphate and phosphate (Probst).
Chloroplatinate of Chelidonine. Bichloride of platinum throws.
down from hydrochlorate of chelidonine a yellow flocculent precipitate,
afterwards becoming granular. It may be washed with water without
decomposition, and is not acted on by boiling nitric acid. Contains
17.42 to 17.6 p. c. of platinum (CN³H¹706, HCl, PtCl requires 18-23
p. c. Pb) (Will).
Acetate of Chelidonine. Obtained by decomposing sulphate of
chelidonine with acetate of lead. The solution of chelidonine in
acetic acid [which is obtained with difficulty (Polex)] deposits chelido-
nine when evaporated by heat. On spontaneous evaporation the salt
dries up to a gum, easily soluble in water and alcohol (Probst).
The salts of chelidonine are precipitated by tincture of galls.
Crystallised chelidonine dissolves with difficulty, and only on pro-
longed boiling, in alcohol and ether (Polex). The statement of Probst that
chelidonine is soluble in alcohol and ether is to be understood only in this sense, as
is shown by other statements (Kr.). Dissolves easily in volatile and fat oils
(Polex, Reuling). It is precipitated from solutions of its salts by
animal charcoal (Probst).
Primary Nucleus C38H26; Oxygen-nucleus C38H²²O¹.
Pyroguaiacin.
C'38H2206 = ('38H2204,02.
Literature xii., 349; further:
NACHBAUR (& HLASIWETZ). Wien. Acad. Ber. 30, 81; Ann. Pharm.
106, 382; J. pr. Chem. 75, 1; Kopp's Jahresber. 1858, 451.
HLASIWETZ & VON GILM. Ann. Pharm. 119, 277.
According to Hlasiwetz, the pyroguaiacin obtained by the dry dis-
tillation (especially by slow distillation) of guaiacum resin and guaiacic
acid is not Ĉ¼4H8O2, but C38H22O. (See xiv, 349.)
Pyroguaiacin forms inodorous and tasteless lamine, which melt at
183°, and solidify in a crystalline mass.
Nachbaur.
Dried at 100° or melted.
mean.
38 C
228
76.51
76.56
22 H.......
22
6 0 ....
4.8
7.38
16.11
7.37
16.07
C38H2206.
298
100.00
100.00
-
1
THEBAÏNE.
167
According to Hlasiwetz it is not a phenyl-compound.
Pyroguaiacin combines with bases. An alcoholic solution colours
sesquichloride of iron green. - Does not yield oxalic acid on prolonged
boiling with caustic potash.
Potassium-pyroguaiacin.-A solution of pyroguaiacin in boiling
caustic potash forms, on cooling, a semi-solid mass of crystals, which
are pressed and dissolved in boiling alcohol. — Fine, delicate prisms
and needles, having a satiny lustre. When heated in the air, it
assumes first a green, afterwards a blue-green colour. On recrystal-
lisation it gives up potash (Hlasiwetz & v. Gilm).
38 C.......
24 H
80
ко
C38H21KО6 + 3aq.
Hlasiwetz & v. Gilm.
Over oil of vitriol.
228
62.81
62.46
24
6.61
6.55
64
17.64
18.85
47
12.94
12.14
363
100.00
100.00
Contains, at 100°, 13.89 p. c. KO (by calc. 13.89 p. c. in the anhydrous compound)
(Hlasiwetz and v. Gilm).
Sodium-pyroguaiacin. Iridescent lamine, turning green in warm
air. Contains, at 100°, 7·1 p. c. Na, corresponding to the formula
C38H21NaO6 (by calc. 7.18 p. c. Na) (Hlasiwetz and v. Gilm).
Over oil of vitriol.
Hlasiwetz and v. Gilm.
38 C
228
66.57
66.27
23.5 H
Na
23.5
6.86
6.57
23
6.72
6.85
8.5 O
68
19.85
20.31
C3H21NaО6 + 23 aq.
342.5
100.00
100.00
Oxyazo-nucleus C38NH1006.
Thebaïne.
C38NH2106 = C³NH¹906,H³.
PELLETIER. J. Pharm. 21, 565; N. Br. Arch. 5, 165; Schw. 67, 325;
Ann. Pharm. 16, 38; abst. Pogg. 27, 658. In opposition to
Couerbe: J. Pharm. 22, 29.
COUERBE. Ann. Chim. Phys. 59, 153; Ann. Pharm. 17, 171. — In op-
position to Pelletier: J. Pharm. 22, 22.
KANE. Ann. Pharm. 19, 7.
ANDERSON.
Trans. Roy. Soc. Edin. 20, 3, 347; Chem. Soc. Qu. J. 5,
257; abstr. Ann. Pharm. 86, 179; J. pr. Chem. 57, 358; Kopp's
Jahresber. 1852, 537.
Paramorphine (Pelletier). — Discovered by Thiboumery in Pelletier's
manufactory in 1835.
Source. In opium. To the amount of about 1 per cent. (Merck)
168 PRIMARY NUCLEUS C3H26; OXYAZO-NUCLEUS CNH906.
Couerbe obtained from 40 pounds of opium about an ounce of thebaïne.
Occurs also in the poppy cultivated in France (Calloud, N. J. Pharm.
20, 276).
Preparation. In the preparation of morphine by the Couerbe-Mohr
process (xvi, 416), when the aqueous extract of opium is precipitated
with milk of lime, the morphine remains dissolved in excess of
lime, whilst the lime precipitate takes up the thebaine. The pre-
cipitate is washed, dried, and boiled with alcohol; the alcoholic solu-
tion is evaporated; and the brown granular mass which remains is
treated with ether, which takes up thebaïne, and leaves it on evapora-
tion in the form of a brown, crystalline mass. Purification is effected
by dissolving in acids, precipitating with ammonia, and crystallising
from alcohol or ether (Pelletier; Couerbe). Anderson obtains thebaïne ac-
cording to xvi, 420. See Winckler's method (Repert. 53, 384).
Mixtures of thebaïne and morphine may be separated by means of
ether or weak alcohol, which readily dissolve thebaïne (Pelletier).
Properties. White, silvery, quadratic lamina (Anderson). Needles
or small granular crystals, without pearly lustre (Pelletier). Shining,
smooth rhomboidal prisms, crystallising from alcohol in cauliflower-
like masses, like grape-sugar (Couerbe). Melts without loss of weight
(Kane) at 150° (Pelletier), at 130°, and solidifies again at 110°
(Couerbe). Becomes strongly electric when rubbed or powdered.
Tastes acrid and styptic rather than bitter. Has an alkaline reaction
(Pelletier; Couerbe). Poisonous : one grain given to a dog causes
tetanus and death (Magendie).
228 ... 73.31
at 100°
38 C
N
14
....
21 H ....
21
60
48
....
4.50
6.75
15.44
100.00
Couerbe. Pelletier. Kane.
mean.
70.99
....
6.38
6.46
16.17
....
Anderson.
mean.
mean.
...
73.23
6.94
6.82
73.08
4.43
7.04
....
13.01
15.45
....
72.09.....
4:40
6.29
17.22
100.00 100.00 100.00 100.00
....
....
CYNH2106 311
....
Isomeric with bebirine.
The above is Anderson's formula.
Earlier formula: C3+NH1806 (Pelletier)
C25NH13 504 (Couerbe); 025NHO³ (Kane). - Couerbe's statement, that air-dried
thebaïne loses 4 p. c. of water when melted, was not substantiated by Kane's experi-
ments.
Decompositions. 1. Thebaïne yields, when heated, the ordinary
decomposition-products of nitrogenous substances, without volatilising
(Pelletier). - 2. It is coloured deep-red by oil of vitriol, even when free
from nitric acid (Anderson; Winckler). Forms a yellow solution with
oil of vitriol (Riegel). Cold sulphuric acid of sp. gr. 1.3 dissolves
thebaïne, and deposits on heating a semi-solid resin, probably a product
of decomposition, which dissolves in boiling water and separates on
cooling in microscopic crystals (Anderson). 3. Thebaïne is violently
attacked by nitric acid, with evolution of red fumes, and forms there-
with a yellow solution, which yields a volatile base with caustic potash,
assuming a dark colour (Anderson). When digested with strong nitric
acid, thebaïne turns soft and yellow, and before dissolving, melts to a
soft resin (Pelletier). — Oil of vitriol containing nitric acid immediately
THEBAÏNE.
169
colours thebaïne red [blood-red (Riegel)], the solution becoming darker
on standing: thin layers appear yellowish (Couerbe). The solution in
oil of vitriol is coloured first green, afterwards brown, by permanganate
of potash (Guy, Anal. Zeitschr. 1, 93); it is not altered by peroxide of
lead at first, but after 24 hours assumes a faint violet-red colour
(Riegel). Chromate of potash produces in the sulphuric acid solution
a brisk evolution of gas and a dirty-brown coloration in the course
of 24 hours a white precipitate is deposited, and the liquid becomes
colourless (Riegel, N. Br. Arch. 58, 287). 4. Chlorine and bromine
convert thebaïne into a resin (Anderson). — 5. Dry hydrochloric acid
gas converts it [with evolution of heat (Couerbe, Kane)], into sal-
ammoniac and a resinous body, which does not form salts (Liebig, Ann.
Pharm. 26, 60). Thebaïne is resinised by strong aqueous hydrochloric
acid (Pelletier): the solution in dilute acid assumes a dark colour on
evaporation, with simultaneous formation of resin, and is no longer
completely soluble in water (Anderson). 100 parts of thebaïne absorb
8.35 parts of hydrochloric acid gas (Couerbe); 16:58 parts at 100°, and
17.35 parts more at ordinary temperatures (altogether 33.93 parts)
(Kane). — Thebaïne does not colour ferric salts blue (Pelletier).
It
Combinations. Thebaïne is very slightly hygroscopic (Kane).
is insoluble, or nearly so, in water (Pelletier; Anderson), and in aqueous
ammonia and potash (Anderson).
Thebaïne dissolves readily in acids, forming salts which cannot be
crystallised from aqueous solutions, but are easily crystallised from
alcohol or ether (Anderson). The salts are precipitated by ammonia
and potash (Pelletier), and by the carbonates and bicarbonates of the
alkalis, in the case of the last-named reagents even in presence of
tartaric acid (Riegel). The precipitates are insoluble in excess of the
precipitant.
Sulphate of Thebaine. - Obtained, partly in crystals and partly in
the form of a resin, which solidifies to a crystalline mass on standing,
by adding sulphuric acid to an ethereal solution of thebaïne (Ander-
son).
Hydrochlorate of Thebaïne. Thebaïne is mixed with a small
quantity of strong alcohol, and alcoholic hydrochloric acid, not in
excess, is added till solution is effected: the salt then separates, on
standing, in fine rhombic crystals. Dissolves easily in water and
resinises on evaporating the solution. Difficultly soluble in alcohol,
especially in absolute alcohol, and insoluble in ether (Anderson).
Anderson,
at 100°
mean.
38 C
N
228
62.38
62.29
14
3.83
24 H
24
6.56
6.71
80
CI
64
17.52
35.5
9.71
10.00
......
CasNH2¹06, HCl + 2HO
365.5
100.00
....
Mercuric chloride produces with thebaïne a bulky precipitate, and
with the hydrochlorate a white crystalline precipitate, neither of which
can be obtained of constant composition (Anderson).- Terchloride of
1
170
PRIMARY NUCLEUS C3H6; OXYAZO-NUCLEUS CNH¹ºOº.
gold forms with hydrochlorate of thebaïne an orange-yellow precipitate,
which melts to a resin at 100° (Anderson).
Chloroplatinate of Thebaine.-Obtained from hydrochlorate of thebaïne
and bichloride of platinum. - Yellow crystalline powder, slightly
soluble in boiling water, apparently with decomposition (Anderson).
Anderson.
38 C
N
24 H
SO
3 Cl
Pt
C3NH2106, HCI,PtCl² + 2HO
at 100°
228
42.60
mean.
42.56
42
2.61
2-4
4:48
4:55
....
64
11.98
106.5
19.89
98.7
18.44
18.71
....
563.2
100.00
Thebaine dissolves easily in alcohol [in 10 parts cold (Pelletier)] and
ether, especially when boiling.
Bebirine.
(38NH2106 = C38NH1906, H2.
MACLAGAN. Ann. Pharm. 48, 106.
MACLAGAN & TILLEY. Ann. Pharm. 55, 105; Phil. Mag. 27, 253;
J. pr. Chem. 37, 247.
V. PLANTA. Ann. Pharm. 77, 333; N. Phil. Mag. 1, 114; J. pr. Chem.
52, 287. Die Alkaloide, Heidelberg, 1846, 26.
Discovered by Rodie in 1834. Occurs in the bark and fruit of the
bebeeru or greenheart tree of Guiana, Nectandra Rodixi, Nat. order
Lauracea: See Guibourt (N. J. Pharm. 10, 89).
Preparation. From the bark. The bark is exhausted by boiling
with water containing sulphuric acid; the decoction is concentrated,
and filtered from the tannin and sulphate of lime which separate on
cooling; and the yellowish-green filtrate is precipitated with ammonia.
The dark-grey precipitate thus obtained is washed and dried in the air,
whereupon it blackens from containing tannin: it is then dissolved in
dilute sulphuric acid and treated with animal charcoal; and the now pale-
yellow solution is again precipitated with ammonia, whereby a white
precipitate is obtained. This is dried and dissolved in alcohol; the
solution is evaporated; and the residue treated with absolute ether,
which takes up bebirine and leaves sipeerine undissolved. Both bodies
are still to be purified by treating their alcoholic solutions with animal
charcoal (Maclagan). Or the grey precipitate produced by ammonia
may be freed from tannin by exhausting it with water containing 6 per
cent. of caustic potash. The undissolved portion is then to be dissolved
in alcohol, and the residuc, after evaporation, treated with ether. In
this way, however, both bebirine and sipcerine dissolve in the alkaline
liquid, from which they may be thrown down in an impure state by sal-
ammoniac (Maclagan).
BEBIRINE.
171
In a later process adopted by Maclagan & Tilley, commercial
sulphate of bebirine is decomposed by ammonia, and the precipitate
triturated while still moist with freshly precipitated hydrated oxide of
lead. This mixture is dried over the water-bath, and the bebirine and
sipcerine are extracted by absolute alcohol, and afterwards separated
by means of ether. The product obtained in this manner by v. Planta
was still impure, as it absorbed oxygen and turned brown on prolonged
drying over the water-bath. To purify it, he dissolved it in acetic
acid; filtered the solution; added thereto first neutral acetate of lead
and then caustic potash; and after completely washing and drying the
precipitate of bebirine and oxide of lead, extracted the bebirine by
ether. The ethereal solution was evaporated to a syrup and dissolved
in alcohol, and on dropping the solution into water, with constant
stirring, the bebirine was precipitated as a dense flocculent powder.
Properties. White, highly electric powder, permanent in the air
(v. Planta). IIas a powerful and persistent bitter taste, with a faint
resinous after-taste. The alcoholic solution blues litmus strongly
(Maclagan). Melts (without loss of weight, after drying at 120°)
at 180 to a vitreous mass (v. Planta). Anti-febrile (Maclagan).
Resembles caffeine in its physiological effects (N. Repert. 11, 521).
Maclagan
and Tilley.
T. Planta.
inean.
mean.
38 C
228
73.31
71.46
72.91
N
14
4.50
5.49
4.53
21 H
21
6.75
6.39
6.89
60
48
15.44
16.66
15.67
C35NH2106
311 100.00
100.00
100.00
The above is v. Planta's formula: Maclagan and Tilley proposed C¾5NH2O6. —
Isomeric with thebaïne.
Decompositions. Bebirine decomposes at a temperature above 180°,
without subliming (v. Planta). In the fire it froths up, evolves strongly-
smelling vapours, and leaves a slowly combustible charcoal (Maclagan &
Tilley). Aqueous iodic acid colours hydrochlorate of bebirine a bright
red-brown, changing to dark-red (v. Planta). — Bebirine boiled with
dilute nitric acid evolves nitric oxide, and is converted into a yellow
powder, which dissolves easily in hot, but difficultly in cold water.
From a dilute solution of sulphate of bebirine nitric acid throws down
the base, for the most part, in its original state (Maclagan, Winckler).
Bebirine forms a black resin with chromate of potash and sulphuric
acid. Does not yield chinoline when distilled with caustic potash
(Maclagan & Tilley).
Bebirine dissolves in 6650 parts of cold, and in 1466 parts of
boiling water (Maclagan). It is precipitated from its alcoholic solution
in a great measure by water (v. Planta).
Bebirine neutralises acids completely, and forms therewith un-crys-
tallisable salts. From the hydrochlorate, the base is precipitated by
ammonia, the fixed alkalis, and their carbonates and bicarbonates, in
white flocks, which dissolve in excess of ammonia or potash somewhat
more freely than in excess of the other precipitants. Phosphate of
soda throws down white flocks, tincture of iodine a red-brown pre-
172
PRIMARY NUCLEUS C3H6; OXYAZO-NUCLEUS CNH¹ºOº.
cipitate (v. Planta). Biniodide of potassium precipitates bebirine
completely (Wagner). The salts are all amorphous, and have a very
bitter taste, with an accompanying harsh taste (Maclagan).
Sulphate of Bebirine. - Pale-yellow, shining. Soluble in water.
C3SNH2106
HO.....
SO³
C3NH2¹06,HO,SO³
Maclagan.
311
86.38
86.39
9
2.50
40
11.12
13.61
360
100.00
Hydrochlorate of Bebirine. - Bebirine absorbs hydrochloric acid gas,
without melting, and is converted into a yellow soluble salt, which is
left, on evaporating the solution, in transparent scales (Maclagan).
C38NH2106
HCI
311
89.5
Maclagan.
86.39
a
36.5
10.5
13.61
C35NH2¹06,HCI
347.5
100.0
100.00
The hydrochlorate forms with ferric chloride, cupric chloride and mer-
curic chloride, double salts slightly soluble in hot water and alcohol, from
which they separate in a non-crystalline form on cooling (Maclagan &
Tilley). Its solution throws down white or yellowish-white amorphous
precipitates from iodide and iodomercurate of potassium (v. Planta; Delffs).
The white precipitate produced by mercuric chloride in hydrochlorate of
bebirine is converted into a green sticky resin by boiling with water
(Hinterberger, Ann. Pharm. 82, 319).
The gold-salt is yellowish-white and decomposes on exposure to the
air (v. Planta).
Chloroplatinate of Bebirine. Formed by dropping a strong solution
of hydrochlorate of bebirine into dilute chloride of platinum, stirring
constantly so that the precipitate may not cake together. Yellowish-
white precipitate, triturable to an orange-yellow powder after drying
(v. Planta).
Maclagan
& Tilley.
V. Planta.
mean; at 120°.
42.42
44.09
2.53
4.21
4.66
38 C
22 H
60
228
44.08
4.
44
N
14
2.70
22
4.25
48
9.30
3 Cl
Pt....
106.5
20.59
98.7
19.08
19.12
18.90
100.00
C35NH2106,HCl,PtCl2.... 517.2
Contains 19.2 p. c. of platinum; but if the same bebirine be dissolved in ether
and the solution evaporated in the air, the dark residue yields a platinum-salt con-
taining only 14 p. c. of platinum (Winckler, N. Repert. 1, 14).
Hydrochlorate of bebirine precipitates chloride of iridium and sodium
of an ochre colour; sulphocyanide of potassium white; picric acid sulphur-
yellow; it forms precipitates also with tincture and infusion of galls
(v. Planta).
Bebirine dissolves in 5 parts of absolute, and easily in aqueous
alcohol, and in 13 parts of ether (Maclagan).
BUXINE.
173
Appendix to Bebirine.
1. Sipeerine. Preparation, see p. 170. Dark red-brown, shining,
non-crystalline, resinous mass, separating from the vessel in which it
is prepared in scales. Very slightly soluble in water. Neutralises
acids and forms therewith olive-brown salts. Dissolves easily in
absolute and in weak alcohol, but not in ether (Maclagan).
M
2. Bebiric acid. Occurs in the fruit of the bebeeru or greenheart
tree. A cold aqueous extract is concentrated and, after cooling,
filtered. The bebirine and sipeerine are thrown down by ammonia,
and nitrate of baryta is added to the filtrate. The dirty precipitate
thus obtained is washed with cold water, dissolved in boiling water, and
the solution is evaporated till it crystallises. The crystals, purified by
re-crystallisation, are dissolved in boiling water and mixed with neutral
acetate of lead; the precipitate thereby produced is washed, and de-
composed by hydrosulphuric acid; the filtrate, evaporated to a syrup, is
allowed to crystallise over oil of vitriol; and the crystals are purified
by dissolving in ether and evaporating the solution in a vacuum.
Deliquescent, white crystalline mass, having a waxy lustre. Melts
at 150°, and sublimes undecomposed, in tufts of needles, at a little over
200°. The potash and soda salts are deliquescent and soluble in
alcohol; the lime, baryta, and magnesia salts very slightly soluble in
water; the lead-salt but little soluble, even in boiling water
(Maclagan).
3. Buxine.
FAURÉ. J. Pharm. 16, 432; N. Tr. 33, 2, 219.
BLEY. N. Tr. 25, 2, 64.
WALZ.
N. Jahrb. Pharm. 12, 302; 14, 15; Pharm. Virtelj. 10, 36;
abstr. Chem. Centr. 1861, 7.
Occurs in the bark and leaves of Buxus sempervirens.
Preparation. The leaves are boiled with water containing sulphuric
acid; the decoction is precipitated by carbonate of soda; and the
precipitate thereby formed is washed by decantation, dried, and ex-
hausted with alcohol. The alcoholic solution is evaporated, and the
residue is extracted with water slightly acidulated with hydrochloric
acid. To this solution is added a large quantity of hydrochloric acid,
whereby hydrochlorate of buxine, which is insoluble in strong hydro-
chloric acid, is thrown down. The precipitate is dissolved in a large
quantity of water, again precipitated with carbonate of soda, and the
precipitated buxine, dissolved in alcohol, is digested with a mixture of
hydrated oxide and basic acetate of lead, by which yellow colouring
matter [buxoflavin (Walz)] is removed. The oxide of lead dissolved in
the filtrate is removed by dilute sulphuric acid; the solution is pre-
cipitated by ammonia; and the precipitate, which runs into a resinous
mass on warming, is dried, dissolved in ether, and recovered from the
solution by evaporation (Walz). The portion insoluble in ether con-
174
PRIMARY NUCLEUS C3H30; OXYGEN-NUCLEUS CHO16.
tains Walz's buxinic acid. Fauré precipitates an aqueous solution of
the alcoholic extract of the bark with neutral acetate of lead; frees the
filtrate from lead by means of hydrosulphuric acid, and boils with cal-
cined magnesia; and after washing and drying the precipitate, extracts
his buxine with alcohol, which leaves it on evaporation in the form of
a red mass, triturable to a red-brown powder. By repeated treatment
with animal charcoal it may be obtained nearly colourless. Bley adopts
a similar process; or, he precipitates a solution of the aqueous extract
with basic acetate of lead, decomposes the precipitate under water by
hydrosulphuric acid, and boils the washed sulphide of lead with
alcohol, which takes up the buxine and leaves it on evaporation as a
yellow, crystalline, very deliquescent mass, still contaminated with
chloride of calcium (Bley). In this way the greater part of the buxine
remains in solution, since it is not precipitated, or only mechanically, by
basic acetate of lead (Walz).
Properties. Buxine is obtained by the evaporation of its ethereal
solution in the form of a coloured resin; when precipitated from its
acid solutions by ammonia, or from an alcoholic solution by water, it
forms a white powder. It is tasteless at first, but afterwards very
bitter. Has an alkaline reaction. Remains unaltered at 180°, but
decomposes at higher temperatures (Walz; Fauré).
Walz.
38 C
229
73.31 ...... 72.90
N
14
4.50
4.51
21 H
21
6.75
6.87
60
48
15.44
15.72
100:00
100.00
CSNHO…... 311
Isomeric, and according to Walz, identical with bebirine.
Buxine dissolves in 6600 parts of cold, and in 1800 parts of boiling,
water. - It dissolves in acids, forming neutral non-crystallisable salts,
which behave like salts of bebirine with caustic alkalis and their car-
bonates, with nitric acid, and with all other reagents. The hydrochlorate
C'35NH2¹06, HCl, forms double salts with mercuric chloride and bi-
chloride of platinum (Walz).
Buxine dissolves in 3 parts of alcohol of sp. gr. 0·85, and in 5 parts
of absolute alcohol [less freely, therefore? (Kr.)]. It is soluble in
10 parts of commercial, and in 13 parts of absolute ether (Walz).
According to Fauré it is insoluble in ether.
Primary Nucleus C38H30; Oxygen-nucleus C8H14016.
Daphnetin.
C138 II 14018
C39H14016,02.
ZWENGER. (1860.) Ann. Pharm. 115, 1.
Formation. From Daphnin. 1. By boiling with dilute sulphuric or
hydrochloric acid.-2. By warming with emulsin.-3. By contact
DAPHNETIN.
175
with yeast to which a little grape-sugar is added. 4. By dry distil-
lation. In all cases its production is attended with the formation of
sugar or the decomposition-products thereof.
Preparation. A. From Daphnin. Daphnin is boiled with dilute
hydrochloric or sulphuric acid till the liquid becomes yellow. It is
then diluted with water, and the crystals which separate on cooling are
collected, dissolved in hot water, and precipitated with neutral acetate
of lead. The washed precipitate is decomposed under boiling water
by hydrosulphuric acid, and the solution filtered. Colourless daphnetin
then crystallises out on cooling, and may be purified by re-crystallisa-
tion from boiling water. The solution filtered through paper containing iron
has a green colour.
B. From the alcoholic extract of Mezereon bark, and also from the
extract previously exhausted with ether (p. 177). — 1. The extract,
mixed with strong hydrochloric acid, is evaporated over the water-
bath, and the dry residue is heated more strongly so long as hydro-
chloric acid is given off, and until it begins to carbonise. The
resulting mass is boiled with water; the filtrate is concentrated; and
the dark deposit formed on standing is collected and washed with cold.
water, after which the daphnetin is extracted by boiling water and
purified by repeatedly converting it into the lead-salt and decomposing
by hydrosulphuric acid.-2. The alcoholic extract is slowly heated in
a half-filled retort, the heat being continued so long as vapours pass
The crystals which form in the distillate are separated from the
liquid portion, and crystallised successively from water and very
dilute alcohol, whereby a mixture of daphnetin and umbelliferone is
obtained. The crystals dissolved in boiling water, are precipitated
by neutral acetate of lead, the liquid is filtered hot, and the precipi-
tated compound of daphnetin with oxide of lead is purified as above.
The filtrate, on cooling, yields crystals of umbelliferone.
over.
Properties. Delicate, colourless, highly refractive prisms, belonging
to the oblique prismatic or monoclinic system. Melts above 250° to a
yellowish liquid, which cools to a crystalline solid, and sublimes, even
at lower temperatures, especially in a current of air. Has a slightly
harsh taste, and when warmed, an agreeable smell, resembling that of
coumarin. Its reaction is very slightly acid.
Zwenger.
at 100°.
mean.
38 C
228
59.06
59.17
14 H
14
3.62
3.81
18 O
144
37.32
37.02
CESH14018
386
100.00
100.00
Contains at 220°, when it begins to sublime, 607 p. c. C., or the same proportion
as æsculetin (xvi, 23): it does not, however, resemble the latter body in its behaviour
with bisulphites of the alkalis (Rochleder, Wien. Acad. Ber. 48, 236).
Decompositions. 1. Daphnetin is partially decomposed by heating
in a closed vessel till it melts. 2. Dissolves in slightly warmed oil of
vitriol with yellow colour, and is precipitated by water unchanged; the
solution is decomposed by heat.-3. Colours nitric acid dark-red.
176 PRIMARY NUCLEUS CSH30; OXYGEN-NUCLEUS CH¹016.
4. Throws down cuprous oxide from a cold alkaline solution of cupric
oxide, and rapidly reduces nitrate of silver.
Combinations. Daphnetin dissolves easily, with yellowish colour, in
boiling water. Soluble without alteration in boiling hydrochloric acid.
Dissolves in caustic alkalis and their carbonates with yellow or red-
yellow colour, and, when dissolved in water, produces yellow precipi-
tates with lime- or baryta-water.
Lead-compound of Daphnetin. - Aqueous daphnetin forms yellow precipitates
with both the neutral and the basic acetate of lead.. A warm aqueous solution
of daphnetin is precipitated by aqueous neutral acetate of lead, and the
pale yellow precipitate is washed and dried at 100°. Dark coloured,
brittle mass, triturable to a yellow hygroscopic powder. It is partially
decomposed by prolonged boiling with water, and then contains
57.60 p. c. of oxide of lead. Dissolves in acetic acid, and colours nitric
acid red.
Zwenger.
at 100°.
mean.
38 C
228
28.61
28.17
10 H
10
1.25
1.38
14 O
112
14.07
14.46
4 PbO
448
56.07
55.99
CsH10Pb4018
798
100.00
100.00
....
Aqueous daphnetin is coloured green by a small quantity of a ferric
salt, the colour being destroyed by a larger quantity of the salt, or
by the addition of an acid. It is coloured faintly greenish by a very
little of a proto-salt of iron.
Daphnetin dissolves easily in boiling alcohol, and slightly in ether.
Glucoside of Daphnetin.
Daphnin.
C162H34038 = C38H14018,2C12H10010.
VAUQUELIN. Ann. Chim. 84, 174.
C. G. GMELIN & BÄR. Ueber die Seidelbastrinde. Tübingen, 1822;
Schw. 35, 1.
CONST. ZWENGER. Ann. Pharm. 115, 1; abstr. J. pr. Chem. 82, 196;
Pharm. Viertelj. 10, 93; Chem. Centr. 1860, 823; Rep. Chim. pure.
3, 77; Kopp's Jahresber. 1860, 552.
ROCHLEDER. Wien. Acad. Ber. 48, 236; Chem. Centr. 1864, 481;
N. Repert. 13, 326; J. pr. Chem. 90, 442.
Discovered by Vauquelin, and regarded by him and by Gmelin &
Bär as a salifiable base, but recognised by Zwenger as a glucoside.
Occurs in the bark of Daphne alpina and D. Mezereum (Handbuch, viii
[2], 72), most abundantly at the time of flowering; also in the
flowers of the latter plant (Enz, Pharm. Viertelj. 8, 25).
DAPHNIN.
177
The seeds of Daphne Gnidium contain Göbel's coccogninic acid, which may be
obtained by exhausting the alcoholic extract with water. It forms acid, long, 4-sided
prisms, and is not precipitated by chloride of barium, lime-water, neutral acetate of
lead, or proto sulphate of iron. — Concerning the acrid principle of mezereon, see
p. 178.
Preparation. The alcoholic extract which has been exhausted with
ether for the preparation of the officinal Extractum Mezerci ethereum
may be used instead of the fresh bark.
The alcoholic extract is boiled with water, and the liquid is left
for 24 hours to deposit resin. Neutral acetate of lead is then added;
the resulting precipitate is removed; and the daphnin is thrown
down from the filtrate by basic acetate of lead. This precipitate is
decomposed under water by hydrosulphuric acid; the liquid, filtered
from sulphide of lead, is evaporated to a syrup, diluted, filtered from
resin, again concentrated, &c.; and the syrup is finally freed from
resin by repeatedly shaking it with 5 or 6 times its volume of ether.
The aqueous liquid separated from the ether quickly solidifies to a
mass of crystals of daphnin, which is washed and crystallised from hot
water (Rochleder). Zwenger proceeds in a similar manner, but pre-
cipitates the daphnin by prolonged boiling with basic acetate of lead:
according to Rochleder, however, the liquid filtered from the precipitate
produced in the cold yields, on boiling, only a little daphnin, difficult to
purify.
Properties. Crystallised daphnin (see below) turns opaque below
100°, and loses 8 at. of water at 100°, becoming anhydrous. Anhy-
drous daphnin melts at about 200° to a colourless liquid, which forms a
crystalline solid on cooling (Zwenger).
62 C.........
34 H
at 100°.
372
34
52.39
4.78
42.83
Zwenger.
mean.
52.42
4.95
42.63
སྤ། ༣
38 O.....
C62H34033
304
710
100.00
....
100.00
Bears a strong resemblance to æsculin (xvi, 22) (Rochleder).
Decompositions. 1. Daphnin when heated decomposes at a tempera-
ture near its melting-point, evolves vapours and a sublimate of daph-
netin, and leaves an amorphous residue which becomes coloured when
more strongly heated, burns like sugar with access of air, and leaves
charcoal if air be excluded (Zwenger).-2. By boiling with dilute
acids it is converted into daphnetin and sugar :
C62H34038+ 4HO C33H¹018 + 20H12012 (Zwenger).
=
3. Nitric acid colours daphnin red in the cold, and converts it into
oxalic acid when heated (Gmelin; Zwenger). 4. A solution of daphnin
in caustic alkalis or their carbonates, or in lime- or baryta-water, turns
brownish-red and decomposes on standing, and more rapidly on boiling
(Zwenger). 5. Daphnin slowly reduces cuprous oxide from a boiling
alkaline solution of cupric oxide. 6. It reduces nitrate of silver partially
only on boiling, but rapidly in the cold, after addition of ammonia
(Zwenger).-7. It is resolved into daphnetin and sugar by warming
VOL. XVII.
N
178
PRIMARY NUCLEUS CI30; OXYGEN-NUCLEUS CH¼016.
with emulsin, and partially also by contact with yeast and a little grape-
sugar (Zwenger).
Combinations. With Water. - Hydrated or Crystallised Daphnin.
Colourless, transparent rectangular prisms, attaining a length of half an
inch, or when rapidly crystallised, slender needles (Vauquelin; Zwenger).
Tastes extremely bitter (Vauquelin), moderately bitter, afterwards
harsh (C. G. Gmelin; Zwenger). Neutral (Zwenger); slightly acid
(C. G. Gmelin). Loses on an average 9.36 p. c. of water at 100°
(8 at. 9.20 p. c. HO), and becomes anhydrous.
Zwenger.
Crystals.
mean.
62 C...
42 H
372
47.57
47.17
42
5.37
5.57
46 O.......
368
47.06
47.26
C62H34038 +8 aq.
782
100.00
100.00
Daphnin dissolves very slightly in cold water, but easily in hot
water, crystallising from the solution on cooling.
Daphnin dissolves in caustic alkalis and their carbonates with golden-
yellow colour; also in lime- and baryta-water. The latter solutions
throw down gelatinous precipitates on boiling. It is not precipitated
by aqueous neutral acetate of lead (Vauquelin and others), but is coloured
yellow by the basic acetate in the cold, and precipitated in combination
with oxide of lead on boiling. It is completely withdrawn from its
solutions by boiling with hydrated oxide of lead (Zwenger). - Colours
sesquichloride of iron bluc, the colour changing to yellow on boiling,
while a dark-yellow precipitate is thrown down (Zwenger). Dissolves
in cold alcohol rather more freely than in water, and very easily in
boiling alcohol. Easily soluble in warm acetic acid, from which it
crystallises on cooling (Zwenger). According to Vauquelin, it is easily
soluble, but according to Zwenger perfectly insoluble, in ether.
Appendix to Daphnin.
Resin and Acrid Principle of the Daphnads.
Besides the observations
of Landerer given at page 472, vol. xiv, the following have been
published.
The alcoholic tincture of the bark of Daphne alpina yields on distil-
lation a non-acrid distillate, but on precipitating the resin from the
residue by water and distilling the supernatant liquid, an acrid distil-
late is obtained, while the residue almost entirely loses its harshness.
The distillate has an alkaline reaction, and a persistent burning taste:
the taste, however, it possesses only after 24 hours. The precipi-
tated resin is brown and soft, and has a very acrid taste, even when
dissolved in alkalis. By treatment with hot water containing sulphuric
acid, the acrid principle is removed, and passes over on distilling the
acid liquid (Vauquelin, Ann. Chim. 84, 186). — Vauquelin afterwards
obtained an ammoniacal distillate, also having a persistent acrid taste,
either by distilling a decoction of mezereon with alkalis, or by first
neutralising the decoction with sulphuric acid, concentrating, and then
DOEGLIC ACID.
179
distilling with alkalis; or, lastly, by washing the alcoholic extract
with hot water, at last containing sulphuric acid, and distilling the
liquid with magnesia.
By precipitating an alcoholic extract of the bark of Daphne Meze-
reum, concentrated and freed from wax, with water, C. G. Gmelin
(Schw. 35, 11) obtained an acrid resin, the acrid principle of which was
not extracted by boiling with hydrochloric acid. On adding alcoholic
neutral acetate of lead to an alcoholic solution of the resin, precipi-
tating the filtrate therefrom with hydrosulphuric acid, and evaporating
the resulting liquid, there remained a thick yellow oil, containing the
whole of the acrid principle of the resin. This oil, saponified with
caustic potash, yielded a soap which, when distilled with tartaric acid,
evolved a powerful odour of phosphoretted hydrogen. - See also
Giesse (Taschenbuch, 1822, 113), Coldefy-Dorly (J. Pharm. 11, 167),
Dublanc (J. Pharm. 15, 637). — The resinous acid of the bark of
Daphne Mezereum yields by umbelliferone dry distillation (Zwenger, Ann.
Pharm. 115, 17).
Primary Nucleus C38H35.
Doeglic Acid.
C38H3604 = C¹38H36,04.
SCHARLING. J. pr. Chem. 43, 257; Lieb. Kopp's Jahresber. 1847 &
1848, 568.
Source. Forms the principal part of doegling train oil.
Preparation. The oil is heated to 110-130° with oxide of lead for
10 hours, with frequent additions of a little water, and the plaster
thereby formed is boiled with water and afterwards digested with
ether; the ethereal solution is filtered; the ether distilled off; and the
residual lead-salt decomposed by hydrosulphuric acid.
Properties. Yellow-oil, becoming turbid at 16°, and solidifying at a
few degrees above 0°. Reddens litmus.
Dried over chloride of calcium.
Scharling.
38 C
228
77.03
77.06
36 H....
36
12.16
12.47
4 O.....
32
10.81
10.47
C38H 3604
296
100.00
100.00
SAN
Baryta-salt. Obtained by neutralising the acid with aqueous am-
monia, precipitating with chloride of barium, washing the precipitate
without exposure to the air, and crystallising from hot alcohol. Turns
yellow and runs together at 100°, without melting.
38 C
35 H
Scharling.
at 100° (mean).
228
62.74
62.71
35
9.61
9.63
30
24
6.61
6.46
BaO
76.5
21.04
21.20
C33H35BaO
363.5
100.00
100.00
N 2
180
PRIMARY NUCLEUS CH36.
Doeglic Ether.
CH*O* = CIIBO,C38H36O3.
Deposited in the form of a yellow oil on passing hydrochloric acid
gas into an alcoholic solution of doeglic acid, and purified by washing
with water.
Neutral.
Scharling.
42 C.......
40 H
252
77.77
40
12.34
40....
32
9.89
....
324
100.00
mean.
77.5
12.7
9.8
100·0
Doegling Train Oil.
From the doegling (the Balana rostrata of Chemnitz, Hyperodon of
later zoologists), a kind of dolphin.
Nearly colourless, or often darker oil, much thinner, and with a less
repulsive odour than the other train oils. Sp. gr. 0.8807 at 11°.
Becomes turbid at 8°, and semi-solid at 0°, from formation of crystals.
Contains, on the average, 78.97 p. c. C., 13.36 H., and 6·77 O., ap-
proximating to the formula CHO, which represents a compound of
1 at. doeglic acid with 1 at. oxide of doeglyl. Free from iodine and
ash-constituents.
4 8
When the oil is cooled to 0°, and afterwards filtered, first at 0°, and
then repeatedly at increasing temperatures, and the residue is ex-
pressed, a solid fat is obtained, amounting to th of the oil. This
solid fat contains spermaceti, and is partially saponified by potash.
The soap, freed from spermaceti, yields a silver-salt containing 42.82
p. c. C., 6·93 H., and 38.90 Ag, corresponding to the formula C2º¹⁹AgОª
(the silver-salt of capric acid).
19
The oil absorbs oxygen in large quantity, and becomes thicker and
specifically heavier. When exposed to the air in a shallow basin, it
becomes covered with a pellicle, after the removal of which the re-
mainder dries up only slowly. — By dry distillation it yields a much
smaller quantity of acrolein than other fats, and no sebacic acid.
When it is rapidly distilled, a gascous mixture is evolved, containing
about 1 vol. of carbonic acid to 6 vols. of hydrocarbons, and a colourless
distillate passes over, while a little charcoal and oil remain behind. The
distillate is a mixture of various hydrocarbons, volatile acids, and pro-
bably undecomposed oil. When it is treated with carbonate of soda
and rectified over potassium, at first in the water-bath, the principal
product is the hydrocarbon C2H2 (containing 85.16 C., 1451 H.:
vapour-density = 5.81). The hypothetical combination this hydro-
carbon with I at. water forms Scharling's oxide of doeglyl. The oil
solidifies with nitrous acid.
21
The oil combines with oxide of lead to form a plaster, from which
boiling water extracts, not glycerin, but a small quantity of an acid
dark-brown substance. Ether extracts from the plaster the lead-salt of
EUXANTHONE.
181
doeglic acid, and leaves a mixture of lead-salts, the acids of which
partly crystallise from alcohol.-Scharling (Ann. Pharm. 96, 236)
afterwards found in the oil a large quantity of spermaceti, and by
saponifying it with potash, obtained doeglal (corresponding to ethal),
which solidifies only at temperatures below 0°.
Doegling train-oil dissolves in 2 parts of boiling alcohol, and in 22
parts of alcohol at 37°.
Primary Nucleus C38138.
139
Fatty Acid C38 H38,04.
Obtained in an impure state by Heintz, from cyanide of stethal,
C37C37Cy, by boiling crude cyanide of cetyl containing that compound
with alcoholic potash. See under Margaric acid (xvi, 472).
COMPOUNDS CONTAINING 40 ATOMS OF CARBON.
Primary Nucleus CH22; Oxygen-nucleus C40H12010.
Euxanthone.
C40H12012 = C40H12010,0².
STENHOUSE (1844). Phil. Mag. 25, 322; Ann. Pharm. 51, 429.
ERDMANN. J. pr. Chem. 33, 205; 37, 386; abstr. N. J. Pharm. 10,
154; J. pr. Chem. 71, 195.
LAURENT. Compt. chim. 1849, 377; abstr. Compt. rend. 26, 33.
Purrenone.
Formation. 1. By heating euxanthic acid or its salts (Erdmann;
Stenhouse):
C42H18022
=
2CO² + 6HO + C40H12O12 (Gerhardt, N. J. Pharm. 10, 157).
2. Together with hamathionic acid, by dissolving euxanthic acid in
oil of vitriol (Erdmann).-3. By passing hydrochloric acid gas into
alcoholic euxanthic acid, and in small quantities by evaporating euxan-
thic acid with aqueous hydrochloric acid (Erdmann).
Preparation. 1. Euxanthic acid is heated in an air-bath to 160° or
180°, or until it begins to melt, when water and carbonic acid are set
free, the decomposition being complete in a few minutes. From the
residue warm dilute ammonia-water takes up unchanged cuxanthic
acid, a brown decomposition-product, and a little euxanthone, which last
is deposited again on cooling. The greater part of the euxanthone
remains undissolved in the form of a yellow powder, and is purified by
182
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS CHO10.
crystallisation from alcohol (Erdmann).-2. Euxanthone is obtained in
fine crystals, though less abundantly than in 1, by heating euxanthic
acid in Mohr's sublimation apparatus (Stenhouse).-3. When a solu-
tion of cuxanthic acid in oil of vitriol is diluted with a large quantity
of water, euxanthone separates in the form of a yellowish-white pre-
cipitate, which is washed with water, digested with dilute carbonate of
ammonia to remove unchanged euxanthic acid, and crystallised from
alcohol (Erdmann).
Properties. Pale-yellow, broad needles or lamina (Erdmann); or,
when prepared according to 2, crystals more than an inch long (Sten-
house). Sublimes undecomposed when carefully heated. Neutral.
Stenhouse.
mean.
Erdmann.
Laurent.
40 C............ 210
12 H
12 O
12
96
CHEO¹.... 348
....
68.96
3.45
27.59
68.02
...
....
3.65
28.33
***
100.00
....
100.00
mean.
Earlier.
....
68.33
3.61
28.06
....
Later.
68.86
3.40
27.74
68.73
3:47
27.80
....
100.00
100.00
....
....
100.00
Stenhouse examined euxanthone prepared according to 2; Erdmann, according
to 1, 2, and 3, with similar results. The above formula, proposed by Gerhardt (N.
J. Pharm. 10, 157) is now generally adopted, instead of the earlier one of Erdmann
and Stenhouse (С¹³¹О¹).
Decompositions. 1. Euxanthone burns on platinum-foil, without
leaving a residue (Stenhouse). — 2. Dissolves in cold nitric acid of sp.
gr. 1·31, without decomposition at first, but the solution on standing för
some time becomes warm, and evolves red vapours, whilst porphyric acid
is produced. When it is heated with nitric acid a violent action takes
place, continuing after the removal of the source of heat, with forma-
tion of porphyric and oxyporphyric acids, and on boiling, of styphnic
and oxalic acids (Erdmann). - 3. Euxanthone does not reduce alkaline
solution of cupric oxide (W. Schmid, Ann. Pharm. 93, 88).
Combinations. Euxanthone dissolves very slightly in water (Sten-
house).
It is very little soluble in dilute acids (Stenhouse), and nearly
insoluble in dilute ammonia, but soluble in strong, warm, aqueous
ammonia, forming a yellow solution, from which it is deposited unchanged
on evaporation (Erdmann). The ammoniacal solution forms a yellow
precipitate with chloride of magnesium mixed with sal-ammoniac
(Erdmann). The alcoholic solution does not precipitate chloride of
barium, chloride of calcium, nitrate of silver, or neutral acetate of lead, but
throws down a yellow, slimy precipitate from basic acetate of lead
(Stenhouse).
Euxanthone is but slightly soluble in alcohol or ether (Stenhouse). It
dissolves very freely in boiling alcohol, and crystallises from the solu-
tion on cooling (Erdmann).
PORPHYRIC ACID.
183
Appendix to Euxanthone.
1. Porphyric Acid.
ERDMANN. J. pr. Chem. 37, 403.
Dinitro-euxanthone (Gerhardt).
A solution of euxanthone in cold nitric acid of sp. gr. 1.31, becomes
warm on standing, evolves red vapours, and on cooling deposits por-
phyric acid, which is purified by digesting it with aqueous carbonate of
ammonia, washing with water containing carbonate of ammonia,
crystallising from pure water, and decomposing with hydrochloric
acid.
Yellow crystalline powder, or reddish-yellow, very small crystals.
Electric when rubbed.
Erdmann.
mean.
20 C.......
2 N.
120
45.45
43.63
28
10.62
11.82
.....
4 H....
4
1.51
1.45
14 O.......
112
42.42
43.10
C20X2H40
264
100'00
100.00
The above formula was proposed by Gerhardt, who regarded porphyric acid as
dinitro-euxanthone (euxanthone C20H6O6). Erdmann's formula is C26X3H507;
=
Laurent's (Compt. chim. 1849, 384) contains 1 at. oxygen more.
By boiling with nitric acid it yields styphnic (xi, 228) and oxalic
acids.
Slightly soluble, with red colour, in water; insoluble in acidulated
water.
The salts of porphyric acid explode when heated. The neutral
ammonia-salt throws down from chloride of barium, chloride of calcium,
neutral acetate of lead, and nitrate of silver, red, for the most part
crystalline precipitates, which dissolve in a large quantity of water.
The acid ammonia-salt precipitates from nitrate of silver, pale orange-
coloured crystalline scales.
Ammonia-salt. a. Acid.
When the salt b is kept in a state of
fusion at 130°, so long as water and ammonia (amounting to 20.19 p. c.)
are given off, the residue dissolves less easily than before in water, and
crystallises on cooling in pale-red, feathery crystals, containing 4141
p. c. C., and 2·16 H.
b. Neutral. Aqueous carbonate of ammonia converts porphyric
acid into a blood-red salt, which is insoluble in carbonate of ammonia,
but slightly soluble, with yellowish-red colour, in pure water. On
drying it becomes darker, brown-red, and gives off water, and at 130°
also ammonia.
184
OXY-CHLORINE-NUCLEUS CC1H9010.
Erdmann.
mean.
20 €.......
3 N
120
42.71
40.76
42
14.94
15.45
7 H.....
14 0.....
7
2.46
2.41
....
112
39.89
41.38
C0X2H³ (NH4) O
281
100.00
100.00
Copper-salt. Precipitated on mixing hot solutions of the ammonia-
salt and sulphate of copper, in black-red flocks, which become granular
on standing, or more quickly when heated. Microscopic, acute octa-
hedrous. By boiling with caustic potash, it forms a brown solution and
a black precipitate, which is difficult to wash, and explodes when
heated.
Porphyric acid is very slightly soluble in cold, but more easily
soluble in boiling, alcohol.
2. Oxyporphyric Acid.
ERDMANN. J. pr. Chem. 37, 407.
Obtained by heating euxanthone with nitric acid till a violent action
takes place, and leaving the resulting solution to cool. The acid
which precipitates is dissolved in strong aqueous carbonate of ammonia,
to free it from porphyric acid, and precipitated from the filtrate by
hydrochloric acid.
Yellow, microscopic crystals, closely resembling porphyric acid.
Does not lose weight at 130°. Contains, on the average, 42.76 p. c. C.,
11.95 N., 1.38 H., and 43.91 0.
According to Erdmann, its formula is CX3H508, but according to
Laurent it is probably identical with porphyric acid (Compt. chim. 1849,
384).
Nitric acid converts it into styphnic (xi, 228) and oxalic acids, and
at length completely into oxalic acid.
Oxyporphyric acid forms, when digested with carbonate of ammonia,
a dark-red salt, remaining on evaporation as a black-red, granular,
crystalline mass, which does not turn pale-red when heated (as does
the porphyrate of ammonia), and dissolves easily in aqueous carbonate
of ammonia. (Hereby it is distinguished from porphyrate of ammonia.)
The ammonia-salt throws down from salts of the earths and heavy metals
red-brown precipitates, which explode when heated, and dissolve in
water more easily than those produced by the ammonia-salt of por-
phyric acid. Oxyporphyric acid forms a soluble salt with excess of
bicarbonate of potash.
Oxy-chlorine-nucleus C40C131I9019.
Chloreuxanthone.
C40C¹³90¹² = C¹ºC³H³¹º,0².
ERDMANN. J. pr. Chem. 37, 397.
BERBERINE.
185
From a solution of chlorcuxanthic acid in oil of vitriol, water pre-
cipitates chloreuxanthone as a yellow powder, which crystallises from
alcohol in yellow, feathery crystals.
Crystals.
Erdmann.
40 C
240.0
53.15
52.28
3 Cl......
9 H
106.5
23.59
23.30
9.0
1.99
2.14
12 O
96.0
21.27
22.28
....
C40C13H9012
451.5
100.00
100.00
Primary Nucleus C40H24; Oxy-azo-nucleus CNH1508.
Berberine.
CNHQ = C*NH150®, H.
CHEVALLIER & PELLETAN. J. Chim. méd. 2, 314; Berz. Jahresb. 7,
266.
J. A. & L. A. BUCHNER. Repert. 52, 1; Ann. Pharm. 24, 228; Berz.
Jahresb. 16, 228; Repert. 56, 177.
G. POLEX. N. Br. Arch. 6, 264.
G. KEMP. Repert. 73, 118; Chem. Gaz. 1847, 209; Lieb. Kopp's Jahresb.
1848 and 1849, 636.
HERBERGER. Jahrb. pr. Pharm. 4, 82.
FLEITMANN. Ann. Pharm. 59, 160.
SCHAFFNER. Jahrb. pr. Pharm. 12, 281.
BÖDEKER. Prelim. notice: Ann. Pharm. 66, 384; J. pr. Chem. 43,
501; Instit. 1848, 193; Lieb. Kopp. Jahresber. 1847 and 1848, 635;
Ann. Pharm. 69, 37; abstr. Pharm. Centr. 1819, 145; Chem. Gaz.
1849, 149.
J. D. PERRINS. Phil. Mag. (4) 4, 99; Ann. Pharm. 83, 276; Lieb. Kopp's
Jahresber. 1852, 549; J. pr. Chem. 57, 248; N. J. Pharm. 23, 153.
Chem. News, 1862, No. 204; Pharm. J. Trans. (2) 3, 546 and 567; N.
Repert. 11, 308; Chem. Centr. 1862, 551. Chem. Soc. Qu. J. 15, 339;
Ann. Pharm. Suppl. 2, 171; abstr. Chem. Centr. 1862, 890; Zeitschr.
Ch. Pharm. 5, 414; Pharm. Journal, 4, 464; Kopp's Jahresber. 1862,
379; with remarks by A. Buchner, N. Repert. 12, 546.
STENHOUSE. Ann. Pharm. 95, 108; Pharm. J. Trans., 14, 455; Lieb.
Kopp's Jahresber, 1855, 568.
L. HENRY. Prelim. comm. Instit. 1858, 264; Kopp's Jahresber. 1858,
375; Complete; Ann. Pharm. 115, 132; Bull. Acad. Belg. (2) 7, 8;
Kopp's Jahresber. 1859, 399.
IILASIWETZ & V. GILM.
256; Complete: Ann. Pharm.
330; Chem. Centr. 1863, 897.
13, 185.
Ann. Pharm. 115, 45. Ann. Pharm. 122,
Suppl. 2, 191; Zeitschr. Ch. Pharm. 7,
Wien. Acad. Ber. 49, 1; N. Repert.
MAHLA. Sill. Amer. Journal, 83, 43; Chem. Centr. 1862, 550; Kopp's
Jahresber. 1862, 379.
Discovered as Xanthopicrite, in 1826, by Chevallier and Pelletan, in the
bark of Xanthoxylum Clava Herculis, L., and as berberine iu 1835, by
186 PRIMARY NUCLEUS CH24; OXY-AZO-NUCLEUS CONH¹508.
L. A. Buchner in Berberis vulgaris, Buchner & Herberger (Repert. 36, 1)
and Brandes (Br. Arch. 11, 29) having previously described a yellow
bitter principle, a colouring matter, and a resin from barberry root.
Berberine was first investigated more fully by Fleitmann, who showed
that the body obtained by Buchner's process, was the hydrochlorate and
not pure berberine. Kemp recognised berberine as a vegetable base in
1841. Perrins, in 1862, showed the identity of xanthopicrite with ber-
berine. Perrins and Illasiwetz & v. Gilm corrected Fleitmann's
formula.
Berberine occurs also in the following plants and organs of plants:
-in the flowers of the barberry (Ferrein, Pharm. Viertelj. 7, 257); in
Indian varieties of barberry (Solly); in the columbo root of Cocculus
palmatus (Menispermea), (Bödeker); in the bark of Cæloelyne polycarpa
(Anonaceae) from Abecouta in Western Africa (Stenhouse); in the wood
of Coscinium fenestratum (Menispermen), from Ceylon (Perrins); in Xan-
ihorriza apifolia (Perrins) and Hydrastis canadensis (Mahla), two Ameri-
can Ranunculacea.
The following also contain berberine :-A yellow dye-wood from
Upper Assam, the Woodunpar of the natives; the wood of St. John's
root from the Rio Grande; the yellow bark of the Pachnelo tree of Bogota;
the root of Coptis Tecta or Mahmira, an Indian and Chinese species of
ranunculus.
The Papaveracea, Leontice thalichroides, Jeffersonia diphylla, and
Podophyllum pellatum contain berberine: the podophyllin (Pharm.
Viertelj. 9, 121) prepared from the last named plant, is a mixture of
resin and berberine (F. F. Mayer, Pharm. Viertelj, 13, 108).
The berberine in barberry root is not perceptible under the micro-
scope; but when a thin slice of the root is moistened with alcohol and
afterwards with nitric acid, crystals of nitrate of berberine form in the
vessels, which are thus shown to be the parts in which the berberine
occurs (Apoth. Zeit. 1863, 27). The wood of a Mexican variety of
barberry contains berberine in the form of a golden-yellow powder
deposited in the cracks (Wittstein, Repert. 86, 258).
Concerning barberry-orange, see Herberger (Jahrb. pr. Pharm. 4, 82). — On the
identity of jamaicine and berberine see under Jamaicine (Appendix to Quinine).
Preparation. 1. From the bark of Barberry-root. The comminuted
bark is exhausted with boiling water, and the liquid is evaporated to a
soft extract, which is treated with boiling alcohol so long as it imparts
thereto a bitter taste. The tincture, freed from the greater part of the
alcohol by distillation, deposits on standing for twenty-four hours in the
cold, delicate yellow crystals, which are separated from the mother-
liquor by pressing, and purified by washing with cold water and
crystallising from boiling water or alcohol (Buchner).
The crystals thus obtained are not pure, but consist partly or
wholly of hydrochlorate of berberine. Fleitmann, therefore, converts
them into sulphate by means of dilute sulphuric acid; dissolves the
salt in water; adds baryta-water to alkaline reaction; and passes
carbonic acid into the liquid. After evaporation, the berberine is ex-
tracted by alcohol; the alcoholic solution is precipitated by ether;
and the precipitate is crystallised from water. The nitrate of berberine
obtained by other modes of preparation may be decomposed in a similar manner.
2. From the roots of Hydrastis canadensis. The powdered root is
BERBERINE.
187
:
exhausted with hot alcohol in a percolator; the tincture is evaporated;
the residue is mixed with water, filtered, and precipitated by hydro-
chloric acid; and the precipitated hydrochlorate of berberine is
purified by crystallisation from boiling alcohol (Mahla). Or, the root is
exhausted with boiling water and the liquid evaporated to an extract,
which is digested with boiling alcohol. The alcoholic solution is dis-
tilled, and to the residue a little dilute nitric acid is added, when, on
standing for a day or two, nitrate of berberine crystallises out, and
may be freed from resin by repeated crystallisation from water con-
taining nitric acid, with the help of a little animal charcoal (Perrins).
Hydrastis canadensis yields 4 p. c. of crude berberine (Perrins).
3. From Columbo root. An alcoholic extract of the root is ex-
hausted with hot lime-water, and the brown-red solution thus obtained
is filtered and neutralised with hydrochloric acid, whereby an amor-
phous precipitate is thrown down. The filtrate, to which an excess of
hydrochloric acid is added, throws down, on standing for two days, a
crystalline deposit of hydrochlorate of berberine, which is dissolved in
alcohol of 85 p. c., precipitated from the solution by ether, and washed
with ether on a filter (Bödeker).
Properties. The anhydrous (? Kr.) crystals obtained by drying at
100° (see Hydrated Berberine, p. 189) melt at 120° to a red-brown resin
(Fleitmann). Neutral towards vegetable colours. Without action on
polarised light (Henry). Not poisonous. Tastes bitter (Buchner).
Fleitmann.
Henry.
mean.
at 120-140°.
69.50
mean.
40 C
240
71.6-1
at 100°.
67.01
N
14
418
17 H
17
5:08
5.68
5.32
80
64
19.10
335
100.00
....
C4°NH1708
Buchner's analysis (Repert. 52, 17) refers only to hydrochlorate of berberine.
According to Fleitmann, the formula at 100° is CNH¹809+ 2HO; according to
Kemp CNH707; according to Henry (who adopted Gerhardt's supposition)
C42NH19010; according to Stas (Inst. 1859, 462) C4NH190¹. The above formula
was shown to be correct by Perrins, from analyses of the salts, and by Hlasiwetz,
from analysis of hydroberberine.
Decompositions. 1. Berberine heated to 160°-200° evolves yellow
vapours which condense to an oil, and leaves a difficultly combustible
charcoal (Fleitmann). This yellow body is produced also by the dry distillation
of chromate of berberine; it dissolves in alcohol and is precipitated of a yellow
colour by neutral acetate of lead and by water. It reduces nitrate of silver
(Fleitmann). 2. Sodium-amalgam decolorises boiling solution of ber-
berine, with separation of yellow hydroberberine (Hlasiwetz). -
3. When heated to 190°-200° with water in a sealed tube, for several
days, it becomes uncrystallisable and dark-brown, and on slow eva-
poration deposits on the sides of the vessels a mass, which has a red
colour and bronze-like lustre by transmitted light, and a green colour
by reflected light. This mass is but slightly soluble in cold water, but
dissolves in acids with fine purple colour, which is changed to green by
alkalis. Its alcoholic solution is dichroic, red and green (Illasiwetz).
188
PRIMARY NUCLEUS CH; OXY-AZO-NUCLEUS CONH1509.
4. Hydrochlorate of berberine is not altered by trituration with
bromine (Buchner). Bromine added to the extent of 2 at. to aqueous
berberine or the hydrochlorate, colours the solution dark-red and
throws down a dirty-yellow precipitate, a solution of which in boiling
alcohol yields crystals of hydrobromate of berberine. A black resin
precipitable by ammonia, is also produced (Henry). 5. In an atmos-
phere of dry chlorine, berberine assumes a blood-red colour, and becomes
easily soluble in water; chlorine passed into this solution turns it of
a pale-brown colour and throws down brown flocks, which dissolve in
caustic potash and are precipitated by acids (Buchner). According to
Polex, chlorine colours aqueous hydrochlorate of berberine a fine purple-
red; according to Schaffner, it throws down a brown precipitate,
whilst the alcoholic solution is only rendered darker in colour. (See
also Henry). Chloride of lime decomposes berberine (Chevallier &
Pelletan).
6. Strong nitric acid dissolves hydrochlorate of berberine, forming
a dark-red liquid, from which ammonia precipitates brown flocks; on
continued heating, the solution becomes clearer, evolving at the same
time nitric oxide gas, and after evaporating to a syrup and diluting
with water, deposits a yellow, difficultly soluble wax (Fleitmann).
Buchner obtained only oxalic acid; Henry obtained oxalic acid, resin,
and small crystalline nodules.-7. Hydrochlorate of berberine dis-
solves in oil of vitriol, forming an olive-green (Buchner), a greenish-
yellow (Mahla), a red-brown (Chevallier & Pelletan), a violet-red solu-
tion (Polex). These differences may perhaps be caused by the presence of nitric
oxide (Kr.). The olive-green solution is decolorised by dilution with
water, depositing brown flocks of humus (Buchner). Prolonged boiling
with dilute sulphuric acid renders berberine partly uncrystallisable
(Chevallier & Pelletan).
8. Hydrosulphate of ammonia saturated with sulphur throws down
from hydrochlorate of berberine a brown-red precipitate, having a re-
pulsive odour of mercaptan, and containing, after washing, 1653 p. c.
of sulphur. When treated with hydrochloric acid, it does not evolve
hydrosulphuric acid or other gas, but becomes paler, and deposits
yellowish-red crystals, a solution of which, as well as that of the pre-
cipitate, yields a fine red precipitate with ncutral acetate of lead
(Fleitmann).
9. Berberine is not decomposed by a day's boiling with strong alco-
holic potash, or by heating therewith in a scaled tube; but if it be
evaporated with caustic potash and a little water till the melting mass
froths up and gives off hydrogen, together with an odour of chinoline,
the mass, supersaturated with sulphuric acid, throws down a large
quantity of a dirty-brown humus, whilst an acid, C¹HO³, resembling
protocatechuic acid, soluble in ether, and a second acid insoluble in
ether, remain in solution (Hlasiwetz & v. Gilm). - 10. By distilling
berberine with milk of lime or oxide of lead, chinoline is obtained
(Bödeker).
11. Berberine heated with iodide of ethyl is converted, according
to Perrins, into hydriodate of berberine, but, according to IIenry,
into iodide of ethylberberine. Henry obtained pale-yellow needles,
BERBERINE.
189
slightly soluble in alcohol and cold water, and more freely soluble
in hot water, containing 52.66 to 53·48 p. c. C., and 4.70 to 491,
C40 NH¹6 (C¹¹H³) O®, H = 53·76 p. c. C., 4.81 H. When heated with iodide
of amyl, it yields hydriodate of berberine (Henry).
16
9
Combinations. With Water. - Hydrated or Crystallised Berberine.
Delicate yellow needles, which give off 19.26 p. c. of water at 100°
(Fleitmann).
C4°N H¹708.....
9 HO
Crystals.
335
Fleitmann.
80.53
81.
19.47
19.26
.....
100.00
C40NH¹708 + 9 aq.?.... 416
Berberine dissolves with difficulty in water (Chevallier & Pelletan).
It easily forms supersaturated solutions.
With Ammonia? - Hydrochlorate of berberine dissolves in warm
aqueous ammonia, forming a dark-brown liquid, which deposits brown
crystals on cooling. After washing and drying, the crystals evolve
with aqueous potash a large quantity of ammonia (Schaffner). Accord-
ing to Buchner also, berberine combines with ammonia.
Dilute solution of caustic potash throws down berberine from its
[aqueous? (Kr.)] solution in conglomerated masses (Fleitmann).
Solutions of pure berberine are not coloured red by alkalis
(Perrins).
With acids berberine forms crystallisable salts (Kemp; Fleitmann).
The salts are for the most part mon-acid, and more easily soluble in
pure water than in acid or saline solutions. Mineral acids and glacial
phosphoric acid throw down crystals from aqueous hydrochlorate of
berberine. Acetic, tartaric, racemic, citric, and oxalic acids dissolve
hydrochlorate of berberine in the same manner as water (Buchner).
The salts are generally golden-yellow, neutral and bitter (Kemp).
They are obtained pure only by repeated crystallisation till the
mother-liquor is no longer deepened in colour by ammonia (Perrins).
Ammonia decomposes the salts incompletely (Fleitmann). Caustic
potash throws down berberine, which cakes together to a brown resin
on boiling (Buchner; Mahla).
Hydrochlorate of berberine forms yellow double salts, crystallising
in needles, with the chlorides of magnesium, zinc, cadmium, and
uranium, and with sesquichloride of iron, bichloride of tin, and ter-
chloride of antimony (Henry). It precipitates [by forming double-
salts, or on account of the difficult solubility of hydrochlorate of ber-
berine in saline solutions? (Kr.)] chloride of manganese, proto- and
bichloride of tin, nitrate of cobalt, and tartar emetic, yellow; the sul-
phates of copper and nickel, yellowish-green; sesquichloride of iron
and nitrate of bismuth, orange. It does not form precipitates with the
sulphates of iron and zinc, or with neutral or basic acetate of lead
(Buchner).
Sulphate of Berberine. - Bi-acid. The reddish-yellow solution of
hydrochlorate of berberine turns pale-yellow on addition of dilute
sulphuric acid, and after standing for some time deposits delicate, pale
190
PRIMARY NUCLEUS CIT; OXY-AZO-NUCLEUS CNHOS.
reddish-yellow needles, which do not lose weight by drying in a vacuum
at 100° (Fleitmann).
Fleitmann.
40 C
N
19 H
10 O
2 S03
at 100º.
mean.
240
55.42
55.40
...
14
3.23
19
4.39
4.60
.......
80
18.48
80
18.48
17.99
100.00
.....
CNHO,2(HO,SO3).... 433
Hydriodate of Berberine. - Formed by dissolving berberine in hydri-
odic acid (Henry), or by precipitating a weak solution of nitrate of
berberine in hot dilute alcohol with iodide of potassium (Perrins). –
Small yellow (Perrins) or reddish-yellow needles, soluble in 2130 parts
of cold water, more easily in boiling water, and insoluble in alcohol
(Henry). Does not undergo any alteration at 100° (Perrins).
Perrins.
Henry.
at 100-120°.
mean.
40 C
N
•
240
51.83
51.59
51.75
14
3.03
18 H
18
3.88
4.23
3.94
80
6.1
13.83
I
127
27.43
25.71
27.07
CªNIIVOS,HI... 463
100.00
Todo-hydriodate of Berberine.-A. When iodine in slight excess is
added to aqueous or alcoholic solutions of berberine-salts, red-brown
prisms are produced, which after drying over oil of vitriol do not lose
weight at 100°. These crystals are very slightly soluble in cold water
or alcohol: nitrate of silver precipitates from their solutions the whole of
the iodine, forming nitrate of berberine.-B. Besides crystals of hydrio-
date of berberine and the red crystals just mentioned, shining green
spangles are obtained on adding dilute biniodide of potassium, not in
excess, to a hot alcoholic solution of a berberine-salt. The same
green spangles but of larger size, are formed from hydriodate of ber-
herine, when this salt has been prepared by heating alcoholic berberine
with iodide of ethyl to 100°, and afterwards exposing the tube contain-
ing the mixture to sunshine for an hour or two, or to diffused day-
light for some days. When thus formed, it passes on longer exposure
to sunshine into the red salt.-Black-green, rhombic prisms and laminæ,
having a metallic lustre: when very thin, they transmit light of a red-
brown colour and polarise it completely; thicker crystals are perfectly
opaque. The green crystals are easily converted into red, and vice versâ.
Permanent at 100° (Perrins).
Perrins.
A.
B.
40 C
N
210
33.47
33.49
35.65
14
1.95
18 HI
18
2.51
2.58
2.78
80
6-4
8.93
3 I
381
53.14
53.36
CHON HO8,12,HI.... 717
100.00
BERBERINE.
191
The above is the formula given by Perrins. B contained hydriodate of berberine,
which cannot be separated.
IIydrobromate of Berberine. Formed by dissolving berberine in
hydrobromic acid (Henry), or thrown down as a yellow precipitate by
adding bromide of potassium to a mixture of nitrate of berberine and
acetic acid (Perrins). Delicate, fawn-coloured needles, which, after
drying in a vacuum, lose 5.75 p. c. of water at 100° (3 at. = 6·07 p. c.
HO.), and assume a bright orange colour (Perrins). Easily soluble in
water and alcohol (Henry); insoluble in aqueous bromide of potassium
(Perrins).
Henry.
Perrins.
at 100°.
mean.
40 C
N
18 H
240
57.69
56 37
57.61
14
3.37
18
4:32
4.78
4.34
80
64
15.39
Br
80
19.23
18.16
19.00
C40NH1708,HBr
416
100.00
....
Hydrochlorate of Berberine. Preparation, see above. 100 parts of ber-
berine take up 11.07 parts of hydrochloric acid gas (1 at. 10-9 parts)
(Schaffner). Shining, bright-yellow, loose, inodorous powder, consist-
ing of microscopic crystals (Buchner; Mahla). Long, delicate, golden
needles, having a silky lustre (Perrins). Neutral. Has a pure, in-
tensely bitter taste, which is very persistent (Buchner). Gives off 8.65
of water at 100° (4 at. 8.33 p. c. HO.) (Fleitmann), decomposing
slightly, so that it afterwards forms a red solution with water (Perrins).
The dried salt is very hygroscopic. It dissolves with difficulty in cold
water and alcohol, but colours both liquids deep-yellow, and dissolves.
in all proportious in the boiling liquids. Insoluble in ether and bisul-
phide of carbon (Buchner; Mahla).
at 100--110°
Buchner. Fleitmann. Bödeker. Perrins.
62.65.... 62.71....
Mahla.
40 C
N
240
64.60
60.40
....
...
62.79 64.77
14
3.76
4.03
3.60
3.78 ...
3.56
18 H
18
4.8.4
5:49
5.55 ...
5'07 ....
....
80
Cl
64
17.24
19.31
5.67
18.74
5.14
17.95
35.5
9.56
8.89.... 9.06 ....
9.02
8.58
....
100.00
100.00 ... 100.00
C40NH¹708, HCl.... 371.5.... 100'00
—
Chlorate of Berberine. Chlorate of potash throws down from
aqueous hydrochlorate of berberine, a yellow bulky precipitate, which
is to be washed with water and crystallised from alcohol. - Greenish-
yellow crystals, which explode by friction or percussion. Soluble in
water; difficultly soluble in aqueous chloride of potassium or chlorate
of potash (Fleitmann).
Fleitmann.
40 C
N
18 H
240
57.21
57.02
14
3.33
18
4.29
4.29
14 O
112
26.69
Cl
35.5
8.48
CONHOS,HO,C105
419.5
100.00
192 PRIMARY NUCLEUS CH; OXY-AZO-NUCLEUS C¹NH¹OS.
Nitrate of Berberine. - Preparation (p. 187). Or hydrochlorate of
berberine is decomposed by nitrate of silver, and the solution is filtered
while hot, and left to crystallise, after addition of nitric acid. -
Pale-yellow needles (Fleitmann), perfectly stable at 100°. It is almost
completely precipitated from its aqueous solution by dilute nitric acid
(Perrins).
40 C........
2 N......
18 H
Dried over oil of vitriol, or at 100°. Fleitmann.
14 0....
CNH!OHO,NOS
Henry.
Perrins.
mean.
60.16
mean.
240
28
60.30
7.03
60.15
59.27
***
....
....
18
4.52
4.75
4.84
4.57
....
112
28.15
398
100.00
....
Chromate of Berberine. Bi-acid. Bichromate of potash throws
down from hydrochlorate of berberine a pale-yellow precipitate, diffi-
cultly soluble in water, but easily soluble in sulphuric and hydrochloric
acids (Fleitmann). On adding bichromate of potash to a boiling very
dilute solution of hydrochlorate of berberine, the salt crystallises almost
entirely on cooling, and may be recrystallised from a large quantity of
hot water. Dissolves very slightly in cold water and in aqueous
chromate of potash (Perrins).
Fleitmann.
Perrins.
40 C
N
18 H
12 O
Cr203
at 100°.
mean.
mean.
240
53.86
54.58
53.71
14
3.14
18
4.04
4.30
4.04
96
21.55
77.6
17.41
17.24
17.43
100.00
CNHOS,HO,2CrO³ .... 445'6
Phosphomolybdic acid throws down dirty yellow flocks from solutions
of salts of berberine.
Chloromercurate of Berberine. A solution of berberine in a large
quantity of strong alcohol mixed with hydrochloric acid, and added
boiling hot to an alcoholic solution of mercuric chloride also containing
hydrochloric acid, yields, on cooling, fine yellow needles, having
a silky lustre. The needles are washed with alcohol, and with
a mixture of water and alcohol in succession. Thus prepared, they
contain 1 at. chloride of mercury to 1 at. hydrochlorate of ber-
berine. Their solution in a very large quantity of hot water, however,
yields longer and larger crystals of a compound with 2 at. chloride
of mercury (Hinterberger, Wien. Acad. Ber. 7, 432; Ann. Pharm. 82,
314).
Hinterberger.
mean, at 100°.
With 1 at. 11gCl.
40 C
N
18 H
80
240
47.33
47.10
14
2.76
18
3.55
3.59
64
12.62
2 Cl
71
14.00
Hg
100
19.74
19.93
CNHOS, HCl,HgCl
507
100·00
BERBERINE,
193
40 C
N
18 H
With 2 at. HgCl.
8 0
3 Cl
2 Hg
Hinterberger.
240
37.35
37.70
14
2.18
18
2.80
2.87
64
9.96
....
106.5
200
16.58
31.13
30.42
100.00
C40NH¹708,HC1,2HgCl.... 642.5
Berberine and Oxide of Silver? Nitrate of silver throws down from
a hot aqueous solution of berberine (hydrochlorate?) a yellow precipi-
tate, which may be obtained in delicate crystals from a solution in
warm water (Buchner).
Buchner.
at 100°.
mean.
CN¥1708
AgO
335
74.28
74.02
116
25.72
25.98
?C40NH¹708,AgO 451
100.00
100.00
....
Since Buchner's berberine contained hydrochloric acid, the value of the analysis is
questionable.
Hyposulphite of Berberine and Silver. A solution of nitrate of silver
in aqueous hyposulphite of soda precipitates from cold neutral salts of
berberine a yellow amorphous powder. By mixing the nitrate of
silver solution with hot alcoholic nitrate of berberine, small lemon-
yellow prisms are obtained on cooling. Insoluble in water, but easily
soluble in alcohol and in aqueous hyposulphite of soda, the latter solution
being decomposed by boiling, with separation of sulphide of silver.
The dry salt is stable at 100° (Perrins).
Perrins.
40 C
N
18 H
14 O
4 S
Ag
mean.
240
43.16
43.07
14
2.52
18
3.23
3.23
112
20.16
64
11.51
11.47
108
19.42
19.45
100.00
C40NH¹708, HO,S2O2 + AgO,S202 556
Chloro-aurate of Berberine. Previously noticed by Chevallier and Pelletan.
Terchloride of gold throws down from hydrochlorate of berberine an
amorphous brown precipitate, which, when washed with water and
dissolved in boiling dilute alcohol, crystallises in chestnut-brown needles
(Perrins).
40 C
N
18 H
80
4 Cl
Au
Henry.
Amorphous.
Perrins.
Crystals.
at 100°.
(mean.)
240
35.57
35.50
35.50
14
2:08
18
2.67
2.94
******
2.74
64
9.49
142
21.05
196'6
29.14
27.75
29.16
100.00
C40NH¹708,HCl,AuCl³.... 674-6
VOL. XVII.
194 PRIMARY NUCLEUS C40H24; OXY-AZO-NUCLEUS C40NH1508.
Chloroplatinate of Berberine. A hot aqueous solution of hydro-
chlorate of berberine is precipitated by chloride of platinum, and the
precipitate is washed with cold water till the washings cease to indicate
the presence of platinum on addition of iodide of potassium. - Small
crystalline needles (Perrins).
Fleitmann.
Kemp.
at 100°.
mean.
40 C
240
44.35
44.39
46.23
....
N
18 H
14
2.59
18
3.33
3.50
3.68
8 0
3 Cl
Pt
64
11.83
106.5
19.68
98.6
18.22
18.11
18.05
C40NH¹708,HCl,PtCl²
541.1
100.00
Bödeker.
Stenhouse.
Henry.
Perrins.
mean.
C
N
OZHOOL
Pt..
45.22
44.87
44.38
44.33
2.80
3.92
3.81
3.57
3.41
....
17.58
17.54
17.82
18.21
In the salt prepared with berberine from barberry flowers, Ferrein found 17-87
p. c. of platinum.
M
Hydrocyanate of Berberine. Aqueous hydrochlorate of berberine
assumes a dark-red colour when mixed with cyanide of potassium, and
throws down dirty-yellow flocks which, after washing with water,
crystallise from alcohol in brown-yellow rhombic laminæ. Stable at
100° when dry, but not in the moist state. It dissolves slightly in
water from which it does not crystallise, and is soluble in cold, and
more freely in hot, alcohol. The solutions smell of hydrocyanic acid
(Henry).
42 C
2 N
18 H
....
80
C40NH¹708,HCy
at 100-110°.
Henry.
252
69.62
66.93
28
7.73
18
4.97
5.22
64
17.68
362
100.00
....
Contains 6.22 p. c. of cyanogen; (Henry) (calc. 7·18 p. c.).
Hydrocyanate of Berberine with Nitric acid? Very dilute nitric acid colours
hydrocyanate of berberine red, without liberating hydrocyanic acid. The concen-
trated acid produces a red to black substance, a solution of which in water or alcohol
yields red needles of (according to Henry) hydrocyanate of nitroberberine. The
needles contain, at 100-110°, 60·35 p. c. C., and 4.80 H. (Henry).
Hydroferrocyanate of Berberine. — Precipitated by ferrocyanide of
potassium from aqueous hydrochlorate of berberine. Greenish-yellow,
microscopic needles, which in the moist state decompose at 100°, evolving
an odour of hydrocyanic acid. - Dissolves in 1250 parts of cold water,
and slightly in hot water and alcohol (Henry).
BERBERINE.
195
at 100-120°
Henry.
750
96.41
Fe........
28
3.59
3.86
778
100.00
2 C40NH¹708,H2Cy3.
2 CNH!7O,HFeCy3
Hydroferricyanate of Berberine.
Resembles the preceding salt, but
is yellower, and after drying apple-green (Henry).
at 100-110°
3 C40NH¹708,H³Cy
2 Fe
Henry.
1164
95.41
56
4.59
4:30
100.00
3 C¹NH¹³‚ͳFe²Cy6.... 1220
Hydrochlorate of Berberine with Cyanide of Mercury. Solutions of
hydrochlorate of berberine and cyanide of mercury, mixed together
while hot, deposit on cooling, yellow needles soluble in hot water and
alcohol (Kohl & Swoboda, Wien. Acad. Ber. 9, 252; Ann. Pharm. 83,
340).
at 100°
Kohl & Swoboda.
C40NH1708,HCl,Cy
397.5
79.90
Hg
100
20.10
19.17
100.00
C40NH¹708,HCl + HgCy.... 497.5
Hydrosulphocyanate of Berberine. Sulphocyanide of potassium
throws down from concentrated hot solutions of hydrochlorate of ber-
berine, a greenish-yellow powder, which crystallises from boiling water
in siskin-yellow, and from boiling alcohol in brown-yellow needles.
Dissolves in 4,500 parts of water, and in 470 parts of alcohol (Henry).
42 C
2 N
Henry.
61.85
18 H
80
2 S
C40NH¹70s, CNHS2
....
252
63.95
28
7.12
...
18
4.57
4.64
64
16.24
32
8.12
8.10
394
100.00
Contains 14:16 p. c. of sulphocyanogen (Henry).
Acetate of Berberine forms golden-yellow crystals (Kemp).
Oxalate of Berberine. — Formed from oxalic acid and berberine.
Brownish warts formed of clusters of needles (Henry).
44 C
02
N
19 H
16 O
C4NH1708,C+H2O8
at 100-110°
Henry.
264
62.11
60.78
14
3.29
19
4:47
4.67
128
30.13
425 ...... 100'00
Glycocoll with Hydrochlorate of Berberine. A warm alcoholic solu-
tion of hydrochlorate of berberine mixed with excess of alcoholic
glycocoll solidifies on cooling, from the formation of delicate pome-
granate-yellow needles, which are insoluble in water (Horsford, Ann.
Pharm. 60, 32).
0 2
196
PRIMARY NUCLEUS C40H24; OXY-AZO-NUCLEUS C40NH1508.
Horsford.
44 C
2 N
22 H
11 O
Cl
264
60.34
60.80
28
6.40
22
5:03
5.87
88
20.12
35.5
8.11
100.00
C¹HN¹O³,CNH'70s, HCl.... 437.5
Gerhardt (it seems to me justly) doubted the correctness of this formula (Kr.).
Succinate of Berberine. A solution of berberine supersaturated
with succinic acid deposits brownish needles, triturable to a yellow
powder. Dissolves in water and alcohol, more especially when hot
(Henry).
48 C
N
23 H
16 O
C40NH1708, CH6O8
at 100-110°.
Henry.
288
63.57
61.99
14
3.09
23
5:09
5.80
128
28.25
453
100.00
Tartrate of Berberine. - Long siskin-yellow, silky needles, obtained
by supersaturating berberine with the acid. Dissolves in 130 parts of
cold water or alcohol, and much more freely in the hot liquids.
Loses 1.62 p. c. of water at 100° (1 at. = 1·82 p. c. HO) (Henry).
48 C.........
N.....
23 H
....
20 O.......
CNH17O,CHQ12
Dried.
Henry.
288
59.38
58.15
14
2.88
3.16
23
4.75
5.08
160
32.99
33.61
485
100'00
100.00
....
Tartrate of Berberine and Antimony. — Formed, with separation of
oxide of antimony, by boiling berberine with a cold saturated solution
of tartar-emetic. Crystallises from the filtrate (which contains also
tartrate of potash) in fibrous masses resembling wavellite, and is
purified by washing with cold water or by recrystallising from alcohol
(Stenhouse, Ann. Pharm. 129, 26).
48 C
N
22 H
22 O
Sb
C40NH¹708,HO,SьО³, CH¹¹0
In vacuo.
Stenhouse.
288
46.43
46.46
14
2.25
22
3.54
3.76
176
28.39
120.3
19.39
19.85
620-3
100.00
Picrate of Berberine. Formed from picric acid and berberine.
Golden-yellow lamina (Henry); yellowish-brown or pinchbeck-
coloured shining prisms (Kemp). Nearly insoluble in cold, and
slightly soluble in boiling alcohol (Henry).
52 C
at 100°.
Henry.
312
55.32
........
54.83
4 N
56
9.93
20 H
20
3.55
3.93
22 O
176
31.20
C4UNH¹708,C12X³Í³02
564
100.00
OXYACANTHINE.
197
Berberine dissolves in alcohol. It is precipitated from its solutions
by charcoal, and again extracted therefrom by alcohol (Chevallier &
Pelletan).
Appendix to Berberine.
Oxyacanthine.
POLEX. N. Br. Arch. 6, 271.
WITTSTEIN. Repert. 86, 258.
HERBERGER. Jahrb. pr. Pharm. 4, 82.
WACKER. Pharm. Viertelj. 10, 177.
Discovered by Polex in 1836. Occurs, together with berberine, in
the bark of the root of Berberis vulgaris (Polex), and also, together
with a little berberine, in the bark of an undetermined species of
Berberis from Mexico (Wittstein).
Preparation. The mother-liquor from which the berberine has been
crystallised as completely as possible, in the preparation of berberine
from the bark of barberry root, is diluted with 4 or 5 parts of water
and precipitated with carbonate of soda; the precipitate is collected,
washed with cold water, and dissolved in dilute sulphuric acid; the
solution is decolorised with animal charcoal and again precipitated with
carbonate of soda; and the washed precipitate is dried and dissolved
in cold alcohol. From the solution thus obtained, the oxyacanthine may
be recovered by evaporation, or by precipitation with water (Polex).
Wittstein (and Wacker) exhausts the precipitate produced by car-
bonate of soda with dilute hydrochloric acid; precipitates the filtrate
by ammonia; and exhausts the washed precipitate, after drying and
pulverisation, with ether in a percolator. The oxyacanthine left on
evaporating the ethereal solution is again dissolved in hydrochloric
acid, thrown down by ammonia, and purified by crystallising its hy-
drochlorate, which is then decomposed by ammonia. The portion
insoluble in ether still contains a large quantity of oxyacanthine,
which it gives up to ether only after first removing the humic acid
present by means of water containing soda. Oxyacanthine is difficult
to obtain in the pure state, inasmuch as it oxidises in the air, espe-
cially when precipitated by ammonia (Polex). Wittstein obtained
from 350 pounds of the fresh bark 13 drachms of oxyacanthine.
Properties. Dazzling white powder, turning yellow in sunlight ;
under a magnifying-power of 130 diameters it is seen to consist of
amorphous round granules (Wacker). According to Buchner, jun., it
is converted, by digestion with a little ether or alcohol, into fine
needles and prisms. It is deposited from an alcoholic solution in
resinous laminæ, or if the solution is mixed with a quantity of water
barely sufficient to produce turbidity and evaporated, in the form of a
yellowish crystalline crust (Polex). Has a pure bitter taste and an
alkaline reaction. - Loses 3.13 p. c. of its weight at 100°, and not more
at 120°. Melts to a yellow liquid at 139° (Wacker).
198
PRIMARY NUCLEUS CH24; OXY-AZO-NUCLEUS CºN͹50⁹.
Calculation according to Wacker.
Wacker.
at 100°.
32 C .......
192
60.56
60.26
N
14
4.42
4.51
23 II
23
7.26
7.53
11 O......
88
27.76
27.70
C32NH23011
317
100.00
100.00
This formula is, doubtless, incorrect; but the analysis does not admit of the
calculation of any other probable one.
Decompositions. 1. When submitted to dry distillation it yields.
aqueous vapour, a brown thick empyreumatic oil and ammonia, and
evolves an odour of animal oil, whilst a very porous charcoal remains
behind (Polex).-2. Melts to an oil in the fire and burns rapidly
with a luminous flame.-3. Dissolves in oil of vitriol, forming a
brown-red solution which, on warming, assumes a splendid red colour,
afterwards turning brown. 4. Softens to a resin in strong nitric
acid and dissolves with yellow colour, which changes to a fine purple-
red on warming. The solution turns yellow on boiling, with libera-
tion of nitric oxide and formation of oxalic acid, and when diluted with
water deposits yellow flocks, which behave like berberine (Polex).
5. Dissolves in chlorine-water, forming a yellow solution, which is
rendered darker, but not turbid, by ammonia. 6. Reduces sesqui-
oxide of chromium from bichromate of potash and sulphuric acid.
7. Iodic acid in contact with oxyacanthine is coloured yellow and de-
posits iodine (Wacker).
Oxyacanthine is nearly insoluble in water.
It combines with acids to form easily crystallisable salts soluble in
water and alcohol (Polex). From solutions of the salts, ammonia,
carbonate of ammonia, caustic alkalis and their carbonates, and lime-
water, throw down oxyacanthine as a white precipitate, soluble in a
large excess of ammonia and more easily soluble in excess of caustic
potash (Wacker). The hydrochlorate is precipitated white by iodide.
of potassium, chloride of mercury, sulphocyanide of potassium, and
ferrocyanide of potassium; yellowish-white by phosphomolybdic acid
and tannic acid; yellow-orange by nitrate of palladium; clay-coloured
by chloride of gold, and sulphur-yellow by ferricyanide of potassium
(Wacker). The acetate is precipitated also by nitrate of silver, tartar-
emetic, and chloride of tin (Polex).
Sulphate of Oxyacanthine.-Neutral white nodules (Wacker), or tufts
of needles (Polex), easily soluble in water and alcohol.
at 100°.
Wacker.
C3NH230¹¹,HO
326
89.07
SO3
40
10.93
11.2
CNHO"HO,SO3
366
100.00
Hydrochlorate of Oxyacanthine.
Clusters of needles (Polex), or
neutral white nodules, easily soluble in nodules and alcohol (Wacker).
CINCHONINE.
199
C32NH23011
HCI
C32NH23011, HCI
Wacker.
317.0
36.5
89.78
....
10.32
9.33
353.5
100.00
Wacker supposes it to contain 4 at. of water.
Iodomercurate of potassium throws down from oxyacanthine a
yellowish-white precipitate, which remains amorphous (Delffs).
Nitrate of Oxyacanthine. Warts and needles, more difficultly
soluble in water than the sulphate and hydrochlorate (Wacker).
C32NH23011
317
83.42
77.88
HO,NO5
63
16.58
C32NH230¹¹, HO,NO5.... 380
100.00
Wacker supposes this salt also to contain 4 at. of water.
Chloroplatinate of Oxyacanthine. - Pale grey-yellow precipitate.
Wacker.
C32NH23011,HC13
Pt
424.5
98.7
81.13
18.87
18.81
....
523.2
100.00
banon CAO
C32NH23011, HCl,PtCl²
Acetate of oxyacanthine is not crystallisable.
Oxalate of Oxyacanthine. - Needles, difficultly soluble in water.
Contains, at 100°, 10·30 p. c. of anhydrous oxalic acid (Wacker).
Picrate of Oxyacanthine. - Previously observed by Kemp (Repert, 71, 164).
Lemon-yellow precipitate, soluble in a large quantity of water, and
in dilute acids and alcohol (Wacker).
Oxyacanthine dissolves easily in weak and in absolute alcohol
(Polex); in 30 parts of cold, and 1 part of boiling alcohol (Wacker). —
Dissolves in 4 parts of boiling, and 125 parts of cold ether, in all propor-
tions in chloroform, and in volatile and fixed oils (Wacker).
Primary Nucleus C40H26; Oxy-azo-nucleus C¹ºN²H²²O².
Cinchonine.
C40N2H2402 C40N2H2202,H².
For the literature relating to Cinchonine and Quinine in common, see QUININE.
REGNAULT. Ann. Pharm. 26, 15; J. pr. Chem. 16, 262.
LIEBIG. Ann. Pharm. 26, 50.
LAURENT. N. Ann. Chim. Phys. 19, 365; Ann. Pharm. 62, 99; J. pr.
Chem. 40, 404; Kopp's Jahresber. 1847 and 1848, 615 and 617
Compt. rend. 20, 1116; N. Ann. Chim. Phys. 24, 303; Ann. Pharm.
69, 8; J. pr. Chem. 46, 52- Compt. rend. 23, 811.
200
PRIMARY NUCLEUS C40H26; OXY-AZO-NUCLEUS C40N2H22O2.
HLASIWETZ.
Wien. Acad, Ber. 1850, 1, 9, and 276; Ann. Pharm. 77,
49; J. pr. Chem. 51, 409; Pharm. Centr. 1851, 74; Kopp's Jahresber.
1850, 420.
A. ERDMANN. Ann. Pharm. 100, 341; abstr. J. pr. Chem. 70, 422 ;
Kopp's Jahresber. 1856, 545.
H. HAHN. N. Br. Arch. 96, 33; Kopp's Jahresber. 1858, 372.
SCHWABE (& LÖSCHE). N. Br. Arch. 103, 273; abstr. N. J. Pharm.
38, 389; Chem. Centr. 1860, 936; Kopp's Jahresber. 1860, 362.
O. HESSE. Ann. Pharm. 122, 226.
Discovered by Pelletier & Caventou in 1820. Occurs in the true
cinchona barks; most abundantly in the grey and brown barks; to a
less extent, together with more quinine, in the red and yellow barks,
and in small quantity in calisaya bark. For more exact details see
Quinine.
A. Erdmann described as Huanokine a base prepared from China Huanoco plana,
which he distinguished from cinchonine chiefly on the ground of its susceptibility of
sublimation: he seems, however, to have compared it with commercial cinchonine
containing quinidine or cinchonidine, and not with the pure alkaloïd. Seeing that
this body possesses, according to Gössmann, the same composition, and according to
De Vrij (N. J. Pharm. 32, 328), the same molecular rotatory power as cinchonine,
and since, moreover, its hydriodate resembles the hydriodate of cinchonine, and
its combinations exhibit, so far as can be ascertained from Hahn's approximate
and not strictly accurate measurements, the same crystalline form as salts of cincho-
nine, there is no reason to suppose that it differs from this last-named base.
Schwabe's Betacinchonine, which was discovered in working with crude commercial
quinoïdine, is also, according to Hesse, to be identified with cinchonine. Lösche's
measurements of the crystals are not sufficiently exact to establish any difference in
form; and Schwabe's statements either agree with those of other authors on cincho-
nidine, or may be explained by the supposition that he did not, in all cases, work with
a pure substance (free from quinidine). Betacinchonine is coloured yellow by chlorine-
water and ammonia; but ferrocyanide of potassium alone, or together with chlorine-
water, turns the sulphate red, whereupon ammonia produces a green coloration.
In excess of acid, it forms only mono-acid salts, the solutions of which, when shaken
in not too concentrated a state, with ammonia and ether, form two clear layers, the
upper containing the betacinchonine. [This statement does not accord with the fact
of the difficult solubility of betacinchonine in ether (Kr.)] For Schwabe's other
statements see Cinchonine. Schützenberger affirnis the existence of a cinchonine of
the formula C36N2H2O¹ (Compt. rend. 46, 895).
The base observed by Gruner (Br. Arch. 12, 156) in China flava [China de
Carthagena dura (Wiggers)] is not sufficiently characterised to distinguish it from
cinchonine. It forms delicate, tasteless needles, easily soluble in alcohol but insoluble
in ether. The sulphate forms slightly bitter 4-sided prisms, which are easily soluble
in water, and contain 12.81 p. c. of sulphuric acid.
Cinchonine is obtained as a secondary product in the preparation of
quinine. When it is required to be prepared specially, huanoco-bark
is employed, and the following, or a similar, process is adopted :-
Four pounds of the coarsely powdered bark are boiled for some
hours with 54 pounds of water, to which 2 ounces of hydrochloric acid
of sp. gr. 1.2 have been added. The decoction is pressed, and the
residue again boiled twice, the last time with only half the quantity of
acidulated water; and the united liquids are evaporated down to 12
pounds, filtered, and mixed with sufficient caustic soda to produce an
alkaline reaction. The precipitate thereby produced is washed, dis-
solved in hydrochloric, or better, in acetic acid, and again precipitated,
by which means the colouring matter is got rid of. The precipitate is
then dried and exhausted by boiling with alcohol, from which the cin-
CINCHONINE.
201
chonine crystallises on concentration. It is still to be purified by
recrystallisation, with aid of animal charcoal (A. Erdmann).
Purification. Commercial cinchonine is mostly contaminated with
cinchonidine or quinidine (De Vrij). To purify it, the larger yellowish
crystals obtained in the manufacture of quinine are powdered, washed
with a large quantity of cold alcohol, and converted into sulphate,
which is then purified by recrystallisation and decomposed by ammonia.
The pure alkaloïd is, lastly, crystallised from alcohol (Hesse).
u:
Properties. White, transparent needles, permanent in the air, and
containing no water of crystallisation (Pelletier & Caventou). Oblique
prismatic (monoclinic). u, t, i (fig. 106). The crystals are elongated in
the direction of the clinodiagonal axis. u: u = 109° 5·5'; t:iin front
= 107° 19' ; t: i behind
: ¿ beł ind — 72° 41'; i : u = 100° 5·5'; l sharply curved,
m plane; cleavable parallel to 1, less perfectly parallel to m (Schabus).
u: u = 110° 22' ; ù: t = 124° 35′; t: i = 108° 30′ (Delffs, Jahrb.
pr. Pharm. 8, 377). u : u = 109° ; u : t = 125°; t : i = 110° ; i : u
90° (!) (Hahn). According to Lösche, monoclinic. p, m, i (fig. 53).
ii above = 119° ; i: : p = 120·5°. - Cinchonine melts only as it
begins to decompose, and volatilises partly undecomposed, especially
when moist (Pelletier & Caventou, J. Pharm. 7, 305; Robiquet). Pre-
cipitated or crystallised cinchonine undergoes no alteration at 165°;
it partly sublimes at 220°, and the rest melts at 240-250° to a brown
mass, which solidifies on cooling (Hesse). Schwabe's cinchonine
melted, at 150°, to an oil which cooled to a crystalline solid: that of
Duflos melted at 161°, without loss of weight, and on further heating
sublimed partially in dazzling white needles, in the same manner as
benzoic acid (Duflos). In the air the vapour forms light white flocks
(Fr. Esenbeck, Ann. Pharm. 6, 319; Erdmann); in hydrogen or am-
monia-gas, shining prisms an inch long are obtained (Hlasiwetz).
Cinchonine turns reddened litmus blue; tastes slightly bitter after some
time (Pelletier & Caventou). Rotates a ray of polarised light to the
right; (a) r = 237.5° in alcoholic solution, and to a less extent when
dissolved in acids. Ammonia seems to restore the original rotatory
power (Bouchardat, N. Chim. Phys. 9, 213). Rotatory power of Pelletier's
cinchonine dissolved in hydriodic acid; (a) j = 242·58°; of Erdmann's huanokine
242·55° (De Vrij); of both, dissolved in hydrochloric acid 237.3° (Hahn).
Liebig.
Regnault.
Pelletier.
& Dumas.
mean.
mean.
40 C
240
77.92
76.97
76.36
76.59
2 N
28
9.09
9.02
8.87
9.48
24 H
24
7.79
6.22
7.38
7-72
20
16
5.20
7.79
7.39
6.21
C40N2H2402
308
100.00
100.00
100.00
100.00
...
Gerhardt.
Laurent.
(Rev. scient. 10, 192.) mean.
C................
77.63
N
H
7.99
O........
77.29
Hlasiwetz.
mean (10).
78.02
Gössmann.
Schwabe.
mean.
mean.
77.61
77.29
8.83
9.09
7.49
7.66
7.73
7.87
D
5.83
5.75
100.00
100.00
202
PRIMARY NUCLEUS C40H6; OXY-AZO-NUCLEUS C40N2H22O2.
Gössmann analysed crystals of huanokine; Schwabe crystallised betacinchonine.
The formula, according to Dumas, is CN2H2003; according to Laurent CN2H22O²;
according to Liebig C20NHO. The above formula was shown by Regnault to be
the correct one. It cannot be halved either for this body or for the two other
alkaloids of cinchona, as in that case, the mono-acid salts, formed to some extent in
an excess of acid, would have to be regarded as a basic. Moreover, the behaviour of
the base with bromine, and with iodide of ethyl, chloride of acetyl, and sulphuric
acid, makes the halving of the formula impossible. See Laurent and Gerhardt
(Compt. chim. 1849, 167).
Decompositions. 1. Melted cinchonine turns brown on continued
heating (Duflos), takes fire at a higher temperature, and leaves a light,
easily combustible charcoal (Merck). Besides the sublimate of cin-
chonine (see above) a carmine-red product is obtained (Wigaud, N. Br.
Arch. 115, 230).
When cinchona-bark is heated, at first gently and afterwards gradually to redness,
in a test-tube held in a horizontal position, white vapours and water are given off,
followed by a reddish vapour, which is at first deposited in the form of a powder,
then condenses in fine carmine-red oily drops and streaks, and at last a brown tar is
obtained. The carmine-red oil turns brown-red in the air, and has a bitter, burning
taste; it is thrown down from its alcoholic solution by water in the form of a resin,
and contains acetic acid, volatile bases, a neutral oil, and empyreumatic resin. This
behaviour is exhibited only by the true cinchona-barks, not by false cinchona-barks
or by those from which the cinchona-bases have been extracted by acids. The red
body is not formed by heating the cinchona-bases per se, but is readily obtained when
they are heated with organic acids (Grahe, Chem. Centr. 1858, 97). Batka (Chem.
Centr. 1859, 865) obtained the red distillate from cinchona-bases only in presence of
woody fibre, starch, gum, dextrin, or sugar, and not under the conditions mentioned
by Grahe; Wigand (N. Br. Arch. 115, 230) obtained it from pure cinchonine, and
also from the sulphate, but not from pure quinine. See also N. Br. Arch. 121, 265.
2. Solutions of cinchonine-salts, when exposed to sunshine, even for
a few hours, assume a dark red-brown colour, and undergo the same
decomposition as when heated (Pasteur). See below.
3. Cinchonine in combination with nitric acid is rapidly decomposed
by the electric current (obtained from 6 pairs of Bunsen elements), the
liquid becoming brown, and evolving, at the positive pole, oxygen, and
afterwards also carbonic acid and nitric oxide, and at the negative pole
hydrogen, nitrogen, and ammonia. After 24 hours the liquid in which
the positive pole is placed contains unchanged nitrate of cinchonine,
while that surrounding the negative pole is of a red-brown colour, and
contains formic acid, ammonia, chinoline (xiii, 243), and resin precipi-
table by potash, and is found to have deposited a large quantity of
resin soluble in alcohol and nitric acid. Sulphate of cinchonine is
scarcely decomposed by the electric current. The hydrochlorate
evolves chlorine, oxygen, and hydrogen, and yields crystals of a mixture
of mono- and bi-chlorocinchonine (v. Babo, J. pr. Chem. 72, 73). See also
Hlasiwetz & Rochleder (Wien. Acad. Ber. 5, 447).
4. Cinchonine, when acted upon by nitrous acid, is capable of taking
up 2 at. of oxygen, and forming a body isomeric with quinine
(Schützenberger, Compt. rend. 46, 895; J. pr. Chem. 74, 76). Cincho-
nine is not coloured by strong nitric acid (Merck; Duflos). Mercurous
nitrate colours cinchonine (and quinine) yellow (Lassaigne & Labaillif).
-5. Cinchonine is less easily attacked than quinine (which sce) by
permanganate of potash (Cloëz & Guignet).
6. By treating cinchonine with a mixture of peroxide of lead, sul-
CINCHONINE.
203
phuric acid, and water, a dark-violet mass, E. Marchand's cinchonetin,
is obtained (N. J. Pharm, 4, 27).
On boiling sulphate of cinchonine with water and excess of peroxide
of lead, with addition of dilute sulphuric acid, so long as a filtered test-
portion of the liquid is precipitated by ammonia, the liquid assumes a
dark colour, and evolves carbonic acid copiously; and if it be then
saturated with litharge, the solution filtered and evaporated to dryness,
and the residue again dissolved, freed from lead by hydrosulphuric
acid, and evaporated, the cinchonetin remains behind. It is of a dark-
violet, or in thin films, of a yellow-red colour, translucent, and bitter.
Melts on heating, evolving white non-ammoniacal fumes; burns with
a smoky flame, and leaves a difficultly combustible charcoal. Dis-
solves in oil of vitriol, forming a red solution, from which it is not
precipitated by water. Deliquesces in the air, and dissolves in water,
or better in alcohol, but not in ether. Basic acetate of lead precipitates
the aqueous solution violet. By the further action of peroxide of lead
and sulphuric acid, it is converted into colourless products, amongst
which acetic acid appears to occur (E. Marchand, J. Chim. méd. 20, 362).
7. Cinchonine in contact with dilute sulphuric acid and zinc, takes
up 2 at. of hydrogen, and is converted into hydroquinine (Schützen-
berger). 8. By dissolving it in fuming sulphuric acid, cinchonine-
sulphuric acid is formed (Schützenberger). Oil of vitriol does not
colour cinchonine, even when hot (Guy; Merck; Duflos).
9. The salts of cinchonine fuse, for the most part, when heated, and
immediately undergo decomposition, the sulphate yielding thereupon a
brilliant red resin; but on heating the same salt to 120-130° with water
and sulphuric acid (or on heating a salt the melting-point of which
lies below the temperature of decomposition) cinchonicine is formed
(Pasteur).
After cinchonine had been heated too strongly and with too large a quantity of
sulphuric acid, in preparing the sulphate, a portion only crystallised from the solu-
tion, the rest remaining as a brown mother-liquor, from which alkalis precipitated a
dark-brown, intensely bitter, turpentine-like mass. By repeatedly dissolving this
mass and finally precipitating it with ammonia, a black substance was removed, and
the base was obtained as a nearly white tenacious precipitate, capable of further purifica-
tion by charcoal. The body thus obtained is tough, resembles quinoïdine, is soluble
in all proportions in alcohol, but insoluble in water and absolute ether. It neutralises
acids completely, and is precipitated from its solutions by alkaline carbonates. The
hydrochlorate forms with hyposulphite of soda a dark red-brown oil, but no crystals;
it yields a pale brown-yellow, loose, crystalline platinum-salt, containing 23.5 to 25
p. c. of platinum (Winckler, Repert. 98, 381; Jahrb. pr. Pharm. 15, 281).
10. Cinchonine assumes a dirty-yellow colour in vapour of iodine
(Donné). On triturating 1 part of iodine with 2 parts of cinchonine,
dissolving the mixture in alcohol of 36°, and allowing the solution to
evaporate spontaneously, there separate first iodocinchonine, and after-
wards mushroom-shaped crystals of hydriodate of cinchonine. If the
latter be removed by hot water, the iodocinchonine remains as a dark,
saffron-yellow, friable, slightly bitter mass, which softens at 25° and
melts at 80°. It contains 28.87 p. c. of iodine and 71.13 of cinchonine
(equal numbers of atoms requiring 70-81 cinchonine and 29.19 iodine);
dissolves very slightly in boiling water, but freely in alcohol and ether,
and is decomposed by successive treatment with acids and alkalis.
When solutions of hydriodate and of iodate of cinchonine are mixed
204 PRIMARY NUCLEUS C40H26; OXY-AZO-NUCLEUS C40N2H22O2.
together, iodocinchonine separates, more especially on concentration, or
immediately on addition of an acid, in the latter case together with
free iodine (Pelletier, Ann. Chim. Phys. 63, 181; Ann. Pharm. 22, 125).
See also Thomson, (N. J. Pharm. 8, 275). - Tincture of iodine throws down
from hydrochlorate of cinchonine a dense brown precipitate (Planta),
which becomes crystalline on standing (Seligsohn). The precipitate
thrown down by biniodide of potassium from sulphate of cinchonine is
decomposed by hyposulphite of soda, with formation of hydriodic acid
and cinchonine, and when freshly precipitated, requires for its decom-
position the same quantity of hyposulphite as would be required to
convert the iodine contained in it into hydriodic acid (Wagner, Dingl.
161, 40). Aqueous periodic acid is decomposed by cinchonine, with
liberation of iodine (Bödeker). - Cinchonine, sulphuric acid, and iodine
yield iodocinchonine (Herapath). See below.
11. Cinchonine assumes an orange-yellow colour in vapour of bromine
(Donné). Moist bromine forms with bi-hydrochlorate of cinchonine,
mono- and sesqui-bromocinchonine; and on warming with excess of
bromine, bi-bromcinchonine is formed (Laurent). Strecker obtained
only the last product. 12. Chlorine passed into a warm, concen-
trated aqueous solution of hydrochlorate of cinchonine, throws down
bichlorocinchonine (Laurent). Pure cinchonine, or sulphate of cincho-
nine, suspended in water, is less attacked than quinine when treated
with a stream of chlorine; the solution, which is of a less deep-red
colour, and not green even with excess of chlorine, deposits flocks, an
alcoholic solution of which leaves, on spontaneous evaporation, a brick-
red mass (Pelletier, J. Pharm. 24, 163). Cinchonine dissolves in
chlorine-water, without apparent change (Leers), and even on passing
chlorine for ten minutes into cinchonine dissolved in 400 parts of water
acidulated with sulphuric acid, the solution remains colourless and clear
(Lepage). Ammonia precipitates the solution in chlorine-water, white
(Leers), whereupon dilute acids colour it yellow-red, and after 12 hours
a brown precipitate is formed (André, J. Pharm. 22, 134).
13. When cinchonine is added to fused hydrate of potash, and the
mass is more strongly heated, it turns brown, puffs up from evolution
of hydrogen, and yields a distillate of water and chinoline, the browned
alkaloïd disappearing only partially, and some of the potash being con-
verted into carbonate (Gerhardt, N. Ann. Chim. Phys. 7, 251). No
ammonia, or only a trace, is produced in this reaction (Gerhardt). The
distillate contains pyrrol (xv, 5); pyridine (x, 406); picoline (xi, 263);
lutidine (xii, 337); collidine (xiii, 148); chinoline (xiii, 243); and lepidine
(xiv, 103), the latter in larger quantity; also dispoline, C22NH", and
two unnamed bases C26NH15, and C28NH7 (Gr. Williams). Stenhouse
employs this reaction for the detection of cinchonine and quinine in
barks. When hydrate of soda is used, no cyanide of sodium is formed
(Rochleder, Ann. Pharm. 63, 201).
13. Cinchonine heated to 200° in a sealed tube with alcohol, turns
black, does not evolve gas, but forms a small quantity of ether (Rey-
noso (Compt. rend. 42, 686).—14. Iodide of methyl combines with cin-
chonine to form iodide of methyl-cinchonine (Stahlschmidt); chloride of
acetyl and chloride of benzoyl form chloride of acetyl-cinchonine and
chloride of benzoyl-cinchonine (Schützenberger). 15. When cin-
chonine is heated with chloride or iodide of mercury, with tartaric,
CINCHONINE.
205
oxalic, or phosphoric acid, with chloride of carbon, C²Cl, or with iodide
of ethyl or iodide of amyl, red or violet-red colouring matters are pro-
duced, which are soluble in alcohol, wood-spirit, and ether, and are not
altered by dilute acids (Köchlin, Rép. Chim. appliquée, 3, 380; Kopp's
Jahresber, 1861, 951). — 16. Cinchonine is decomposed in the animal
organism, as, after the administration of 10 grains of the hydrochlorate,
it is not found in the urine (Seligsohn).
According to Hlasiwetz, chlorine, oxide of manganese and sulphuric
acid, permanganic acid, the chlorides of phosphorus, boiling acid solu-
tions of platinum, as well as emulsin, are either without action on cin-
chonine, or form with it resinous bodies, from solutions of which the
cinchonine is precipitated by ammonia.
Combinations. Cinchonine dissolves in 3810 parts of water at 10°,
and in 3670 parts at 20° (Hesse). It dissolves in 2500 parts of boil-
ing water, the solution becoming opalescent on cooling (Pelletier and
Caventou. Riegel, N. Br. Arch. 70, 197), and depositing only traces
of cinchonine (Hesse). The cooled solution does not exhibit any
reactions, except a white turbidity with tincture of galls (Duflos).
Cinchonine combines readily with phosphorus, and forms with sulphur
a grey brittle mass, which is decomposed by sulphuric acid, with evo-
lution of hydrosulphuric acid.
Cinchonine dissolves in aqueous ammonia much less easily than the
other cinchona-bases. The precipitate produced by ammonia in a satu-
rated solution of the sulphate does not dissolve in excess of ammonia
in the cold (Kerner, Anal. Zeitschr. 1, 155). — It is insoluble in aqueous
alkalis.
With Acids. Cinchonine completely neutralises even the strongest
acids, forming mono- and bi-acid salts, which are for the most part
crystallisable. Mono-acid salts are obtained only by employing an
excess of cinchonine, and filtering when the solution exhibits an alka-
line reaction (De Vrij). The salts have a powerful and persistent
bitter taste. Their solutions are precipitated by caustic alkalis and
their carbonates and bi-carbonates, and by magnesia, ammonia, and
carbonate of ammonia, the cinchonine being thrown down in the form
of a dense, white, pulverulent precipitate, which does not dissolve to
any great extent in excess of the precipitant (Pelletier & Caventou ;
v. Planta). The precipitate becomes crumbly on standing for some time
(Schwabe; Hesse). A solution of cinchonine to which acetic acid has
been added, is precipitated by bicarbonate of soda only on heating,
carbonic acid being evolved (Hesse). According to Riegel (Jahrb. pr.
Pharm. 25, 340) acetic acid does not prevent the precipitation when the
salt is dissolved in 300 parts or more of water. Pentasulphide of
sodium throws down from hot solutions of cinchonine, a white pulveru-
lent mixture of sulphur and cinchonine (Palm, Russ. Pharm. Zeitschr.
1863, 342; Böttg. Notizblatt, 19, 112). Solutions of cinchonine-salts.
containing excess of acid are not fluorescent (Raupp, Repert, 33, 466).
In the voltaic circuit they deposit cinchonine at the negative pole
(Stratingh).
Determination of Cinchonine in its Salts. The finely powdered salt
is heated with excess of ammonia, and the liquid evaporated to 6 cub.
cent. when gramme of the salt is employed. After adding a little
1
206 PRIMARY NUCLEUS C40H26; OXY-AZO-NUCLEUS C40N2H22O2.
ammonia, the precipitate is allowed to stand for a few hours, and is
then washed with an aqueous solution of cinchonine containing
ammonia (Ilesse).
Carbonate of Cinchonine. The cinchonine thrown down by car-
bonate of potash from soluble salts of cinchonine retains a little car-
bonate of potash, but is free from carbonate of cinchonine (Langlois,
Ann. Pharm. 32, 106). Freshly precipitated cinchonine suspended in
water, dissolves less easily than quinine when treated with a stream
of carbonic acid, and afterwards crystallises free from carbonic acid on
standing in the air (Langlois, N. Ann. Chim. Phys. 41, 89).
Phosphate of Cinchonine. Phosphate of soda throws down from
hydrochlorate of cinchonine a dense granular precipitate, which is
converted into needles on standing (v. Planta). - A solution of cin-
chonine in dilute phosphoric acid deposits, on spontaneous evaporation,
well-formed crystals, which easily effloresce, and are more soluble in
alcohol than in water (Schwabe). - Phosphoric acid and excess of cin-
chonine yield concentric prisms, very easily soluble in water (Hesse).
2040N22402
24 HO
PO5,3HO
2 C¹ºNºH÷¹0‍,3HO,PO³ + 24
Hesse.
616
66.23
66.68
216
23.22
22.95
98
10.55
aq.
930
....
100·00
Hyposulphite of Cinchonine. Formed in a mixture of cinchonine,
alcohol, and hydrosulphate of ammonia, on standing in the air (How).
- From a moderately strong solution of hydrochlorate of cinchonine
hyposulphite of soda almost immediately throws down small four-
sided prisms (Winckler, Jahrb. pr. Pharm. 15, 286). Large, colourless,
four-sided prisms (IIow). White rhombic prisms (Hesse), which give
off 2:31 p. c. of water at 106° (1 at. = 2·41 p. c.) (How), 4·67 p. c.
2 at., at 110° (IIesse). Neutral. Dissolves in 157 parts of water at
16° (Hesse), in 205 parts of cold, and easily in hot water (H. How,
N. Edin. Phil. J. new series 1, 47; Pharm. Centr. 1858, 94).
C40N2H2402
S202,110
Air-dried.
Hesse.
308
80.42
80.69
57
14.88
2 aq.
18
4.70
4.67
C4°N 2H²40², HO,S²O² + 2 aq.
383
100.00
...
at 100°.
How.
40 C
2 N
210
65.75
64.98
28
7.67
25 II
25
6.85
7.05
*******
50
28
A.
40
10.96
32
8.77
8.91
100.00
C¹N÷H²¹O²,HO,SO².... 365
Hyposulphate of cinchonine behaves in the same way as the quinine-
salt (Heeren).
Sulphate of Cinchonine.
·A. Mono-acid salt.
Obtained from sul-
phuric acid and excess of cinchonine in hard, transparent crystals.
Prisms of the oblique prismatic (monoclinic) having a vitreous lustre
CINCHONINE.
207
2
=
(Delffs, Schabus). Fig. 91. u : u' = 96° 30′; u: i about 91° 23′.
Cleavable parallel to u and u'. The t-faces are curved and but slightly
reflective (Delffs, Jahrb. pr. Pharm. 8, 377). t, 2, u, i, (fig. 107); z pre-
dominating over u; i:t ( u: u' of Delffs) 96° 43′ 5″ [= 97°
(Baup)]; it behind 83° 16′ 5″; t: z =112° 37'; i: u (= u : i of
Delffs) = 90° 33'; : 2 = 92° 35'. The faces parallel to the
cleavage-planes exhibit a high pearly lustre. Semi-transparent; of
the hardness of rock-salt (Schabus, Bestimm. 74). According to
Pelletier & Caventou, rectangular; according to Lösche, four-sided, most
probably rectangular prisms of the right prismatic (trimetric) system,
t, m (fig. 73) terminated above by the face y. yy
y: y above = 136°;
y: m = 112° (Lösche); these two angles are evidently equal to z: z
and tz of Schabus.
The salt heated to 100° becomes electric when rubbed, and ex-
hibits a pale-green light, fainter than that of the quinine-salt (Stra-
tingh; Pelletier; Dumas). The crystals lose their water at 100°, melt
at a little over 100° like wax, decompose at a higher temperature,
with fine red coloration, and burn with an odour almost like that of
burning animal matter (Pelletier & Caventou, J. Pharm. 7, 305, Robi-
quet; Stratingh). Neutral. Very bitter.
Sulphate of cinchonine easily forms supersaturated solutions with
water, but it is difficult to obtain a saturated solution by agitation
with cold water (Hesse). Dissolves in 54 parts of water (Baup), at
15° (Kerner), at 183° (Abl). Dissolves in 65.5 parts of water at 13°
(Hesse), in 75 parts at 13°, and in 14 parts of hot water (Schwabe).
Dissolves in 5-8 parts of 80 p. c. alcohol at 11° (Hesse); in 6·5 parts
of alcohol of sp. gr. 0.85 at 13° (Bauss); in 13.6 parts of cold, and 1.5
parts of boiling alcohol of 80 p. c. (Schwabe). Soluble in 33.3 parts
of chloroform at 17.5° (Schlimpert, N. Br. Arch. 100, 152). Insoluble
in ether.
C40N2H2402
SO3
HO
2 aq.
Air-dried.
308
....
40
9
18
....
Hesse.
Baup. Regnault. Schwabe. Lamina. Crystals.
....
82.14
10.66
2.40
4.80
P
....
10.91
4.67
....
375 100.00
....
G
....
82.20
....
....
10.67 10.81
10.86
4.98 ... 466
4.78 .... 4.64
The dry salt contains 11.52 p. c. of sulphuric acid (calc. 11.20 p. c.) (Pelletier &
Caventou), 66.20 p. c. C., and 7:33 H. (Regnault) (calc. 67-22 p. c. C., 7·00 H.)
B. Bi-acid. The salt A is evaporated with dilute sulphuric acid.
till a pellicle forms on the surface, and the product is purified by re-
crystallisation. Transparent rhombic octahedrons, frequently truncated
at the summits, very easily cleavable parallel to the principal axis
(Baup). Diclinic? Rectangular, four-sided prisms, a, b, with an end-
face c, resting obliquely on u. Angle ac 83° 50′; b : c = 95° 50'
(Brooke, Ann. of Phil. 22, 375).- Effloresces only slightly in warm dry
air, but more rapidly than A when heated. Dissolves in 0.46 parts of
water at 14°, in 90 parts of alcohol of sp. gr. 0·85, and in 100 parts of
absolute alcohol. Însoluble in ether (Baup).
Baup.
C40N2H2402
2 SO3
308
64.42
80
16.73
17.24
2 HO
18
3.76
8 aq.
72
15.09
15.52
C40N2H2402,2(HO,SO³) + 8 aq.
478
100.00
208
PRIMARY NUCLEUS C4H26; OXY-AZO-NUCLEUS C40N2H22O².
Iodate of Cinchonine.-Iodic acid does not precipitate hydrochlo-
rate of cinchonine (v. Planta).
-The salt is obtained from aqueous
iodic acid and cinchonine. Very delicate white needles, which explode
violently at 120° (Serullas, Ann. Chim. Phys. 45, 274, Regnault). Dis-
solves very easily in water, but not in alcohol (Pelletier). From a
moderately strong solution (also from the chlorate) aqueous iodic acid
precipitates an acid salt (Serullas).
40 C
2 N
25 H
80
I
at 105°.
Regnault.
240
49.58
48.69
... ....
28
5.78
25
5.16
5.20
64
13.24
127
26.24
100'00
CNH”O,HO,IO5.... 484
Contains 56.80 p. c. of cinchonine and 35·07 of iodic acid (Serullas).
Periodate of Cinchonine. — Cinchonine neutralises aqueous periodic
acid only partially; on evaporation in a vacuum, the solution deposits
a resin, in which crystals are afterwards formed. The crystals soon
decompose, with formation of iodic acid. On adding an alcoholic
solution of periodic acid to alcoholic cinchonine, and carefully
evaporating the neutral liquid, short prisms are obtained, which turn
yellow in the air and then contain iodic acid, and at last hydriodic acid.
(Langlois, N. Ann. Chim. Phys. 34, 257; Ann. Pharm. 83, 153).
Hydriodate of Cinchonine. Iodide of potassium throws down from
hydrochlorate of cinchonine, a white powder which becomes crystalline
on standing (v. Planta). The salt is deposited from the slightly
warmed solution, on cooling, partly in the form of a pale-yellow oil
which quickly solidifies in a crystalline mass, and partly in delicate
white crystals containing the same proportion of water (Hesse).
Long, thick, colourless prisms (Herapath). Its taste is at first slight,
but afterwards bitter and metallic. Dissolves less freely than the
hydrochlorate (Regnault) in cold water, and crystallises from hot water
in needles having a pearly lustre (Pelletier). - Gives off 4.34 p. c.
of water at 140°, and then contains 30.68 p. c. of iodine (calc.
29.13 p. c. I) (Regnault). Schwabe obtained from sulphate of betacin-
chonine and iodide of barium, oblique prisms containing only 1 at. of
water, easily soluble in water and alcohol.
Hesse.
C40N2H2402
HI
308
67.87
128
28.19
28.43
2 aq.
18
3.94
4.05
C40N2H2402,HI + 2 aq.
454
100.00
Chlorate of Cinchonine.
Very white, loose scales and prisms, less
fusible than the quinine-salt, and easily decomposible (Serullas, Ann.
Chim. Phys. 45, 278).
C4N2H2402.
CIOS
308
76.71
75.5
18.80
Serullas.
..... 76:00
18.40
2 IIO.....
18
4.49
CN÷H²¹0²,HO,ClO5 + aq.
401.5
100.00
CINCHONINE.
209
Perchlorate of Cinchonine. — Obtained by precipitating perchlorate
of baryta with sulphate of ciuchonine and evaporating the filtrate.
Large, highly lustrous prisms, permanent in the air (Bödeker).
Rhombic prisms with perpendicular truncation of the oblique lateral
edges b, and an oblique end-face c, resting on the obtuse prismatic
edge, and unequally inclined to the two prismatic faces. The face
parallel to this is wanting at the opposite end, and instead of it there
occurs a face standing to it in the relation of right to left.
p: p'
= 125° 46′ and 54° 14'; p: b = 117° 7'; p : c = 123° 46';
p' : c = b:
122° 37'; b : c = 91° 6'. Cleavable parallel to b (Dauber,
Ann. Pharm. 71, 66). Exhibits fine dichroïsm of blue and yellow, even
in very dilute acid solutions. - Melts at 160°, losing water of crystal-
lisation, amounting to 3.57 p. c. of the salt dried at 30°; and explodes
with flame when more strongly heated. Dissolves easily in water
and alcohol (Bödeker, Ann. Pharm. 71, 59).
C40N2H2402,2HO
2 C107
2 HO
Crystals.
Bodeker.
326
61.86
60.51
183
34.72
35.41
18
3.42
3.57
527
100.00
99.49
....
C40N2H2402,2CIHO8 + 2 aq.
Hydrochlorate of Cinchonine.— A. Mono-acid. - Formed with hydro-
chloric acid and excess of cinchonine. Needles, fusible below 100°
(Pelletier & Caventou). Right prismatic; t and m (fig. 78), form a
quadratic prism, bevelled above and below by 1. Angle : above
126°; 7: t = 116-75° (Lösche). The same form was observed also
by Hesse. Retains its lustre in the air, but effloresces easily in the
desiccator; loses its water of crystallisation at 100°, and melts above
130°. Sp. gr. = 1·2342 (Hesse).
1.2342 (Hesse). Exerts a right-handed action on
polarised light; [a] r = 139.5° (Bouchardat). The salt, with 4 at.
water dissolves in 24 parts of water at 10° (Hesse); in 24 parts at
18.75° (Abl); in 22 parts of cold, and in 3.2 parts of hot water
(Schwabe). It dissolves in 1·3 parts of alcohol of sp. gr. 0·85 at 16°
(Hesse); in 1 part of cold, and part of boiling alcohol (Schwabe).
Soluble in 550 parts of ether (Schwabe); in 273 parts of ether of
sp. gr. 0·7305 at 15° (Hesse).
C40N2H2402
HCI
Crystals.
308.0
Schwabe.
Hesse.
80.95
4.
36.5
9.59
9.83
9.67
4 aq.
36.0
9.46
9.49
9.47
C4°N2H2402,HCl + 4 aq.
380.5
100.00
....
Dried.
Hesse.
C40N2H2402
HCI
C40N2H2402 HCI
308.0
89.46
89.4
36.5
10.54
10.6
3445
100.00
100.0
.....
B. Bi-acid. 100 parts of cinchonine take up 227 parts of hydro-
chloric acid (Liebig); when exposed to a stream of hydrochloric acid
gas, and afterwards to dry air of 165°, they retain 22.6 parts of hydro-
chloric acid (2 at. 23.6 p. c.). The solution of the salt in water
yields a strongly acid gum (Regnault). On evaporating cinchonine
VOL. XVII.
P
210 PRIMARY NUCLEUS CH; OXY-AZO-NUCLEUS C40N2H22O².
with excess of hydrochloric acid, dissolving the residue in weak
alcohol, and allowing the solution to evaporate spontaneously, fine
tables are obtained, which have an acid reaction, and are easily soluble
in water, but less freely in alcohol. Right prismatic. Right rhombic
prisms, u, u, with the base p; the acute lateral edges replaced by
i (fig. 80); tabular from predominance of p. Angle u: u = 101°;
pi= 137 to 138° (Laurent). To this belong also the crystals
obtained by Hahn; rhombic prisms y (fig. 53) having the obtuse
lateral edge perpendicularly truncated by p, which is perpendicular to
the base t. Angle y : y = 30°, y : p = 165° (IIahn). ´Also Laurent's
salt with the macrodiagonal three times as long (Guthe).
2
40 C
2 N
26 H
20
2 01
Crystals.
240
Laurent. Gössmann.
62.99
......
62.00
28
7.34
26
6.82
6.66
16
4.20
71
18.65
19.35
19.3
381
100.00
....
C40N2H2402,2HC1
Hydrofluate of Cinchonine. By evaporating cinchonine with ex-
cess of hydrofluoric or hydrofluosilicic acid, a strongly acid varnish is
obtained (Serullas, Ann. Chim. Phys. 45, 282). Cinchonine dissolves
freely in dilute hydrofluoric acid; on concentrating the solution by
evaporation, colourless right rhombic prisms with four-sided pyramids
are obtained. A solution in weak alcohol yields very fine crystals;
the solution in stronger alcohol, when almost completely evaporated,
yields only needles and a viscid syrup. The crystals lose 2.81 p. c. of
water at 100° (1 at. = 2.52 p. c. HO), becoming milk-white, and on
further heating, purple-red, after which they give off a red sublimate
and hydrofluoric acid, and carbonise (Elderhorst, Ann. Pharm. 74, 80).
at 100°.
Elderhorst.
C40N2H2402
2 HF
C40N2H2402, 2HF
308
40
...
88.51
11.49
87.52
348
100.00
....
Nitrate of Cinchonine. A solution of the salt, obtained by double
decomposition, or by saturating very dilute nitric acid with cinchonine,
deposits, on evaporation, oily drops, which cool to a waxy solid, and
become converted into crystals when kept under water. Large mono-
clinic twin-crystals, often an inch long (Hesse). According to Pelletier
& Caventou, oblique rectangular prisms, easily cleavable parallel to
two side-faces, and having on these faces a pearly lustre. According to
Lösche, flat oblique-prismatic crystals, bevelled at the ends by two faces
forming a very obtuse angle. Exerts a right-handed action on
polarised light; [a] = 172° 48' (Bouchardat). - Permanent in the
air (Schwabe). Loses at 100°, on an average, 2.57 p. c. of water
(1 at. = 2.37 p. c. HO). The hydrated salt dissolves in 26-4 parts of
water at 12°, and freely in water at 40°; the solution heated to boiling
deposits the salt in the form of an oil on cooling (Hesse).
Cinchonine is not precipitated by excess of fluosilicic alcohol
(xv, 437) (Knop); phosphomolybdic acid (xiii, 164) precipitates it
whitish-yellow (Sonnenschein).
CINCHONINE.
211
Phosphantimonic acid (xiv, 227) throws down bluish-white flocks
from a solution containing th of cinchonine (Schulze).
1
000
Chromate of Cinchonine. By double decomposition in neutral or
acid solutions a bi-acid salt is obtained (André). Warm aqueous
hydrochlorate of cinchonine becomes turbid on dropping into it a solu-
tion of bichromate of potash, and afterwards deposits small ochre-
yellow prisms (Hesse), orange-yellow needles (André), or at too high
a temperature, or on too hasty addition of the bichromate, a resin,
which does not crystallise (Hesse). A similar observation was made
by Elderhorst (Ann. Pharm. 74, 80). The precipitate, amorphous at
first, becomes crystalline on standing (Seligsohn). Decomposed by
exposure to light in the moist state, but not after drying (Hesse).
Decomposes at 60° (André), and carbonises at 100°, glowing on ex-
posure to the air (Hesse). Dissolves in 80 parts of boiling water.
Hesse.
Dried over oil of vitriol.
C40N2H2402
2 CrO3
но
308
73.86
74.00
100
23.98
24.05
9
2.16
C40N2H2402,HO,2CrO³.... 417
100.00
Arseniate of Cinchonine.
Bibasic.
cinchonine and arseniate of potash.
Formed from hydrochlorate of
Long white prisms, very easily
soluble in water. Loses its water of crystallisation at 100° (Hesse).
Hesse.
2 C40N2H2402
AsО5,3HO
616
63.24
142
14.59
24 aq.
216
22.17
21.71
2C40N2H2402,3HO,AsO5 + 24 aq. 974
100.00
•
Chlorocadmiate of Cinchonine. - C40N2H2O2, HCl, CdCl+aq. By mix-
ing hydrochlorate of cinchonine and chloride of cadmium, a stiff mass
is obtained, which becomes transformed into large crystals (Galletly,
Pharm. Centr. 1856, 697; N. Edin. Phil. J. 4, 94).
Chlorostannite of Cinchonine. - Hydrochlorate of cinchonine throws
down from a solution of protochloride of tin containing hydrochloric acid,
a pale-yellow oil, which afterwards solidifies. The supernatant liquid
deposits heavy, pale-yellow prisms, melting at 100° to a yellowish
oil, which solidifies to a brittle mass. Contains, after drying at
100°, 27.65 p. c. Cl, rather more than is required by the formula
C¹ºN²H²O²,2HCl, 2SnCl (cale. 24.93 Cl), the excess being derived from
adhering hydrochloric acid. Cannot be recrystallised (Hesse).
Mixed solutions of ferric sulphate and sulphate of cinchonine do not
yield a double salt (Will, Ann. Pharm. 42, 111).
Iodomercurate of Cinchonine.— Iodomercurate of potassium throws
down from hydriodate (or from acetate or hydrochlorate) of cinchonine
a white precipitate, which cakes together in hydrochloric acid, without
dissolving (v. Planta; Delffs). The precipitate turns sulphur-yellow
on drying: it is amorphous, has a faint taste, and when heated melts,
gives off iodine, and decomposes. It is nearly insoluble in water and
in alcohol (Caillot, Ann. Chim. Phys. 42, 265).
P 2
212
PRIMARY NUCLEUS C40H26; OXY-AZO-NUCLEUS C40N2H22O2.
C40N2H2402
2 HI
2 HgI
Caillot.
308
30.25
256
25.16
-
454
44.59
42.67
100.00
CN2H2402,2HI + 2HgI .... 1018
Cinchonine [hydrochlorate? (Kr.)], chloride of mercury, and iodide
or bromide of potassium yield double salts corresponding to those of
morphine (xvi, 433), nearly insoluble in cold and in boiling water, but
soluble in almost all proportions in boiling alcohol (Groves).
Hydriodate of Cinchonine with Chloride of Mercury? On adding a
solution of mercuric chloride to hydriodate of cinchonine, a white
uncrystallisable precipitate, tasting of corrosive sublimate and cin-
chonine, is produced. The precipitate is decomposed by acetic acid,
with formation of red iodide of mercury. It contains an amount of
mercury corresponding to 34.91 p. c. HgCl (Caillot, Ann. Chim. Phys.
42, 268). Probably either the iodine-compound or a mixture of the
iodine and chlorine compounds (Gmelin).
Previously obtained by Caillot, Ann.
Chloromercurate of Cinchonine.
Chim. Phys. 42, 263. Chloride of mercury throws down from hydro-
chlorate of cinchonine a white powder, easily soluble in hydrochloric
acid, and soluble with difficulty in sal-ammoniac (v. Planta).
When a
solution of hydrochlorate of cinchonine in strong alcohol acidulated
with hydrochloric acid, is mixed with an equal quantity of alcoholic
chloride of mercury, the mixture quickly solidifies to a mass of crystals.
Purification is effected by washing with water, alcohol, and ether-
alcohol in succession. Stable at 100°. - Dissolves in water or weak
alcohol on heating only. Freely soluble in strong hydrochloric acid
(Hinterberger, Ann. Pharm. 77, 202). Schwabe obtained the salt in
the form of a white, resinous mass.
Hinterberger.
40 C
2 N
26 H
20
2 g
H
4 Cl
Dried over the water-bath.
240
36.62
35.50
28
4.29
26
3.98
3.83
16
2.66
200
30.67
31.48
142
21.78
21.67
100.00
CN2H2O2,2HCl + 2HgCl.... 652
Contains 29-31 p. c. Hg (Caillot).- According to Hinterberger C39N2H22O2,2HC1+
211gCl. Hinterberger afterwards regarded the salt as impure, containing Hlasiwetz's
cinchotine. He states also that only commercial cinchonine, when in alcoholic solu-
tion, solidifies to a crystalline mass with chloride of mercury; and that on recrystal-
lising the cinchonine, the first crop of crystals obtained yields no double salt, even
after standing for 24 hours; but on addition of water, the salt is thrown down as a
white precipitate, becoming crystalline in the cold (Hinterberger, Wien. Acad. Ber.
7, 432; Ann. Pharm. 82, 318).
Chloroplatinate of Cinchonine. - Bichloride of platinum throws down
from alcoholic hydrochlorate of cinchonine, a crystalline precipitate,
which is at first almost white or light-yellow. On dissolving it by
long boiling with water, it is deposited, first as a whitish powder, and
afterwards in fine dark orange-yellow crystals (Hlasiwetz). Pale
lemon-yellow precipitate, crystallising from excess of chloride of pla-
CINCHONINE.
213
tinum in perfect yellow needles (Erdmann). Right prismatic. The
faces y, p, t of fig. 53; the microscopic crystals are prismatic; y : y
(over m) = 119° (Lösche). y and p (fig. 53), with the octohedron a.
y: y = 5° ;_ p : y = 120° (!); the edge aa: á á (fig. 43) = 123°
(Hahn). Loses 2.8 p. c. of water at 180-200° (Laurent). Dissolves
in 500 parts of hot water, one-half crystallising on cooling (Duflos).
Insoluble in alcohol and ether.
Duflos.
C40N2H2402........
308
42.75
43.43
2 H
2
0.28
6 Cl
2 Pt....
213
29.57
29.20
197.4
27.40
26.80
C¹ºN²H²+O²,2HCl,2PtCl² .... 720.4
100.00
Hlasiwetz.
40 C ....
2 N
26 H
20
6 Cl......
2 Pt
C40N2H2402,2HCl,2PtCl²
240
33.31
33.1
28
3.89
26
3.61
3.6
16
2.22
213
29.57
197.4
27.40
27.36
720.4
100.00
..3.
Contains, at 100°, 27-25 p. c. (Laurent), 27.8 p. c. (Gössman), 27.5 p. c. of
platinum (Schwabe).
Chloride of iridium and sodium throws down from hydrochlorate of
cinchonine, a pale-yellow precipitate soluble in hydrochloric acid (v.
Planta).
Terchloride of gold throws down from solution of cinchonine a
sulphur-yellow precipitate, soluble in alcohol, and slightly also in
water [and hydrochloric acid (v. Planta)], but insoluble in ether
(Larocque & Thibierge, J. Chim. méd. 18, 696).
Hydrocyanate of Cinchonine. The precipitate obtained by the
double decomposition of hydrochlorate of cinchonine and cyanide of
potassium, consists of cinchonine free from hydrocyanic acid (Hesse).
Contrary to Schwabe, who regarded the precipitate as hydrocyanate of cin-
chonine.
Hydroferrocyanate of Cinchonine. - Obtained by precipitating alco-
holic cinchonine with alcoholic hydroferrocyanic acid. Yellow crystal-
line precipitate, difficultly soluble in alcohol. Evolves a large quantity
of hydrocyanic acid when heated, the aqueous solution depositing at
the same time a white precipitate, which quickly turns blue (Dollfus,
Ann. Pharm. 65, 212).
52 C
8 N
Dolifus.
312
55-71
54.90
112
20.00
32 H
32
5.72
6.10
60
48
8.57
2 Fe......
56
10.00
10.30
C40N2H2402,2Cy³FeH² + 4 aq.
560
100.00
The yellowish-white precipitate produced by ferrocyanide of potas-
214
PRIMARY NUCLEUS C40H26; OXY-AZO-NUCLEUS CN2H22O³.
sium in solutions of cinchonine free from excess of acid, contains,
according to Seligsohn, hydroferrocyanic acid and cinchonine in the
same proportions. The precipitate disappears on slowly warming
the liquid, and is deposited again on cooling in golden-yellow, wedge-
shaped prisms. It dissolves in mineral acids, but is insoluble in excess
of ferrocyanide of potassium (J. W. Bills, Sill. Amer. J. (2) 26, 108;
N. J. Pharm. 35, 36; J. pr. Chem. 75, 484; further: Schmidt's medic.
Jahrb. 107, No. 7; Chem. Centr. 1861, 231). This precipitate is not
formed in perfectly neutral solutions of cinchonine: ferrocyanide of
potassium produces therein only a resinous precipitate, or in dilute
solutions a milky turbidity; on the subsequent addition of hydrochloric
acid, however, long prisms and rhombic tables are formed in the liquid.
The same compound is obtained in scales or needles on dropping ferro-
cyanide of potassium into a boiling slightly acid solution of a salt of
cinchonine, and cooling. The flocculent precipitate thereby produced
is also converted into crystals on standing, though only when pure
cinchonine-salts are employed, and not with the commercial lævo-
rotatory salts. The crystals are neutral, intensely bitter, insoluble in
alcohol and cold water, and difficultly soluble in warm water. The
more easily formed solution in water acidulated with hydrochloric acid
contains hydroferricyanic acid (Seligsohn, Medicin. Centralzeit. 30, 129;
Chem. Centr. 1861, 231).
J
Hydroferricyanate of Cinchonine. Ferricyanide of potassium, in not
too dilute solution, throws down a yellow precipitate from aqueous
hydrochlorate of cinchonine. — Lemon-yellow, hard, pointed crystals,
stable at 100° when perfectly dry. The aqueous solution assumes a
blue colour on spontaneous evaporation (Dollfus).
52 C
8 N
31 H
60
2 Fe
at 100°.
Dollfus.
312
55.82
55.22
112
20.04
31
5.54
5.70
18
8.58
56
10.02
10.34
100.00
CN2H2¹0², Cy Fe H3 + 4 aq….... 559
Cyanide of mercury throws down from hydriodate of cinchonine a
white, curdy precipitate, insoluble in water and alcohol, from which
acids separate red iodide of mercury, evolving hydrocyanic acid at the
same time. The precipitate contains an amount of mercury corre-
sponding to 33-94 p. c. HgCy (Caillot, Ann. Chim. Phys. 42, 269).
(CNH2O2,2HI+ 2HgCy requires 30.8 p. c. HgCy). The precipi-
tate produced by mono-acid hydrochlorate of cinchonine in a mixture
of cyanide of mercury and bromide of potassium is, according to Caillot,
a compound of cyanide of mercury with hydrobromate of cinchonine (J.
Pharm. 17, 356).
Cyanoplatinate of Cinchonine. —By the double decomposition of
cyanoplatinate of barium and sulphate of cinchonine, sulphate of
baryta and bulky colourless needles are obtained. When heated the
needles melt to a red-brown mass, and afterwards carbonise, leaving
a residue of platinum. Anhydrous. Difficultly soluble in water; more
easily soluble in alcohol (C. A. Martius, Ann. Pharm. 117, 376). -
Cyanoplatinate of potassium precipitates from solutions of cinchonine
CINCHONINE.
215
the compound C40N2H2O2,HCy, PtCy + 3 aq., which melts to a violet
liquid, and dissolves in hot water (Delffs, N. Jahrb. Pharm. 21, 31; N.
Repert. 13, 36).
C40N2H2502,2Cy
Pt..........
Martius.
363
98.7
78.62
21.38
21.38
.....
100.00
C¹¹0N²H²40²,HСy,PtCy .. 461.7
....
Martius's formula contains 1 at. H. less than the above.
Hydrosulphocyanate of Cinchonine. Sulphocyanide of potassium
throws down from acetate (O. Henry, J. Pharm. 24, 194) or hydro-
chlorate of cinchonine (v. Planta) a white curdy precipitate, which
rapidly disappears when heated, and is transformed into shining lamina
on standing. The precipitate is insoluble in liquids containing sulpho-
cyanide of potassium, but dissolves in water and easily in alcohol
(Lessage, J. Pharm. 26, 140).
Hot solutions deposit the salt, on cooling, in very long, thin needles,
which effloresce readily in dry air (Schwabe). Microscopic six-sided
prisms, mingled with irregular, flattened rectangular prisms (Anderson).
An alcoholic solution of cinchonine is neutralised with not too dilute
hydrosulphocyanic acid. Transparent, shining, anhydrous needles,
containing 16.97 p. c. of hydrosulphocyanic acid (calc. 16·07 p. c.
CyHS²) (Dollfus).
42 C
3 N
25 H
20
2 S
C40N2H240²,Сy HS2
at 100º.
Dollfus.
68.67 ..... 67.86
252
42
11·44
25
6.79
16
4.36
32
8.74
367
100.00
6.63
Formate of Cinchonine. - Crystallises with difficulty. The solution,
evaporated to a syrup, solidifies to a mass of needles (Bonaparte, J.
Chim. méd. 18, 685).
Acetate of Cinchonine. A neutral solution of cinchonine in acetic
acid deposits crystals of cinchonine and becomes acid when heated to
30° or 40° (Hesse). The acid solution yields on evaporation crystalline
granules and pellicles, which are no longer acid, and are but slightly
soluble in water [cinchonine? (Kr.)], but ultimately there remains a
gummy mass, from which water takes up an acid salt, leaving a neutral
salt behind (Pelletier & Caventou). By spontaneous evaporation
Schwabe obtained apparently rectangular prisms (y: y = 114°; y: m
= 123°), resembling the sulphate, permanent in the air, and easily
soluble in water and alcohol. Mono-acetate of cinchonine turns litmus
red and blue at the same time (De Vrij).
Oxalate of Cinchonine. A. Bibasic. Oxalate of ammonia throws
down from salts of cinchonine, a white neutral powder, slightly soluble
in cold, but more freely soluble in hot water and hot alcohol; soluble
also in excess of aqueous oxalic acid (Pelletier and Caventou). It is
obtained from a dilute aqueous solution in large prisms, which dissolve
in 104 parts of water at 10°, and lose their water of crystallisation at
130° (Hesse).
216 PRIMARY NUCLEUS C40H6; OXY-AZO-NUCLEUS CON²H²²O².
2 C40N2H2402
C406
2 HO
4 aq.
Air-dried.
616
Hesse.
83.03
72
9.70
9.96
18
2.42
36
4.85
5.11
100.00
2C40N2H2402,C+H2O8+ 4 aq..... 742
B. Mono-acid. Schwabe obtained oxalate of cinchonine in oily
drops, changing to tufts of efflorescent crystals. Probably the mono-
acid salt.
Cyanurate of Cinchonine. On boiling freshly precipitated cinchonine
with a boiling saturated aqueous solution of cyanuric acid and filtering,
this salt is deposited in flat rhombic prisms, which lose 17.79 p. c. of
water at 100°, or over oil of vitriol, and nothing more at 200°; when
more strongly heated, they evolve vapour smelling of bitter almond oil.
The salt dissolves with difficulty in water, but is insoluble in alcohol
and ether (Elderhorst, Ann. Pharm. 74, 84).
Oxalurate of Cinchonine. Parabanic acid is saturated, at the boiling
heat, with excess of cinchonine. The filtrate dries up to a yellowish
transparent mass, which gradually becomes white and crystalline. It
is decomposed by cold hydrochloric acid, with separation of oxaluric
acid, and by the boiling acid, with formation of oxalic acid (Elderhorst).
Mellitate of Cinchonine. Obtained as a white precipitate on adding
alcoholic cinchonine to an alcoholic solution of mellitic acid (Karmrodt,
Ann. Pharm. 81, 171).
Karmrodt.
mean.
C40N2H2402
308
57.46
2 C806
4 HO
192
35.82
37.50
36
6.72
C40N2H2402,2CH²08....
536
100.00
Succinate of Cinchonine.
Obtained from cinchonine and excess of
succinic acid. Long oblique needles, and thick large crystals. Has
a strongly acid reaction. Dissolves easily in cold, and more especially
in boiling water. Melts at about 100° to a dark-red mass (Hesse).
C40N2H2402
2 C$H608
3 HO
Needles.
Hesse.
308
67.99
67.43
S...
118
26.05
27
5.96
6.51
453
100.00
C40N2H2402, C8H6O³ + 3 aq. .
The larger crystals lose 4.24 p. c. =
2 at. of water at 100° (Hesse).
Aspartate of cinchonine crystallises easily in needles (Plisson, J.
Pharm. 15, 274).
Tartrate of Cinchonine. Whilst the compounds of tartaric acid and
antitartaric acid (dextrotartaric and levotartaric acids, x, 365) with
optically inactive substances are identical in every respect, save in the
position of the hemihedral faces of their crystals and in their opposite
action on polarised light, the compounds of the two acids with optically
CINCHONINE.
217
active bodies exhibit differences in composition, in solubility, in their
behaviour on heating, &c. An optically active substance may form with
one of the acids a compound to which there exists no corresponding
compound with the other acid (Pasteur).
A. Dextrotartrate of Cinchonine. a. Neutral. Precipitated on
mixing solutions of cinchonine-salts with alkaline tartrates (Pelletier
and Caventou), or on adding neutral tartrate of potash to hydro-
chlorate of cinchonine (Hesse). A solution of cinchonine in
neutral tartrate of potash, in which it dissolves abundantly, deposits
this salt in crystalline tufts on cooling (Arppe). Small crystals, per-
manent in the air, having an alkaline reaction, and dissolving in 33
parts of water at 16° (Hesse). Loses 4.65 p. c. of water at 110°, and
not more at 180°, beyond which it decomposes. The anhydrous salt
is electric (Arppe). After dehydration the salt rapidly takes up water
again in moist air. Less easily fusible than the mono-acid salt
(Hesse).
Arppe.
Hesse.
2 C40N2H2402
CSH6O12
Crystals.
616
77.78
140
17.67
4 aq
36
4.55
4.65
4.68
2040N2H2402,CH6O12 + 4aq.
792
100.00
b. Acid. When 294 parts of cinchonine are dissolved, together
with 132 parts of dextrotartaric acid, in warm water, the solution
yields on cooling star-shaped groups of well-formed, highly lustrous
crystals: the same salt is obtained also, though less abundantly, with
twice the quantity of dextrotartaric acid; but if not less than four
times the quantity of acid is employed, a bi-acid salt is produced.
Rhombic prisms u, with bevelling faces n, resting on the acute lateral
edges, and a right rhombic tetrahedron ɑ. Angle u: u= 130° 20′
about; n: u = 127° 40′ about; a: q = 151° 13'. See also Hahn's
measurements. Exerts a dextro-rotatory action on polarised light.
Neutral in alcoholic, acid in aqueous solution (Pasteur).
The air-dried salt gives off 18.8 p. c. of water in a vacuum, and 13·75
to 14 p. c. at 100° [13.6 p. c. at 110° (Hesse)], at which temperature
it assumes a faint red colour, becoming darker at 120°, without further
loss of weight (Pasteur). The dried salt slowly absorbs water in moist
air (Hesse). Dissolves very slightly in cold [in 101 parts at 16°
(Hesse)], freely in hot water, and abundantly in absolute alcohol
(Pasteur).
Hesse.
C40N2H2402
C8H6O12
Crystals.
308
Pasteur.
59.23
140
26.92
8aq
72
13.85
13.75
13.60
A
C40N2H2402,CH6O¹² + 8aq.... 520
100.00
B. Antitartrate of Cinchonine. Obtained from anti-tartaric acid
and cinchonine in the same manner as the corresponding dextrotartrate.
When a large excess of acid is employed, very delicate pearly needles.
of a bi-acid salt are obtained. Neutral in alcoholic, acid in aqueous
solution. Exerts a dextro-rotatory action on polarised light, about 1th
less powerful than the salt A, b. Loses 4.5 p. c. in weight at 100°,
and not more at 120° to 140°: at the latter temperature it becomes
W
218 PRIMARY NUCLEUS CH6; OXY-AZO-NUCLEUS C4N2H220².
coloured only after a considerable time (CN2H2O², CHO¹² + 2aq.
requires 3-78 p. c. HO). Dissolves very slightly in water: the
hydrated salt dissolves in 338 parts of absolute alcohol at 19° (Pasteur).
48 C
2 N
32 H
16 O
Crystals.
Pasteur.
288
60.50
59.85
28
5.88
32
6.72
6.66
.......
128
26.90
100.00
C40N2H402, CH6O12 + 2aq 476
...
When dextrotartrate or antitartrate of cinchonine is heated at
gradually increasing temperatures, dextrotartrate or antitartrate of
cinchonicine is first formed and is afterwards converted, with loss of
water, into a coloured quinoïdine-salt. If the temperature at this point
has reached 170°, and is then maintained constant for five or six hours,
a part of the dextrotartaric or antitartaric acid is converted into
racemic acid, which by a further change is partially converted into
inactive tartaric acid, not resolvable into dextrotartaric and lævotartaric
acids (Pasteur).
The solution obtained by
Tartrate of Cinchonine and Antimony.
decomposing sulphate of cinchonine with baryto-antimonic tartrate
yields, on spontaneous evaporation, white nodules containing 24-77
p. c. of water of crystallisation and efflorescing rapidly in the air, and
afterwards large crystals, which resemble nitrate of cinchonine, and lose
9.95 p. c. of water at 100°. The dried salt contains 26.4 p. c. of
antimony, and 47.48 of cinchonine (Hesse). When treated in the
same way as quinidine it does not yield a double salt (Stenhouse).
Croconate and Rhodizonate of cinchonine are deep-yellow or red
amorphous masses, soluble in water and alcohol (Heller).
Urate of Cinchonine. Uric acid is boiled with freshly precipitated
cinchonine and a large quantity of water for some time, and the solution
is filtered hot. Prisms, amongst which are many twins, resembling
harmotome. Over oil of vitriol, or when heated, the transparent
crystals become opaque and break up into a white powder, which
ultimately assumes a sulphur-yellow colour. They lose 13.73 p. c. of
water at 100°, and no more at higher temperatures (8 at. = 13·14 p. c.
HO); at 183° they begin to decompose and carbonise (Elderhorst).
at 100°.
C40N2H2402
C10N H¹06...
308
168
64.69
35.31
64.89
.....………
C4°N²H²², C¹ºN4H4O6.... 476
100.00
Citrate of Cinchonine. A solution of the salt prepared in the cold
is decomposed on heating, with separation of cinchonine (Hesse).
A. Terbasic. Obtained from hydrochlorate of cinchonine and
citrate of potash. By dissolving it in alcohol and leaving the solution
to evaporate spontaneously, it is obtained as a colourless oil, which is
converted, after some time, into long, concentrically arranged prisms.
The crystals dissolve in 48·1 parts of water at 12°. They lose their
water at 100° (Hesse).
CINCHONINE.
219
3 C40N2H2402
C12H8014
8 HO
Hesse.
924
77.77
77.76
94
16.17
72
6.06
6.21
100.00
3C4°N²H²402,C¹2H8O4 + Saq... 1090
B. Bibasic. Prepared from cinchonine and excess of citric acid.
Small prisms, which dissolve in 55.8 parts of water at 15°. Does not
take up water from the air after drying (Hesse).
2 C40N2H2402
C12H8014
8 HO
Hesse.
616
70.00
70.31
94
21.82
72
8.18
8.45
100.00
.......
2040N2H2402, C12H8O14 + 8aq 782
Picrate of Cinchonine. Alcoholic picric acid throws down from an
alcoholic solution of cinchonine, a yellow precipitate insoluble in acids
(Kemp, Repert. 71, 164). A warm aqueous solution of hydrochlorate
of cinchonine yields with aqueous picric acid, a yellow precipitate
résembling iodide of lead, and becoming dense and crystalline on
standing. Contains 46.75 p. c. of cinchonine, corresponding to the
formula 2C40N2H2402,3C12X3H302 (calc. 47.2 p. c. cinchonine) (Hesse).
A solution in water deposits on boiling, oily drops which do not solidify
on standing under water for some days (Bonaparte, J. Chim. méd.
18, 685).
A strong aqueous solution of orcin throws down from bisulphate of
cinchonine, oily drops which solidify in dry air and contain orcin and
cinchonine (Du Luynes, Compt. rend. 57, 162). Picrotoxin forms with
cinchonine, a compound resembling that formed with brucine (Pelletier
and Couerbe, Ann. Chim. Phys. 54, 187).
Benzoate of Cinchonine. Obtained with excess of cinchonine.
Deposited from a boiling aqueous solution on cooling, in small star-
shaped prisms, which dissolve in 163 parts of water at 15° (0. Hesse).
C40N2H240².....
C14H604
Crystallised.
308
122
Hesse.
71.62
28.38
.......
71.25
100.00
...
C40N2H2402,C¹4H6O¹.... 430
Hippurate of Cinchonine. - The solution obtained by boiling excess
of cinchonine with a hot saturated aqueous solution of hippuric acid
and filtering, does not crystallise on cooling, but when evaporated to a
syrup, solidifies to a transparent, amorphous mass (Elderhorst).
Gallic acid does not precipitate sulphate of cinchonine (Pfaff;
Bonnet).
Tannate of Cinchonine. Tincture or infusion of galls, in small quan-
tity, precipitates from dilute solutions of hydrochlorate of cinchonine,
yellowish-white flocks, which disappear on the addition of a drop of
hydrochloric acid, but re-appear in the form of a dense precipitate, on
adding more hydrochloric acid (v. Planta).
Cinchonine behaves towards cinchona-red (xv, 482) in the same
manner as quinine (Henry & Plisson).
220 PRIMARY NUCLEUS CH26; OXY-AZO-NUCLEUS C40N2H22O².
Kinate of Cinchonine. Occurs in cinchona-barks, according to Henry &
Plisson. Freshly precipitated cinchonine is dissolved in aqueous kinic
acid, and the solution is concentrated and left to stand in the air.
More distinctly crystalline than the quinine-salt: easily soluble in
water, less freely in alcohol (Henry & Plisson, Ann. Chim. Phys. 35,
173). The crystals contain 4 at. water: they dissolve in part of
water at 15°, and are decomposed by alcohol. A hot alcoholic solu-
tion, which reddens litmus, deposits short flat 4- and 6-sided prisms,
colourless and shining, permanent for a time in dry air, but ultimately
becoming opaque; deliquescent in moist air, and very soluble in water,
whereby a little cinchonine is deposited, and an alkaline solution pro-
duced (Baup, Pogg. 29, 70; Ann. Pharm. 6, 12).
Roccellate of Cinchonine. The easily formed solution of 2 at.
cinchonine and 1 at. roccellic acid (xvi, 476) in warm alcohol leaves
on evaporation an unctuous mass, insoluble in water and ether
(Hesse).
Cinchonine behaves in the same manner as quinine towards oleic
acid and olive oil (Attfield).
Cinchonine dissolves in 140 parts of alcohol of sp. gr. 0.852 at 10°,
and in 125-7 parts at 20° (Hesse). Dissolves in 600 parts of cold
alcohol of 20° B. (Merck), in 126.5 parts of absolute alcohol, and in
1152 parts of alcohol of 90 p. c. at 15° (Bussy & Guibourt); in 400 parts
of 80 p. c. alcohol at 17°, and in 110 parts at the boiling heat (Erdmann);
in 173 parts of cold, and in 43 parts of boiling alcohol (Schwabe).
Water throws down a crystalline precipitate from the alcoholic solution
(Schwabe). A boiling alcoholic solution deposits two-thirds on cooling
(Duflos).
Cinchonine dissolves in 371 parts of ether of sp. gr. 0·7305 at 20°
(Hesse); in 830 parts of ether (Bussy & Guibourt); in 378 parts of ether
(Schwabe); in 600 parts of ether at 17°, and in 470 parts of boiling ether
(Erdmann). It dissolves in cold creosote and picamar (Reichenbach);
in 23.2 parts of chloroform (M. Pettenkofer); in 40 parts (beta-cin-
chonine in 268 parts) of chloroform (Schwabe). Riegel found cinchonine
insoluble in chloroform. Dissolves to a very small amount in oil of turpentine
and fat oils (Pelletier & Caventou); in 100 parts of olive oil (Petten-
kofer). According to Schwabe, beta-cinchonine dissolves easily in vola-
tile and fixed oils, but not in rock oil.
Cinchonine does not precipitate gelatin.
Cinchonidine.
C40N2H2O2 = C40N2H22O2,H².
F. L. WINCKLER. Repert. 85, 392; 98, 384; 99, 1; abstr. Kopp's
Jahresber. 1847 & 1848, 620.
J. A. BUCHNER. Repert. 98, 388.
H. G. LEERS. Ann. Pharm. 82, 147; abstr. J. pr. Chem. 58, 21;
Pharm. Centr. 1853, 65; N. Ann. Chim. Phys. 36, 112; N. J.
Pharm. 22, 339; Chem. Gaz. 1853, 161; Kopp's Jahresber. 1852,
533.
STAHLSCHMIDT. Ann. Pharm. 90,
218.
CINCHONIDINE.
221
BUSSY & GUIBOURT. N. J. Pharm. 22, 401; Chem. Centr. 1853, 205;
J. pr. Chem. 59, 225; Kopp's Jahresber. 1852, 745.
PASTEUR.
N. J. Pharm. 23, 123; Compt. rend. 36, 26; J. pr. Chem.
58, 376; Kopp's Jahresber. 1853, 472.
HERAPATH. Phil. Mag. [4] 14, 224; J. pr. Chem. 72, 104; Kopp's
Jahresber. 1857, 405.
KERNER. Anal. Zeitschrift, 1, 153.
C. MANN. Russ. Pharm. Zeitschr. 2, No. 3 and 4; Pharm. Viertelj. 13,
245.
F. Kосн. N. Jahrb. Pharm. 22, 240.
The Cinchonidine of Pasteur; Chinidine of Winkler, Leers, Stahlschmidt, and
Bussy & Guibourt. Not to be confounded with the cinchonidine of Wittstein
(xiii, 336 and xvii, 228).
Discovered by Winckler in 1845, but not obtained free from quinine
or quinidine, as it was coloured green by chlorine-water and ammonia.
It occurs in a bark resembling China Huamalies, and also in China
Maracaibo (Wiggers, 415) (Winckler). A bark described as China
Bogota contains 2.64 p. c. of cinchona-bases, principally cinchonidine
with a little quinine (Leers). It probably occurs in the bark of Cinchona
ovata micrantha and cordifolia, and in Bolivian barks (Howard). In
many other cinchona-barks, together with quinine and cinchonine.
According to Kerner, a long-unrecognised cinchona-base, differing
from cinchonidine, is found in commerce under that name. It forms
shining laminæ and needles; its hydrochlorate crystallises in hard,
long, rhombic prisms: the sulphate is pulverulent, and soluble in 108
parts of water at 15°. Leers also found in Zimmer's cinchonidine, an
unknown base richer in carbon.
F. Koch distinguishes Winckler's quinidine from Pasteur's cincho-
nidine, but does not adequately characterise the two bases. Winckler's
quinidine occurs generally in Carthagena bark, together with cincho-
nidine; less frequently in Pitayo barks, and never in Calisaya bark.
It forms small granules, which do not turn dull in the air, and dissolve
abundantly in alcohol and ether-alcohol, but are nearly insoluble in ether.
The sulphate forms long transparent needles, harder and less flexible
than those of sulphate of quinine, and having a vitreous lustre. The
crystals turn brown in sunlight, do not fluoresce when dissolved in
sulphuric acid, and give off 20 p. c. of water at 80-100°. The hydro-
chlorate forms large transparent octahedrons. Pasteur's cinchonidine
occurs to the extent of 1 per cent. in the Carthagena barks, which are
scarcely known in commerce (see above).
It forms short, six-sided
prisms, permanent in the air, and difficultly soluble in alcohol and ether.
The sulphate resembles the sulphate of cinchonidine described below
(Koch).
-
Sulphate of cinchonidine is sometimes obtained in the preparation of
sulphate of quinine, and on this account it formerly occurred as an
admixture in the quinine and quinine-salts of commerce. It is also
sold under the name of Chinidinum sulphuricum.
Purification. 1. Commercial cinchonidine is exhausted with ether,
which dissolves out a large quantity of quinine and resin. The undis-
solved portion is treated with hot alcohol of 80 p. c., and the solution
is digested with animal charcoal and allowed to evaporate slowly,
whereby coloured crystals are obtained. The crystals are converted
222
PRIMARY NUCLEUS C4H6; OXY-AZO-NUCLEUS C40N2H20².
into sulphate, and purified in the same manner as sulphate of quinine,
and the sulphate is dissolved in hot water and decomposed by carbonate
of soda; the precipitate is washed, dried, and dissolved in alcohol;
and the solution is treated with animal charcoal, filtered, and evapo-
rated till it crystallises. In this way colourless crystals are obtained,
amounting to th of the crude product (Winckler). 2. Commercial
cinchonidine is dissolved in alcohol of 90 p. c, and the solution is left
to evaporate in the air, whereupon a yellowish-green resin is first de-
posited at the edges, and afterwards crystals make their appearance.
The crystals are picked out and again dissolved in alcohol, when a
second portion of resin is deposited; and this treatment is repeated
until the resin is completely removed. The crystals obtained after
five or six recrystallisations are triturated and washed with ether
until chlorine-water and ammonia no longer indicate the presence of
quinine (Leers).
When a solution of 1 part of sulphate of cinchonidine containing
quinine in 10 parts of alcohol of 90 p. c. is supersaturated with am-
monia, and the solution is filtered from sulphate of ammonia, and
warmed with its own weight of water, shining lamina of cinchonidine
are obtained on cooling. The mother-liquor, mixed with more warm
water, deposits a further quantity of cinchonidine on cooling, but ac-
companied by oily drops of quinine (Bussy and Guibourt).
Properties. Colourless, highly lustrous, hard prisms, y, y (fig. 53)
of 86° and 94°, with deeply striated faces, including the face p,
parallel to which the crystals are cleavable. Terminated above by
two shining faces u, forming an angle of 114° 30' (Leers). Rec-
tangular or rhombïodal prisms (Bussy & Guibourt). Rectangular four-
sided prisms, sometimes perpendicularly truncated, sometimes bevelled
with two faces, or terminated by one oblique face. When rapidly
crystallised, it forms a scaly powder, consisting of transparent, micro-
scopic rhombic tables (Winckler). A solution in chloroform (or acetic
acid) yields on evaporation fine crystalline nodules, which exhibit a
black cross and white or coloured rings in polarised light (Herapath).
Hard and easily powdered. According to Leers, it is electric when
rubbed, but according to Winckler it is not. The anhydrous crystals
retain their form and lustre when heated, and melt at 175°, without
loss of weight, to a wine-yellow liquid, which solidifies to a whitish-
grey crystalline mass on cooling (Leers; Winckler). Less bitter than
quinine (Leers). Tastes at first slightly, afterwards intensely bitter
(Buchner). Rotates a ray of polarised light to the left: [a]j=144.61°
(Pasteur), 142.8° (Bouchardat & Boudet); stronger in hydrochloric
or sulphuric acid solution (Bouchardat & Boudet, N. J. Pharm. 23,
288).
40 C
According to Pasteur.
According to Leers.
Leers.
mean (6).
240
•
2 N
24 II
28
77.92
9.69
36 C........
216
76.59
76.66
2 N
28
9.93
9.99
....
20
24
16
7.79
5.20
22 H
22
7:80
7.74
20
16
5.68
5.61
C40N2H2402.... 308
100.00
C36N2H202..
282
100.00
100.00
....
....
Leers' formula, which agrees with his analyses better than that of Pasteur, is not
admissible, if, as Pasteur states, cinchonidine yields cinchonicine when heated, like
cinchonine. For this reason Gerhardt (Traité 4, 138) gives the preference to
CINCHONIDINE.
223
Pasteur's formula, whereas Limpricht (Lehrb. 1180) regards Leers and Stahlschmidt's
base as different from Pasteur's cinchonidine, and considers the latter body identical
with Schwabe's betacinchonine (p. 200). But inasmuch as Pasteur's base exerts a
left-handed, and Schwabe's a right-handed action on polarised light, Limpricht's
view is obviously erroneous. Moreover Stahlschmidt's analysis of methyl-cinchoni-
dine (p. 233) can scarcely be accepted as evidence of the correctness of Leers's
formula, and his analyses of the cinchonine derivatives also gave too little carbon
(Kr.).
Decompositions. — 1. When heated (under the conditions stated under
cinchonine) the salts of cinchonidine are converted into salts of cin-
chonicine (Pasteur). 2. Fused cinchonidine takes fire when more
strongly heated, burns with a red smoky flame, evolving an odour of
chinoline and bitter almonds, and leaves a little easily combustible
charcoal (Winckler; Leers). A slight sublimate is sometimes obtained
in a glass tube, and consists, according to Winckler, of unchanged
cinchonidine. 3. Cinchonidine dissolves in oil of vitriol and strong
nitric acid, without colour: the solutions turn brown and decompose
when heated (Winckler). On addition of chromate of potash, the solu-
tion assumes a pale-yellow colour, as with cinchonine, not dark-yellow,
as is the case with quiniue (Buchner). - 4. Cinchonidine forms, with
iodine and sulphuric acid, a compound closely resembling sulphate of
iodo-quinine (Herapath). See below. 5. A solution of cinchonidine in
chlorine-water is not altered by ammonia (Leers): according to
Wittstein, ammonia colours the solution a dirty-yellow, and at the
same time throws down grey-white flocks, which dissolve to a wine-
yellow liquid in a larger quantity of ammonia. Cinchonidine is not red-
dened by chlorine-water, ferricyanide of potassium, and ammonia
(Mann).6. Cinchonidine combines with iodide of methyl, forming
hydriodate of methyl-cinchonidine (Stahlschmidt).7. Yields chinoline
(xiii, 243) when heated with hydrate of potash.
Combinations. Cinchonidine dissolves less freely than quinine in
water (Winckler); in 2580 parts of water at 17°, and in 1858 parts
boiling (Leers).
Cinchonidine dissolves somewhat slowly in acids, forming neutral
salts. According to Winckler, solutions containing excess of acid are
fluorescent, but according to Herapath, very feebly so. The salts are
either mono- or bi-acid, and for the most part crystallisable. They
dissolve in water more easily than the corresponding quinine-salts, and
very freely in alcohol, but are nearly insoluble in ether. From aqueous
solutions of the salts, ammonia and caustic alkalis, and their carbon-
ates and bicarbonates, throw down white precipitates, which become
crystalline on standing, and are (nearly) insoluble in excess of the pre-
cipitants (Leers; Winckler). Ammonia in excess dissolves freshly
precipitated cinchonidine less easily than quinidine or quinine (Kerner;
Mann).
Phosphate of Cinchonidine. - Thrown down from the mono-sulphate
as a white precipitate, by a slight excess of phosphate of soda. Micro-
scopic, transparent 4-sided prisms, perpendicularly truncated. Loses
its water at 100° (Winckler).
224
PRIMARY NUCLEUS C40H26; OXY-AZO-NUCLEUS C40N²H²O².
Air-dried.
Winckler.
3 C40N2H2402
924
69.16
2 PO5
142
10.63
10.23
6 HO
54
4:04
24 HO
216
16.17
17.20
3C4°N²H²40º,2(PO5,3HO) + 24aq
1336
100.00
Winckler gives no formula.
Hyposulphite of Cinchonidine. A solution of the mono-sulphate
mixed with hyposulphite of soda yields, on cooling, long slender
needles, difficultly soluble in water, but more easily soluble in alcohol
(Leers).
Sulphate of Cinchonidine. A. Mono-acid. Obtained by neutralis-
ing dilute sulphuric acid with cinchonidine and evaporating. Radiated
groups of long needles, having a silky lustre (Leers). Resembles
sulphate of quinine, but appears under the microscope as delicate,
transparent, 4-sided needles, perpendicularly truncated (Winckler).
The moist sulphate is gelatinous and curdy; when dry it resembles
magnesia (Kerner). Dazzling dead-white (Winckler). Neutral
(Leers).
Dissolves in 97 parts of cold water (Bussy & Guibourt); in 73 parts
of cold, and in 4.2 parts of hot water (Howard); in 95 to 100 parts of
water at 15° (Kerner). The salt dried at 110° dissolves in 130 parts of
water at 17°, and in 16 parts boiling (Leers). Dissolves in a cold
saturated solution of Glauber's salt, but is almost insoluble in aqueous
Rochelle salt, so that the filtrate is not rendered turbid by ammonia
(Mann). Dissolves very easily (Leers), more freely than sulphate of
quinine (Bussy & Guibourt), in alcohol, but is almost insoluble in
ether (Leers). The air-dried salt contains 17.52 p. c. of water, and
9.48 of sulphuric acid (Winckler) (CN2H2O²,SO³,HO + 8 aq. = 16·94
p. c. aq., 9.41 SO³).
40 C
2 N
25 H
30
SO3
....
According to Pasteur.
Leers.
According to Leers.
240
....
67.22 36 C
216
65.25 ... 64.75
28
7.84
2 N
28
25
7.00
23 H
23
8.46
6.95
7.05
24
6.72
3 0
40
11.22
SO3
24
40
....
....
7.26
12.08
....
12.01
100.00
....
100.00
...
C40N2H2402,SO³,HO 357
B. Bi-acid.
C36N2H22O2,SO³,HO 331
Delicate, dull, asbestos-like needles, losing 17.5 p. c.
of water at 100°, and 19 p. c. on melting (Winckler).
C40N2H2402
2 SO3
2 HO
10 HO
C¹¹ºN2H240²,2(SO³,HO) + 10aq
Air-dried.
Winckler.
308
62.09
80
16.13
16.55
18
3.63
90
18.15
17.5 to 19
496
100.00
Leers found varying quantities of sulphuric acid, probably on account of the pre-
sence of mono-acid salt.
-
Chlorate of Cinchonidine. Obtained by decomposing the mono-
sulphate with chlorate of potash and crystallising the product from
CINCHONIDINE.
-225
alcohol. Tufts of long white prisms, which melt to a transparent liquid
when heated and then explode violently (Leers).
Hydrochlorate of Cinchonidine. - A. Mono-acid. Warm aqueous
hydrochloric acid is neutralised with cinchonidine, and the solution is
left to evaporate spontaneously. The salt forms large rhombic prisms
having a vitreous lustre (Leers); nearly regular, thick rhomboïdal
octahedrons, whereas the hydrochlorates of all other cinchona-bases
crystallise in long needles (Kerner). When dried at 100° it dissolves
in 27 parts of water at 170° and very easily in alcohol, but scarcely
in ether (Leers).
40 C
According to Pasteur.
240
69.67
2 N.
25 H....
2 O....
CI
28
8.11
25
7.26
16
4.64
***
35.5
10.32
C40N2H2402,HCI
344.5
100.00
According to Leers.
Leers.
36 C
2 N
25 H
40
CI
C36N2H22O2, HCl + 2aq.
216
64.19
64.34
28
8.32
25
7.43
7.17
……..
32
9.52
35.5
10.54
10.05
336.5
100.00
Leers supposes the salt dried at 100° to contain water, which, however, is not
proved.
:
B. Bi-acid. To the salt A is added as much hydrochloric acid as
it contains already, and the mixture is allowed to evaporate spontane-
ously. Large shining crystals belonging to the oblique prismatic
system. u, i, ƒ (fig. 85). u: u' right and left = 95°; i : u =
98°;
f: u= 116° ;i:f 127° about. From predominance of i and f the
crystals have the appearance of horizontal rhombic prisms (Kopp).
After drying over oil of vitriol, the salt loses 5.8 p. c. of water at
100° (2 at,? - 4.5 p. c. HO). Dissolves very easily in water and
alcohol (Leers).
36 C
2 N
26 H
at 100°.
Leers.
216
57.93
58.30
28
7.52
26
6.97
7.12
4 O
32
8.59
2 Cl
71
18.99
18.98
C36N2H22O2,2HCl + 2HO
373
100.00
....
In this salt also the amount of water is not definitely established.
Hydrofluate of Cinchonidine. - Cinchonidine suspended in water is
dissolved by hydrofluoric acid vapour to an opalescent liquid, which on
spontaneous evaporation deposits white silky needles, easily soluble in
water (Leers).
Nitrate of Cinchonidine. - Fine large warty crusts, having the ap-
pearance of enamel, obtained by neutralising nitric acid with cinchoni-
VOL. XVII.
226
PRIMARY NUCLEUS C40H26; OXYAZO-NUCLEUS C40N2H22O².
dine and leaving the solution to evaporate. Dissolves very easily in
water (Leers).
Iodomercurate of potassium throws down a yellowish-white amor-
phous precipitate, even from very dilute solutions of cinchonidine
(Delffs).
Chloromercurate of Cinchonidine. Obtained by adding a warm
alcoholic solution of cinchonidine acidulated with hydrochloric acid,
to an equal quantity of alcoholic mercuric chloride, and leaving the
mixture to cool. Small pearly scales, which do not lose water at
100° after drying over oil of vitriol. Dissolves with difficulty in cold
water (Leers).
40 C
2 N
26 H
According to Pasteur.
36 C
2 N
24 H
20
4 Cl
240
36.81
28
4.29
26
3.98
20
4 Cl
2 Hg
C40N2H2402,2HCl,2HgCl
16
2.46
142
21.78
200
30.68
652
100.00
....
According to Leers.
Leers.
216
34.51
34.77
28
4.47
24
3.83
4.01
16
2.56
142
22.68
22:46
200
31.95
31.95
100'00
2 Hg.
C36N2H22O2,2HCl,2HgCl.... 626
Cinchonidine-salts form a white precipitate with nitrate of silver;
bright-yellow with terchloride of gold; brown with chloride of palladium
(Leers).
Chloroplatinate of Cinchonidine. - Orange-yellow precipitate, con-
taining, on an average, after washing with acidulated water and drying
at 110°, 27-11 p. c. platinum (Leers).
C40N2H2402
2 HC1,4C1
2 Pt
According to Pasteur.
C40N2H2402,2HCl,2PtCl²
308
42.76
215
29.84
...D
197.4
27.40
720.4
100.00
....
*****
Leers.
Winckler.
According to Leers.
282
C36H2H2202
2 HC1,4C1
2 Pt
C¹36N2H22O2,2HCl,2PtCl²....
215
197.4
694-4
40.61
30.96
28.43
27.11
26.37
100.00
Leers supposes the salt to contain 4 at. of water which is not shown by the
analysis.
Cinchonidine is not precipitated by platinocyanide of potassium
(Delffs).
क्षे
CINCHONIDINE.
227
Sulphocyanide of ammonium gives a white precipitate with salts of
cinchonidine.
Formate of cinchonidine forms long silky needles, easily soluble in
water (Leers).
Acetate of Cinchonidine. Obtained by dissolving cinchonidine in
warm dilute acetic acid, and cooling. Fine silky needles, which give off
acid on drying, and are very sparingly soluble in water.
liquor yields other needles, more easily soluble in water (Leers).
The mother-
Oxalate of Cinchonidine. Alcoholic oxalic acid, neutralised with
cinchonidine, crystallises on cooling in long silky needles, very sparingly
soluble in water. The mother-liquor yields, by spontaneous evapo-
ration, dull white nodules, more easily soluble (Leers).
Butyrate of Cinchonidine. - Large porcelain-like nodules and crusts,
having an odour of butyric acid. Easily soluble (Leers).
J
Tartrate of Cinchonidine.
A. A neutral solution of cinchonidine in
tartaric acid deposits first slender needles having a vitreous lustre, and
afterwards dull white nodules. - B. A hot acid solution yields, on
cooling, small pearly needles, very difficultly soluble in water (Leers).
The dextrotartrate and antitartrate of cinchonidine undergo, when
heated, the transformation into cinchonicine-salts described under
cinchonine (p. 217) (Pasteur).
Cinchonidine when boiled with tartar-emetic, does not yield a
double salt corresponding to that obtained with cinchouine (Stenhouse).
Valerate of Cinchonidine. - Warty crusts smelling of valerianic
Turns brown and decomposes on evaporation over the water-
bath (Leers).
acid.
Citrate of Cinchonidine. The neutral solution yields small needles,
sparingly soluble in water (Leers).
Hippurate of Cinchonidine. Hot alcoholic hippuric acid is neu-
tralised with cinchonidine and left to cool. Long, silky, fern-like
laminæ, easily soluble in water and alcohol (Leers).
Kinate of Cinchonidine. -- White silky needles, easily soluble in
water and alcohol (Leers).
The salts of cinchonidine are precipitated of a dirty-yellow colour
by tannic acid (Leers). Cinchonidine behaves towards oleic acid and
olive oil in the same manner as quinine (Attfield).
Cinchonidine dissolves slowly in cold alcohol of 80 p. c. to nearly
the same extent as quinine, and in all proportions in boiling alcohol.
Water turns the solution milky, and after some days throws down a
crystalline powder (Winckler). Dissolves in 12 parts of alcohol of
sp. gr. 0.835 at 17° (Leers); in 105 parts of alcohol of 90 p. c. at 15°
(Bussy & Guibourt).
Soluble in 144 parts of ether at 12.5° (Winckler); in 143 parts of
sp. gr. 0-728 at 17° (Leers); in 158.5 parts of ether (Bussy & Gui-
bourt).
Q 2
228
PRIMARY NUCLEUS C40H26; OXYAZO-NUCLEUS C40N2H22O³.
Appendix to Cinchonidine.
1. Wittstein's Cinchonidine.
Already treated of as C18NH100 (xiii, 336). Resembles most nearly
the cinchonidine of Pasteur, from which, however, it differs, according
to Herapath, in the properties of its compound with iodine and sul-
phuric acid. Cinchonidine prepared by Wittstein was examined by
De Vrij (Haaxmann's Tijdschrift vor Wetensch. Pharm. [2] 4 Jahrg.;
Kopp's Jahresber. 1857, 405); it was coloured and contained sulphuric
acid, and was found to be a mixture of Pasteur's lavo-rotatory cinchoni-
dine, dextro-rotatory cinchonine, and probably a third base. After-
wards a body prepared by Howard, and recognised by Wittstein as
cinchonidine, was found to have a lævo-rotatory action on polarised light,
and was identical with Pasteur's cinchonidine (De Vrij, N. J. Pharm.
31, 187). The description of the salts given below seems to show
also that the substance investigated by Crawfurd (Pharm. Viertelj. 7,
535), if it belonged to the known cinchona-bases, may be regarded as
identical with Pasteur's cinchonidine.
Sulphate of Cinchonidine.
a. Mono-acid. Prepared with excess
of cinchonidine and dilute acid. Radiate groups of pearly needles,
which in concentrated solutions are matted together in a jelly, and
dry up to an apparently amorphous, curdy mass. Neutral. Dissolves in
94.6 parts of water at 10°; in its own weight of boiling water; in 47.9
parts of alcohol at 10°; and 13 parts of boiling alcohol; in 18 parts of
ether of sp. gr. 0·74 at 10° (Crawfurd).
C36N2H2002
SO3
4 HO
Crawfurd.
280
78.66
76.36
40
11.23
11.66
36
10.11
11.98
100.00
100'00
C36N2H2002,HO,SO3 + 3aq. 356
****
b. Bi-acid. Acid amorphous gum, easily soluble in water and
in alcohol (Crawfurd).
Hydrochlorate of Cinchonidine. Formed by warming dilute hydro-
chloric acid with cinchonidine till the solution acquires a neutral reaction.
Colourless octohedrons, turning cloudy at 80° from loss of water.
Dissolves in 27.76 parts of water at 10°, and in part of boiling
water; in 5.37 parts of alcohol at 10°, and in part of boiling
alcohol in 10.5 parts of ether of sp. gr. 0.74 at 10° (Crawfurd).
Crawfurd.
C36N2H2002
2 HC1
14 HO
280
58.45
58.36
73
15.24
15.18
126
26.31
26.46
100.00
100.00
a. Mono-acid.
C36N2H2O2,2HCl + 14aq..... 479
Nitrate of Cinchonidine.
On neutralising warm
dilute nitric acid completely with cinchonidine, there separates an oily
layer, which solidifies to a crystalline mass, whilst colourless rhombo-
hedrons containing a larger proportion of water crystallise from the
liquid beneath.Neutral. Very bitter. The salt containing 8 atoms.
PSEUDOQUININE.
229
of water dissolves in 73.52 parts of water at 10°, and in its own
weight of boiling water (Crawfurd).
C36N2H2002
NO5
7 HO
C36N2H200²,HO,NO5 + 6aq.
Oily layer.
Crawfurd.
280
70.51
70.08
54
13.60
13.52
63
15.89
16.40
397
100.00
100.00
....
1040
Rhombohedrons.
Crawfurd.
C36N2H2002
280
67.47
67.90
NO5
54
13.01
13.09
9 HO
81
19.52
19.01
C36N2H2002,HO,NO5, + 8aq.
415
100.00
100.00
b. Bi-acid. Acid, amorphous gum, easily soluble in water and
in alcohol (Crawfurd).
Acetate of Cinchonidine. - White, crystalline powder, bitter and
neutral. Dissolves easily in water and alcohol, less freely in ether
(Crawfurd).
Crawfurd.
C36N2H2002
C+H303
280
72.73
72.97
51
13.25
13.10
6 HO
54
14.02
13.93
C¹36N2H200²,C+H*Oª + 5aq.
385
100.00
100.00
Dextrotartrate of Cinchonidine. Precipitated on mixing alcoholic
solutions of the acid and cinchonidine. According to Crawfurd
2CNˆH²ºO²,C®H4010. Nearly insoluble in water, alcohol, and ether
(Crawfurd).
2. Pseudoquinine.
MENGARDUQUE. N. J. Pharm. 14, 343; Compt. rend. 27, 219; J. pr.
Chem. 45, 356; Kopp's Jahresber. 1847 & 1848, 621.
From the extract of an unknown cinchona-bark, which yielded
neither quinine nor cinchonidine. The extract, boiled with water and
an equal quantity of sal-ammoniac till the evolution of ammonia ceased,
deposited on cooling a large quantity of a brown syrup, after which
aqueous ammonia added to the supernatant liquid threw down yellow
flocks. These flocks were dried and treated with cold ether, in which
a large proportion dissolved; and on evaporating the ethereal solution
the pseudoquinine remained in the form of a white powder.
Tasteless, irregular prisms, melting when heated. Contains, on an
average, 76·60 p. c. C., 10·3 N., 8·15 H., and 4·95 0.
Pseudoquinine, when heated, burns with a blue flame and leaves no
residue. Its solution in chlorine-water is coloured reddish-yellow by
ammonia.
Insoluble in water, but soluble even in very dilute acids, including
ཤྭ
230
CONJUGATED COMPOUNDS OF CINCHONINE, ETC.
the organic acids. The salts are precipitated by ammonia, potash, and
soda, but pseudoquinine expels ammonia from sal-ammoniac on boil-
ing. A neutral solution may be formed with sulphuric acid: it
tastes slightly bitter, and when concentrated yields fine flat prisms.
The hydrochlorate does not crystallise.
Pseudoquinine dissolves in alcohol, especially when hot, and is pre-
cipitated from the solution by water. Boiling ether dissolves only
traces of it.
Conjugated Compounds of Cinchonine and Cinchonidine, and Compounds
derived therefrom.
Cinchonicine.
C4N2H240² = C4°N²H²20²,H².
PASTEUR. Compt. rend. 37, 110; N. J. Pharm. 24, 161; J. pr.
Chem. 60, 129; Ann. Pharm. 88, 209; Chem. Gaz. 1853, 321;
Kopp's Jahresber. 1853, 473.
Formation. By heating salts of cinchonine or cinchonidine`to a
temperature at which they melt without undergoing complete decompo-
sition, both bases are converted into one and the same isomeric
product, cinchonicine.
Preparation. Sulphate of cinchonine, with the addition of a little
water and sulphuric acid, is heated to 120° or 130° for three or four
hours, whereby a slightly coloured product is obtained.
Properties. Cinchonicine is precipitated from its solutions in the
form of a semifluid resin. It is very bitter and antifebrile. Exerts a
slight dextrorotatory action on polarised light.
Cinchonicine is insoluble in water. It combines with carbonic and
other acids, and expels ammonia from the salts of that base. - A
solution of cinchonicine in aqueous racemic acid deposits, at first,
crystals consisting principally of antitartrate of cinchonicine, whilst the
mother-liquid contains the cinchonicine salt of dextrotartaric acid. The
racemic acid is, therefore, split up in the manner described at page
366, vol. x.
Cinchonicine dissolves very easily in alcohol and ether.
Hydrocinchonine.
C40N2H2604 C40N2H2404, H2.
SCHÜTZENBERGER. Compt. rend. 46, 1067; J. pr. Chem. 74, 227; Ann.
Pharm. 108, 347; Kopp's Jahresber, 1858, 370.
Hydrate de cinchonine. Contains H2O2 more than cinchonine.
OXYCINCHONINE.
231
Hydrogen is evolved in a mixture of sulphuric acid and sulphate of
cinchonine by the addition of zinc; and after some time the solution is
precipitated by excess of ammonia. The oxide of zinc redissolves in
the ammoniacal liquid, and there remains undissolved a tenacious sub-
stance, which is purified by dissolving it in alcohol and evaporating the
filtered solution.
Amorphous, not bitter resin, obtained in the anhydrous state by
drying at 150°. — Hydrocinchonine dried at 120° contains 2 at. water,
one of which is expelled at 140°.
Schützenberger.
at 140°.
40 C
2 N
240
b
28
71.61
8.35
71.56
...
27 H
27
8.06
8.04
50
40
11.95
C40N2H2604,HO
335
100.00
at 120°.
40 C
240
69.76
Schützenberger.
69.46
2 N
28
8.14
28 H
28
8.14
8.02
60
48
13.96
C40N2H260,2HO
344
100.00
The salts of hydrocinchonine are very soluble. The platinum-salt
dried at 100° contains 27.1 p. c. of platinum, corresponding to the
formula CN2H2604,2HCl,2PtCl2 (calc. 27.06 p. c. Pt.).
Hydrocinchonine dissolves easily in cold alcohol and ether.
Oxycinchonine.
C40N2H240 = C40N2H2204,H².
H. STRECKER. Ann. Pharm, 123, 379; abstr. N. Br. Arch. 115, 169.
An alcoholic solution of bibromocinchonine is boiled with alcoholic
potash (or oxide of silver) so long as bromide of potassium continues to
be formed; the free potash is neutralised by carbonic acid; the solution
is evaporated; and the residue is treated with water to remove salts
soluble in that liquid. The insoluble portion, dissolved in alcohol,
yields crystals of oxycinchonine on cooling and evaporating the
solution.
Colourless crystalline laminæ.
H. Strecker.
mean.
40 C
240
74.07
73.80
2 N
28
8.64
24 H
24
7.41
7.45
40
32
9.88
C40N2H2404
324
100.00
****
Isomeric with quinine, quinidine, and quinicine, also with Schützenberger's pro-
duct obtained by the action of nitrous acid on cinchonine (p. 202).
232
CONJUGATED COMPOUNDS OF CINCHONINE, ETC.
Oxycinchonine does not produce the green colour which is produced
by quinine with chlorine-water and ammonia.
It dissolves in acids, forming solutions which are not fluorescent.
The mono-acid salts crystallise with difficulty; the sulphate and oxalate
most easily. Bi-acid salts have not been obtained.
Sulphate of Oxycinchonine. - Crystals which lose their water
partially in dry air, and completely at 100°.
CON³H404
HO
803
C4NH204,HO,SO³
at 100°.
H. Strecker.
324
86.86
9
2.41
40
10.73
10.8
373
100.00
....
Platinum-salt. Bichloride of platinum throws down from the
solution in hydrochloric acid, pale yellow flocks, which are sparingly
soluble in hot water, and insoluble in alcohol and ether. Contains
26.3 p. c. of platinum, corresponding to the formula CN2H2404,2HCI,
2PtCl (calc. 26.87 p. c. Pt.).
Oxycinchonine dissolves in alcohol, and slightly in ether.
Cinchonine-sulphuric Acid.
C40N2H24S05 C40N2H2402,SO³.
=
SCHÜTZENBERGER. Compt. rend. 47, 235; J. pr. Chem. 75, 254; Ann.
Pharm. 108, 353; Chem. Centr. 1858, 684; Kopp's Jahresber.
1852, 370.
Acide sulphocinchonique.
Cinchonine is dissolved in fuming oil of vitriol; the solution, after
standing for some time, is diluted with water and neutralised with baryta ;
the filtrate is evaporated; and from the baryta-salt which remains
the cinchonine-sulphuric acid is separated by means of sulphuric
acid.
Solid, amorphous, acid mass. Dissolves in all proportions in
water.
J
-
Baryta-salt. Transparent, friable, vitreous mass, having a
slightly bitter taste. Non-deliquescent: soluble in all proportions
in water. The salt, dried at 100°, contains 28.13 p. c. of sulphate of
baryta, corresponding to the formula CN2H23Ba02,SO3 (by calc. 28.03
p. c. BaO,SO3).
The acid dissolves in alcohol,
Methyl-cinchonine.
C42N2H2602
=
C40N2H2(C2H³)02,H².
C. STAILSCHMIDT. Ann. Pharm. 91, 218; Pharm. Centr. 1854, 680;
J. pr. Chem, 63, 89; Kopp's Jahresber. 1854, 509.
METHYL-CINCHONIDINE.
233
སྐལ་ ་ ་ཀ་ མཐོན་ པ་ རི་ ན་འི ་ ད་ ་ ་ ་ ་ ་
Powdered cinchonine, digested with iodide of methyl, evolves heat
and is converted into hydriodate of methyl-cinchonine, from an aqueous
solution of which, oxide of silver throws down iodide of silver. The
methyl-cinchonine remaining in solution is obtained by evaporation as
a brown crystalline mass, which deposits oily drops with water.
The salts of methyl-cinchonine crystallise with difficulty: they
dissolve easily in water and alcohol. An aqueous solution of the base
precipitates the salts of the sesquioxides.
Hydriodate of Methyl-cinchonine. - Deposited from its solution in
boiling water in fine needles on cooling. It is not altered by iodide of
methyl at 100°, nor decomposed, in aqueous solution, by ammonia,
potash, or soda.
42 C
2 N
27 H
20
I
at 100°.
Stahlschmidt.
252
56.00
55.08
28
6.22
D
27
6:00
5.89
16
3.56
127
28.22
29.19
100.00
C40N2H23 (CH3) O2, HI.... 450
The
Chloride of mercury, chloride of gold, and bichloride of platinum throw
down double-salts from hydrochlorate of methyl-cinchonine.
platinum-salt contains, at 110°, 26.73 p. c. of platinum (calc. 26.81
p. c. Pt.).
Methyl-cinchonidine.
19
C38N2H2402C3NH2(CH3)02,H²?
STAHLSCHMIDT. Ann. Pharm. 90, 221; Pharm. Centr. 1854, 680; J. pr.
Chem. 63, 89; Kopp's Jahresber. 1854, 509.
Methylchinidine. See page 223.
Cinchonidine becomes warm when iodide of methyl is poured upon
it, and is converted into hydriodate of methyl-cinchonidine, from an
aqueous solution of which, oxide of silver precipitates iodide of silver,
aqueous methyl-cinchonidine being formed at the same time. On evapo-
rating the solution, the base remains as a brown crystalline mass.
Hydriodate of Methyl-cinchonidine. Crystallises in white, shining
needles on cooling the hot aqueous solution. Ammonia produces in the
aqueous solution a milky turbidity, which disappears on the addition
of more ammonia.
38 O
Stahlschmidt.
228
53.76
53.87
28
6.60
25
5.89
5.92
16
3.79
127
29.96
29.84
(36N2H2¹ (C²H³) 02,HI
424
...
100.00
2 N
25 H
20
I
234
CONJUGATED COMPOUNDS OF CINCHONINE, ETC.
Acetyl-cinchonine.
23
CN²H²O¹ = Cª°N²H²¾(C4H³O²)O².
SchützenbergER. Compt. rend. 47. 235.
By the action of chloride of acetyl, cinchonine is converted into
hydrochlorate of acetyl-cinchonine, from which the base may be sepa-
rated in the same way as benzoyl-cinchonine.
Semi-fluid resin, having a burning, not bitter taste. It saturates
the same quantity of acid as would be saturated by the cinchonine
contained in it.
Benzoyl-cinchonine.
C54N2H2O = C40N2H23(CH502)0².
C4°N²H²3(C¹¹H50²)0³.
SCHÜTZENBERGER. Compt. rend., 47, 233; J. pr. Chem. 75, 125; Ann.
Pharm. 108, 351; Chem. Centr. 1858, 677; Kopp's Jahresber. 1858,
369.
Cinchonine dissolves in chloride of benzoyl, with evolution of heat,
and after heating for some time, solidifies to a crystalline mass of hydro-
chlorate of benzoyl-cinchonine. The mass is digested with water, and
the resulting solution obtained is decanted and precipitated with
ammonia, whereby the benzoyl-cinchonine is thrown down as a soft
resin, hardening as it cools.
White, amorphous, tasteless resin.
54 C
2 N
Schützenberger.
324
78.64
78.47
28
6.79
28 H
28
6.79
6.98
40
32
7.78
C¹¹ºN²H23 (C¹¹H50²) O² 412
100.00
....
zene.
Insoluble in water.
Benzoyl-cinchonine heated on platinum-foil melts and burns, with
partial volatilisation. When heated with soda-lime, it evolves ben-
Forms very soluble salts.
Chloroplatinate of Benzoyl-cinchonine.
at 140°.
Schützenberger.
54 C
324
39.27
38.97
2 N
28
3.39
30 H
30
3.63
3.84
4 0
32
3.89
6 Cl
213
25.83
2 Pt
197.4
23.99
23.94
C'40N2H23 (C¹¹H502) O2,2HCl, 2PtCl2.... 824-4
100.00
....
Benzoyl-cinchonine dissolves in all proportions in alcohol and ether.
SESQUI-BROMOCINCHONINE.
235
Oxy-bromazo-nucleus C40N2BrH2¹0².
Bromocinchonine.
C40N2Br H2302
C40N2Br H²¹0², H².
LAURENT. Compt. rend. 20, 1586; N. Ann. Chim. Phys. 24, 307; Ann.
Pharm. 69, 9; J. pr. Chem. 46, 52.
Bromcinchonin. Cinchonine bromée. — According to Laurent = C38N2BrH2102.
Bromine is poured upon moist bi-hydrochlorate of cinchonine, and
after a few minutes the excess of bromine is washed off with alcohol.
The mixture of salts then remaining is boiled with a little alcohol, which
takes up hydrochlorate of cinchonine and hydrobromate of bromo-
cinchonine, and leaves behind the corresponding nearly insoluble salts
of sesqui-bromocinchonine. From the alcoholic solution the bromo-
cinchonine is obtained by adding ammonia, boiling till the alcohol is
driven off, and cooling. It is still to be purified by crystallisation.
Laurent.
40 C........
Crystals.
240
62.02
59.3
2 N.
28
7.23
Br
80
20.67
23 H..
23
5.94
5.6
2 0.
16
4·14
C40N2BrH302.... 387
100.00
Bi-acid. Resembles the bi-acid
Hydrochlorate of Bromocinchonine.
hydrochlorate of cinchonine. Contains 15.4 p. c. chlorine (calc. 15·43
p. c. Cl).
Platinum-salt. Pale-yellow powder. Contains, after drying at 50°,
24.25 p. c. of platinum.
Sesqui-bromocinchonine.
LAURENT. Compt. rend. 20, 1588; N. Ann. Chim. Phys. 24, 309.
Obtained, together with bromo-ciuchonine, by the action of bromine.
on bihydrochlorate of cinchonine, and remains behind as a salt of
hydrochloric or hydrobromic acid, insoluble in boiling alcohol. This
insoluble residue is boiled with water; the solution is decomposed by
ammonia, and the base thereby separated is crystallised from boiling
alcohol.
Very slender, slightly bitter needles, having an alkaline reaction. -
Melts when heated, and then suddenly blackens and froths up.
80 C
4 N
480
56
3 Br
240
45 H
45
....
40
32
2C40N2H22 5Br¹·5C2
853
56.27
Laurent.
55.45
*****
6.57
28.13
5.28
3.75
100.00
28.30
5.18
236
OXYBROMAZO-NUCLEUS C40N2Br2H2002.
According to Laurent, it is not to be regarded as a mixture of bromo-cinchonine
and bibromo-cinchonine, inasmuch as hot alcohol does not take up from it any of
the former body, and its salts do not split up.
Hydrochlorate. - When hydrochloric acid is added to a solution of
the base in boiling alcohol, rhombic tables of this salt crystallise on
cooling. Right prismatic (Fig. 50), u': u 107° to 108. Contains
145 p. c. of chlorine (calc. for the bi-acid salt, 14-2 p. c.).
When the residue insoluble in boiling alcohol, which is obtained
in the preparation of sesqui-bromocinchonine, and consists of a mix-
ture of hydrochlorate and hydrobromate, is digested with ammoniacal
alcohol, it is at once dissolved; and on adding hydrochloric acid to the
solution, small rhombic tables, soluble in water, but very slightly soluble
in boiling alcohol, make their appearance as the liquid cools. The
crystals belong to the right prismatic system. (Fig. 50) u' : u = 107°
to 108. They contain 43.60 p. c. C. and 4.47 II., with equal numbers
of atoms of hydrochloric and hydrobromic acids, and are consequently
Bichlorobromhydrate de Cinchonine sesquibromée, CN2Br¹5H2502, HCl,HBr
(Laurent).
The nitrate forms shining needles, sparingly soluble in water and in
alcohol. The platinum-salt is a pale-yellow precipitate, containing
23 p. c. platinum at 100°; the salt contains by calculation 22.2 p. c.
platinum; but according to Laurent (Compt. rend. 20, 1588), the pre-
cipitate loses 2 at. of water, at 180°.
Oxybromazo-nucleus CN2Br H200².
Bibromocinchonine.
CN2B2H22O2 = C40N2Br2H2002, H2.
LAURENT. Compt. chim. 1849, 312; Ann. Pharm. 72, 305.
H. STRECKER. Ann. Pharm. 123, 379.
An excess of bromine, together with a little water, is poured upon
hydrochlorate of cinchonine; the mixture is warmed to complete the
reaction, and to drive off the excess of bromine; and the product is
diluted with water, boiled, and filtered. Alcohol is then added; and the
whole is boiled afresh, and neutralised with ammonia: the bibromocin-
chomine then crystallises out on cooling (Laurent). Strecker removes
the excess of bromine by means of a little alcohol, dissolves the residue
in boiling alcohol, adds ammonia to the solution, and leaves it to crystal-
lise.
Colourless, laminar needles, exerting a right-handed action on
polarised light (Laurent).
Laurent.
Strecker.
40 C
2 Br
240
51.50
51.20
160
34.34
34.00
33.2
2 N
28
6.01
22 H
22
4.72
.....
4.40
20
16
3.43
CN Br2H02
466
100.00
BICHLOROCINCHONINE.
237
Bibromocinchonine does not lose water at 160°; at 200° it blackens
and puffs up, and forms a substance soluble in caustic potash and pre-
cipitable from the solution in brown flocks by acids (Laurent). When
it is boiled with alcoholic potash, or with alcohol and oxide of silver,
bromide of potassium or bromide of silver is deposited, and oxycincho-
nine formed (Strecker).
Combinations. With Water. The (alcoholic ?) solution of bibromo-
cinchonine set aside for some days in an open vessel, deposits square
based octahedral crystals of the size of pins' heads. The crystals
lose 4.2 p. c. of water at 160° (2 at. 3·72 p. c. HO) (Laurent).
Bibromocinchonine is insoluble in water.
Hydrochlorate of Bibromocinchonine. - CON Br H202,2HCl. Depo-
sited from a boiling solution on cooling in rhombic tables, truncated on
the four acute summits. Isomorphous with hydrochlorate of sesqui-
bromocinchonine. u: u' = 104 to 105°; p : i = 137° (Laurent).
Bibromocinchonine dissolves slightly in boiling alcohol.
Oxychlorazo-nucleus C40N2C12H200².
Bichlorocinchonine.
C40N2C12H222
C'¹ºN²Cl²H²º0², H² ?.
A. LAURENT Compt. rend. 20, 1588; N. Ann. Chim. Phys. 24, 304;
J. pr. Chem. 46, 52; Ann. Pharm. 69, 9; Kopp's Jahresber. 1847 and
1848, 618.
Chloré-cinchonine. Cinchonine bichlorée.
When chlorine is made to act upon a warm concentrated aqueous
solution of hydrochlorate of cinchonine, hydrochlorate of bichlorocin-
chonine is thrown down as a heavy crystalline powder, which is puri-
fied by crystallisation from boiling water. From a boiling aqueous
solution of the salt, ammonia throws down the bichlorocinchonine in
light flocks, crystallisable from boiling alcohol.
Microscopic needles, having an alkaline reaction, and containing 18.9
p. c. chlorine (calc. for CN2H22C120² = 18.83 p. c. Cl). Exerts a right-
handed action on polarised light.
Bichlorocinchonine distilled with caustic potash yields chinoline.
It forms with acids, crystallisable salts resembling those of bromocin-
chonine and isomorphous therewith.
Hydrobromate of Bichlorocinchonine. Shining needles, isomorphous
with bihydrochlorate of cinchonine and hydrochlorate of bichlorocin-
chonine. The crystals belong to the right prismatic system (Fig. 50),
and exhibit the same faces as the cinchonine-salt, but from the pre-
dominance of the faces i and p they have the appearance of six-sided
prisms bevelled by u and u'. Angle u : u' = 104°; p: i
104°; p: i = 137°. Con-
tains 30.2 p. c. bromine, and may therefore be represented by the
formula CNC12H2O2,2HBr (calc. 29.79 p. c. Br). Dissolves with
difficulty in water.
238
PRIMARY NUCLEUS C40H26.
Hydrochlorate of Bichlorocinchonine.
Crystals of the right pris-
matic system (Fig. 50) u' : u = 106° ; p : i = 136·5° to 137·5°. - Dis-
solves slightly in water and in about 50 parts of alcohol.
40 C
2 N
24 H
2 Cl
2 Cl
20
Laurent.
240
53.33
51.81
28
6.22
24
5.33
5.18
.....
71
15.78
71
15.77
16.40
16
3.57
100.00
C40N2C1H2202,2HCl.... 450
Nitrate of Bichlorocinchonine. Right prismatic. Small tetrahe-
drous of scalene triangles having two opposite edges truncated.
Slightly soluble in water.
Platinum-salt. Pale-yellow powder, losing 2.4 p. c. of water at
180° after drying at 100°.
C40N2C12H2202
H2C16
....
Laurent.
at 100°.
377
46.71
215
26.64
197
24.41
25.00
18
2.24
2:40
C40N2H2C1202,2HC1,2PtCl2 + 2aq.
807
100.00
....
2 Pt
2 HO
Primary Nucleus C40H26.
Blue Galbanum-oil.
C40H3002
C40H28, H20².
MÖSSMER (& HLASIWETZ). Wien. Acad. Ber. 43, 477; Ann. Pharm. 119,
257; J. pr. Chem. 86, 159. Zeitschr. Ch. Pharm. 4, 512; Chem. Centr.
1861, 673; Repert. Chim. pure, 3, 462; Kopp's Jahresber. 1861, 687.
Purified galbanum-resin submitted to dry distillation, yields water,
a greenish-yellow oil, and crystals of umbelliferone. The oil is freed
from the crystalline body by repeated boiling with water, and at last.
with very dilute potash; it is then dehydrated by heating it to 110°
in a current of air, and rectified, the first and last portions of the dis-
tillate being rejected.
Pure blue, thick oil, of the colour of ammoniacal oxide of copper.
Boils at 289°. Does not solidify in the cold. Has a slightly aromatic
odour, and an acrid, very bitter taste.
Mössmer.
mean.
40 C..
30 H
240
83.91
83.75
30
10.49
10.44
2 O......
16
5.60
5.81
C40H3002
286
100.00
100.00
Bromine converts the oil into a resin, with evolution of hydrobromic
GALBANUM-RESIN.
239
acid. Nitric acid colours it a yellowish-red, turning darker on heating.
Oil of vitriol colours it brown-yellow. - Galbanum oil is decolorised
by warming with anhydrous phosphoric acid, and when distilled there-
with, yields a yellowish oil, boiling at 250° to 253°, and containing, on
the average, 86.81 p. c. C., 10.76 H., and 2.43 O., corresponding to the
formula Č⁰H5802 (calc. 86.66 p. c. C., 10:47 H.). The yellow oil there-
fore stands in the same relation to the blue oil as ether to alcohol. The blue
oil boiled with sodium in a retort the beak of which inclines upwards,
till the colour of the distillate disappears, yields a colourless oil, having
an odour of herbs and a mild taste, and boiling at 254° : it contains 88.74
p. c. C. and 11.24 H., corresponding to the formula C40H30 (calc.
88.88 p. c. C., 11·12 H). The blue oil is not altered by alkalis, or by
distillation with lime. It is coloured light green by alcoholic sesqui-
chloride of iron.
The oil dissolves in alcohol with deep blue colour.
MEISSNER. N. Tr. 1, 1, 3.
Galbanum-resin.
JOHNSTON. Phil. Trans. 1840, 362.
MÖSSMER. Wien. Acad. Ber. 43, 477; Ann. Pharm. 119, 257.
HLASIWETZ & BARTH. Wien. Acad. Ber. 49, 203; Chem. Centr. 1864,
806.
Galbanum is freed from volatile oil by distillation with water; the
remaining resin is separated from the supernatant milky liquid, and
boiled with milk of lime; and the dark-yellow filtrate is precipitated
by hydrochloric acid, which throws down whitish-yellow flocks to
be purified by washing, dissolving in ether, and evaporating (Möss-
mer). Meissner and Johnston investigated the alcoholic extract
purified by boiling with water.
Galbanum-resin forms whitish-yellow flocks, which soften and melt
when warmed. On evaporating its ethereal solution, it remains as a
honey-yellow mass, no longer completely soluble in alcohol (Mössmer).
Tasteless (Meissner).
Calculation according to
Hlasiwetz.
52 C
38 H
312
....
38
10 O
80
C52H38010.
430
Johnston.
a.
b.
Mössmer.
melted.
...
73.16
8.47
18.37
....
73.20
8.12
18.68
71.60
8.44
19.96
72.05
....
8:00
19.95
100.00
100.00
100.00
100.00
....
****
....
72.56
8.84
18.60
....
....
100.00
a was heated to 66 or 92°; b to 150° for 2 hours, whereby 10 per cent. was
volatilised (Johnston).
Galbanum-resin submitted to dry distillation yields a blue oil
(p. 238), water, and umbelliferone (Mössmer). Probably thus:
C52H3SO 10 C40 H3002 + C¹²H¹O¹ + 4HO (Hlasiwetz).
Umbelliferone.
With warm nitric acid, it forms acetic and oxalic acids. Dissolves in
oil of vitriol with dark yellowish-brown colour, without evolving sul-
phurous acid (Meissner). A concentrated alcoholic solution, satu-
240
PRIMARY NUCLEUS C40H26.
rated with hydrochloric acid gas and heated to 100°, yields umbelli-
ferone and a brown mass, but no sugar (Mössmer). When melted with
caustic potash, it froths up and evolves aromatic vapours, the residue
containing resorcin (infra), oxalic acid, and one or more volatile fatty
acids (Hlasiwetz & Barth).
Galbanum-resin dissolves slightly both in cold and in hot solutions of
caustic potash, and forms with the latter a soap which floats on the surface
of liquid, and is perfectly soluble in water (Meissner). It dissolves.
partially in bisulphide of carbon, and easily in alcohol; and is completely
soluble in commercial, but only partially soluble in absolute ether
(Mössmer). It is not perceptibly soluble in alcohol of 50 p. c., and but
very slightly soluble in hot oil of turpentine and oil of almonds
(Meissner).
Galbanum. Mother-resin. From Galbanum officinale. Brown and
white; brittle in the cold, but becomes tough on warming.
Has an
unpleasant odour, and an acrid, bitter taste. An alcoholic solution
reddens litmus. Contains volatile oil, resin, and gum, together with
woody fibre and other vegetable residue. By dry distillation,
it yields umbelliferone (Sommer, N. Br. Arch. 98, 1), a yellow water
containing acetic acid, a pale-green, afterwards blue, and at last brown-
red oil, beside carbonic acid and hydrocarbons (Meissner), With nitric
acid of sp. gr. of 1.2, it yields styphnic or other acids (Bottger & Will).
It is more violently attacked than gum ammoniacum by nitric acid of
sp. gr. 1.34, dissolving rapidly and forming camphretic acid (Schwanert,
Ann. Pharm. 128, 123). Forms a milky liquid with water and
yields a volatile oil by distillation (Pelletier, Bull. Pharm. 4, 97).
Volatile oil of galbanum is colourless, of sp. gr. 0.8842 at 9°
(Mössmer), 0-895 (Finkh, N. Jahrb. Pharm. 4, 285), 0-912 (Meissner).
It exerts a right-handed action on polarised light, boils at 160°, and is
isomeric with oil of turpentine. Hydrochloric acid gas passed into it,
turns it red and forms crystals; dilute nitric acid renders it dark coloured
without forming crystals in three months (Mössmer).
HLASIWETZ & BARTH.
Addendum to vol. xi, p. 379.
Resorcin.
C2H604 C2H6O2,02 ?
=
Wien. Akad. Ber. 49, 203; Ann. Pharm. 130,
354; Chem. Centr. 1864, 806.- Zeitschr. Ch. Pharm. 7, 285.
Formation. By melting guaiacum, galbanum, or ammoniacum resin
with caustic potash.
Preparation. The portion of galbanum-resin soluble in alcohol is
melted with 2 to 3 parts of caustic potash, till the mass becomes
homogeneous, the reaction being attended with much frothing and the
evolution of aromatic vapours. The fused mass is at once poured
into water and acidulated with sulphuric acid; and after cooling and
filtering, the liquid is repeatedly shaken with ether, which takes up
resorcin. The ethereal solution is evaporated, and the residue sub-
GUAIARETIC ACID.
241
mitted to distillation, when a distillate is obtained consisting at first of
a thick oil, and afterwards of resorcin, which solidifies to a crystalline
mass. The product is purified either by rectifying and collecting the
portion passing over between 269° and 279°, or by dissolving in a
little warm water, adding baryta-water to alkaline reaction, and taking
up the resorcin by ether, in which case the fatty acids are left in
combination with baryta.
Properties. Colourless, rhombic tables, or short thick prisms, melt-
ing and volatilising slightly at 99°, and boiling without decomposition
at 271°. Neutral; inodorous. Has a disagreeable, harsh, sweet taste.
Vapour-density 4.1, which is a little too high, owing to decom-
position indicated by a deep-brown coloration of the substance.
Hlasiwetz & Barth.
mean.
12 C
6 H
72
65.45
65.3
6
5.45
5.7
40
32
29.10
29.0
C12H604........ 110
100.00
100.0
Volume.
Vapour-density.
Carbon-vapour..... 12
4.9920
Hydrogen..
6
0.4158
Oxygen
2
2.2186
Resorcin-vapour
2
7.6264
....
1
3.8132
Isomeric with hydrokinone (xi, 161) and pyrocatechin (xi, 379);
homologous with orcin (xii, 353).
Resorcin burns with a luminous flame. When exposed to the air
it acquires a faint reddish colour. Saturated bromine-water throws
down from moderately dilute aqueous resorcin soft needles of tribromo-
resorcin, C¹Br³H³04, which dissolve with difficulty in cold, and easily in
boiling water and in alcohol, and give off water of crystallisation at
100°. — Aqueous resorcin, mixed with ammonia and exposed to the air,
assumes a rose-red to brown colour, and leaves on evaporation a dark-
blue residue, which dissolves in water and is reddened by acids.
Chloride of lime colours it a transient violet; sesquichloride of iron
dark-violet to black, the colour disappearing on addition of ammonia,
whilst sesquioxide of iron is precipitated. Resorcin throws down
suboxide of copper from alkaline solutions of the oxide, and reduces
nitrate of silver.
Resorcin dissolves very easily in water, alcohol, and ether, also in
bisulphide of carbon and chloroform.
Oxygen-nucleus C402602.
Guaiaretic Acid.
C402608 C40H260²,06.
HLASIWETZ. Ann. Pharm. 112, 182; Chem. Centr. 1860, 97; Kopp's
Jahresb. 1859, 514.
VOL. XVII.
R
242
PRIMARY NUCLEUS C40H28; OXYGEN-NUCLEUS C40H2602.
HLASIWETZ & V. GILM.
v.
Wien. Acad. Ber. 43, 463; Ann. Pharm. 119,
266; J. pr. Chem. 86, 363; Zeitschr. Ch. Pharm. 4, 499; Chem.
Centr. 1861, 641; N. J. Pharm. 41, 88; Kopp's Jahresb. 1861, 685.
HLASIWETZ & BARTH. Wien. Acad. Ber. 49, 1; Ann. Pharm. 130, 346;
N. Repert. Pharm. 13, 193.
HADELICH.
Ueber die Bestandth. des Guajakharzes. Dissert. Gött. 1862;
J. pr. Chem. 87, 321; Zeitschr. Ch. Pharm. 6, 104; Chem. Centr.
1863, 305; Rép. Chim. pure 5, 271; Kopp's Jahresb. 1862, 466.
Source. In guaiac-resin. (See below.)
Preparation. One pound of guaiac-resin is dissolved in a suffi-
cient quantity of alcohol to form a thin syrup; the solution, clarified
by straining, is mixed with a strong warm alcoholic solution of half
a pound of caustic potash; and the mixture is left to itself for
twenty-four hours. It then solidifies to a pulpy mass, which is to be
purified by pressing it between linen cloth, mixing it repeatedly with
strong alcohol and pressing, and lastly by triturating and washing it
with cold water, then dissolving in a large quantity of boiling weak
alcohol. On cooling the filtrate it is obtained in crystals, which must
be twice recrystallised. The potash-salt of guaiaretic acid thus ob-
tained is decomposed by hydrochloric acid, whereupon the guaiaretic
acid is thrown down as a soft, sticky precipitate, which is washed and
dissolved in alcohol, and crystallises from the solution by spontaneous
evaporation (Hlasiwetz).-2. The powdered resin is boiled for half an
hour with half its weight of lime previously made into a milk; the
liquid is strained off; and the solid residue is dried and exhausted with
hot alcohol in a percolator. The light-yellow tincture thus obtained is
freed from alcohol by distillation; the residue is dissolved in solution
of caustic soda of sp. gr. 1·3; and the soda-salt formed on cooling is
pressed, recrystallised from water containing soda, and decomposed
by hydrochloric acid (Hlasiwetz & v. Gilm).
Purification.-1. By recrystallisation from alcohol. 2. By re-
crystallisation from warm concentrated acetic acid. The crystals are
washed with strong acetic acid, with weaker acetic acid, and with
water, in succession. 3. The alcoholic solution of the acid, diluted
with water till it becomes turbid, deposits crystals on standing over
night, as is also the case with an alcoholic solution of the soda or
potash-salt diluted with a large quantity of water, after addition of
hydrochloric acid (Hlasiwetz & v. Gilm). The pure acid remains
colourless in the air; its alcoholic solution assumes a pure grass-green
colour with sesquichloride of iron, but is not rendered blue or green
by chlorine-water; neither does the solution, diluted with water to a
milk, turn blue on dropping red fuming nitric acid into it (Hlasiwetz
& v. Gilm).
Properties. The crystals, which are hydrated, according to Hade-
lích, are obtained in the anhydrous state by melting or by long ex-
posure to heat.
They exert a left-handed action on polarised
light, [a]j = 13-25° (Hadelich). When rapidly distilled, the greater
part volatilises unchanged (Hlasiwetz & v. Gilm).
GUAIARETIC ACID.
243
Hlasiwetz &
v. Gilm.
Hadelich.
Dried.
mean.
mean.
40 C .........
240
72.72
72.53
71.93
26 H....
26
7.87
7.91
7.85
8 0....
64
19.41
19.56
20.22
C40H2608
330
100.00
100.00
100.00
....
Decompositions. 1. Guaiaretic acid, submitted to dry distillaton, yields
a thick yellow oil, consisting of guaiacol, guaiacin, and pyroguaiacin,
the last of which speedily crystallises out (Hlasiwetz & v. Gilm).
2. Burns on platinum-foil with luminous flame, leaving no residue. —
3. Nitric acid acts violently upon it, forming a yellow, brittle resin
(Hlasiwetz & v. Gilm), but no oxalic acid (Hadelich). 4. Guaiaretic
acid dissolves in oil of vitriol with purple colour; water added to the
solution throws down a white product. — 5. Bromine converts its solu-
tion in bisulphide of carbon into bromoguaiaretic acid. Chlorine evolves
a large quantity of hydrochloric acid, and forms a red, glutinous, non-
crystallisable resin. Pentachloride of phosphorus acts in a similar
manner (Hlasiwetz & v. Gilm). Hydrochloric acid passed into the
alcoholic solution does not form an ether (Hadelich). 6. The acid
melted with caustic potash yields the same products as guaiac-resin,
with the exception of the acid, which turns alkalis green (Hlasiwetz
& Barth).—7. Chloride of acetyl forms a substitution-product, which
crystallises from alcohol in granules (Hlasiwetz).
Combinations. With Water. Mono-hydrated Guiaiaretic acid.
Crystallises from alcohol in soft small nodules and scales, having a faint
odour of vanilla; from acetic acid in inodorous brittle needles; from
alcohol diluted with water in shining, thin lamina (Hlasiwetz & v. Gilm).
Rhombic pyramids having their terminal summits acuminated (Hadelich).
Melts at 75° to 80°, and if cooled immediately solidifies to a crystalline
mass; but if heated above its melting-point, it solidifies to a resin
(Hlasiwetz & v. Gilm). Loses 6.73 p. c. of water on melting
(Hadelich) (1 at. 5.17 p. c.).
The acid is perfectly insoluble in water. It forms with bases mono-
and semi-acid salts, and is therefore bibasic (Hlasiwetz & v. Gilm); but
according to Hadelich, who obtained a quadrimetallic lead-salt, it is
quadribasic. The salts of the alkalis are crystallisable, those of the
earths and metallic oxides are amorphous precipitates. The semi-acid
(neutral) salts of the alkalis are obtained only with excess of alkali.
Their solutions, after boiling, deposit mono-acid salts on cooling, while
the solutions of the mono-acid salts suffer further change, a mixture of
free acid and acid salt being deposited. The salts are decomposed by
mineral acids (Hlasiwetz & v. Gilm).
Guaiaretic acid dissolves very slightly in cold or warm ammonia-
water. Sal-ammoniac precipitates the acid from the potash-salt (Hlasi-
wetz & v. Gilm).
Potash-salt. A. Bibasic.-A hot moderately strong solution of
caustic potash dissolves guaiaretic acid, and on cooling deposits fine
scales of the salt. Strong solution of potash solidifies, on addition of
the acid, to a pulpy mass, a solution of which in warm alcohol deposits
the salt in scales and lamina on cooling. The salt is also thrown
R 2
244
PRIMARY NUCLEUS C40H28; OXYGEN-NUCLEUS C40H260².
down by alcoholic potash from an alcoholic solution of the acid in the
form of an indistinctly crystalline precipitate.-Contains, at 100°,
sometimes 4 at., sometimes 6 at. water, which are expelled at 140°.
By dry distillation it yields white vapours, water, and a little empyreu-
matic oil. - A solution of the salt in dilute alcohol, after boiling for
some time and cooling, deposits the mono-acid salt (Hlasiwetz &
v. Gilm).
Hlasiwetz & v. Gilm.
α.
mean.
40 C.........
28 H
240
54.30
54.57
28
6.33
....
6.44
2 K............
78
17.66
17.28
12 O........
96
21.71
21.71
C40H24K208 + 4Hо
44.2
100.00
100.00
...
b.
Hlasiwetz & v. Gilm.
40 C.........
240
52.17
52.33
30 H
2 K
30
6.52
6.26
78
16.99
16.58
...
112
24.32
24.83
460
100.00
100.00
....
........
14 0........
C40H24K208 + 6HO
a lost 8.16 p. c. of water at 140° (4 at.
=
8.16 p. c.); b was likewise dried at 100°
before analysis. Both salts exhibited, at 140°, the composition of the semi-acid salt,
a containing 23·0, b 22-3 p.c. KO (by calc. 23·15).
-
B. Mono-acid. Friable crystals, obtained also by adding carbonate
of potash to a solution of the acid in weak alcohol, heating, and adding
dilute alcohol till solution is effected. Decomposed by prolonged boil-
ing of the solution. Gives off 4.8 p. c. of water at 120° (2 at. = 4·66
p. c. HO) (Hlasiwetz & v. Gilm).
40 C.........
27 H
K........
10 0 .....
at 100°.
Hlasiwetz & v. Gilm.
240
62.17
61.42
27
6.99
7.20
39
10.10
9.83
80
20.74
21.55
100.00
100.00
C40H25K08 + 2HO.... 386
Soda-salt. A. Bibasic. Alcoholic soda throws down from an
alcoholic solution of the acid, an abundant precipitate, which when dis-
solved by heating it with caustic soda and water, quickly crystallises
in shining laminæ. Dissolves in a hot mixture of water with an equal
quantity of alcohol, the solution depositing the mono-acid salt on cooling
(Hlasiwetz & v. Gilm).
40 ℃.....
28 H
Hlasiwetz & Gilm.
at 100°.
240
58.29
58.05
28
6.83
6.84
2 Na
46
11.22
11.47
12 O......
96
23.66
23.64
C40H24Na2O8+ 4HO.... 410
100.00
100.00
The salt dried at 120° contains 12.35 p. c. of sodium, and is therefore anhydrous
(calc. 12:30 p. c. Na).
B. Mono-acid. Small shining lamine, which, after drying at
BROMOGUAIARETIC ACID.'
245
100°, lose 7:01 p. c. of water at 120° (2 at. HO= 4.86 p. c.) (Hlasiwetz
and v. Gilm).
40 C........
at 100°.
240
Hlasiwetz & v. Gilm.
64.86
65.01
27 H.......
27
7.29
7.58
Na
23
6.21
6.14
10 O..........
80
21.64
21.27
C40H25Na08 + 2HO
370
100.00
100.00
at 120°.
Hlasiwetz & v. Gilm.
40 C........
240
68.18
67.91
25 H
25
7.10
7.62
Na
23
6.53
6.39
8 0.......
64
18.19
18.08
C40H25Na08.... 352
100'00
........
100.00
Baryta-salt. The bibarytic salt, precipitated from chloride of
barium by the potash-salt, is amorphous and chalk-white.
Hlasiwetz & v. Gilm.
C40H2406
2 BaO
312
67.09
153
32.91
32.61
100.00
....
C40H24Ba²08 465
Lead-salt. Quadribasic? An alcoholic solution of the acid is
added to boiling alcoholic basic acetate of lead, in quantity not suffi-
cient to produce complete precipitation; the whole is warmed for an
hour without access of air; and the precipitate is washed by decantation
with boiling alcohol and water. White precipitate, which, after drying
at 100°, does not give off any water at 130° (Hadelich).
Hadelich.
mean.
at 130°.
C40H2208
4 Pb
326
43.94
416
56.06
55.79
C40H22Pb408
742
100.00
....
Guaiaretic acid dissolves in 1.86 parts of alcohol of 90.2 p. c. at
15°, and in the same quantity of ether. It is soluble in bisulphide of
carbon, chloroform, acetic acid, acetate of ethyl, and benzene (Hadelich).
Oxy-bromine-nucleus C4Br4H220ª.
Bromoguaiaretic Acid.
C40 Br4H2208 C40Br4H2202,06.
HLASIWETZ & V. GILM. Ann. Pharm. 119, 275.
Bromine is dropped into a solution of guaiaretic acid in bisul-
phide of carbon till the liquid passes through carmine-red and violet,
and assumes a brown colour: the solution is then evaporated over
the water-bath. The crystals which remain are washed with cold
246
APPENDIX TO GUAIARETIC ACID.
alcohol and dissolved in a large quantity of boiling alcohol, from which
the acid is rapidly deposited on cooling.
Colourless, loose, shining short needles.
at 100°.
Hlasiwetz & v. Gilm.
mean.
40 C..........
240
.......
37.15
37.37
4 Br
320
49.39
49.35
22 H
22
3.40
3.76
80
64
10.06
9.52
C40 Br4H2208
646
100.00
....
100.00
Appendix to Guaiaretic Acid..
1. Guaiac Beta-resin.
C40H20012 or C28H1408.
Obtained as a residue insoluble in ether in the preparation of guaia-
conic acid (p. 155). This residue is completely freed from guaia-
conic acid by mixing it with sand and treating with ether; it is then
dissolved in alcohol, decolorised by animal charcoal, and precipitated
by pouring the solution into ether. The brown flocks are still to be
purified by again dissolving and precipitating, and lastly by precipitating
the alcoholic solution with water.
Red-brown powder, melting at 200° to a black mass. Neutral. Dis-
solves in alkalis, from which it is precipitated by acids. The alcoholic
solution is precipitated by basic acetate of lead, but not by the neutral
acetate. Dissolves easily in alcohol, acetic acid, and acetate of ethyl,
but is insoluble in ether, chloroform, and benzene. Contains at 100°,
on an average, 67.81 p. c. C., 5.81 H., and a little nitrogen
(Hadelich).
2. Guaiac-yellow.
HADELICH. Dissertation, page 9.
Yellow colouring matter of Guaiac resin. Observed by Pelletier.
Powdered guaiac resin is boiled with milk of lime, and the liquid is
filtered and evaporated, so that, by the action of carbonic acid, the
greater part of the lime may be precipitated as carbonate, whilst most of
the guaiaretic acid deposited. The residue is exhausted with water,
and the solution is supersaturated with acetic acid, filtered, and left
to stand for 14 days or longer, when small pale-brown tables crystallise
out. The crystals dissolve with difficulty in a large quantity of water,
leaving resin, but are easily soluble in ether and alcohol, and crystallise
from the latter on evaporation.
Pale-yellow, quadratic octohedrons with truncated summits, or quad-
ratic tables. Inodorous, bitter, and grating between the teeth. Contains
nitrogen. Neutral. Without action on polarised light.
When heated in a tube, it yields a distillate of brown oil.
- Melts
GUAIAC-RESIN.
247
on platinum-foil to a greenish-yellow mass, with loss of water, and
afterwards burns, evolving suffocating vapours. Dissolves in oil of
vitriol, forming a fine blue solution, which becomes green and yellow
as it absorbs water, but turns blue again on warming. It is de-
colorised by the addition of water. Dissolves in fuming nitric acid
with orange colour, which is changed to red by oil of vitriol.
Difficultly soluble in water, and scarcely at all in boiling hydrochloric
acid, either strong or dilute, by which it is not decomposed. Dissolves
easily in aqueous ammonia, alkalis, and alkaline earths, with deep yellow
colour, which is destroyed by acids. The aqueous solution is not
precipitated by salts of the metals, with the exception of the neutral
and basic acetates of lead.
Dissolves easily in bisulphide of carbon, alcohol, ether, and acetate of
ethyl, and with difficulty in chloroform, benzene, and oil of turpentine.
3. Guaiac-resin.
BRANDE. Ann. Chim. 98, 140.
WOLLASTON. Gilb. 39, 294.
BUCHNER. Repert. 3, 281.
PAGENSTECHER. N. Tr. 3, 1, 447.
TADDEI. N. Tr. 4, 2, 159.
PLANCHE. J. Pharm. 6, 16; N. Tr. 4, 2, 261; Berl. Jahrb. 1820, 16,
Berl. Jahrb. 1821, 143.
BRANDES.
UNVERDORBEN. N. Tr. 8, 1, 57. — Pogg. 8, 481; 16, 369.
TROMSDORFF. N. Tr. 21, 1, 27.
FR. JAHN. N. Br. Arch. 33, 269.
SCHACHT. N. Br. Arch. 35, 3.
W. MÜLLER. N. Br. Arch. 35, 262.
SCHÖNBEIN. Pogg. 67, 97; 73, 489; 75, 351.
OSANN. Pogg. 67, 372.
From Guaiacum officinale (Handbuch, viii [2], 20). Obtained partiy
by spontaneous exudation: Gummi Guaiacum, Resina Guaiaci nativa;
partly by exhausting the wood with alcohol: Resina Guaiaci. Greenish
externally, reddish and greenish-brown within; easily triturable to a
grey-white powder; translucent; of conchoïdal and splintery fracture.
Sp. gr. 1.205 (Pfaff), 1·2289 (Brande). Becomes tough when chewed.
The resin prepared from the wood melts in boiling water. In the
form of powder and when heated it has a balsamic odour. Tastes
sweetish-bitter, and hot and harsh in the throat: the resin of the
wood, however, is tasteless (Buchner; Trommsdorff).
Guaiac resin contains 71'00 p. c. C., 7·03 H., and 21.97 O. It is,
however, not a single substance, but contains th its weight of a
resin insoluble in ether, besides yellow-colouring matter (Pelletier,
J. Pharm. 27, 386). The commercial resin contains, besides resin
proper, bark, woody fibre, gum, and brown extractive (Buchner,
Repert. 3, 281). On evaporating its solution in cold alcohol on flat
plates, and heating the residue for 12 hours to 120°, there remains a
transparent, ruby-red, brittle resin, containing 68.54 p. c. C., 6.83 H.,
and 24.63 0. (Johnston, Phil. Trans. 1839, 291).
248
APPENDIX TO GUAIARETIC ACID.
Guaiac resin contains, in 100 parts, 10.50 parts of guaiaretic acid
(p. 241) 70-35 of guaiaconic acid (p. 155), 9.76 of beta-resin, besides
gum, woody fibre, solid constituents insoluble in water, guaiacic acid
(xi, 397; and xvii, 252) and guaiac yellow (p. 240) (Hadelich).
According to Unverdorben, guaiac resin consists of a portion which
is soluble in all proportions in aqueous ammonia, but insoluble in
boiling carbonate of soda, and precipitates acetate of copper at
the boiling heat; together with a large quantity of a second resin,
which forms with ammonia a tarry compound, difficultly soluble in
water, and giving off its ammonia on boiling. — Jahn distinguishes
three resins, two of which are soluble in ether, and separable from
one another by ammonia.
According to Kosmann (N. J. Pharm. 38, 82) the purified resin is
decomposed by heating with dilute sulphuric acid, with separation of
guaiaretin and formation of sugar. This observation was found by
Hadelich not to be correct, either in the case of crude guaiac resin or
of any of its constituents. Kosmann (Par. Soc. Bull. 5, 391), however,
still maintains the modified statement that guaiac resin yields with
acids a very small quantity of a brown substance, which reduces
cuprate of potash.
Pelletier's pure guaiac resin, or guaiacin, is obtained by precipi-
tating the tincture with neutral acetate of lead, washing the precipi-
tate with water and alcohol, decomposing it with hydrosulphuric acid,
and extracting with alcohol. Or alcoholic guaiac resin is treated with
hydrated oxide of lead, whereby an easily decomposible compound is
formed. It possesses, in a high degree, the property of becoming
blue in the air, or under water containing air, or under boiled water,
with evolution of hydrogen, and is again decolorised by hydrosulphuric
acid and other bodies (Pelletier, J. Pharm. 27, 386).
a fine
Alcoholic guaiac resin deposits, on standing, delicate white groups
of needles, which redden litmus, melt, and volatise incompletely, with
decomposition; Landerer's guaiacin. The crystals assume
grass-green colour with nitrous acid or strong nitric acid, and a pale-
green with chlorine-water or iodine, the colour disappearing on the
volatilisation of the iodine. They are insoluble in oil of vitriol and in
water, but strong hydrochloric acid takes up a portion which is precipi-
tated by alkalis. They are insoluble in caustic potash or its carbonate,
but soluble in boiling ammonia-water: they do not dissolve in cold
alcohol or ether, but are soluble in the boiling liquids, from which they
Landerer also ob-
crystallise on cooling (Landerer, Repert. 52, 94).
tained from ammoniacal tincture of guaiacum, splendid green prisms
containing ammonia, only partially soluble in water and alcohol (Repert.
56, 83).
Guaiacum wood contains a resin resembling commercial guaiac
resin in its behaviour with solvents, together with guaiacic acid,
guaiacin, Riegel's gum, and salts. It gives up to boiling water guaiacic
acid (xi, 397), precipitable by basic acetate of lead, and afterwards
yields to alcohol, resin and guaiacin, which are deposited on evapo-
rating the alcohol. Guaiacin forms neutral yellow nodules, having a
bitter and acrid taste, soluble in boiling water, and more easily in ether.
It is not turned blue by nitric acid, as is the resin soluble in alcohol
and ether (Riegel, Jahrb. pr. Pharm. 14, 243). — Guaicum bark contains
an acrid extractive substance, and a dark-brown, brittle resin: the
tincture of this last named body does not acquire a blue colour with
GUAIAC-RESIN.
249
fuming nitric acid, and differs, therefore, from ordinary guaiac resin
(Trommsdorff).
Guaiac resin burns with a powerful aromatic odour. It melts
easily, begins to decompose about 300°, and when subjected to dry
distillation yields at first water smelling of the resin, then a slightly
acid water, and a yellow, light oil of penetrating odour, and at last a
thick, yellowish-brown, heavy oil, whilst charcoal remains behind.
(Unverdorben; Völckel; Sobrero). During the distillation carbonic
acid and hydrocarbons are evolved (Brandes). No umbelliferone is ob-
tained (Sommer).
When the product obtained by the dry distillation of guaiac resin
in an iron retort is rectified, there pass over first guaiacene (x, 411)
with a large quantity of water, then a heavier, thick product, and at
last pyroguaiacin (xii, 349), which solidifies in a crystalline mass. On
separating, by a second rectification, the middle portion from the first,
which consists chiefly of guaiacene, and the last, which contains a large
quantity of pyroguaiacin, there remains an oil which, when treated
according to xii, 350, yields the pyroguaiacic acid (Pyrojaksaüre) of this
work, i.e., Völckel's guaiacol. According to Hlasiwetz, it is a mixture
of two homologous oils of the formula C¹H*O* and C¹6H¹º04, the latter
of which may also be obtained from creosote (see xv, 161). See further
below. Hlasiwetz's statement that the oil also contains furfurol was refuted by
Schwanert (Ann. Pharm. 116, 285).
Powdered guaiac resin and tincture of guaiacum, as well as paper
moistened with the tincture and dried, are turned blue by ozonised
oxygen, but not by ordinary oxygen: they are coloured blue also by
iodine, bromine, chlorine, the peroxides of manganese, lead, and silver,
by oxide of silver, oxide of mercury, teroxide of gold, permanganic
acid, chromic acid, hyponitric acid, alkaline hypochlorites, finely
divided platinum, and by sesquichloride of iron, chloride of copper, and
ferricyanide of potassium. The blue colour is destroyed by heat, and
also by reducing agents, as phosphorus, finely divided tin, iron,
zinc, and other metals, hydrosulphuric acid, hydroselenic acid, sul-
phurous acid, proto-salts of iron and tin, ferrocyanide of potassium,
mineral acids, and alkalis. The colour disappears also spontaneously,
the rate of its disappearance depending upon the nature of the sub-
stance producing it. After being frequently coloured and decolorised
the tincture loses the property of turning blue (Schönbein).
Ordinary air also produces the blue coloration when a very small
quantity of the tincture is placed in strong sunlight and shaken with a
large quantity of air (Schönbein). The blue (or green) colour is not
produced in carbonic acid, and in oxygen gas only on exposure to
colourless or violet light, whilst the red rays of light concentrated to
a focus, reduce the green to yellow again (Wollaston). See also Jodin
(N. J. Pharm. (4) 1, 56; Compt. rend. 59, 857). The tincture, mixed
with common salt, and submitted to the electric current, immediately
becomes blue: crude impure salt, however, itself produces the blue
coloration (Osann). See also Arnaudon (Cimento 8, 281; Kopp's
Jahresber. 1858, 451); Regimbeau (J. Pharm. 15, 14); Schacht (N. Br.
Arch. 35, 3); H. Schiff (Ann. Pharm. 111, 373).
Powdered guaiac-resin acquires a bright blue colour when triturated
with gluten which is not spoiled, or with flour containing a large quan-
tity of gluten, but in all cases exposure to air is necessary. The colour
is not formed with starch (Taddei; Ridolfi). — Tincture of guaiacum
250
APPENDIX TO GUAIARETIC ACID.
!
turns blue also, even without exposure to light, when dropped upon
slices of the following fresh roots: Cochlearia Armoracia and C. officinalis,
Brassica Napus, Symphytum off., Borago off., Solanum tuberosum, Leon-
todon Taraxacum, Cichorium (the sap of which also possesses the pro-
perty), Inula Helenium, Arcticum Lappa, Scorzonera hispanica, Glycyr-
rhiza glabra, Fumaria off., Eryngium campestre, Daucus Carota, Angelica
Archangelica, Althea off., Asparagus off., Saponaria off., Rumex acetosa,
Iris germanica, Nymphæa alba, Colchicum autumnale and Allium Cepa.
Most of these roots lose the property on drying, and some even when
heated to 100°. The fresh roots of Rumex acutus, Fragaria Vesca, Poly-
podium Filix Mas, and others do not produce the blue colour (Planche).
The substance producing the blue colour occurs in all parts of the
potato, but the colour is most rapidly and vividly produced in the peel,
and at the places where eyes occur. Boiled potatoes do not possess
the colouring property (Schönbein, Pogg. 75, 357). See also Schacht,
Van der Broek (Scheikund. Onderzoek. 5, 3; Stuck, 210; and 5, 6, Stuck,
226; abstr. Pharm. Centr. 1850, 635, and 645). Concerning the blue
colour produced by Vinum. Sem. Colchici, see W. Müller (N. Br. Arch.
35, 362).
Gum arabic made with cold water colours powdered guaiacum blue,
but this property is not possessed by a solution in hot water, nor by
gum tragacanth. Milk behaves in a similar manner, fresh milk pro-
ducing the blue colour, whilst the boiled liquid no longer possesses the
property, even after cooling and saturating it with air (Planche).
Tincture of guaiacum is not coloured blue by peroxide of hydrogen,
but on adding to the mixture a little platinum-black, it immediately
assumes a deep blue colour; mercury also, and gold, silver, osmium,
gluten, diastase, emulsin, myrosin, yeast, and all vegetable and animal sub-
stances which have the property of decomposing peroxide of hydrogen
(ii, 77) act in the same way as platinum (Schönbein, N. Repert. 13, 338).
Chlorine gas and aqueous chlorine quickly colour powdered guaiac-
resin green, blue, and brown; ammonia changes the brown to green,
and assumes itself the same colour (Brande). Chlorine throws down a
blue precipitate from tincture of guaiacum. This precipitate is the
guaiaretic acid of Jonas (N. Br. Arch. 69, 20); it has the property of
rapidly turning fresh tincture of guaiacum blue. - Strong nitric acid
dissolves guaiac resin, even in the cold, with evolution of nitric oxide
and formation of a large quantity of oxalic acid and other substances
(Brande). Dilute nitric acid turns the tincture blue when it contains
nitrous acid only (Gmelin; Schacht). Spiritus nitr. æther. turns it blue
immediately; the neutralised liquid only after a few minutes (Schacht).
Oil of vitriol dissolves guaiac-resin, forming a fine dark-red solution,
which is rendered violet by water, and violet-blue by alcohol, and car-
bonises when heated (Dulong; Trommsdorff; Schiff).
Guaiac-resin dissolves partially in aqueous ammonia to a brown liquid.
It dissolves still more easily in aqueous alkalis and their carbonates,
forming red-green or brown-green solutions, which are precipitated
by acids and by metallic salts.
With melted caustic potash and a little water, guaiac resin dissolves
only when strongly heated, frothing up and forming a homogeneous
mass, from which sulphuric acid throws down a black tar, and evolves
an odour of volatile fatty acids, whilst protocatechuic acid (xvi, 236),
or an acid of similar composition, and a second acid which turns alkalis
green, remain in solution (Hlasiwetz & Barth).
GUAIAC-RESIN.
251
On supersaturating the fused alkaline mass with dilute sulphuric
acid, filtering from tar, and agitating with ether, these two acids are
dissolved, and remain behind when the ether is evaporated. They are
dissolved in water and precipitated with neutral acetate of lead; the
washed precipitate is decomposed under warm water by hydrosulphuric
acid; and the liquid is filtered and evaporated, whereupon procatechuic
acid crystallises out, until the mother-liquor becomes brown and thick.
After long standing, the mother-liquor solidifies to a friable mass, which
is pressed, decolorised, and purified by repeated solution and solidifica-
tion. In this way a white, mealy powder, or on evaporating the
alcoholic solution, a fissured varnish is obtained, containing, after dry-
ing at 150°, 64.75 p. c. C. and 6.39 H. This acid dissolves in water,
alcohol, and ether: its solution in aqueous alkalis quickly assumes a
dark emerald-green colour on exposure to the air; sesquichloride of
iron colours it olive-green, which is changed to a fine violet-red by
soda. It reduces cold ammoniacal nitrate of silver, and the hot nitrate
free from ammonia, also alkaline solutions of oxide of copper. Its
red solution in oil of vitriol turns green on standing, yellowish-green
on warming; oxide of manganese colours it olive-green in the cold,
and dirty-red on warming. The acid decomposes carbonates; it is
precipitated from its aqueous solution by neutral acetate of lead, the
precipitate being soluble in acetic acid (Hlasiwetz & Barth).
Alcoholic neutral acetate of lead throws down from tincture of
guaiacum a white precipitate, which quickly turns blue in sunshine;
from the filtrate ammonia throws down a second precipitate (Johnston).
An alkaline solution of the resin does not precipitate acetate of copper
(Unverdorben). The tincture reduces nitrate of silver in the light
(Johnston).
Guaiac resin dissolves abundantly in alcohol, with brown colour
[and in wood-spirit, the solution turning blue in the same way as the
alcoholic solution (Schönbein)]; the tincture is rendered milky by water,
and is precipitated by hydrochloric and sulphuric acids, but not by acetic
acid. It dissolves slowly but completely [only partially (Brande)]
in ether Trommsdorff). - Dissolves completely in fusel oil and amylic
aldehyde, and partially in valerianic acid and valerianate of amyl (Tranti-
vein). Dissolves completely in creosote (Reichenbach). Cold oil of
turpentine dissolves only a trace of guaiac-resin, the undissolved portion
turning blue and then green (Trommsdorff); the hot liquid dissolves.
rather more, forming a colourless solution, which is coloured blue, red,
and yellow on evaporation (Pfaff). — The resin is insoluble in fat oils.
Addenda to the products from Guaiac-resin previously described.
1. To Guaiacene (x, 411).
Guaiol of Völckel. Since investigated
by Völckel (Ann. Pharm. 89, 348) and v. Gilm (Ann. Pharm. 106,
379).
After the distillate from guaiac resin has been subjected to frac-
tional distillation, and the portion passing over below 120° is collected
apart, this portion is to be repeatedly distilled off lime, till it ceases to
be altered by cold caustic potash, and is no longer turned green by
alcoholic sesquichloride of iron. It then forms a colourless, highly
refractive, limpid liquid, boiling at 118°, and having a burning, aromatic
252
APPENDIX TO GUAIARETIC ACID.
taste, and a powerful stupefying sweetish odour of bitter almonds. It
contains 7155 p. c. C., 9.82 H, and 18.63 O., corresponding to
Deville's formula, C¹ºHO². It is oxidised to oxalic acid by nitric
acid, and to acetic acid by chromic acid. When warmed with solid
caustic potash, it forms a brown resin, which is decolorised by melting
the mass (without formation of angelic acid (x, 413). Guaiacene is
insoluble in ammonia-water, and in cold solution of caustic potash of
sp. gr. 1.25, and does not combine with alkaline bisulphites (v. Gilm).
Völckel examined impure guaiacene, to which he gave the formula
C⁹H70².
2. Guaiacic acid (xi, 397). Obtained from the resin in very small
quantities only-about 1 decigramme from 4 pounds (Hadelich).
3. Guaiacol or Pyroguaiacic acid (xii, 350). Guaiacol obtained by
fractional distillation, and purified by Völckel's method (xii, 351, 2) is a
mixture of two homologous oils of the formulæ CHO and C¹6ɹ004,
the latter of which may also be obtained from creosote (see xv, 161).
By agitation with strong ammonia, or by the passage of ammonia-gas,
it is converted into a slightly coloured crystalline mass, which is
pressed, dissolved immediately in a little warm ether, and after cooling
in a closed vessel, decomposed by strong alcoholic potash. Ammonia
is thus liberated, and the whole solidifies to a white crystalline mass,
which is again pressed, washed with ether, dried in a vacuum, and
afterwards decomposed by aqueous oxalic acid or sulphuric acid. The
oil thereby separated is washed, dried, and rectified. It is colourless,
and has a very agreeable odour.
The oil heated to boiling in a retort yields, between 203° and 230°,
products which have at first a greater density, and contain a smaller
proportion of carbon and hydrogen, and afterwards, at a higher boiling-
point, a lower specific gravity.
Specific gravity at 13° according to Hlasiwetz.
Portion at 210°
11171
216-218°
1.1162
>>
">
رو
Portion at 220°
""
220-225° = 1·0900
1.0894
ور
ور
218°
1.1115
205-210°.
14 C
8 H
40
C4H8O4.... 100.00
67.74
6.45
25.81
****
67.95
6.93
25.12
...
Hlasiwetz.
216-218.
68.61
6.93
24.46
219-220°.
69.83
16 C
69.56
7.53
10 H
7.24
22.64
40
....
23.20
100.00
100.00
100'00
....
C16H1004.... 100.00
The potash-salt of the compound C16H100 forms with chloride of
phenyl an aromatic smelling oil, but no pyroguaiacin.
Both oils form compounds with ammonia and potash, the compound
with the latter base, when prepared with oil of low boiling-point,
having the composition CH'KO. By treating crude guaiacol as above,
and crystallising the product from alcohol, white potash-salts are pro-
duced, containing either at., or, when an excess of caustic potash is
흐
​employed, 1 at. of potassium to 16 at. of carbon.
HYDROBERBERINE,
253
C14H70³.........…………………
58.03
KO......
23.81
....
4 HO.......
18.16
23.33
18.40
Hlasiwetz.
C16H903
KO......
4 HO.....
....
C¹4H7KO4 + 4aq. 100.00
Hlasiwetz.
60.84
22.17
22.68
16.99
C¹6H³KO4 + 4aq. 100·00
The bi-acid salt contains 14.75 p. c. of potash, corresponding to the
formula C32H19KO8 + (2 aq) (calc. 14.15 p. c. KO). (Hlasiwetz.)
Guaiacol does not reduce moist oxide of silver (Schwanert).
Oxy-azo-nucleus C40NH1908.
Hydroberberine.
C40NH2108 C40NH1908,H2.
HLASIWETZ AND V. GILM. Ann. Pharm. Suppl. 2, 191.
Preparation. Six parts of berberine, 100 parts of water, 10 parts
of oil of vitriol, and 20 parts of glacial acetic acid, together with a
large quantity of granulated zinc, and a few pieces of platinum foil,
are introduced into a capacious flask provided with an upright con-
denser, so that the condensed products may flow back into the flask.
The contents of the flask are heated to the boiling-point, and kept at
that temperature for an hour or two, or until the colour of the liquid
has passed through dark gold-brown to light wine-yellow. The
liquid is then filtered; any crystals that may have separated are dis-
solved in a little very dilute sulphuric acid; and the whole is precipitated
with excess of ammonia. The yellowish-white precipitate thus pro-
duced is washed with water, dried, triturated, and repeatedly boiled
with alcohol. The hydroberberine, which is difficultly soluble in alcohol,
is deposited in crystals, partially during filtration, but chiefly after
standing and concentration. The crystals are purified by oft-
repeated crystallisation from alcohol; or, the solution containing zinc is
mixed with an excess of a saturated solution of chloride of sodium,
and the hydrochlorate of berberine thereby separated is decomposed
by alcoholic ammonia. In this way ths of the berberine employed is obtained
as hydroberberine.
Properties. Small colourless or yellowish needles, having an
adamantine lustre, or long, flat needles of the monoclinic system.
Does not lose weight at 100°.
Hlasiwetz & v. Gilm.
at 100°.
mean.
40 C........
240
70-79
70.65
N........
14
4.13
4.14
21 H
21
6.19
6.50
8 0......
64
18.89
18.71
C40NH2108
339
100.00
100.00
Decompositions. 1. Solutions of hydroberberine assume a yellow
colour on standing in the air, or on prolonged boiling.-2. Dilute
254
PRIMARY NUCLEUS C40H28; OXYAZO-NUCLEUS C40NH1908.
nitric acid, dropped into an alcoholic solution of the hydrochlorate,
gradually forms berberine; on heating the solution, red vapours are
evolved. ·3. Bromine converts hydroberberine dissolved in bisulphide
of carbon, into hydrobromate of berberine:
C40NH210S + 4Br
C40NH¹708, HBr + 3HBr.
4. Hydroberberine dissolves in oil of vitriol with yellowish-green
colour, which becomes darker on standing, and is changed to red-
brown by chromic acid. — 5. Iodide of ethyl forms hydriodate of ethyl-
hydroberberine.
Combinations. Hydroberberine is insoluble in water.
It combines
with acids to form mono- and bi-acid salts, which are, for the most part,
easily crystallisable. From their solutions ammonia and potash throw
down the base in white flocks, which run together to a plaster in hot
liquids.
Phosphate of hydroberberine forms large rhombic tables.
Sulphate of Hydroberberine. A. Mono-acid. Prepared by heating
very dilute sulphuric acid to the boiling point with excess of hydro-
berberine. From the solution, which still has an acid reaction, the salt
is deposited in tufts of colourless, hair-like crystals, turning yellow
when warmed, and losing their water of crystallisation over oil of
vitriol, or more easily at 100°.
40 C
N
22 H
90
SO3
Dried.
Hlasiwetz & v. Gilm.
240
61.86
59.48 to 60.16
14
3.61
22
5.67
5.80, 6·10
72
18.55
40
10.31
11.21 12.68
""
388
100.00
....
C40NH2108,HO,SO³
It probably contained an admixture of the following salt.
B. Sesqui-acid. A solution of hydroberberine in slight excess of
dilute sulphuric acid, yields by spontaneous evaporation, large, trans-
parent, very regular rhombohedrons, frequently accompanied by the salt
A. The crystals are 2C4NH2¹08,3(HO,SO³)+8aq.; they become dull
and fissured in the air, and at a moderate temperature lose 8.27 p. c. of
water (8 at. = 8·02 p. c.), and are converted into the lemon-yellow
anhydrous salt. At 100° it turns darker, and melts to a glassy mass,
losing weight, and becoming insoluble in water. A solution of the
salt in water deposits crystals of A.
Hlasiwetz & v. Gilm.
Air-dried.
80 C
480
53.50
53.48
.......
2 N
28
3.15
53 H
53
5.90
5.93
27 O
216
24.08
3 SO3
120
13.37
13.16
2C40NH2108,3 (HO,SO³) + 8aq.
897
100.00
....
HYDROBERBERINE.
255
80 C
2 N
45 H
19 O
3 SO3
2C40NH2¹08,3 (HO,SO³)
Dried.
58.18
Hlasiwetz & v. Gilm.
mean.
57.94
480
28
... ....
3.39
45
5.45
5.97
4
152
18.43
120
14.55
14.49
825
100.00
....
The salt contains 8 at., not 4 at. water; the dried salt 45 at., not 47 at. hydro-
gen, as erroneously stated in Ann. Pharm. Suppl. 2, 208 (Kr.).
C. Bi-acid. Moderately dilute solutions of A and B are rendered
turbid by excess of sulphuric acid, and, when more concentrated,
deposit a tough resin, which, on standing, is converted into nodules of
a bi-acid salt, crystallisable from absolute alcohol.
Hlasiwetz & v. Gilm.
40 C
N
23 H
10 O
2 SO3
at 120°.
mean.
240
54.92
54.73
14
3.22
23
5.26
5.61
....
80
18.30
80
18.30
18.59
100.00
C40NH2¹08,2 (HO,SO³).... 437
Hydriodate of Hydroberberine. White, crystalline precipitate or
colourless granules, precipitated by iodide of potassium from sulphate
of hydroberberine. Very difficultly soluble in water.
Hlasiwetz & v. Gilm.
at 120°.
mean.
40 C
N
240
51.37
51.30
14
2.99
22 H
22
4.71
5.02
80
I
64
13.74
127
27.19
27.37
C40NH2¹08, HI
4.67
100.00
....
Hydrobromate of Hydroberberine. — Obtained in the same way as the
preceding salt, which it resembles.
Hydrochlorate of Hydroberberine. Hydroberberine in contact with
hydrochloric acid gas, is converted into a white powder, which crystal-
lises from hot water in laminæ. The easily formed solution of hydro-
berberine in warm dilute hydrochloric acid solidifies in the cold to a
jelly, which is converted into difficultly soluble crystals on standing.
The salt is precipitated from the sulphate by chloride of sodium; it
dissolves in alcohol containing hydrochloric acid more easily than in
water, and, on adding water to the solution till turbidity is produced,
heating, and setting aside, the salt crystallises in small colourless tables
or nodules.
40 C
N
22 H
at 100°.
Hlasiwetz & v. Gilm.
240
63.91
63.70
14
3.73
22
5.85
6.12
80
64
17.06
CI
35.5
9.45
9.44
C40NH2¹08, HCI
375.5
100.00
256
PRIMARY NUCLEUS C40H28; OXYAZO-NUCLEUS C4NH190º.
Nitrate of Hydroberberine. Obtained with difficulty (on account of
the oxidising action of the acid) by dissolving hydroberberine in nitric
acid, or more easily in a pure state by mixing hot very dilute solutions
of sulphate of hydroberberine and nitrate of soda. Fine, iridescent
laminæ or rhombic tables, drying up to a silvery pellicle.
at 100°.
Hlasiwetz & v. Gilm.
40 C
2 N
240
59.70
59.85
28
6.96
7.02
22 H....
22
5:47
5.81
...
14 O
112
27.87
27.32
C40NH2¹08, HO,NO5
402
100.00
100.00
Chloroplatinate of Hydroberberine. Bichloride of platinum throws
down from aqueous hydrochlorate of hydroberberine an abundant preci-
pitate, which, when a hot alcoholic solution is employed, is obtained in
orange-yellow crystals. - Dissolves with difficulty in water and alcohol,
more easily in alcohol containing hydrochloric acid.
40 C.......
N
at 100°.
240
Hlasiwetz & v. Gilm.
22 H
80
Pt
3 Cl
C40NH2108,HCl,PtCl²
44.03
43.93
...
14
2.56
22
4.04
4.44
64
11.74
98.5
18.07
18.14
106.5
19.56
545.0
100.00
....
The acetate forms large tables and prisms; the oxalate small rhombic
tables; the tartrate clusters of needles.
Hydroberberine dissolves in alcohol, more especially when hot. It
dissolves in bisulphide of carbon and chloroform more easily than in cold
alcohol, and crystallises from the solutions.
Ethyl-hydroberberine.
C44NH2508C40NH19 (CH)0°,H².
HLASIWETZ & V. GILM. Ann. Pharm. Suppl. 2, 191.
Obtained in combination with hydriodic acid by heating triturated
hydroberberine with excess of iodide of ethyl in the water-bath, and
crystallising the semi-fluid product from alcohol. Pale yellow,
rhombic prisms, brittle and bitter, soluble in hot, and less easily in
cold water.
44 C
N
26 H
-
Prisms.
Hlasiwetz & v. Gilm.
264
53.33
52.95
14
2.82
26
5.25
5.52
80
64
12.95
I....
127
25.65
25.41
C40NH20 (C4H5) 0º,HI
495
100.00
PAPAVERINE.
257
G. MERCK.
Papaverine.
C40NH2108 = C40NH 1908, H².
Ann. Pharm. 66, 125; Pharm. Centr. 1848, 939; N. Br.
Arch. 56, 312; N. J. Pharm. 15, 167. — Ann. Pharm. 73, 50; Pharm.
Centr. 1850, 52.
ANDERSON.
Trans. Roy. Soc. Edinb. 21, 1, 195; Chem. Gaz. 1855, 21;
Ann. Pharm. 94, 235; Pharm. Centr. 1855, 279; J. pr. Chem. 65,
233.
Discovered in 1848 by Merck, in opium.
Preparation. An aqueous extract of opium is precipitated with
caustic soda; the precipitate, consisting chiefly of morphine, is treated
with alcohol; the brown tincture thereby obtained is evaporated; and
the residue is mixed with a little ammonia, whereby (at first) a brown
resinous precipitate is produced. This is dissolved in dilute hydro-
chloric acid, and mixed with acetate of potash, which separates a dark
resin. This last body is washed with water and boiled with ether, from
which papaverine crystallises on cooling. A simpler plan is to dry
the brown resin over the water-bath, and add to it an equal quantity
of alcohol, whereby a thick syrup is produced, which solidifies in a
crystalline mass on standing for some days. The crystals are pressed,
and purified by recrystallisation from alcohol with the help of animal
charcoal. The papaverine thus obtained contains narcotine, which is
removed by dissolving the crystals in hydrochloric acid and recrystal-
lising the hydrochlorate (Merck).
Anderson prepares papaverine from the black mother-liquor obtained
in the preparation of morphine, codeine, &c., according to xvi, 420, as
follows: 1. From narcotine containing papaverine. When this substance
is crystallised repeatedly from boiling alcohol, the more easily soluble
papaverine remains in the mother-liquors and crystallises therefrom
mixed with narcotine. The crystals last obtained are triturated and
treated repeatedly with small quantities of acetic acid so long as the
acid is completely neutralised, and the filtered solutions are precipitated
with ammonia (or caustic potash). The precipitate thus obtained must
be crystallised from boiling alcohol, as otherwise it retains a large
quantity of ammonia (Chem. Soc. Qu. J. 15, 466). 2. From the precipitate
thrown down by basic acetate of lead, and containing resin, narcotine, and
papaverine. The precipitate is boiled with alcohol; the alcohol is eva-
porated; the residue is dissolved in hydrochloric acid; and the solution,
filtered from resin, is left to crystallise, whereupon hydrochlorate of
papaverine separates, whilst hydrochlorate of narcotine remains in the
mother-liquor.-3. Papaverine is also obtained in the preparation of
opianyl (Meconin) according to xiv, 423.
Properties. Papaverine crystallises from alcohol in confused masses
of white needles. Its solutions scarcely restore the colour of reddened
litmus. It has no particular action on the organism (Merck). Its
rotatory action on polarised light is but slight, and on account of the
difficult solubility of papaverine, cannot be determined with certainty
(Bouchardat & Boudet, N. J. Pharm. 23, 192.)
VOL. XVII.
S
Τη
258
PRIMARY NUCLEUS C40H28; OXY-AZO-NUCLEUS C40NH1909.
Merck.
Anderson.
mean.
40 C
240
70.79
70.59
70.63
N
14
4.13
4.75
4.17
21 H
21
6:20
6.53
6.40
80
64
18.88
18.13
18.80
C40NHOS.... 339
100.00
100.00
100.00
Isomeric with hydroberberine.
Decompositions. 1. Papaverine assumes a purple [deep blue (Merck)]
colour with oil of vitriol (Anderson; Guy). Permanganate of potash
colours the solution green, then slate-grey (Guy, Anal. Zeitschr. 1, 93).
-2. It dissolves in dilute nitric acid without decomposition, but on
warming the solution with excess of strong nitric acid, it acquires a
dark-red colour, evolves red fumes, and deposits orange-coloured
crystals of nitrate of nitropapaverine (Merck; Anderson). 3. Bromine-
water, dropped into hydrochlorate of papaverine, produces hydrobromate.
of bromopapaverine (Anderson).-4. Chlorine, passed into a solution.
of hydrochlorate of papaverine, turns it brown and throws down a
dirty-grey precipitate, a solution of which in boiling alcohol deposits,
on cooling, the hydrochlorate of a chlorinated base in the form of a
resin (Anderson).5. Papaverine heated with soda-lime, evolves a
volatile base, probably propylamine or ethylamine, the platinum-salt of
which contains 36 21 p. c. of platinum (Anderson). 6. Papaverine
turns brown when heated with peroxide of manganese (or peroxide of
lead), sulphuric acid, and water, and after boiling for some hours
deposits brown crystalline flocks, which dissolve in alcohol, and also in
water when washed therewith, and are precipitated from the aqueous
solution by sulphuric acid (Merck).-7. Papaverine heated with iodide
of ethyl yields hydriodate of papaverine without forming ethyl-
papaverine. The reaction is attended either by the formation of
alcohol:
C¹H®O².
C40NH2108 + CHI+ 2HO = C40NH2108, HI + CH6O2.
or (since a portion of the papaverine is converted into hydriodate even
in the absence of water) by the formation of ether:
CONHOS + CH³I + C4H6O²
=
C40NH2108,HI + 204H5O.
(How, Trans. Roy. Soc. Edinb. 21, 1, 27; Ann Pharm. 92, 336.)
Combinations. Papaverine does not dissolve in water.
for the most part difficultly soluble in water (Merck).
Its salts are
Carbonate of papaverine is prepared in the same way as carbonate
of morphine, by precipitating the hydrochlorate with carbonate of
silver, and not by precipitation with alkaline carbonates (How, Chem.
Gaz. 1854, 341).
Sulphate of papaverine is crystallisable (Merck). The hyposulphite
is soluble and is obtained by the action of hydrosulphate of ammonia, in
the same way as the morphine salt (xvi, 430) (How).
Papaverine and Iodine. a. With 3 at. Iodine. Crystallises after
some time from tincture of iodine to which papaverine has been added.
PAPAVERINE.
259
-Small rectangular prisms, dark-red by transmitted, purple-red by
reflected light. Not altered by dilute acids, but decomposed by am-
monia or potash, with separation of papaverine. Insoluble in water.
Soluble in boiling alcohol (Anderson).
Anderson.
40 C
N
240
33.33
33.02
14
1.95
21 H
21
2.92
3.21
80
64
8.88
3 I.
381
52.92
52.90
100.00
C40NH2¹08,31........ 720
b. With 5 at. Iodine. By evaporating the mother-liquor of the
preceding salt, crystals are obtained, which separate from alcohol in
thin reddish needles, appearing orange-coloured by transmitted light.
-Evolves iodine when heated over 100°. Rapidly decomposed by
ammonia (Anderson).
Anderson.
40 C
240
24.64
24.78
N
14
1·43
21 H
21
2.15
2.59
80
64
6.57
5 I
635
65.21
64.60
100.00
C40NH2¹08,51........ 974
Hydriodate of Papaverine. - Papaverine dissolves in a mixture of
alcohol and iodide of ethyl, partially in the cold, and completely when
heated in the water-bath; on concentrating the solution, crystals of
hydriodate of papaverine are obtained. (See above.) Colourless rhombic
crystals, which turn brown at 100°, with loss of weight, and after-
wards throw down a brown resin when dissolved in hot water. Dis-
solves easily in boiling water, the solution becoming milky on cooling
and depositing oily drops, which afterwards solidify in needles. Solu-
ble in alcohol, but in absolute alcohol the crystals dissolve only on
boiling (How).
How.
C40NH22OS
340
72.8
I
127
27.2
27.02
C40NH2¹08, HI
467
100.0
Hydrochlorate of Papaverine. Papaverine dissolves easily in dilute
hydrochloric acid, and is precipitated from the solution by a larger
quantity of hydrochloric acid in the form of a thick heavy oil. On
standing for some time, crystals form in the oil, as well as in the super-
natant liquid, so that the oily layer is converted at last into a heap of
short needles (Merck). Right prismatic, hemihedral. Rhombic prism y
(fig. 53) having the obtuse lateral edges slightly truncated by p, the
bevelling faces u resting on the acute lateral edges, and the octahedron
a being hemihedrally developed. yy over p = 100° (Kopp); u:
u above 119° 20' (Kopp); a: u =
a : u = 149° 15' (Pasteur); Kopp, Ann.
Pharm. 66, 127.-Pasteur, N. Ann. Chim. Phys. 38, 456. Very slightly
soluble in cold water (Merck).
$ 2
260
OXYNITRAZO-NUCLEUS C40NXH1808.
40 C........
N
22 H
80
Cl
at 100°.
Merck.
240
63.91
63.74
14
3.72
22
...
5.86
6.07
64
17.03
35.5
9.48
9.42
100.00
C40NH2¹08,HCl.... 375.5
Nitrate of Papaverine. A hot solution of the hydrochlorate is
decomposed by nitrate of silver: the filtrate crystallises on cooling.—
It is not obtained pure by treating papaverine with nitric acid, as the slightest excess
of acid colours the solution yellow (Merck).
Merck.
40 C
2 N
240
59.70
60.94
28
6.96
22 H
22
5.47
6.21
14 O
112
27.87
C40NH2108,HO,NO5.... 402
100.00
Iodomercurate of potassium precipitates papaverine, even from very
dilute solutions, yellowish-white and amorphous (Delffs).
Chloroplatinate of Papaverine. Aqueous hydrochlorate of papa-
verine produces with bichloride of platinum a yellow pulverulent pre-
cipitate, insoluble in water and alcohol (Merck).
40 C......
N
22 H
80
Pt
3 Cl
C40NH2108,HCl,PtCl²
at 100°.
Merck.
240
4.4.02
43.71
14
2.57
22
4.04
4.55
64
11.74
98.7
18.10
17.82
106.5
19.53
5.15.2
100.00
...
Papaverine dissolves with difficulty in cold alcohol and ether, but
more easily in the hot liquids (Merck).
Oxynitrazo-nucleus C40NXH1808
Nitropapaverine.
C40N2H20012 C40NXH1808,H2.
=
ANDERSON. Trans. Roy. Soc. Edinb. 21, 1, 195; Ann. Pharm. 94,
237.
On adding to a solution of papaverine in dilute nitric acid an excess
of concentrated nitric acid, the liquid assumes a dark-red colour,
evolves red vapours, and deposits orange-coloured crystals of nitrate
of nitropapaverine. The crystals are decomposed by boiling aqueous
ammonia, and the flocks which separate are crystallised from boiling
alcohol.
Pale reddish-yellow needles, which give off 2.29 p. c. of water
(= 1 at.) when heated. Has an alkaline reaction.
BROMOPAPAVERINE.
261
Dried.
Anderson.
40 C
240
62.50
62.31
2 N
28
7.29
20 H
20
5.20
5.21
12 O
96
25.01
C40NXH2008
384
100.00
Nitropapaverine melts when heated, and afterwards explodes.
With oil of vitriol it exhibits the purple coloration of papaverine.
When heated with boiling strong caustic potash, it evolves traces of a
volatile base.
Nitropapaverine is insoluble in water. It neutralises acids com-
pletely, forming pale reddish-yellow salts, but little soluble in water.
From solutions of the salts, ammonia precipitates the base in pale-
yellow flocks.
-Sulphate of Nitropapaverine forms small prisms, slightly soluble in
water; the hydrochlorate, pale-yellow needles, little soluble in water,
but easily soluble in aqueous hydrochloric acid and in alcohol.
Nitrate of Nitropapaverine. — Yellow four-sided tables, orange-
yellow in an impure state. Very slightly soluble in cold, and but little
more so in boiling water; easily soluble in aqueous acids and in alcohol
and ether.
40 C
3 N
21 H
18 O
C40NXH 2008, HO,NO5
Crystals.
240
Anderson.
53.69
53.68
42
9.38
21
4.69
4.95
144
32.24
447
100.00
Chloroplatinate of Nitropapaverine.
40 C
2 N
21 H
12 O
3 Cl
Pt
Pale-yellow precipitate.
Anderson.
240
40.66
40.47
28
4.72
21
3.55
3.80
N
96
16.26
106.5
18.09
98.7
16.72
16.56
100.00
C40NXH2008, HCl,PtCl².... 590·2
Nitropapaverine dissolves in alcohol and in ether.
Oxybromazo-nucleus C40NBrH1808.
Bromopapaverine.
C40N BrH2008 = C40NBгH1808, H².
ANDERSON. Trans. Roy. Soc. Edinb. 21, 1, 195; Ann. Pharm. 94, 238.
Bromine-water is dropped into aqueous hydrochlorate of papaverine
262
PRIMARY NUCLEUS C40H28; OXY-AZO-NUCLEUS C40N2H22O4.
till the precipitate of hydrobromate of bromopapaverine, which disap-
pears again at first, remains permanent. The precipitate is decom-
posed by ammonia, and the bromopapaverine is crystallised from boil-
ing alcohol.
Small white needles.
Anderson.
40 C
240
57.41
57.23
N
14
3.34
20 H
20
4.78
5.02
80
64
15.34
Br
80
19.13
19.45
100.00
C40NBrH200s........ 418
Bromopapaverine is insoluble in water.
Hydrobromate of Bromopapaverine. (See above.) Yellow precipitate,
deposited from boiling alcohol as a crystalline powder. Melts and
decomposes when heated. Insoluble in water.
Anderson.
40 C
240
48.09
48.36
N
14
2.80
21 H
21
4.20
4.35
80
64
12.85
2 Br
160
32.06
32.48
100.00
C40NBrH2008........ 499
Hydrochlorate of bromopapaverine dissolves slightly in water.
Bromopapaverine dissolves easily in alcohol and ether.
Oxy-azo-nucleus C40N2H2204.
Quinine.
C40N2H2404 C40N2H2204, H2.
On Cinchonine and Quinine:
PELLETIER & CAVENTOU. Ann. Chim. Phys. 15, 291 and 337; Schw.
32, 413; 33, 62; J. Pharm. 7, 49.
GEIGER. Repert. 11, 79. — Mag. Pharm. 7, 41.
BUCHNER. Repert. 12, 1.
PELLETIER & DUMAS. Ann Chim. Phys. 24, 169; Mag. Pharm. 5, 164
and 243.
BAUP. Ann. Chim. Phys. 27, 323; Schw. 43, 471; N. Tr. 10, 2, 130.
0. HENRY & PLISSON. J. Pharm. 13, 268 and 369; N. Tr. 15, 2, 59
and 16, 1, 200; Berl. Jahrb. 29, 2, 113.
DUFLOS. Schw. 42, 306.
MERCK. N. Tr. 20, 1, 134.
LIEBIG. Pogg. 21, 23. · Ann. Pharm. 26, 47; 29, 63.
REGNAULT. Ann. Pharm. 26, 11; J. pr. Chem. 16, 258. - Ann. Pharm.
29, 58.
·
QUININE.
263
LAURENT. N. Ann. Chim. Phys. 19, 363; Ann. Pharm. 62, 98; J. pr.
Chem. 40, 403; Kopp's Jahresber. 1847 and 1848, 615.
PASTEUR. Compt. rend. 36, 26; N. J. Pharm. 23, 123; J. pr. Chem.
58, 376; Pharm. Centr. 1853, 95; Ann. Chim. Phys. 38, 437; Compt.
rend. 37, 110; N. J. Pharm. 24, 161; J. pr. Chem. 60, 129; Ann.
Pharm. 88, 209; Chem. Gaz. 1853, 321. Compt. rend. 37, 162;
J. pr. Chem. 60, 134; Ann. Pharm. 88, 211; Chem. Gaz. 1853, 401.
Abstract of the whole of the memoirs: Kopp's Jahresber. 1853, 419.
SCHÜTZENBERGER. Compt. rend. 46, 894; J. pr. Chem. 74, 76.
Compt. rend. 46, 1065; J. pr. Chem. 74, 227; Ann. Pharm. 108,
347; Chem. Centr. 1858, 541. Compt. rend. 47, 81; J. pr. Chem.
75, 124; Ann. Pharm. 108, 350; Chem. Centr. 1858, 678; Compt.
rend. 47, 233; J. pr. Chem. 75, 125; Ann. Pharm. 108, 351; Chem.
Centr. 1858, 677. Compt. rend. 47, 235; J. pr. Chem. 75, 254;
Ann. Pharm. 108, 353; Chem. Centr. 1858, 684. Abstract of the
whole of the memoirs: Kopp's Jahresber. 1858, 369.
On Quinine alone:
ROBIQUET. Ann. Chim. Phys. 17, 316; N. Tr. 6, 2, 30.
STRATINGH. Scheikund. Verhandl. Gröningen, 1822; abstr. Repert. 15,
139.
PELLETIER. J. Pharm. 11, 249; N. Tr. 11, 2, 140.
DUFLOS. Berl. Jahrb. 27, 1, 100.
STRECKER. Ann. Pharm. 91, 155; abstr. J. pr. Chem. 62, 445; Pharm.
Centr. 1854, 661; N. Ann. Chim. Phys. 42, 369; Compt. rend. 39,
59; Phil. Mag. [4], 8, 123; Kopp's Jahresber. 1851, 505.
Cinchona-resin of the older chemists.
Chinin.
Fourcroy (Ann. Chim. 8, 113; 9, 7) distinguished in cinchona-barks
a peculiar resinous extractive, which Vauquelin (Ann. Chim. 59, 130 and
148) prepared in a purer form as Chinastoff. The same substance was
obtained in a still purer state by Gomez (Edinb. Med. and Surg. J.
1811, art. 420) and Pfaff (Schw. 10, 265).
Pelletier & Caventou showed that the substance was of a twofold
nature, and consisted of quinine or cinchonine, according to the kind of
bark from which it was extracted. They showed further that the
brown or grey cinchona-barks contain a large quantity of cinchonine
with very little quinine; that Royal bark contains a large quantity of
quinine, with very little cinchonine, whilst the red bark contains the
two substances in about equal proportions. Guided by Sertürner's dis-
covery of the existence of organic salt-bases, they established the
basic nature of these substances, rendered very probable by previous
investigations, and investigated their compounds more exactly.
Schützenberger (Compt. rend. 47, 235) supposes the existence of a
second quinine, to which, from analyses of the substance itself and of
its platinum-salt and benzoyl-derivatives, he assigns the formula
C42N2H2804. When this quinine is precipitated from its acid solution
by ammonia, the liquid deposits, on standing for some time, scales com-
posed of long needles, larger than the needles of ordinary quinine.
A third quinine is said to form flat laminæ.
Source. In the barks of various species of Cinchona, accompanied
in all cases by larger or smaller quantities of cinchonine, and in some
264 PRIMARY NUCLEUS C40H28; OXY-AZO-NUCLEUS C40N2H2O*.
instances also by quinidine and cinchonidine. The different kinds of
bark contain, on an average, the following quantities of quinine and
cinchonine:
1. Brown or grey barks.
Huanoco
Loxa
Pseudoloxa
Huamalies
Jaen pallida
0-40 p. c. quinine, 170 p. c. cinchonine.
0.35
0.34
""
>>
""
""
0.35
0.66
""
>>
""
0.30
0.85
""
""
0.56
0.60
""
>>
""
2. Yellow or orange barks.
Royal or Calisaya bark.
a. plana
b. convoluta
Cinchona flava fibrosa
Cinchona flava dura
Pitayo
2.2 p. c. quinine, 0.28 p. c. cinchonine.
1.1
"
1.05
0.42
0.83
""
""
""
""
""
....
0.54
0.48
""
""
1.68
0.90
""
""
>>
""
3. Red bark.
Cinchona rubra
0.91 p. c. quinine, 1.05 p. c. cinchonine.
According to M'Ivor, a covering of moss on the bark during its
growth increases the percentage of the alkaloïds, and this observation
has been confirmed by De Vrij, who found in a young bark covered
with moss, 8.4 p. c. of alkaloïds.
For fuller statements see Handbuch viii. [2], 50, and Watts's Dictionary of
Chemistry i, 970; also tables of the percentage of alkaloïds in cinchona-barks,
by Pfaff (Berger's Monographie der Chinarinden, J. Chim. méd. 16, 192), Winckler
(Repert. 75, 323), Guillermond (N. J. Pharm. 44, 124; Pharm. Fiertelj. 13,
432; Chem Centr. 1864, 239), Wigand & Dronke (N. Br. Arch. 115, 231); for a
summary of the earlier statements, see Handwörterbuch, 2nd ed. 2, [2] 989.
See also Karsten (Berl. Acad. Ber. 1858, 260; J. pr. Chem. 74, 66; Kopp's
Jahresber 1858, 364), who found the percentage of alkaloids in the same kind
of bark to vary greatly with its age and locality. - Concerning East Indian
barks, see Howard (N. Br. Arch. 115, 249), De Vrij (N. Jahrb. Pharm, 14, 243; and
further Pharm. Trans., 5, 593; 6, 15; Pharm. Viertelj. 14, 221 and 227). The
leaves of cinchona, especially the older leaves, contain quinine (Ander-
son, Pharm. Viertelj. 13, 593); the roots are richer in alkaloids than
the bark and contain as much as 8.66 p. c. (De Vrij).
Preparation of Cinchonine and Quinine. Any one of the true
cinchona-barks is boiled with water containing a little sulphuric or hy-
drochloric acid; it is then pressed between linen cloth, and the residue
is boiled with fresh quantities of acidulated water so long as the liquid
acquires a bitter taste. The united decoctions, which contain sulphate
or hydrochlorate of quinine and ciuchonine, together with colouring
matter, tannin, cinchona-red, kinic acid, quinidine, cinchonidine, and
lime, are clarified, either by allowing them to deposit and decanting the
clear liquid, or by filtration, and after partial evaporation, are mixed
with sufficient ammonia, potash, or soda to produce a slight alkaline
reaction. Or better, since an excess of these alkalis dissolves the
bases, the liquid is boiled with excess of lime (or magnesia); the cold
liquid is thrown upon a filter; and the residue is washed with a little
cold water and dried. This residue consists of impure quinine and
cinchonine, and where lime or magnesia is employed, the excess of
QUININE.
265
these bases, intimately combined with colouring matter, tannin, and
cinchona-red, and where sulphuric acid and lime are used, together also
with sulphate of lime. It is exhausted several times with boiling
alcohol of sp. gr. 0.84 (and in the case of quinine also with weaker
alcohol); the liquid is filtered hot; the filtrate is distilled to remove
the greater part of the alcohol; and the residue, which still contains
cinchona-red and other colouring matters, is neutralised with sulphuric
acid and evaporated to crystallisation, whereupon the greater part of
the sulphate of quinine crystallises out, whilst à portion remains in the
mother-liquor, together with sulphate of cinchonine and a brown sub-
stance. The mother-liquor, separated from the crystals as far as
possible, is precipitated with carbonate of soda; the precipitate is dis-
solved in alcohol, and the solution is evaporated, whereupon crystals
of cinchonine are obtained.
A special mode of preparation. One kilogramme of coarsely
powdered calisaya bark is steeped in water containing 60 grammes of
hydrochloric acid, and on the following day the liquid is heated to
boiling and boiled for two hours. A second and a third decoction are
made, with addition of 30 grammes of hydrochloric acid each time, and
a fourth decoction, made without any addition of acid, serves to ex-
haust fresh bark. The hot acid decoctions are mixed with a slight
excess of carbonate of soda; the precipitate thereby formed is col-
lected on a close linen filter, pressed, dried, triturated, and treated five or
six times with warm alcohol of 85°; and the tincture is exactly neutralised
with sulphuric acid, filtered, and partially distilled: the residue then
solidifies in a crystalline mass on cooling. The crystals, after being
freed from the black mother-liquor by pressing, are suspended in warm
water, mixed with half their weight of bone-black, and set aside for a
day: they are then dissolved in 25 parts of boiling water, and the
solution is filtered: on cooling, it deposits sulphate of quinine in fine
white crystals (N. J. Pharm. 45, 236).
"
Purification of Quinine and Cinchonine. 1. Sulphate of quinine
may be obtained white by repeated crystallisation, the colouring
matters remaining in the mother-liquors. 2. Animal charcoal, purified
by acids, removes from the aqueous solutions of both salts a large
quantity of brown colouring matter.-3. On precipitating the
sulphates by excess of lime, boiling the dried precipitate with alcohol,
and filtering, a large quantity of colouring matter remains with the
lime. — 4. When the impure quinine or cinchonine remaining from the
distillation of the alcoholic solution, is neutralised with hydrochloric
or acetic acid, and mixed in the former case with protochloride of tin,
or in the latter with neutral acetate of lead, compounds of the oxides
of these metals with colouring matter are precipitated. From the
filtrate the excess of metallic salt is removed by means of hydro-
sulphuric acid or by hydrosulphate of an alkali not in excess; and the
quinine and cinchonine, in a purer state, are then precipitated by
alkalis. 5. Hydrate of alumina, formed by adding alum to aqueous
solutions of the sulphates, and precipitating with somewhat less than
an equivalent quantity of carbonate of potash, carries down with it a
large quantity of colouring matter.-6. Cinchonine may be purified
by recrystallisation from hot alcohol, the colouring matter remaining
in the mother-liquor, according to Stoltze, more especially in presence
of a little ammonia.
266 PRIMARY NUCLEUS C40H28; OXY-AZO-NUCLEUS C40N2H22O4.
Separation of Quinine and Cinchonine. — 1. Sulphate of quinine is
much less soluble in water and far more easily crystallisable than
sulphate of cinchonine, which remains in the mother-liquor. -
2. Quinine is much more easily soluble than cinchonine in cold alcohol,
so that the greater part of the latter substance crystallises from a hot
saturated solution of the two, whilst the whole of the quinine remains
in solution with a little cinchonine. From a mixture of the two
alkaloïds, cold weak alcohol takes up almost exclusively quinine. -
3. Quinine is much more freely soluble than cinchonine in ether.
Commercial sulphate of quinine, even from the best works, contains
traces of quinidine or similar bases. De Vrij and Alluard (N. J.
Pharm. 46, 194) purify it by converting into sulphate of iodoquinine,
which salt, on account of its low solubility, admits of easy separation
from foreign bases. They decompose the sulphate of iodoquinine with
aqueous hydrosulphuric acid, precipitate the cold aqueous solution with
caustic soda, wash the soft resinous precipitate of quinine, and dry it,
first in the air, then over the water-bath; it then becomes hard and
friable.
Amongst numerous other methods of preparation the following
peculiarities occur:—
a. Exhaustion of the bark. To get rid, as far as possible, of tannin,
colouring matter, cinchona-red, and kinic acid, Badollier (Ann. Chim.
Phys. 17, 273) first boils the bark with water containing potash,
and rejects this decoction. Cassola (J. Pharm. 15, 167; Br. Arch.
30, 298), and Scharling (Pogg. 24, 182) and lately also Herring
(Dingl. 132, 211; J. pr. Chem. 62, 505) proceed in a similar manner.
This plan, however, must occasion a loss of quinine and cinchonine,
seeing that they are soluble to a slight extent in alkalis (Stoltze),
unless the alkaloids be recovered from the alkaline decoction, as in
Herring's process. Gilbert exhausts the bark with ammonia; Stoltze
(Schw. 43, 457) and Bischoff (Mag. Pharm. 27, 135) with lime-water,
from which the latter chemist recovers the kinic acid.
In the foregoing processes, the quantity of hydrochloric or sul-
phuric acid used in the extraction of the bark, amounts, at most,
Processes are
to 3 or 5 per cent. of the weight of the bark.
given, however, with quantities of acid varying from 1 to 30 per
cent. When too much acid is used, the excess may be removed by
means of chalk, whereby a large quantity of colouring matter is pre-
cipitated. Henry employs also wood-vinegar for the extraction ;
Stratingh a mixture of sulphuric and hydrochloric acids, so that less
sulphate of lime may be formed afterwards. O. Henry (J. Pharm.
21, 212; Ann. Pharm. 15, 300) exhausts with alcohol containing
sulphuric acid; Veltmann (Schw. 54, 381) with alcohol containing
hydrochloric acid. Inasmuch as acids at boiling heat dissolve a large
quantity of foreign matters from the bark, Stoltze recommends cold
extraction in a percolator, or exhaustion at 30°. In the cold, six times
repeated exhaustion is necessary.
b. Precipitation. Hermann (Mag. Pharm. 25, 71) recommends the
addition of protochloride of tin, to remove colouring matter before pre-
cipitating the bases. Pelletier & Caventou decolorise the mother-liquors
with neutral acetate of lead, and Stratingh employs alum for the same
purpose. See purification 4 and 5 (p. 265). - Hydrate of lime is generally
employed as the precipitant. By its use, however, as well as by the
QUININE.
267
use of potash, and more particularly of ammonia, a loss of substance
is incurred, in consequence of the solubility of quinine in lime-water
and chloride of calcium. This loss may be prevented by the employ-
ment of caustic soda (Calvert, N. J. Pharm. 2, 388). Or, after adding
the hydrate of lime, the liquid is filtered as soon as it exhibits an alka-
line reaction (Henry). Geiger precipitates with a large excess of car-
bonate of soda, in which quinine is nearly insoluble, whilst a large
quantity of colouring matter remains in solution.
C. Further treatment of the Precipitate. After precipitating with
lime, the precipitate must not be exposed to the air, lest by the action
of carbonic acid on the lime-compound, some of the colouring matter
may be rendered soluble (Franquinet, Repert, 33, 92). A preliminary
purification may be effected by dissolving the precipitate in acids,
Lespecially acetic acid (A. Erdmann)], and again precipitating, the
colouring matters then remaining undissolved (Pessina). Hydrochloric
acid, in quantity not sufficient for complete solution of the precipitate,
leaves the greater part of the colouring matter undissolved, and on
carefully adding ammonia [or potash (Bischoff)] to a solution in excess
of acid, the colouring matter is precipitated first (Rabourdin, N. J.
Pharm. 39, 408).
Or the precipitate is boiled with solution of sulphate of copper,
whereby the cinchona-bases are converted into sulphates, with simul-
taneous precipitation of a basic copper-salt; the excess of sulphate of
copper is then got rid of by means of hydrosulphuric acid, and the
alkaloids are precipitated by ammonia (Klötte-Nortier, N. Br. Arch.
86, 165). In this process colouring matter is likewise dissolved
(Wittstein). The alcohol employed for exhausting the precipitate
must be decanted cold in the case of quinine, hot in the case of cin-
chonine (Duflos). Thiboumery (N. J. Pharm. 16, 369) employs oil of
turpentine or coal-oil, Herring also benzene, for the exhaustion, these
substances dissolving quinine and giving it up again to dilute acids.
With precipitates free from lime, hot fatty oils may also be used. -
Charcoal containing lime occasions a loss of substance in acid solutions
(Winckler, Mag. Pharm. 19, 258).
Lebourdais (N. Ann. Chim. Phys. 24, 65; Ann. Pharm. 67, 251;
J. pr. Chem. 45, 363) boils 1 pound of powdered calisaya bark with
water containing sulphuric acid, and filters the decoction through
charcoal previously washed with water, whereupon the liquid runs
through colourless and tasteless. The washed and dried charcoal
boiled with alcohol of 85 p. c., gives up to that liquid the quinine,
which is recovered by evaporating the solution. When an alcoholic
extract of the bark is exhausted with water, and the aqueous liquid
is filtered, first through paper, and then through animal charcoal
purified by hydrochloric acid, the liquid running through is tasteless,
and the charcoal gives up quinine and resin to alcohol. The resin may be
removed by precipitation with neutral acetate of lead before filtering.
W. Clark (Lond. Journal of Arts, Feb. 1864, 94; Polyt. Notizbl. 15,
157; Kopp's Jahresber. 1860, 362) mixes the extract of the bark, pre-
pared with acidulated water, with not too great an excess of ammonia
or carbonate of soda, and boils it with commercial stearic acid, which
gradually takes up the alkaloids and rises with them to the surface of
the liquid in the form of a black cake. After cooling, the cake is boiled
with water containing sulphuric acid, which takes up the alkaloïds.
268 PRIMARY NUCLEUS C40H28; OXY-AZO-NUCLEUS C40N2H22O4.
The filtered liquid is neutralised with caustic potash, and again filtered
from the dark precipitate thereby produced; the sulphate of quinine
then crystallises out on cooling.
The residues of cinchona-barks used for pharmaceutical extracts
still yield quinine and cinchonine (Peters, N. Br. Arch. 46, 284;
Schlotfeldt, N. Br. Arch. 60, 186; Maillet, N. J. Pharm. 14, 352).
Estimation of Quinine and Cinchonine in Cinchona-barks. 1. Ten
grammes of the coarsely powdered bark are exhausted with water
containing sulphuric acid; to the extract magnesia in excess is added,
and the whole is evaporated to dryness over the water-bath. The
residue is triturated, the quinine is extracted by ether, and after-
wards the cinchonine by alcohol. The colourless extracts contain
almost pure alkaloïds; they turn slightly yellow only on evaporation,
and leave quinine or cinchonine with a small quantity of inseparable
bitter substance (C. Claus, Russ. Pharm. Zeitschr. 1, No. 34; Pharm.
Viertelj. 13, 244).—2. Forty grammes of the powdered bark, moistened
with water containing 2 p. c. of hydrochloric acid, are placed in a per-
colator, and exhausted with slightly acidulated water, until the liquid.
flows off free from colour and bitterness, for which purpose 200 to 250
grammes are necessary. The extract is then shaken with 5 or 6
grammes of caustic potash, and 10 to 15 grammes of chloroform, and
set aside for half an hour. The chloroform, which has taken up the
whole of the quinine, is separated, washed repeatedly with water by
decantation, and evaporated over the water-bath. The residue contains
the alkaloïds, contaminated with cinchona-red; it is dissolved in dilute
hydrochloric acid, filtered, and freed from cinchona-red by the cautious
addition of dilute ammonia. After filtering from the red-brown flocks,
the addition of more ammonia to the colourless filtrate throws down the
pure alkaloids (Rabourdin, Compt. rend. 31, 782; N. J. Pharm. 19, 11).
The cinchonine [in case it is taken up by the chloroform (Kr.)] and the qui-
nine are then separated by means of ether. A similar process is adopted
by Kleist (Pharm. Viertelj. 7, 584), and by O. Berg (Handwörterb, 2nd ed.
2 [2], 987) and Schacht (N. Jahrb. Pharm. 20, 166).-3. Fifty grammes
of the powdered bark are exhausted, first with alcohol of sp. gr. 0·87,
and afterwards with dilute hydrochloric acid, for which several days'
digestion are necessary. The alcoholic extract is evaporated; the acid
extract is added to the residue; and the whole is concentrated and
precipitated with phosphomolybdic acid. The precipitate, mixed with
hydrate of baryta, is dried and boiled with alcohol; the alcoholic liquid
is filtered and evaporated; and the residue is dissolved in dilute sul-
phuric acid. The acid solution shaken with ammonia and chloroform,
gives up to the latter liquid the quinine, which is left on evaporation
(De Vrij, N. Jahrb. Pharm. 14, 243).
For the separation of quinine, cinchonine, quinidine, and a fourth
base, which occurs in Java cinchona-bark (see below), the solution in as
small a quantity as possible of strong alcohol is neutralised with hydri-
odic acid; the hydriodate of quinidine, which separates after 24 hours,
in the form of a sandy powder, is removed by filtration; the filtrate is
mixed with caustic soda to alkaline reaction; and the cinchonine is
allowed to crystallise. On longer standing, cauliflower-like crystals of
the fourth alkaloïd also separate, and may be purified by crystallisation.
from alcohol. The mother-liquor, exactly neutralised with dilute sul-
phuric acid, and decolorised by animal charcoal, yields nearly colourless
sulphate of quinine (De Vrij).
QUININE.
269
a
For other methods of testing cinchona barks, see Tilley (Bull. des scienc. technol.
1828, 17; abstr. Schw. 54, 386), Göbel & Kerst (Schw. 54, 384), Tromsdorff (N.
Tr. 18, 2, 60), Duflos (Schw. 62, 310), O. Henry (J. Pharm, 16, 754; Repert. 37,
120), Marggraf (Pharm. Zeitschr. 1850, 81; Kopp's Jahresber. 1850, 616), A. Buchner,
sen. (Repert. (3) 8, 145), Winckler (Jahrb. pr. Pharm. 25, 133), O. Henry, jun.,
(N. J. Pharm. 24, 400; abstr. Pharm. Centr. 1854, 92), Riegel (N. Br. Arch. 70,
162), Faget (N. J. Pharm. 37, 13), Glénard & Guillermond (Compt. rend. 47, 831;
N. J. Pharm. 37, 5), Guillermond (N. J. Pharm. 41, 40).
Concerning the detection of quinine in the urine, see Robert (N. J. Pharm. 4,
197), Bonnewyn (N. J. Pharm. 27, 387), Kletzinsky (N. Repert. 2, 567; Pharm.
Centr. 1854, 239), Herapath (Phil. Mag. [4] 6, 171; J. pr. Chem. 61, 87). A portion
only of the quinine administered is found in the urine, the greater part being decom-
posed in the system (Herapath). See on the contrary, Briquet (Compt. rend. 27,
549).
The hydrate of quinine obtained by precipitating a solution of the
sulphate by potash or ammonia, may be dehydrated by fusion in a
vacuum, or by prolonged heating to 120°.
Properties. White, opaque mass, having a crystalline surface and
a concentric radiated fracture; fusible to a transparent liquid. When
rubbed with a cloth it becomes strongly negatively electric. Permanent
in the air, inodorous, very bitter, and antifebrile. Restores the blue
colour of reddened litmus paper (Pelletier & Caventou; Dumas). Exerts
a left-handed action on polarised light [a] r = 141.33° at 25° (De Vrij &
Alluard), 121-5° at 22.5°, and 129.59° at 16°, weaker, therefore, in
warm than in cold solutions. Acids increase the rotatory power, but
ammonia reduces it to the original amount (Bouchardat, N. Ann. Chim.
Phys. 9-213). [a] j in acetic or sulphuric solution 287.16° at 24°
(consequently [a]r 220-15°) (De Vrij & Alluard, N. J. Pharm. 46, 192;
Compt. rend. 59, 201). Prevents putrefaction (Robin, Compt. rend.
32, 650). Not sublimable.
=
Pelletier
& Dumas. Regnault. Liebig. Laurent. Strecker.
73.38.... 74-09 73.41 74.05
8.55
....
Fused.
40 C.
240
74.07
75.02
....
2 N..
28
8.64
8.45
24 H
24
7.41
6.66
40
32
9.88
9.87
7.65 7.57 ... 7·10.... 7·50
10.42
C40N2H2404........ 324 100 00
100.00
100.00
....
...
According to Pelletier & Dumas, C20NH100; according to Regnault, C41N2H2504;
according to Laurent, C3NH20. The correct formula was deduced from Liebig's
analyses, and was doubled by Regnault to that given above. (See p. 201.)
Decompositions. 1. In the fire quinine turns brown, burns with
flame, evolving an aromatic odour, and leaves a bulky, easily com-
bustible charcoal (Duflos; Pfaff; Merck). No sublimate is obtained thereby
(Nesenbeck, Ann. Pharm. 6, 319). When hydrate of quinine is heated for a long
time in the air, a portion is sublimed, according to Stratingh, in the form of a yellow
powder. 2. Solutions of quinine-salts turn brown in sunshine (Geiger)
in a few hours (Pasteur). 3. They are violently acted on by the electric
current (Hlasiwetz & Rochleder). 4. With aqueous nitrate of potash
sulphate of quinine evolves nitrogen, and is converted into oxyquinine
(Schützenberger). — 5. A solution of quinine in strong nitric acid
becomes coloured on heating (Riegel), without forming picric acid
(Liebig). — 6. A solution in oil of vitriol immediately colours chromate
270
PRIMARY NUCLEUS CH28; OXY-AZO-NUCLEUS C40N2H22O4.
of potash dark-green, with evolution of gas (Riegel; Eboli). -
7. Permanganate of potash acts upon quinine in the cold and more com-
pletely at boiling heat, forming carbonate and nitrate of potash, and a
peculiar acid (Cloez and Guignet, Compt. rend. 47, 710). An aqueous
solution containing to 1 per cent. of quinine is not acted on (Menier).
8. Peroxide of lead colours a solution of quinine in sulphuric acid grey-
brown (Riegel); when employed in the same way as with cinchonine,
it produces a blood-red bitter substance, soluble in alcohol and ether,
and also without decomposition, in sulphuric and nitric acids, forming
solutions of its own colour; it produces also blood-red crystals, which
separate from an alcoholic solution on spontaneous evaporation, and
dissolve in alcohol and ether with violet, and in acids with red colour;
and, at length, as the ultimate product of oxidation, a mixture of acids
is obtained (E. Marchand, N. J. Pharm. 4, 27). See also J. Chim. méd.
20, 363.
9. In contact with zinc and dilute sulphuric acid, quinine takes up
2 at. water, and is converted into hydroquinine (Schützenberger).
10. When heated to 240 or 260° with water in a sealed tube, it forms
chinoline (Reynoso, Compt. rend. 34, 795).
11. The colourless solution [yellow according to Guy] of quinine in
oil of vitriol acquires a yellowish-brown colour when heated (Riegel);
fuming sulphuric acid colours quinine yellowish-green (Schlienkamp),
forming quinine-sulphuric acid (Schützenberger). Salts of quinine,
heated alone, or with sulphuric acid and water, behave in the same
manner as salts of cinchonine, save that quinicine is formed instead of
cinchonicine (Pasteur). — 11a. Anhydrous phosphoric acid, heated with
quinine to 140°, produces a brisk evolution of gas, which burns with
a pale-yellow flame, and is but slightly soluble in water (Wertheim).
12. Quinine assumes a dirty-yellow colour in vapour of iodine
(Donné). When triturated with iodine, it behaves in the same way as
cinchonine (Thompson). Pelletier's iodoquinine is obtained in the
same manner as iodocinchonine, and resembles that body, but contains
69.69 p. c. of quinine and 30-31 of iodine (equal numbers of atoms =
71-7 p. c. quinine, 28.3 iodine). — Quinine is completely precipitated
by biniodide of potassium (Wagner). It is decomposed by aqueous
periodic acid, with liberation of iodine (Bödeker). When quinine, or
its sulphate, is warmed with an equal quantity of iodic acid, an explo-
sive evolution of gas takes place (Brett, N. J. Pharm. 27, 116; N.
Repert. 4, 329).
Quinine, sulphuric acid, and iodine together yield sulphate of iodo-
quinine (Herapath). See p. 311.
14. Quinine exposed to a current of dry chlorine takes up a large
quantity of the gas; according to André, it assumes a carmine-red
colour in a few seconds, and becomes soluble in water; but according
to Pasteur, it turns greenish, and then gives up to boiling or cold
water only a small quantity of a substance having an acid reaction,
whilst the remainder behaves like the body formed by the action of
chlorine on quinine suspended in water. Quinine suspended in
water is reddened by chlorine (André; Pelletier). A solution of
quinine in 400 parts of water acidulated with sulphuric acid, is not
coloured or rendered turbid on passing chlorine into it for 10 minutes
(Lepage, J. Pharm. 26, 140).
QUININE.
271
3
4
A solution of the carmine-red substance in water is rendered green
by ammonia, provided it has not been too strongly heated, or the
chlorine allowed to act too long. On passing chlorine for or 1 hour
into a litre of water in which 5 grammes of quinine are suspended,
the quinine dissolves completely, and the liquid afterwards becomes
turbid from the formation of a white precipitate; after 1 hour the
green colour is no longer produced by ammonia. During the reaction
a tear-exciting odour is evolved. The white precipitate turns brownish
on drying, and is converted by hot water into a soluble reddish-brown
substance. It dissolves with difficulty even in strong acids, but is very
easily soluble in alkalis; the solution in alcohol is acid and very bitter.
A further quantity of this substance is obtained by partially
neutralising the liquid (André, Ann. Chim. Phys. 71, 195). The follow-
ing statements of Pelletier differ from the foregoing: on passing
chlorine into quinine suspended in water till solution is effected, the
liquid assumes a rose colour, changing to violet, and afterwards to
dark-red; on continuing the stream of gas, the liquid becomes paler
and deposits a sticky substance, more of which is obtained by
neutralising the acid filtrate with ammonia, and evaporating. Sulphate
of quinine suspended in water is dissolved by passing a stream of
chlorine into it, the liquid passing through yellow and red to green,
and afterwards depositing grey flocks, after the removal of which,
ammonia throws down only a slight precipitate. If the stream of
chlorine be interrupted when the liquid has acquired a red colour,
ammonia throws down from the liquid the same sticky precipitate.
This precipitate, when freed from acid by boiling water and dried, is
friable, brown, and less bitter than quinine; it is deposited from an
alcoholic solution, on spontaneous evaporation, in the form of a granular
powder, which seems, under the microscope, to consist of microscopic
four-sided prisms. It is very slightly soluble in cold, and somewhat
more freely in boiling water, and in hot dilute acids, from which it is
deposited on cooling; it dissolves also in dilute and in absolute alcohol
(Pelletier, J. Pharm. 24, 161; Ann. Pharm. 29, 54; J. pr. Chem.
14, 180).
14a. When chlorine-water and then ammonia are added to a solution of
a quinine-salt, a green precipitate is produced, which is dissolved by more
ammonia to a fine emerald-green liquid. Exact neutralisation of the
liquid colours it sky-blue, changing to violet or fiery-red on further
addition of acid; ammonia restores the green colour (André, J. Pharm.
22, 132; Meeson, Phil. Mag. 1835, 6, 158; Soubeiran & Henry). In
this way [especially by employing an ethereal solution (Leers)] mere
traces of quinine may be recognised; quinidine, however, exhibits the
same reaction.
The green colour is not produced by other alkalis instead of am-
monia. It is not produced when the chlorine-water is allowed to act
too long, nor with all proportions of chlorine water and ammonia, since
with too little chlorine-water ammonia throws down a greenish-white
precipitate, and with too much it produces a yellow coloration
(Brandes). Reddish-green or brown colours may also be produced
(André).
When 200 grains of sulphate of quinine are dissolved in 80 ounces
of chlorine-water, and the solution is mixed at once with 10 ounces of
ammonia-water, a green precipitate is produced, amounting to about
60 grains, whilst the liquid remains of a deep green colour. The pre-
272 PRIMARY NUCLEUS C40H; OXY-AZO-NUCLEUS CON÷H22O¹.
cipitate is Brandes and Leber's dalleiochine: the colouring matter of the
solution is not removed by agitation with ether, nor in an unchanged
state by other means, but splits up on evaporation into red rusiochine,
soluble in alcohol, and dark-brown melanochine, insoluble in water and
alcohol.
a. Dalleiochine. Green granular powder, bitter and inodorous.
Contains 58.76 p. c. C., 9.26 N., 6·72 H., 25.26 O., and no chlorine
[C4°N³H270¹² = 59.2 p. c. C., 10-3 N., 6·6 H. (Kr.)] When heated it
behaves like quinine. It is insoluble in cold, and nearly so in boiling
water, but easily soluble, with dark red-brown colour, in dilute acids,
from which it is precipitated unchanged, of a green colour, by am-
monia or carbonate of potash. It dissolves in alcohol, but not in
ether.
B. Rusiochine. When the green solution filtered from dalleiochine
is evaporated in the air, there remains a dark-brown residue, from
which water takes up sal-ammoniac and rusiochine, while melanochine
remains undissolved. The solution is evaporated; the sal-ammoniac
is removed by repeated solution in alcohol; and the rusiochine is ob-
tained on evaporation in the form of a fine dark-red hygroscopic
bitter mass. It contains 43·51 p. c. C., 6·38 N., 9.49 H., and 40·62 O.
It dissolves in water and alcohol, and is precipitated from its aqueous
solution by ammoniacal lime- and baryta-salts, and by basic acetate of
lead and chloride of tin.
A
7. Melanochine.
Black-brown, inodorous and tasteless powder,
containing 53.71 p. c. C., 7·45 N., 5·87 H., and 32.97 0. Burns, when
heated, without melting, evolving ammoniacal vapours. Dissolves in
potash and ammonia, but not in water, alcohol, or ether (Brandes &
Leber, N. Br. Arch. 13, 65; 15, 259). On quinine-green, see also
André (Ann. Chim. Phys. 71, 198), Köchlin (Dingl. 159, 66; Chem.
Centr. 1861, 224).
-
When aqueous sulphate of quinine is mixed with chlorine and ferrocy-
anide of potassium in succession, there results a dark-red coloration, pass-
ing in a few hours to green, especially on exposure to light (A.Vogel, jun.,
Ann. Pharm. 73, 221). When water is poured upon sulphate of quinine,
in such quantity that a large quantity of the salt remains undis-
solved, a few drops of the solution mixed with an equal quantity of
strong chlorine-water free from hydrochloric acid, and finely-powdered
ferrocyanide of potassium added a pale, rose-red coloration, passing to
very dark-red, is quickly produced: if a dilute solution of ferrocyanide
be used, the colour appears on addition of a drop of ammonia-water
(Vogel, Ann. Pharm. 86, 122; N. Repert. 2, 289). Instead of ferro-
cyanide of potassium, the ferricyanide may be employed, and instead of
ammonia, lime- or baryta-water, caustic alkalis, or their carbonates,
borates, or phosphates (Livonius; Vogel). Kletzinsky (N. Repert. 6,
66) mixes a hot saturated solution of ferricyanide of potassium with five
times its volume of saturated chlorine-water, adds ammonia to strongly
alkaline reaction, and mixes the filtrate with a solution of quinine to
which chlorine-water has been previously added, whereby a red or
violet colour is produced. Instead of pulverised ferrocyanide of potas-
sium, a cold saturated aqueous solution of that salt, mixed with an
equal quantity of water and th its volume of a strong aqueous solu-
tion of carbonate of ammonia, may be used (A. Vogel, N. Repert. 6, 65).
QUININE.
273
The red colour changes to green in the light: it is destroyed by mineral
acids, and less easily by vegetable acids, but is restored by ammonia
(Livonius, N. Br. Arch. 77, 6; 82, 287). In this way 10th of
quinine may be detected (Flückiger, Anal. Zeitschr. 1, 373).
15. Quinine boiled with a very strong solution of caustic potash,
gives off hydrogen and yields a distillate of chinoline (Gerhardt, Rer.
scient. 10, 186). When distilled with caustic potash, it behaves like
cinchonine (Gerhardt). The decomposition takes place at 170° or 180°;
at a lower temperature formate of potash is also produced (Wertheim,
Wien. Acad. Ber. 1849, 1, 263). —Quinine heated with caustic soda
does not form cyanide of sodium (Rochleder).-16. With iodide of
methyl, quinine forms hydriodate of methyl-quinine, which crystallises
easily on cooling from solution in boiling water (Stahlschmidt, Ann.
Pharm. 90, 218).- 17. With chloride of acetyl and chloride of benzoyl,
acetyl-quinine and benzoyl-quinine are obtained, the former substance
resembling in every respect the corresponding compound of cinchonine
(Schutzenberger).
—
-
Combinations. With Water. A. Hydrate of Quinine. Quinine,
dehydrated by fusion in a vacuum, takes up 3 to 4 per cent. of water,
when immersed therein becoming white and friable.
a. With 2 at. water. When freshly precipitated and washed
quinine is spread out and exposed to the air, and frequently moistened,
the amorphous precipitate is slowly transformed into crystals, which
dissolve in warm alcohol, crystallise again on cooling, and give up their
water of crystallisation at 130° (van Heijningen, Scheik. Onderz. 5, 319;
Lieb, Kopp's Jahresber. 1849, 374).
van Heijningen.
C40N2H2404
2 HO
324
94.74
18
5.26
5.07
C40N2H240 + 2 aq.
342
100.00
....
This hydrate forms van Heijningen's Gamma-quinine. It dissolves
less easily than quinine in alcohol, and forms a mono-sulphate which
differs from the ordinary salt, and loses 4.47 p. c. of water at 130° (2 at.
= 4.61 p. c. HO). De Vrij (N. Jahrb. Pharm. 14, 268) did not succeed.
in preparing it.
b. With 6 at. water. Ordinary hydrate of quinine. Obtained by
precipitating aqueous quinine-salts with pure alkalis, washing the
precipitate, and drying it in the air. Loose, white, easily pulverisable
mass, melting to a colourless oil at 120° (Duflos), and losing its water at
120-130°, after which it solidifies to a translucent resin on cooling, or
when carefully melted in a vacuum, to a crystalline mass.
Regnault. van Heijningen
Fused. at 110-130°.
at 130°.
C40N2H2404
6 HO
Air-dried.
324
54
....
85.72
14.28
13.46
14.19
C40N2H2404 + 6 aq. 378
100.00
14.27
According to Kiessling (Pharm. Viertelj. 8, 339) precipitated and air-dried
quinine loses 3.92 p. c. of water at 100°; it then contains 7.16 p. c. of nitrogen, and
VOL. XVII.
T
274
PRIMARY NUCLEUS C40H28; OXYAZO-NUCLEUS CON2H2204.
150° is, therefore, the hydrate with 6 at. water (calc. 7.41 p. c. N.). At 100° to
it further loses 1.92 p. c. in weight, probably partly volatilised quinine, and melts
at about 196°. — According to Hanamann (Pharm. Viertelj. 12, 526), when a perfectly
cold solution of sulphate of quinine in water containing sulphuric acid is precipitated
by ammonia, and the precipitate is washed and dried in the air, a very light powder
is obtained, melting to a glassy colourless mass, and losing 20 p. c. of water at 120°.
If the solution be precipitated hot, the precipitate runs together and becomes glassy,
and on drying forms a horny mass, losing 8.75 p. c. of water at 120°. See also
Wittstein (Pharm. Viertelj. 12, 258). According to Magouty (J. Chim. méd. 16,
244) quinine becomes anhydrous at 60°. According to Duflos, the hydrate thrown
down by alkalis loses 4 p. c. of water on melting at 120°.
S
Crystallised Hydrate of Quinine separates from a solution in alcohol
of 40° to 42° B. on evaporation in dry cold air, in tufts of silky
needles, whereas on evaporating a solution in alcohol of 38° B., or on
mixing the alcoholic solution with water, an amorphous hydrate is ob-
tained, drying up to a transparent resin, which melts at 90° (Pelletier
Caventou; Dumas). From absolute alcohol, van Heijningen obtained
a resin with few crystals. A hot aqueous solution containing a little
ammonia, yields fine needles on prolonged standing (Liebig; van
Heijningen). Duflos and Magouty also obtained crystals, the former
from alcohol, the latter from water. See also the behaviour of the salts
towards carbonate of ammonia.
Quinine dissolves in 364 parts of cold water (Duflos); in 480 parts
of water at 18-75° (Abl); in 200 parts (Pelletier & Caventou), 267
parts (Duflos), of boiling water. It dissolves easily in water con-
taining sal-ammoniac (Calloud).
Quinine does not combine with sulphur (Pelletier). A solution in
30 to 35 parts of bisulphide of carbon solidifies in a day or two to a
transparent, very firm jelly (Lepage, N. Br. Arch. 97, 240).
Quinine is not insoluble in aqueous alkalis and in ammonia, espe-
cially when freshly precipitated. According to Duflos, however,
aqueous quinine is precipitated by pure alkalis and by their carbonates
and bicarbonates, so that the presence of acids probably influences
its solubility. It dissolves in 2,146 parts of lime-water (Calvert).
With Acids. Quinine neutralises acids completely, forming mono-
and bi-acid salts. The salts are, for the most part, more easily crys-
tallisable and less soluble in water than the salts of cinchonine. They
have a strong bitter taste, and frequently exhibit a pearly or silky
lustre. They are precipitated by alkalis and their carbonates, by the
hydrates of lime and magnesia, and by ammonia and carbonate of
ammonia, hydrate of quinine being thrown down in white flocks.
The precipitate produced by potash, ammonia, or carbonate of potash
is pulverulent, and not crystalline nor soluble, to any great extent,
even in excess of the precipitant; the sulphate alone yields a pre-
cipitate easily soluble in excess of ammonia (v. Planta). The hydrate
precipitated from a cold aqueous solution of the sulphate dissolves
in ammonia far more easily than the other cinchona bases; the
hydrate thrown down in clotty masses from strong solutions of the
salts is difficultly soluble (Kerner, Anal. Zeitschr. 1, 162). Carbonate
of ammonia added to sulphate of quinine throws down crystalline
needles after some hours; from the hydrochlorate and acetate it pre-
cipitates a heavy powder, which dissolves in excess of the precipitant,
and is deposited again in needles on standing for an hour (v. Planta).
Quinine expels ammonia from its salts when boiled therewith (Ma-
QUININE.
275
gouty). Bicarbonate of soda immediately throws down from strong
solutions of quinine-salts a white pulverulent precipitate (v. Planta),
and from dilute solutions, after some time, tufts of needles (Riegel);
but solutions of the salts in 300 parts or more of water are not pre-
cipitated by it, or are precipitated only after several hours, after the addi-
tion of tartaric acid (Oppermann; Riegel). Pentasulphide of potassium
throws down from boiling solutions of quinine-salts a red turpen-
tine-like mass (Palm). Cyanide of potassium colours the salts carmine-
red (Schwabe). Lime-water added in excess to quinine-salts dis-
solves the precipitate formed at first (Riegel; Calvert). Solutions of
quinine-salts containing excess of acid are highly fluorescent.
Carbonate of Quinine. - The precipitate thrown down by alkaline
carbonates from quinine-salts retains a little of the precipitant, but
is free from carbonate of quinine, since it does not evolve carbonic
acid when heated (Langlois, Ann. Pharm. 32, 126). When the quinine
precipitated from 10 grammes of the sulphate by ammonia is suspended
in water, and carbonic acid is passed into the solution for an hour,
the quinine dissolves completely to an alkaline liquid, from which
crystals of carbonate of quinine are deposited on exposure to the air
for twenty-four hours. By spontaneous evaporation of the mother-
liquor, quinine is obtained free from carbonic acid. — Translucent
needles, having an alkaline reaction, efflorescing rapidly in the air, and
decomposing at 110°, with liberation of carbonic acid; they are soluble
in alcohol, but insoluble in ether (Langlois, N. Ann. Chim. Phys. 41,
89; Ann. Pharm. 88, 320).
C40N2H2101
Crystals.
Langlois.
324
80.19
80.45
44
10.89
10.58
36
8.92
8.97
C40N2H2¹04,2HO,2CO² + 2 aq.
404
100.00
100.00
2 CO2
4 HO
Borate of Quinine. A solution of quinine in hot aqueous boracic
acid yields crystalline granules on cooling; by spontaneous evapora-
tion with an excess of boracic acid, a varnish is obtained (Serullas,
Ann. Chim. Phys. 45, 282).
Hypophosphite of Quinine.-100 parts of sulphate of quinine are
heated to 94° with 6,000 parts of water and 38.7 parts of hypophos-
phorous acid; a quantity of hypophosphite of baryta barely sufficient
for the complete decomposition of the sulphate is then added, and the
liquid is filtered and left to crystallise. The mother-liquor and wash-
water yield colourless crystals only when cautiously evaporated. -
Light, very loose mass, having a pure bitter taste. Melts and turns
brown at 150°, with loss of water. Dissolves in 60 parts of water at
15.5°, and more easily in boiling water (L. Smith, Amer. J. Pharm.
31, 285 and 32, 410; Zeitschr. Ch. Pharm. 5, 159; J. pr. Chem. 83, 127).
C40N2H240+......
PO
3 HO
324
83.09
39
10.00
27
6.91
{
100·00
C40N2H2404,PH³0+.... 390
L. Smith.
83.00
10.09
a. 2·30
b. 4.60
99.99
Uor M
T 2
276
PRIMARY NUCLEUS CH28; OXYAZO-NUCLEUS CN2H22O¹.
-
Smith gives the formula CN2H4O¹,PHO² + 2 aq., and distinguishes a as
hydrate-water, b as water of crystallisation. The formula of the salt, therefore,
remains doubtful (Kr.).
Pyrophosphate of Quinine. Obtained by precipitating hydrochlorate
of quinine with ignited phosphate of soda (Winckler, Repert. 41, 418).
Phosphate of Quinine. Phosphate of soda throws down from cold
aqueous solutions of hydrochlorate or acetate (but not from sulphate)
of quinine, a dense precipitate, which soon turns crystalline (v. Planta).
A hot solution of sulphate or hydrochlorate of quinine, mixed with a
slight excess of phosphate of soda, deposits on cooling a white crys-
talline mass, very slightly soluble in water. After drying in the air it
forms a loose mass, made up of microscopic four-sided prisms. Con-
tains 12.38 p. c. of phosphoric acid, and 4.56 p. c. of water, which is
expelled at 100° (Winckler, Repert. 34, 260; 41, 418; 99, 20). Dis-
solves very easily in hydrochloric acid (v. Planta).
The quickly formed solution of quinine in warm aqueous phosphoric
acid solidifies on cooling to a mass of needles. Dilute solutions yield
radiated groups of delicate, silky needles, which unite into a mass on
drying. Neutral. Loses 7.57 to 7.87 p. c. of water at 127°; other
crystals, of similar properties in other respects, lost 15.3 p. c. of water
on warming (10 at. = 7·1; 24 at. 15.6 p. c. HO) (Anderson, Ann.
=
Pharm. 66, 59).
120 C
6 N
78 H
18 O
2 PO5
at 100°.
Anderson.
720
61.65
61.85
84
7.19
78
6.69
6.81
144
12.32
142
12.15
1168
100.00
3C¹ºN²H²¹04,2PO³,6HO....
Anderson supposes the salt to contain 12 at. water of crystallisation, correspond-
ing to 8.4 p. c. The correctness of his formula is doubtful. See Kopp's Jahresber.
1847 and 1848, 616; Gerhardt (N. J. Pharm. 14, 52).
Hyposulphite of Quinine. Formed in a mixture of quinine, alcohol,
and hydrosulphate of ammonia, on standing in the air (How). Hypo-
sulphite of soda immediately throws down from a moderately concen-
trated aqueous solution of hydrochlorate of quinine, a dazzling white
precipitate, nearly insoluble in cold water, dull and crystalline after
drying (Winckler, Jahrb. pr. Pharm. 15, 286). A solution of the washed
precipitate in hot alcohol yields, on cooling, fine semi-transparent
needles, breaking up at 100°, from loss of water of crystallisation [4.57
to 4.67 p. c. = 2 at. (How)], into a powder, which is very electric
when warm (Wetherill, Ann. Pharm. 66, 150), -- Dissolves in 300 parts
of cold, and easily in hot water (H. How, N. Edin. Phil. J. new ser.
1, 47; Pharm. Centr. 1855, 93).
40 C
2 N
25 H
at 100°.
240
62.99
Wetherill.
61.35
H. How.
62.82
28
7.36
8.30
25
6.56
6.72
6.76
70
56
14.69
15.14
2 S
32
8:40
8.49
8.30
.....
CON HO¹,HO,S202
331
100.00
100'00
...
Maou
QUININE.
277
Sulphite of Quinine. Dry quinine absorbs sulphurous acid gas,
with considerable evolution of heat, and forms an anhydrous salt
(Liebig & Pelouze, Ann. Pharm. 19, 256).
Hyposulphate of Quinine. When a hot saturated solution of sulphate
of quinine is precipitated by hyposulphate of baryta, the filtered liquid
deposits crystals on cooling (Herren, Pogg. 7, 193).
Sulphate of Quinine. A. Mono-acid. Basic sulphate (Preparation
p. 264). Delicate, silky, slightly flexible needles, or longish lamina
(Pelletier & Caventou). Diclinic. Rectangular prisms, obliquely trun-
cated (similar to fig. 92), distinctly cleavable parallel to i and t,
less distinctly parallel to m. Angle m: t = 90°; i : t 96° 30'; i:
m = 95° 50'. Frequently also hemitropic, or rather quadruple crystals
(Brooke, Phil. Ann. 6, 375). Light and loose, like magnesia. Tastes
very bitter.-Exerts a left-handed action on polarised light; [a]j for
anhydrous sulphate 255.6°; for sulphate with 15.72 p. c. water
= 210·87° (De Vrij & Alluard, Compt. rend. 59, 201). See also
Bouchardat (N. Ann. Chim. Phys. 9, 213).
=
At a temperature of 160°, it becomes luminous when rubbed
(Calloud), exhibiting a pale-green light, brighter than that of the cin-
chonine-salt (Stratingh), and becomes positively electric (Pelletier &
Dumas). A few ounces of the salt warmed in a silver basin are highly
phosphorescent on cooling (Landerer, N. Repert. 7, 275). — Neutral
towards vegetable colours (Pelletier & Caventou; Baup); slightly alka-
line according to Robiquet, and Delondre & Henry. - Turns brown
in sunshine, both in the dry and in the moist state (Leverköhn, Kastn.
Arch. 17, 128); when exposed to the sun for 7 weeks, it assumes a
cinchona-brown colour (Br. Arch. 28, 235).
The sulphate dried in the air at 8° to 15º, or over oil of vitriol
diluted with 3.2 to 3.5 its volume of water, has the composition
2C40N2H2404,2(HO,SO³)+15 aq.; the moist salt loses its excess of
water when placed over acid of this strength, whilst the air-dried salt
does not alter in weight. When heated to 110° to 120°, it loses the
whole of its water of crystallisation, but rapidly absorbs 4.87 to 5·1
p. c. again on exposure to moist air (4 at. = 4.82 p. c.) (Jobst & Hesse);
the same quantity of water is retained by the salt dried over oil of
vitriol [or in dry air (Baup)]. A solution of 1 part of the air-dried
salt in 40 parts or more of alcohol of sp. gr. 0·852, deposits on evapo-
ration white needles containing 4 at. of water (Jobst & Hesse).
Millon & Comaille (N. J. Pharm. 42, 377; Kopp's Jahresber. 1862,
368), also found the sulphate dried over oil of vitriol at 15°, to contain
4.6 to 4.8 p. c. of water, whilst the air-dried salt did not lose weight
over oil of vitriol with 18 at. of water at 15°. The sulphate dried
over oil of vitriol at 30° retains 0·93 p. c.; that dried over oil of vitriol
with 4 at. of water at 15°, 6 p. c. of water. The salt rendered anhy-
drous by drying at 120° takes up 39 p. c. of water on exposure to very
moist air for 5 to 8 days, at a temperature of 15° tu 18°.
40 C
2 N
Dried.
240
64.36
Regnault.
64.06
Screcker.
28
7.51
25 H
25
6.70
6.98
50
40
10.71
SO3
40
10.72
•
10.75
C40N2H2404, HO,SO³.... 373
делови
100.00
Uor M
278
PRIMARY NUCLEUS C40H; OXYAZO-NUCLEUS C40N2H²²O¹.
Baup. Strecker.
Effloresced. Air-dried. a.
Jobst &
Hesse.
b.
Over oil of vitriol.
2 C40N2H2401
2 SO3
648
82.86
80
10.23
9.57
2 HO
18
2.31
4 aq.
36
4.60
4·31 .... 46 .... 4·64 .. 4.66
2C40N2H2404,2 (HO,SO³) + 4 aq..... 782 100.00
....
a was dried over oil of vitriol, b crystallised from alcohol.
Crystallised.
Delondre Jobst
Baup. & Henry. & Hesse
mean.
2 C40N2H2404
2 SO3
2 HO
1 aq.
11 aq.
618
80
....
18
36
73.55
9.08....
2.04
8:47 ....
8·47 .... 9.3 ...... 9.11
4.09
99 .. 11.24 11.75 .... 15·2 ........ 15:37
....
2C4N2H2404,2 (HO,SO³) + 15 aq. 881 100.00
...
....
CARS
Regnault's salt lost 13.99 p. c. of water in a current of air at 120°, and no more
at 140°.
Commercial sulphate of quinine contains quantities of water vary-
ing between 5.1 and 13.3 p. c. (Millon & Comaille). It usually appears
half-effloresced, but still contains 15.6 p. c. of water (Guibourt). Ch.
Link (Proc. Amer. Assoc. 1849, 275; Kopp's Jahresber. 1850, 419) found
in the commercial sulphate 9·8 p. c. SO³, and 8.4 p. c. of water, which
was expelled at 130°.
Sulphate of quinine does not decompose at 155° (Millon & Comaille).
It melts more easily than sulphate of cinchonine to a waxy liquid,
which assumes a fine red colour when more strongly heated (Pelletier
& Caventou), and evolves purple-red vapours, which condense in the
cool part of the tube. This red substance dissolves in water with fine
red colour, and is not precipitated by acetate of lead or baryta, but is
decolorised by potash or ammonia (Kastner, Kastn. Archiv. 20, 418). Sec
also Jonas (N. Br. Arch. 17, 287), Wigand (N. Br. Arch. 115, 230).
Burns at last with an empyreumatic odour, leaving at first a shining,
and afterwards also a combustible charcoal.
The anhydrous salt dissolves in 793 parts of water at 6°, and in
788 parts at 9.5° (Jobst & Hesse). One part of the salt (crystallised
or dry?) dissolves in 265 parts of cold, and in 24 parts of boiling water
(Bussy & Guibourt); in 335 parts cold, and 33·5 parts boiling (Howard);
in 720° parts at 18.75° (Abl); in 740 parts at 13°, and in 30 parts at
100° (Baup): in 740 parts at 10° (van Heijningen; Cap & Garot).
The commercial salt dissolves in 738 to 770 parts of water at 12° to
15°, in not quite constant proportions (Kerner). Dissolves very
sparingly in a cold saturated solution of Glauber's salt, and scarcely
at all in Rochelle salt, so that the solution is scarcely clouded by
ammonia, or coloured by chlorine-water and ammonia (Mann). The
solubility of sulphate of quinine in water is reduced by sulphate of
soda and sulphate of magnesia, but increased by sal-ammoniac, salt-
petre, and chlorate of potash (Calloud, Pharm. Journ., June 1860, 609;
N. Vogel. Notiz. 13, 276).
Maou
QUININE.
279
One part of anhydrous sulphate of quinine dissolves in 100 to 115
parts of alcohol of sp. gr. 0.852; the strength of the alcohol, how-
ever, is altered by the salt dissolved in it (Jobst & Hesse, Ann. Pharm.
119, 361; abstr. J. pr. Chem. 85, 309; N. Ann. Chim. Phys. 64, 364).
One part of the salt (crystallised or dry?) dissolves in 60 parts of cold
alcohol of sp. gr. 0.85 (Baup); in 60 parts of cold alcohol of 21°
(Delondre & Henry); in 40 parts of alcohol (Cap & Garot); in 7-5
parts of boiling alcohol of 90 p. c. (Bussy & Guibourt), from which it
is deposited almost entirely on cooling. Sulphate of quinine dissolves
in 40 parts of glycerin, but not in fatty oils (Cap & Garot; Attfield).
It dissolves abundantly in creosote at 20°, and slowly in cold picamar
(Reichenbach). It is insoluble in chloroform (Schlimpert).
;
Impurities and Adulterations of Sulphate of Quinine. Sulphate of
quinine may be intentionally adulterated, either with inorganic sub-
stances (such as sulphate or carbonate of lime or magnesia), the presence
of which is detected on heating, or with organic substances. Of the
latter class of bodies, starch-powder and stearin are recognised by their
insolubility in acidulated water, and gum by its insolubility in alcohol
salicin, phlorizin, and cane-sugar assume a red or brown colour with oil
of vitriol; the other varieties of sugar, as well as other substances
soluble in water, remain in solution on boiling the sulphate with baryta-
water, passing carbonic acid into the liquid, and filtering, and may be
recognised on evaporating the solution. The pure sulphate thus treated
leaves only a slight residue, corresponding to the solubility of quinine
in water.
On the adulteration of sulphate of quinine, see Winckler (Repert. 97, 403; Jahrb.
pr. Pharm. 15, 165), Stresemann (N. Br. Arch. 52, 151), Sckeyde (N. Br. Arch. 56,
171), Legrip (J. Chim. méd. 27, 49); with salicin: Peltier (N. J. Pharm. 7, 135),
Bouxlier (N. Br. Arch. 106, 322); with mannite: J. Kral (Anal. Zeitschr. 2,
405).
Since cinchonine and quinidine (or cinchonidine) exist together with
quinine in cinchona-barks, the sulphates of those bases may occur as
impurities in sulphate of quinine: they may be recognised by the fol-
lowing quinine-test of Liebig:-10 grains of the sulphate to be tested
are warmed with 10 drops of dilute sulphuric acid and 15 drops of
water in a test-tube; the solution is cooled; 60 drops of commercial
ether and 20 drops of ammonia-water are added; and the whole is
shaken and the tube stopped. If the quinine was free from cinchonine
and did not contain more than 10 per cent. of quinidine, the whole
remains in solution; but if cinchonidine was present, it is deposited
as a white pulverulent layer between the ether and the water, as is
also the case with quinidine when present in large quantity. Smaller
portions of quinidine crystallise from the ether on standing for a short
time, and still smaller quantities when ether saturated with quinidine
is employed in the first instance. As it sometimes happens that the
upper ethereal layer solidifies to a jelly, even with pure sulphate of
quinine, it is more convenient to employ ether containing alcohol,
or to take a somewhat larger proportion of ether than is directed
above. See Merck, Zimmer & Howard (Jahrb. pr. Pharm, 24, 209; Pharm.
Journ. 11, 393; Pharm. Viertelj. 1, 437), Wollweber (N. Br. Arch. 63, 6), Roger
(N. J. Pharm. 41, 204; Pharm. Viertelj. 11, 398), Bergot (Zeitschr. Ch. Pharm. 5,
123), Demeyer (J. Chim. méd. 1862, 460; Pharm. Viertelj. 12, 256), Kerner (Anal.
Zeitschr. 1, 150), Jandous (Apoth. Ver. Zeit. 1863, 254). Guibourt evaporates
the ammonia before adding the ether (N. J. Pharm. 21, 47). — Înstead
Uorm
280 PRIMARY NUCLEUS CHOH; OXYAZO-NUCLEUS CN2H22O1.
of ether, Riegel (Jahrb. pr. Pharm. 25, 340) employs 100 drops of
chloroform, whereby the quinidine also is dissolved. To separate this
last substance, he dissolves 10 grains of the sulphate in water, with
addition of tartaric acid, and adds bicarbonate of soda to the solution.
The resulting precipitate consists of cinchonine and quinidine, whilst
quinine remains in solution. The cinchonine and quinidine may then
be separated by chloroform.-O. Henry (N. J. Pharm. 13, 107;
J. Chim. méd. 24, 258) likewise separates quinine and cinchonine by
means of ether or cold alcohol, but first removes the greater part of
the quinine by converting it into acetate (by precipitating with caustic
soda and dissolving the precipitate in acetic acid) and crystallising out
as far as possible. Delondre & O. Henry (Ń. J. Pharm. 21, 281)
triturate 10 grammes of the sulphate and 4 grammes of acetate of
baryta with 60 grammes of water and a little acetic acid, separate the
crystals which form after a few minutes, and dilute the filtrate with
twice its volume of alcohol of 36°. After adding a little sulphuric acid
and again filtering, the liquid is boiled with excess of ammonia, and
after standing for 24 hours, the cinchonine crystallises in needles. The
cinchonine may also be obtained in crystals by dissolving 5 grammes
of the sulphate in 120 grammes of warm acidulated alcohol, boiling the
solution with excess of ammonia, and setting it aside for 24 hours.
See further Calvert's method (N. J. Pharm. 2, 393, and 13, 341), O. Henry (N.
J. Pharm. 16, 327), J. Barry (Repert. 92, 65; Pharm. Journ. 5, 113), Kerner (loc.
cit.), C. Mann (Pharm. Viertelj. 13, 245), Stoddart (Pharm. Journ. 6, 241; Pharm.
Viertelj. 14, 395).
B. Bi-acid. Mono-acid sulphate of quinine dissolves very easily
in water containing sulphuric acid. The solution is colourless or pale-
yellow by transmitted light, but exhibits blue fluorescence by reflected
light (Raupp, Repert. 39, 465). It is one of the most highly fluorescent
bodies (S. Niepce de Saint-Victor, J. pr. Chem. 74, 237 and 241). A
solution containing 100000
1 th or less exhibits the fluorescence when a
cone of light from a lens is made to fall upon the liquid (Flückiger,
Schweiz. Pharm. Zeitschr. 7, 22; Anal. Zeitschr. 1, 373). Rectangular
prisms, having a bitter, not acid, taste, and reddening litmus (Robi-
quet). On rapidly cooling the aqueous solution, it forms slender needles;
by slow evaporation large transparent prisms (Baup). Rhombic
prism y (fig. 53) having its obtuse edges truncated by a; a horizontal
prism u rests on the acute edges, and the prism i on p; further the
base t and a face k between i and t. Angle y:y (right and left)
145° 5'; y:p = 107° 27'
107° 27'; t: i = 127° 42'; t:k about = 157° ;
t: u = 130° 39' 43". The crystals have a tabular form from predomi-
nance of t; cleavable parallel to p (Hahn, N. Br. Arch. 99, 148). —
By digestion with water and carbonate of lime, the salt is converted
into A. Melts in its water of crystallisation at 100°. Dissolves in 11
parts of water at 13°, and in 8 parts at 22°; and in dilute or absolute
alcohol, much more freely in the hot liquids than in the cold. From a
solution in absolute alcohol it is deposited in crystals which imme-
diately fall to powder on exposure to the air (Baup).
Dry.
C40N2H2404
324
76.78
2 SO3
2 HO
80
18.96
18
4.26
C4°N³HO¹,2 (HO,SO³)
422
100.00
QUININE.
281
C40N2H2404,2HO
2 SO3
15 HO
Crystals.
Baup.
342
61.43
......
80
14.36
13.70
135
24.21
24.36
557
100.00
C40N2H2404,2(HO,SO³) + 15 aq.
Baup found 18-18 p. c. SO³ in the dry salt.
Iodate of Quinine. — Formed, together with hydriodate of quinine,
on warming iodine with quinine and water (Pelletier & Caventou). See
decompositions.
A. Mono-acid? Obtained from aqueous iodic acid and quinine.
Crystallises, on evaporating and cooling the solution, in silky crystals
like the sulphate. Decomposes when quickly heated, leaving charcoal
(Serullas, Ann. Chim. Phys. 45, 282). See also p. 270. Less soluble in
water than iodate of cinchonine (Pelletier).
B. Bi-acid? Aqueous iodic acid throws down from chlorate or
acid sulphate of quinine an acid iodate, a further quantity of which is
obtained on adding alcohol to the solution (Serullas).
Periodate of Quinine. Freshly precipitated quinine neutralises
aqueous periodic acid but incompletely in the cold, and on warming the
liquid, iodic acid is formed. When the acid solution is evaporated over
oil of vitriol, it becomes covered with oily drops, which are converted
into crystals as the evaporation proceeds. The periodic acid contained
in the crystals is reduced on keeping for a short time, the crystals.
acquiring a yellow colour. On neutralising the alcoholic solution, and
evaporating at 30° to 40°, roundish masses of needles are obtained.
They dissolve easily in water containing nitric acid, but with difficulty
in pure water, and after drying at 40° retain 18 at., and at 100° 12 at.
of water (Langlois, N. Ann. Chim. Phys. 34, 274).
Langlois.
C40N2H²+O+
I07
324
49.85
164
25.23
25.36
18 HO
162
24.92
C40N2H2404,107,18HO
650
100.00
at 100°.
Langlois.
C40N2H2404
I07
12 HO
324
54.36
164
27.52
27.60
108
18.12
596
100.00
C40N2H2404,107,12HO....
Langlois assumes the existence of 22 and 18 at. of water, but he determined only
the periodic acid.
Hydriodate of Quinine. Obtained by direct union of the acid and
base, or by double decomposition, in nodular groups of delicate crystals
(Pelletier). Lemon-yellow prisms (Herapath). A solution of sulphate of
quinine in boiling water, mixed with an equal number of atoms of iodide
of potassium, yields crystals of sulphate of quinine only on cooling; but
when 240 parts of hydrochlorate of quinine are mixed with 460 parts
of iodide of potassium, in hot aqueous solution, a colourless turpentine-
282
PRIMARY NUCLEUS C40H; OXYAZO-NUCLEUS C40N2H2O*.
like mass is deposited as the liquid cools (Winckler). Iodide of potas-
sium throws down from acetate or hydrochlorate of quinine, a heavy
white powder, which runs into drops (v. Planta). Melts to a resin
over the water-bath. Dissolves in water more freely than the sul-
phate; in nearly all proportions in alcohol, and in ether (Winckler,
Jahrb. pr. Pharm. 20, 321).
C40N3H250+............
I .......
Winckler.
325
71.91
127
28.09
28.42
100.00
C4°N²H²¹¹,HI.... 452
By mixing bi-sulphate of quinine with solution of iodide of potassium, Righini
(J. Chim. méd. 13, 116) obtained a red powder, containing, according to his analysis,
50 p. c. of quinine, 30 of hydriodic acid, and 20 of iodine, being a mixture of hydrio-
date of quinine and iodo-quinine. According to Reignier (J. Chim. méd. 13, 119),
on dissolving this precipitate in alcohol, and evaporating the solution, transparent 4-
sided prisms are obtained, which turn dull and brown-red in the air.
Chlorate of Quinine. - Formed. by dissolving quinine in warm aqueous
chloric acid. Tufts of delicate needles, melting to a colourless liquid,
which solidifies to a transparent varnish. Explodes when strongly
heated (Serullas, Ann. Chem. Phys. 45, 279).
Perchlorate of Quinine. When sulphate of quinine is precipitated
by perchlorate of baryta, and the filtrate is evaporated, yellowish oily
drops are deposited, which redissolve on gently warming the liquid,
and afterwards separate in crystals on cooling. By concentration the
mother-liquor yields a further quantity of oil, which solidifies in con-
tact with a crystal. Striated prisms, exhibiting a faint dichroïsm of
blue and yellow (Bödeker). The crystals belong to the right prismatic
system, being truncated rhombic octahedrons, cleavable parallel to the
end-face. Inclination of the octahedral faces, basal 149° 46';
macradiagonal 80° 30'; brachy diagonal 107° 32' (Dauber, Ann.
Pharm. 71, 65). The crystal melts at 45°, and likewise at a moderate
temperature over oil of vitriol, to a clear brittle mass (? Kr.) which
loses 14.3 p c. of water at 110°, puffs up strongly at 150°, and
solidifies again at 160°, having then lost 18 63 p. c. of water. On
further heating, a violent explosion occurs, accompanied by flame.
Aqueous solutions of a certain strength yield highly lustrous,
dichroïtic, rhombic tables, which melt to an oil under water, but fuse
only at 210° when heated alone, losing 6.5 p. c. of water (4 at. = 6·4
p. c. HO) (Bödeker).
=
C40N2H2404,2HO
2 C107
14 HO
=
Crystals.
Bödeker.
342
52.53
50.63
183
28.11
28.21
126
19.36
18.63
...
100.00
97.47
C40N2H2404,2CIHOS + 14HO.... 651
Hydrochlorate of Quinine. A. Mono-acid. A solution of quinine
in slight excess of hydrochloric acid deposits long silky needles which
lose 7·05 p. c. of water in a current of air at 140° (3 at. =
6.96 p. c.
HO) (Regnault). Winckler (Repert. 34, 266) takes 1 part of quinine,
1 part of hydrochloric acid, and 4 parts of water, or, since in this way
it sometimes happens that crystals are not obtained, Winckler (and
QUININE.
283
Leverköhn) decompose 100 parts of sulphate of quinine with 25 parts
of crystallised chloride of barium, and evaporate the filtrate at a gentle
heat (Repert. 32, 215). Radiated groups of white, pearly needles
(Winckler). Dissolves in water more easily than sulphate of quinine,
less easily than hydrochlorate of cinchonine (Pelletier and Caventou);
in 24 parts of water at 18.75° (Abl.) — Dissolves in 9 parts of chloroform
at 17.5° (Schlimpert) (? Kr.), and slowly in cold picamar (Reichen-
bach).
Regnault.
at 130°.
40 C
2 N
240
28
66.57
•
7.77
25 H
25
6.93
...
40
32
8.87
Cl
35.5
9.86
360.5
100.00
mean.
66.23
8.02
7.15
9.32
....
9.28
100.00
C40N2H2404,HCI
The crystals contain 8.75 p. c. of water, and 8.82 of hydro-
chloric acid (Winckler); 6.62 of hydrochloric acid (Pelletier and
Caventou).
B. Bi-acid.Quinine absorbs a large quantity of hydrochloric
acid gas [24.1 p. c. (Liebig), 22.86 p. c. (van Heijningen) 2 at. = 21.91
c.], but gives up portions of it continuously in dry air, ceasing to
lo so only at very high temperatures. Quinine saturated with
hydrochloric acid contains, at 145°, 19.31 p. c., at 160° in a current
of hydrochloric acid gas, 18.77 p. c. of hydrochloric acid (2 at. =
17.97 p. c. HCl); at a few degrees above 160° it turns yellow. From
the highly acid aqueous solution an amorphous gum is obtained
(Regnault; van Heijningen).
Hydrofluate of Quinine. A solution of freshly precipitated quinine
in aqueous hydrofluoric acid is transformed, when evaporated
nearly to dryness, into a crystalline mass of concentrically arranged
needles, which deliquesce rapidly in the air and dissolve very readily
in alcohol. (Elderhorst, Ann. Pharm. 74, 79). Quinine and hydro-
fluoric or hydrofluosilicic acid (whereby silicic acid is thrown down)
yield thin white needles, or with a large excess of hydrofluoric acid,
an acid amorphous gum (Serullas, Ann. Chem. Phys. 45, 282).
Nitrate of Quinine. An aqueous solution deposits on evaporation
oily drops, which turn waxy, and when kept under water for many
days are transformed into very oblique rhombic prisms (Pelletier,
Caventou & Dumas). Crystals are obtained only by evaporating
the excess of acid and dissolving the residue in water (van
Heijningen).
By decomposing mono-acid sulphate of quinine with nitrate of baryta,
and leaving the filtrate to evaporate spontaneously, the nitrate is
obtained in large, transparent prisms, which give off 4.2 p. c. of water
at 100° (2 at. 4.4 p. c. HO) (Strecker).
at 100°.
Strecker.
40 C........
240
62.02
62.1
3 N.......
42
10.85
25 H.
25
6.46
6.6
10 O.......
80
20.67
C40N2H2404,HO,NO5.... 387
100·00
284 PRIMARY NUCLEUS CH; OXYAZO-NUCLEUS C40N2H22O¹.
Fluosilicic alcohol (xv, 437) in excess precipitates quinine (Knop);
phosphomolybdic acid (xiii, 164) precipitates it whitish-yellow (Sonnen-
schein); phosphantimonic acid (xiv, 227) throws down from a solution
containingth of quinine, pale-yellow flocks (Schulze); metatungstic
acid precipitates a still more dilute solution (Scheibler, J. pr. Chem.
80, 204).
Chromate of Quinine. a. Mono-acid. C40N2H2404,CrO³. Precipi
tated from an aqueous solution of mono- or bi-acid sulphate of quinine by
neutral chromate of potash, in the absence of free acids, and is slowly
deposited in tufts of shining golden-yellow needles on recrystallisa-
tion. Permanent in light. Assumes a green colour when heated
above 92°. — Dissolves in 2,400 parts of water at 15°, in 160 parts
of boiling water; in alcohol, but not in ether (André).
b. Bi-acid.C40N2H24, 2CrO3 + 16aq. Bichromate of potash throws
down from a cold aqueous solution of sulphate of quinine con-
taining sulphuric acid, an orange-yellow precipitate consisting of
microscopic needles. Decomposes rapidly in the light. Turns
brown at 60° or 65°, or when boiled with water, evolving oxygen
at the same time. More easily soluble than the mono-acid salt (André,
N. J. Pharm. 41, 341; Zeitschr. Ch. Pharm. 5, 649).
Perchromate of Quinine. Formed by adding quinine to an ethereal
solution of perchromic acid. Dries without decomposition. Dissolves
in alcohol, but not in ether (Barreswil, Compt. rend. 16, 1085).
Arseniate of Quinine. -Needle-shaped prisms, resembling phos-
phate of quinine, but less pearly (Pelletier and Caventou).
Antimonic acid and Quinine. — Aqueous mono-basic antimoniate of
potash (iv. 377, 8) is not precipitated by hydrochlorate of quinine,
even on addition of alcohol; but when hot antimoniate of potash is
poured into boiling hydrochlorate of quinine, a white precipitate of
antimonic acid with a little quinine is thrown down, and the filtrate
on cooling and standing deposits nodules containing quinine, potash,
and variable quantities of antimonic acid. Antimoniate of quinine
cannot be obtained in this way (C. Graf, Pharm. Viertelj. 5, 211).
Sulphate of Quinine and Iron. On leaving a mixture of per-
sulphate of iron and sulphate of quinine to evaporate spontaneously,
small colourless regular octohedrons separate after some months: they
contain sulphuric acid, sesquioxide of iron, and quinine. The salt
tastes slightly bitter, blackens when heated, and carbonises and leaves
sesquioxide of iron on ignition (Will., Ann. Pharm, 42, 111). Langeli
(N. J. Br. Arch. 83, 61) obtained from equivalent quantities of sulphate
of quinine and sulphate of iron (ferric sulphate? Kr.) white prisms of a
double-salt easily soluble in water and alcohol. Baudrimont and
Roussin (N. J. Pharm. 46, 375) dispute the existence of such a double-
salt.
Quinine with Iodide of Iron? A solution of hydriodate of quinine,
formed by decomposing 30 parts of sulphate of quinine with iodide of
barium, is mixed with a solution of iodide of iron prepared from 12
parts of iodine; the liquid is concentrated; and the resin which
QUININE.
285
separates is removed by filtration; alcohol is then added, and the
solution is allowed to crystallise. Long, yellow needles, inodorous,
bitter, and tasting of iron. Dissolves in boiling water, in alcohol, and
in ether (J. Smedt, Apoth Zeit.). Rebillon (N. Br. Arch. 103, 365)
obtained in this way a fine green resin, insoluble in ether, and con-
taining CN2H2404,4Fel.
Hydrochlorate of quinine behaves like cinchonine with iodomer-
curate of potassium (Caillot; v. Planta; Delffs), and with chloride of
mercury mixed with iodide or bromide of potassium (Groves). – A
solution of 6.5 parts of chloride of mercury added to an aqueous
solution of 10 parts of hydrochlorate of quinine and 4 parts of iodide.
of potassium, throws down a yellowish-white precipitate, which
crystallises from alcohol, on spontaneous evaporation, in transparent,
four-sided prisms. The crystals dissolve with difficulty in water, but
more easily in alcohol of 82 p. c., and when mixed with protochloride
of tin throw down mercurous iodide. According to Winckler, they
consist of hydrochlorate of quinine with iodide of mercury (Repert.
35, 62).
Chloromercurate of Quinine. Chloride of mercury throws down
from hydrochlorate or acetate of quinine, a dense, pulverulent pre-
cipitate, which is not soluble to any great extent in sal-ammoniac,
but dissolves easily in hydrochloric acid, and is deposited again from
the solution in crystalline globules on standing. Sulphate of quinine
is precipitated by chloride of mercury only on addition of chloride of
sodium; the precipitate dissolves easily in sal-ammoniac, the solution
being permanent (v. Planta). To prepare the salt, alcoholic quinine
containing hydrochloric acid is mixed with an alcoholic solution of mer-
curic chloride, when, if very strong alcohol is used, a crystalline granu-
lar precipitate, or with weak alcohol, a less crystalline precipitate is pro-
duced. The precipitate is washed on a filter with alcohol, ether, and
water. It dissolves with difficulty in cold water, alcohol and ether,
Hinterberger (Ann. Pharm. 77, 201). See also Winckler (Repert. 35,
57).
40 C
2 N
26 H
40
2 Hg...
4 Cl
Hinterberger.
at 100°.
240
35.92
35.80
28
4.19
26
3.89
3.89
32
4.79
200
29.94
29.82
142
21.27
100.00
C40N2H2404,2HCl,2HgCl.... 668
Nitrate of Quinine with Oxide of Silver. - Alcoholic nitrate of silver
throws down from alcoholic quinine a crystalline precipitate contain-
ing 1 at. of nitric acid and 1 at. oxide of silver to 1 at. quinine.
The precipitate cannot be obtained in a perfectly pure state, on account
of the action of nitrate of silver on alcohol (Regnault). When the
precipitate after washing with alcohol, is dissolved in boiling water,
the solution on cooling solidifies to a jelly, which is transformed into
crystals on standing. Loses 17 p. c. of water at 110°, after drying
over oil of vitriol (1 at. = 1·8 p. c. HO). Dissolves in 286 parts of
water at 15° (Strecker).
286 C40H
PRIMARY NUCLEUS CH23; OXYAZO-NUCLEUS C40N2H04.
C40N2H2404
NO5,0
Ag
Dried.
324
Strecker.
65.59
62
12.55
108
21.86
21.9
100.00
C40N2H2¹0¹,AgO,NO5.... 494
Terchloride of gold throws down from solutions of quinine-salts,
sulphur- to reddish-yellow precipitates but little soluble in water (v.
Planta; Peschier).
Chloroplatinate of Quinine. - Chloride of platinum throws down from
quinine-salts a yellowish precipitate which dissolves easily in hydro-
chloric acid added at the same time (v. Planta). The precipitate is white
or yellow, but when an excess of hydrochloric acid is added, yellow and
crystalline (Liebig). Orange-yellow crystalline powder, having an
acid reaction (Duflos). Neutral (Liebig). Does not lose water at 100°,
but gives up 2.37 p. c. at 140° (Gerhardt, Rev. scient. 10, 187). When
strongly heated, it evolves hydrochloric acid, blackens, and glows.
Dissolves in 1,500 parts of cold, and 120 parts of boiling water, and in
2,000 parts of boiling alcohol of 85°, from which it is deposited on
cooling (Duflos, Schw. 62, 312).
40 C
2 N
26 H
Anhydrous.
240
32.58
28
3.81
26
3.53
40
6 Cl......
2 Pt........
32
4.34
213
28.94
197.4
26.80
C40N2H2¹04,2HCl,2PtCl2.... 736-4
100.00
Gerhardt.
Hydrated.
at 100°.
40 C
240
31.81
31.34
2 N
28 H
60
6 Cl
2 Pt
28
3.71
3.40
28
3.72
3.99
48
6.36
5.52
213
28.23
29.49
197.4
26.17
26.26
C40N2H2404,2HC1,2PtCl² + 2aq.
754-4
100'00
100.00
....
Liebig found, on the average, 26.52 p. c.; Laurent 26.4 p. c. of
platinum. Duflos found 25.8 p. c. of platinum, 28-4 of chlorine, and 44.64
of quinine (the anhydrous salt contains by calculation, 43.9 p. c., the
hydrated 42.94 p. c. of quinine). Duflos likewise obtained from 10
parts of dried quinine, 22-4 parts of platinum-salt (calc. for anhydrous
salt requires 22.72; for hydrated salt 23.29 parts).
Chloride of Iridium and Sodium throws down from acetate or hydro-
chlorate, but not from sulphate of quinine, an ochre-yellow to red-
brown precipitate, very easily soluble in hydrochloric acid (v. Planta).
Hydrocyanate of Quinine. Quinine triturated and shaken with
aqueous hydrocyanic acid dissolves to a yellow liquid (Pezzina, J.
Chim, méd. 8, 569).
QUININE.
28
Hydroferrocyanate of Quinine. Resembles the cinchonine-salt (p.
213), and may be obtained in a similar manner (Dollfus). Ferrocyanide
of potassium produces in cold aqueous quinine-salts, yellowish-white
clouds, which disappear on heating, or on addition of excess of the
ferrocyanide, and do not again make their appearance (Bill, Sill. Amer.
J. (2) 26, 108; J. pr. Chem. 75, 484).
52 C
8 N
34 H
10 0
2 Fe.
312
112
52.55
.....
Dollfus.
52.9
18.85
34
5.72
6.0
80
13.44
56
9.44
9.1
100.00
C40N2H2404, Cy¹Fe³H¹ + 6 aq. 591
...
Concerning
Gerhardt (Traité 4, 121) supposes the salt to contain 4 at. water.
the preparation of this salt as a medicine, see Bertozzi (J. Pharm. 19, 45), Ferrari
(Chim. méd. 11, 361), Geiseler (N. Br. Arch. 8, 66), Pelouze (N. Ann. Chim. Phys.
6, 67), Landerer (N. Br. Arch. 71, 282).
Hydroferricyanate of Quinine. - Concentrated aqueous solutions of
ferricyanide of potassium throw down from strong aqueous solutions
of hydrochlorate of quinine containing a little free hydrochloric acid,
golden-yellow, crystalline laminæ, which, after drying, resemble
mosaic gold. Does not lose weight at 100°. Dissolves easily in
water, and deposits a blue powder on evaporating the solution (Doll-
fus).
52 C
8 N
30 H
70
2 Fe .....
Dollfus.
312
55.11
54.60
112
19.79
30
5.30
5.46
56
9.90
56
9.90
9.86
100.00
.
C40N2H2404,Cy°Fe2H3 + 3 aq..... 566
Quinine does not form any compound with cyanide of mercury (Kohl
& Swoboda, Wien. Akad. Ber. 9, 252); it behaves with that salt in the
same manner as cinchonine (Caillot).
Hydrocyanate of Quinine and Cyanide of Platinum. According to
Delffs, quinine is not precipitated by platinocyanide of potassium.
Wertheim (Wien. Akad. Ber. 1849, 1,263) obtained from sulphate of
quinine and platinocyanide of potassium, the compound C40N2H2404,2HCy,
2PtCy+2 aq., and from hydrochlorate of quinine and platinid-cyanide
of potassium (vi, 49) the salt C40N2H2404,2HC1,2PtCy². Schwar-
zenbach describes the following compounds :-
A. 3C40N2H2404,2HCy,2PtCy. - Platinocyanide of potassium throws
down from a solution of quinine in aqueous acetic acid, an abundant
white precipitate, which, on standing, is converted partly into fine needles
and partly into a resin. The needles melt at 100° to a gum, which
also remains transparent on cooling (Schwarzenbach).
Needles.
3 C40N3H2404,2HCy,2Cy....... 1078
2 Pt
Schwarzenbach.
84.52
197.4
15.48
16.46
1.00.00
3 C40N2H2404,2HCy,2PtCy.... 1275-4
288
PRIMARY NUCLEUS CH28; OXYAZO-NUCLEUS CN2H²²O¹.
B. CON²H² 40¹,2HCy,2PtCy. - Aqueous platinocyanide of potassium
throws down from a clear solution of quinine in not too great an excess
of sulphuric acid, a bulky white precipitate, which, in presence of a larger
quantity of sulphuric acid, disappears again at first. When left at rest,
the precipitate is transformed into tables, warty groups of needles, and
a resin (Schwarzenbach).
a. The tables are transparent, quadratic, or oblong, with parallel
striæ. On drying they become opaque and waxy, and acquire a faint
yellowish-green colour. By picking out the tables, afterwards treating
them with boiling water, in which the other forms are not soluble, and
rapidly cooling, they are obtained pure and in lamina. The air-dried
tables do not lose weight at 120°, but give up 6.35 p. c. of water at 150°,
assuming at the same time a deep-yellow colour, which disappears
again almost entirely on cooling.
C40N2H2404
2 HCу,2Cy.
2 Pt.
4 HO
Tables.
Schwarzenbach.
324
48.83
106
15.98
197.4
29.75
29.66
36
5.44
6.35
....
100.00
C40N2H4O¹,2HCy,2PtCy+ HO.... 6634
b. The warts appear to the naked eye as short prisms or broad
needles. They remain behind, together with amorphous white resinous
globules, on treating the entire precipitate with boiling water, and may
afterwards be dissolved by boiling alcohol, from which they crystallise
unchanged on cooling. They turn yellow to orange in sunlight, and
when dried over oil of vitriol, contain 30-43 p. c. of platinum, corre-
sponding to the formula C40N2H2O*,2HCy,2PtCy +2HO (by calc.
30.52 p. c. Pt.)
c. The resinous globules are pure white, or translucent and waxy, in
the moist state, and insoluble in boiling alcohol. They contain, like b,
30.4 p. c. of platinum (Schwarzenbach, Pharm. Viertelj. 8, 518).
Hydrosulphocyanate of Quinine.-Hydrosulphocyanic acid and quinine
form together a yellow resinous salt, and a white salt, which cannot be
separated by crystallisation (Dollfus). Strong alcoholic solution of
quinine forms with sulphocyanide of potassium, a very small quantity
of a white precipitate, which does not dissolve on warming (Artus, J. pr.
Chem. 8, 253). Neutral acetate of quinine [in concentrated solution only
(v. Planta)] immediately forms a white curdy precipitate, which dissolves
on heating, and in hot alcohol (O. Henry, J. Pharm, 24, 194). Hydro-
chlorate of quinine produces with sulphocyanide of potassium a dense
precipitate and oily drops (v. Planta), or in dilute solutions, microscopic
elongated needles (Anderson). Excess of sulphocyanide of potassium
throws down from a solution of 1 part of quinine in 400 parts of water
containing sulphuric acid, greenish-yellow, delicate needles, which are
more quickly precipitated, in the pulverulent form, on violently agitating
the liquid (Lepage). Large, regular, pale lemon-yellow crystals of
the oblique prismatic system, having the formula C40N2H2404,2CyHS²
(Wertheim, Wien. Akad. Ber. 1, 263). After pouring off the mother-
liquor, in which it is not soluble on account of the presence of sulpho-
cyanide of potassium, it dissolves easily in water, and especially in
alcohol (Lepage, J. Pharm. 26, 140).
QUININE.
289
Chloride of mercury and cyanide of mercury throw down from
hydrosulphocyanate of quinine, double salts of the
of the formulæ
3(C40N2H2404,2CyHS2)+8HgCl and CN2H204,2CyHS2+2HgCy (Wer-
theim).
Formate of Quinine. Crystallises easily in needles resembling the
sulphate (L. L. Bonaparte, J. Chim. méd. 18, 680).
Acetate of Quinine. Strong acetic acid added to an ethereal
solution of quinine throws down a crystalline acetate (Veltmann,
Schw. 54, 187).
A. Mono-acid? The long silky needles of acetate of quinine give
off acetic acid over the water-bath and still more at 140°, when they
melt to a nearly colourless glass (Regnault).
44 C
2 N
28 H
80
C40N2H2404,C4H¹O*
Fused.
264
68.77
. Regnault.
69.47
28
7.29
28
7.29
7.38
64
16.65
384
100.00
*****
B. Acid. Obtained by the spontaneous evaporation of a solution
of quinine in acetic acid, in long silky needles (Schwarzenbach): on
rapid evaporation the whole liquid becomes solid. Faintly acid: dis-
solves slightly in cold, much more easily in hot water (Pelletier &
Caventou). Contains 69.37 p. c. of quinine. Loses 12.75 p. c. of
water (and acetic acid? Kr.) over oil of vitriol. Schwarzenbach (Pharm.
Viertelj. 8, 518) gives the formula C40N2H2404,2C*H*O* + 6aq., which
requires 65 p. c. of quinine, and 10.8 p. c. of water, and should probably
be replaced by C40NH2404,2C*H*0*+2aq. (70-1 p. c. quinine, 39 water)
(Kr.)
Oxalate of Quinine. Bibasic? Acetate (Regnault) or bi-acid sul-
phate of quinine is precipitated by oxalate of ammonia or potash, and
the precipitate is washed with a little cold water and crystallised from
boiling alcohol. Small, very delicate needles. Dissolves in cold, and
more freely in hot water, and very easily in alcohol, especially when hot
(Pelletier & Caventou; Regnault; Landerer, Repert. 52, 40?).
84 C
4 N
50 H
16 O
at 125°.
504
68.29
Regnault.
67.03
56
7.59
50
6.76
7.03
128
17.36
738
100.00
2C40N2H2404,C4H2O8
B. Acid? - Needles easily soluble in water (Pelletier & Caventou).
Cyanurate of Quinine. - White amorphous mass (Elderhorst).
Mellitate of Quinine. - Alcoholic quinine produces with solution of
mellitic acid an abundant white precipitate, which becomes pearly and
crystalline when washed with weak alcohol. Does not lose water at
100°, but evolves a little water and ammonia at 130°, turning sulphur-
yellow. Dissolves very slightly in cold, and somewhat more freely in
VOL. XVII.
T
290
PRIMARY NUCLEUS C40H28; OXYAZO-NUCLEUS C40N2H22O4.
hot water, from which it is deposited as a crystalline powder on cooling
(Karmrodt, Ann. Pharm. 81, 170).
Succinate of Quinine forms pearly prisms (Henry & Delondre).
Aspartate of Quinine. - Indistinct crystals, easily soluble in water
(Plisson, J. Pharm. 15, 273).
Valerate of Quinine. On neutralising alcoholic quinine with a
slight excess of valerianic acid, and allowing a mixture of 1 vol. of the
liquid with 2 vols. of water to evaporate spontaneously, or at 50° at
most, hard rectangular octahedrons or cubes, permanent in the air, are
obtained, and by rapid evaporation also needles (Bonaparte). Wittstein
employs 1 part of the acid, 60 parts of water, and 3 parts of freshly
precipitated quinine. The salt may also be prepared by mixing a solu-
tion of 12 parts of valerianic acid in 10 parts of alcohol with a solution
of 40 parts of quinine in 140 parts of alcohol of 85 per cent., and eva-
porating the liquid to crystallisation at a temperature of 30° to 40°
(N. J. Pharm. 45, 236). Or carbonate of soda is added to slightly
alkaline reaction to a mixture of 1 part of valerianic acid and 2 parts of
water, and the liquid is added, at a temperature of 48°, to a solution of
2 parts of sulphate of quinine in water containing sulphuric acid, where-
upon, on standing for 24 hours, the solution deposits crystals, which must
be washed with water at 36° (Chatin, N. J. Pharm. [4], 1, 268). Pearly
oblique rhomboïdal tables or white needles. Smells of valerianic acid;
tastes very bitter, and afterwards of the acid. Neutral (Wittstein). Melts
at 90° to a transparent liquid, giving off 34 p. c. of water, and solidifies
to a glass on cooling. When more strongly heated, it gives off valeri-
anic acid. The salt, fused at 90°, dissolves easily in alcohol, and
remains on evaporation as an amorphous mass when the alcohol is
strong, or in crystals when weaker alcohol is employed (Bonaparte).
The crystals dissolve in 110 parts of cold [96 parts at 18.75° (Abl)],
and in 40 parts of boiling water (Wittstein). On boiling, the solution
deposits resinous drops of the anhydrous salt, which do not become
crystalline on cooling or standing in water, but crystallise from dilute
alcohol. The same anhydrous salt is precipitated by valerianic acid
from an aqueous solution of the crystals (Bonaparte, J. Chim. méd. 18,
680; 19, 330). It dissolves in 6 parts of cold, and in 1 part of boiling
alcohol of 80 p. c. (Wittstein, Repert. 87, 295). The salt prepared with
natural, but not that made with artificial valerianic acid becomes phos-
phorescent when rubbed, especially after it has effloresced. The two
salts also exhibit different crystalline forms (Landerer, N. Br. Arch.
119, 240).
Wittstein.
Resinous salt.
CON2H2404
C10H903
324
71.52
71.85
93
20.53
20.23
4 HO
36
7.95
7.92
C40N2H2404,C10H1004+ 3 aq.
453
100.00
100.00
Crystals.
Wittstein.
C40N2H2404
324
50.47
51.36
C10H903
93
14.49
14.98
25 HO
225
35.90
33.66
CONH²+0+,C10H10O4 + 24 aq.
642
100.00
100.00
QUININE.
291
Wittstein considers the salt to contain 1 at. water less. See also Riegel (N. Br.
Arch. 45, 315), Fr. Müller (N. Br. Arch. 46, 157), Devay (N. J. Pharm. 6, 382).
Dextrotartrate of Quinine. Acid tartrate of potash dissolves qui-
nine in small quantity only and with difficulty; on evaporating the
solution a mixture of cream of tartar and a quinine-salt remains
(Arppe).
A. Bibasic. When sulphate of quinine is mixed with tartrate of
potash a crystalline powder is precipitated. Neutral. Fusible. Tastes
bitter. Gives off 15 p. c. of water at 145° (Arppe, J. pr. Chem. 53,
334).
Arppe.
79.0
2C40N2H2404
CSH6O12
648
150
81.27
18.08
.......
100.00
2040N2H240+, CH6O12 798
B. Mono-acid. Equal numbers of atoms of the base and acid are
dissolved separately in alcohol, and the solutions are mixed and
allowed to crystallise. Gives off 1.4 p. c. of water at 100°, and the
remainder at 160°, in all 4·4 p. c. Decomposes only on prolonged
heating to 160° (calc. for CNH2404,CHO12+ 2aq. = 3.67 p. c. HO)
(Pasteur).
Antitartrate of Quinine. See x, 365, and xvii, 217. — Obtained in the
same way, and has the same composition as the dextrotartrate; it
exhibits, however, a different crystalline form, gives off its water of
crystallisation almost entirely at 100°, and dissolves far more freely
than that salt, especially in warm water (Pasteur).
Tartrate of Quinine and Potash. — Crystals soluble in alcohol
(Delondre & Henry).
Quinine, boiled with solution of tartar-emetic, does not yield a
double salt analogous to that of quinidine (Stenhouse).
Croconate and Rhodizonate of quinine resemble the cinchonine-salts
(Heller).
Urate of Quinine. Obtained in the same manner as the cinchonine-
salt (Elderhorst). Andreae (Pharm. Viertelj. 10, 382) uses 1 part
of quinine to 15 parts of uric acid. White, amorphous, laminated
mass (Elderhorst). Dull white powder, consisting of microscopic prisms.
Tastes bitter. Burns, when heated, without melting. Dissolves in
855 parts of cold, and 36.2 parts of boiling water; in 1580 parts of
cold, and 45.3 parts of boiling alcohol; still less freely in ether
(Andreae).
C40N2H2404
CION4H406
at 100°.
Andreae.
324
65.85
63
168
34.15
33
C40N2H2404, C10ºN2H+O6
492
100.00
....
......
Andreae's analysis is doubtful: his formula contains 6 at. water more (Kr). See
also Péreyre on urate of quinine (N. Br. Arch. 103, 364).
Strong aqueous pyrogallic acid throws down from bi-acid sulphate
of quinine, a yellow crystalline precipitate (De Luynes, Compt. rend, 57,
U 2
292
PRIMARY NUCLEUS CH; OXYAZO-NUCLEUS C4°N¹H2204.
162). — The compound of quinine with picrotoxin resembles the brucine-
compound (Pelletier & Couerbe).
Orcin and (Sulphate of?) Quinine. - Quinine behaves towards orcin
in the same manner as cinchonine (De Luynes). A moderately dilute
aqueous solution of orcin becomes cloudy at first, when a strong
aqueous solution of sulphate of quinine is dropped into it, but clear again
on further addition of the quinine-salt, after which the solution de-
posits, when pure orcin is employed, small concentrically arranged
needles, but with an impure quinine, an oil which solidifies (Hlasiwetz,
Ann. Pharm. 134, 290).
Citrate of Quinine. Quinine is added to a warm dilute aqueous
solution of citric acid till the alkaloïd is no longer dissolved. On
cooling and concentrating the solution, fine, white, somewhat silky
needles are obtained. Very bitter. Neutral. Dissolves in 820 parts
of cold, and 30 parts of boiling water; and in 44 parts of cold, and
3 parts of boiling alcohol of 85 p. c. Loses 10.6 per cent. in weight
at 100° (10 at. = 9.68 p. c. HO), and no more at 145°. Decomposes
at 160°, as it begins to melt (Wittstein, Pharm. Viertelj. 5, 552;
N. Br. Arch. 89, 27).
92 C
4 N
....
at 100°.
Wittstein.
552
65.72
66.49
56
6.66
6.73
56 H.....
56
6.66
6.58
22 0.
176
20.96
20.20
2 C4N²H²+04, C¹²H$O¹4
810
100.00
100.00
........
Wittstein's formula contains 1 at. water less. See also Galvani (J. Chim. méd.
8, 687).
On citrate of quinine and ferric oxide, see Fleurot (N. J. Pharm. (4)
1, 443).
Lactate of Quinine. Lactic acid saturated with quinine leaves, on
evaporation, tufts of silky needles, more easily soluble in water than
the sulphate (Bonaparte).
Quinine is not precipitated by gallic acid and its salts (Pfaff;
Henry); but salts of quinine are rendered turbid by gallic acid which
has become yellow from long standing (Wackenroder).
Picrate of Quinine. - Alcoholic picric acid forms with alcoholic
quinine [with salts of quinine (v. Planta)], even in very dilute solution,
a yellow pulverulent precipitate (Kemp, Repert. 71, 164). The salt is
also obtained from picrate of potash and sulphate of quinine. Yellow;
slightly bitter (Bonaparte). Very bitter (Winckler). Nearly insoluble
in water; on boiling therewith, the anhydrous salt is deposited in the
form of an oily layer, which does not turn crystalline on standing
(Bonaparte). Dissolves easily in alcohol, crystallising therefrom (ac-
cording to Bonaparte, not) in yellow needles (Carey Lea). Dissolves
in alcohol (Winckler, Repert. 41, 330; Carey Lea, Sill. Amer. J. 26,
379; Chem. Centr. 1859, 122).
Anethol and Quinine. By dissolving 5 parts of quinine and 1 part
of anise-oil in boiling alcohol, cooling and concentrating the liquid,
and recrystallising the product, shining crystals are obtained. Four-
QUININE.
293
sided, mostly acute double pyramids, belonging to the oblique pris-
matic system, with truncated summits. Smells very slightly of anise-
oil, more strongly when heated. Tastes of quinine and the oil. Melts
in hot water; in the dry state only above 400°, giving off water and oil
of anise, amounting together to 21.9 p. c. (by calc. 22.11 p. c.). Dis-
solves slightly in cold, and freely in boiling alcohol, and very easily in
cther (Hesse, Ann. Pharm. 123, 382; abstr. N. Br. Arch. 115, 169).
100 C
Crystals.
600
Hesse.
72.11
72.04
4 N
56
6.73
6.48
64 H
64
7.69
7.70
14 O
112
13.47
13.78
2C40N2H2404, C20H1202 + 4 aq. 832
100.00
100.00
....
Tannate of Quinine.-Occurs in cinchona-barks, according to
Henry & Plisson. Gallo-tannic acid (infusion or tincture of galls)
produces a turbidity in very dilute solutions of quinine; from mode-
rately strong solutions it throws down white flocks, which run together
when warmed, without dissolving. When the proper proportions are
employed, the filtrate produces only a slight blue coloration with ferric
salts. -White spongy mass, drying up to a brittle, friable resin.
Tasteless and inodorous. Permanent in the air. Contains, according
to Delondre & Henry (N. J. Pharm. 21, 286), 1 at. quinine to 2 at.
tannic acid. Very slightly soluble in water [in 480 parts at 183°
(Abl)]. Dissolves in ammonia with red colour, easily in alcohol [in 52
parts (Cap & Garot)], and very slightly in ether. The alcoholic solu-
tion is precipitated by water; it leaves on evaporation a syrup, which
dries up to a brittle gum (N. E. Henry, J. Pharm. 11, 334). Dissolves.
in 130 parts of glycerin, and in 1,200 parts of fat oil (Cap & Garot).
By long contact with water, it is converted into soluble gallate of qui-
nine (Lintner, N. Repert. 1, 411; Wackenroder, N. Br. Arch. 28, 54;
Fr. Müller, N. Br. Arch. 38, 144; Landerer, N. Br. Arch. 83, 1; Bar-
reswil, N. J. Pharm. 21, 206).
Moritannate of Quinine. Moritannic acid forms with quinine a
pale yellow precipitate. The precipitate produced by moritannate of
lime is yellow and non-crystalline. It contains, after drying at 100°,
63.40 p. c. C., 3·89 N., 5·47 H., and 27.24 0. Dissolves slightly in
water, and easily in alcohol (Wagner, J. pr. Chem. 51, 94 and 103).
Cinchona-red and Quinine. When cinchona-red (xv, 482) is dis-
solved in alcohol, together with mono-acid sulphate of quinine, and the
solution is evaporated, water takes up from the residue acid sulphate
of quinine, whilst a compound of cinchona-red and quinine remains
undissolved. Dirty-red powder not tasting bitter at first. Nearly
insoluble in water, but soluble in warm dilute acids, from which it
is deposited almost entirely on cooling; it is precipitated also by in-
complete neutralisation of the acid solution by alkalis, whilst an excess
of alkali separates quinine. Dissolves easily in alcohol, forming a
solution from which lime or magnesia precipitates the whole of the
cinchona-red. According to Henry & Plisson, this compound occurs
in cinchona-barks; it remains behind on boiling the hark with water,
and forms the greater part of the precipitate produced by cold water
in the aqueous extract.
294
PRIMARY NUCLEUS C40H28; OXYAZO-NUCLEUS C40N2H22O¹.
Kinate of Quinine. -Occurs in cinchona-barks according to Henry
& Plisson. Warm aqueous kinic acid is neutralised with freshly pre-
cipitated quinine, and the slightly acid bitter filtrate is evaporated over
the water-bath. After moistening with water, the brown residue soli-
difies to a warty mass, in which small shining crystals are afterwards
formed. The salt dissolves easily in water, less freely in alcohol
(Henry & Plisson, Ann. Chim. Phys. 35, 172; further J. Pharm. 15, 405).
Contains, according to Baup (Pogg. 29, 70), 4 at. water, and dissolves
in 3.5 parts of water at 110, and in 8.88 parts of alcohol.
Oleate of Quinine. —Quinine is nearly insoluble in olive oil, and
does not saponify when heated with it. When 1 part of quinine is
digested with 2 parts of oleic acid for one to two hours at 100°, a
solution miscible with fat oils is obtained (Attfield, Pharm. J. Trans.
1863, 4, 388; Pharm. Viertelj. 13, 230). By the action of quinine on
olive oil or margaric acid, Tripier (N. J. Pharm. 46, 234) obtained soaps
miscible in all proportions with oils and fats. On slowly cooling, the
very viscid “
“Oleomargarate de Quinine" ultimately crystallises in
shining globules.
Quinine is very easily soluble in alcohol (Pelletier & Caventou). It
dissolves in nearly all proportions in alcohol of 90 p. c. at 15° (Bussy
& Guibourt); in 6 parts of alcohol (Cap & Garot); in 30 parts of cold
alcohol of 20° B. (Merck); in about 2 parts of boiling alcohol of sp. gr.
0.820 (Duflos). On spontaneous evaporation of the solution, there re-
mains a resin mixed with a few crystals (van Heijningen). It dissolves
much more easily than cinchonine in ether (Pelletier & Caventou); in
60 parts of ether (Merck), remaining in the form of a resin on spon-
taneous evaporation (van Heijningen). According to Schlimpert, it
dissolves in 6.7 parts of chloroform at 17.5°; according to Pettenkofer
in 1.8 parts of that liquid. The solution leaves a perfectly transparent
residue when evaporated (Herapath). — Quinine dissolves in benzene and
crystallises from the solution on evaporation (Mansfield). It dissolves
in 200 parts of glycerin, in 62 parts of fat oil (Cap & Garot), in 23.8
parts of olive oil (M. Pettenkofer), but according to Pelletier & Ca-
ventou only slightly in warm volatile and fat oils. (See above).
Quinidine.
C40N2H240 = C40N2H22O4, H³.
HENRY & DELONDRE. J. Pharm. 19, 623; 20, 157.
VAN HEIJNINGEN. Scheik. Onderzoek, 5, 4, Stuk. 233; Pharm. Centr.
1849, 465 and 472; Ann. Pharm. 72, 302; Jahrb. pr. Pharm. 18,
367; Repert. [3] 4, 88; Chem. Gaz. 1849, 319 and 325; N. J.
Pharm. 16, 280 and 446; Kopp's Jahresber. 1849, 371.
PASTEUR. N. J. Pharm. 23, 123; Compt. rend. 36, 26; J. pr. Chem.
58, 376; Kopp's Jahresber. 1853, 472.- Compt. rend. 37, 111.
DE VRIJ. N. J. Pharm. 31, 183 and 369; Pharm. J. Trans. 16, 401;
Chem. Centr. 1858, 254; Kopp's Jahresber. 1857, 403.
HERAPATH. Phil. Mag. [4] 14, 224; Chem. Gaz. 1857, 96; J. pr.
Chem. 72, 104; Kopp's Jahresber. 1857, 405. Chem. Gaz. 1858,
56; J. pr. Chem. 74, 415. — Chem. Gaz. 1858, 70; J. pr. Chem.
QUINIDINE.
295
74, 411; Kopp's Jahresber. 1858, 365.
Chem. Gaz. 1858, 437;
J. pr. Chem. 76, 364; Kopp's Jahresber. 1858, 368.
KERNER. Anal. Zeitschr. 1, 152.
J. STENHOUSE. Phil. Trans. 12, 491; Ann. Pharm. 129, 15; Chem.
Centr. 1864, 593.
C. MANN. Pharm. Viertelj. 13, 245.
F. KOCH. N. Jahrb. Pharm. 22, 210.
Beta-quinine (van Heijningen; Koch). Pasteur's Chinidine. To be
distinguished from the quinidine of Winckler and other chemists, which
is the same as the cinchonidine of this Handbook. Discovered in 1833
by Henry & Delondre, who, however, afterwards regarded it as quinine
or hydrate of quinine, on the ground of its similar composition. Van
Heijningen, and afterwards Pasteur, established the individuality of
quinidine. According to the supposition of Pasteur, however, the
quinidine examined by van Heijningen was not perfectly pure.
Kerner distinguishes a-, ß-, and y-quinidine.
1. Alpha-quinidine. Formerly met with in commerce mostly as
sulphate. It is obtained from alcohol in large, short, mostly perpen-
dicularly truncated prisms, which effloresce slowly. The sulphate
dissolves in 180 to 300 parts of cold water, seldom more freely. — Alpha-
quinidine dissolves to a slight extent in luke-warm ether, from which it
is crystallised on standing for a short time.
2. Beta-quinidine. Obtained from alcohol in small needles, which
effloresce rapidly, and are much more easily soluble in ether than
alpha-quinidine.-The sulphate forms brittle, not woolly needles, soluble
in 80 to 110 parts of water. From its cold saturated aqueous solution
vol. of moderately strong solution of iodide of potassium throws
down a pulverulent precipitate, whereas all other cinchona-sulphates,
excepting sulphate of quinine, are precipitated thereby in the oleo-
resinous form.
3. Gamma-quinidine. - Dissolves in ether still more easily than the
foregoing. The sulphate resembles sulphate of quinine, and exhibits
the solubility of the corresponding salt of alpha-quinidine; it produces
an oleo-resinous precipitate with iodide of potassium.
Пе
Koch (N. Jahrb. Pharm. 22, 241) finds van Heijningen's quinidine
in all cinchona-barks, but in largest quantity in Pitoya bark.
describes it as crystallising in long four-sided prisms, which effloresce
rapidly. The sulphate does not give off water at 80°; after drying at
40° to 50° it becomes luminous when pressed in the dark. When
exposed in the moist state to light, it assumes a bright green colour.
It dissolves in 10 parts of boiling, and in 35 parts of cold water: the
solutions become highly fluorescent on addition of sulphuric acid.
De Vrij (N. Jahrb. Pharm. 14, 246; further: Pharm. Viertelj. 14,
221) obtained from Howard, as a peculiar body, a mixture of quinidine
with a not previously recognised cinchona-base, the latter of which he
afterwards found in calisaya bark from Java. It forms dull-white,
cauliflower-like crystals, which cake together at 35°, assume the
consistence of turpentine at 40°, and melt considerably below 100°.
The base exerts a left-handed action on polarised light, and dissolves
very easily in alcohol and ether. Its hydrate is very bulky, entirely
filling the liquid on precipitation. With chlorine-water and ammonia
it produces à green coloration, and with iodine and sulphuric acid a
296
PRIMARY NUCLEUS CH23; OXYAZO-NUCLEUS CON³H²²O*.
very fine herapathite (p. 311). The hydriodate forms neutral crystals,
a solution of which becomes milky, and deposits an oil when concen-
trated. According to De Vrij, this substance is probably identical with
van Heijningen's y-quinine (p. 273).
According to Herapath (Phil. Mag. (4) 14, 224; Kopp's Jahresb.
1857, 405) there exists, together with quinidine, another base which
forms prismatic crystals, like quinidine and cinchonidine. With sul-
phuric acid and iodine it forms crystals which appear of a deep olive-
green by reflected, and orange-yellow by transmitted light. Thin plates
cut at right angles to the axis are brown or black by polarised light.
The solution of this base in chloroform yields on evaporation a gummy
residue, which immediately exhibits a deep blue-green fluorescence in
Canada balsam.
Hlasiwetz (Ann. Pharm. 77, 49) describes as cinchotine, fine rhom-
boïdal crystals of considerable size and diamond-like lustre, which he
obtained from the alcoholic mother-liquor of commercial cinchonine.
The crystals dissolve easily in ether, become opaque when warmed, then
melt, and solidify to an amorphous mass on cooling. They yield no
sublimate either alone or in a stream of hydrogen or ammonia-gas.
Hirschberg (Pharm. Centr. 1851, 175; Kopp's Jahresber. 1851, 467)
believes that these crystals are sometimes formed instead of cincho-
nine in the manufacture of cinchonine, and are always obtained, to-
gether with cinchonine, in working brown cinchona-barks. According
to Delffs, they are identical with quinidine (N. Jahrb. Pharm. 11, 321;
Chem. Centr. 1859, 751). Schabus (Bestimm. 1855, 171) found them
to belong to the oblique prismatic system. Octahedron, having the
anterior and posterior summits truncated by a face t (fig. 43), the upper
summits by the base (fig. 42); the crystals are elongated in the trans-
verse axis. Inclination of a and a to the base 118° 30'; a": t
108° 18'; a" to base 109° 28'; base to t 102° 40'. The faces are
smooth and even; those of the octahedrons slightly shining.
Occurrence of Quinidine. — In cinchona-barks, especially in yellow
barks (which? Kr.), together with quinine and cinchonine (Henry &
Delondre). A cinchona-bark from Bogota contained little quinine or
cinchonine, but 2.5 to 2.6 p. c. of quinidine (Mettenheimer, Jahrb. pr.
Pharm. 24, 229; Pharm. Viertelj. 1, 586); Reichel (Wiggers, 418),
however, found 0.56 p. c. at most; Pereira 1.17 p. c., and Hindsley 4th
per cent. of quinidine in China Bogota.- According to Howard, quinidine
occurs especially in certain varieties of Cinchona condaminea, more
especially in var. pitayensis (De Vrij). According to Henkel (N. Repert.
13, 200) in Cinchona nitida, together with cinchonine and a little
quinine.
The root-bark of Cinchona Calisaya contains quinidine and a little
quinine (Howard, Repert. 13, 204). The red bark of 18 months or
younger plants of Cinchona officinalis, C. micrantha and C. succirubra,
grown in the East Indies, contained 6 p. c. of alkaloids, of which about
4.1 p. c. consisted of quinidine, cinchonidine, and quinine, and 0.9 p. c.
of cinchonicine with traces of cinchonine (Howard, Pharm. Trans. 5,
368; Chem. Centr. 1864, 655).
The quinidine of commerce is, for the most part, a mixture of quinidine and a
second base (Pasteur). The specimens of quinidine in the London Exhibition of
QUINIDINE.
297
1855 [? Paris, 1855, or London, 1862] were exclusively cinchonidine rendered
impure by quinine (De Vrij).
Preparation. 1. The yellow bitter mother-liquors which are obtained
in the manufacture of quinine, and remain on distilling off the alcohol
and separating the quinine, contain a large quantity of quinidine, which
is precipitated partially only by ammonia in white flocks running
together to a yellow resin. From the strongly ammoniacal filtrate
caustic soda throws down a mixture of quinidine, resin, and lime
(Henry & Delondre).
10
2. From the commercial quinoïdine. That soluble in ether answers the
purpose best (Delffs). 100 grammes of commercial quinoïdine are dis-
solved in as small a quantity of ether as possible; the brown-yellow
solution is filtered, decolorised with animal charcoal, and mixed with
1th of its volume of alcohol of 90 p. c.; and the greater part of the
liquid is allowed to evaporate spontaneously; it then deposits a large
quantity of crystals, which are purified by washing with alcohol.
After neutralising with dilute sulphuric acid, the mother-liquor yields
at first a further quantity of quinidine as sulphate, and afterwards
sulphate of quinine (van Heijningen). In this way 50 to 60 p. c. of
quinidine is obtained from quinoïdine.
De Vrij dissolves commercial quinoïdine in the smallest possible quantity of
alcohol, and neutralises the solution with aqueous hydriodic acid, whereupon crystals
of hydriodate of quinidine, amounting to 23 p. c. of the quinoïdine employed, soon
make their appearance.
The sulphate of quinidine is decomposed by dissolving it in dilute sul-
phuric acid and precipitating with ammonia. The washed and dried
precipitate is dissolved in 90 p. c. alcohol, from which hydrated quinidine
crystallises on slow evaporation (van Heijningen).
When recrystallised commercial quinidine is exposed to warm air
the crystals of quinidine effloresce, whilst those of cinchonidine retain
their transparency (Pasteur).
When a very dilute aqueous solution of a pure quir.ne-salt is precipitated by
ammonia, and the granular resinous precipitate is washed, dissolved in warm alcohol
of 32°, and mixed with so much water that the solution is rendered milky, and the
liquid is then exposed to the air, the hydrate which is thrown down at first in the
form of a fluid resin, is converted into fine radiated crystals, and the sides of the
vessel become covered with needles. The crystals are efflorescent, long, six-sided
prisms, which soften when heated, and melt to a yellow transparent resin at 150° to
155° (Henry & Delondre). This statement probably refers to quinidine, which
Henry & Delondre at that time regarded as very pure quinine (Kr.).
Properties. The hydrated crystals (see below) lose their water of
crystallisation at 110° to 130°, becoming anhydrous. The salt melts at
160° to a transparent liquid, which solidifies to a resin on cooling. Has a
slightly alkaline reaction in aqueous solution (van Heijningen; Henry &
Delondre). Very bitter, especially in acid or alcoholic solution (Henry &
Delondre). Exerts a right-handed action on polarised light [a] j=
250-75° (Pasteur; Herapath). According to Bouchardat & Boudet
(N. J. Pharm. 23, 288) Henry & Delondre's quinidine produces a left-
handed rotation. Occurs in the urine after being taken (Herapath).
298
PRIMARY NUCLEUS CH28; OXYAZO-NUCLEUS CN2H22O¹.
Dried.
Henry &
Delondre.
van Heijningen.
mean.
Stenhouse
40 C
240
74.07
74.44
74.08
74.04
2 N
28
8.64
8.68
8.55
24 II
24
7.41
7.10
7.44
7.71
40
32
9.88
9.78
9.93
་་
C40N2H2404
321
100.00
100.00
100.00
Isomeric with quinine (Henry & Delondre).
1
Decompositions. 1. Quinidine burns on platinum foil with an aromatic
odour like that of melilot, a part volatilising (van Heijningen ;
Henry & Delondre).-2. Quinidine-salts, when heated, are converted
into salts of quinicine (Pasteur). See page 302. Chlorine-water and
ammonia colour quinidine green, even in solutions containing only th
of the alkaloid (Pasteur; Herapath). In concentrated solutions a pre-
cipitate is formed, which is not the case with quinine (Herapath).
Chlorine-water, ferricyanide of potassium, and ammonia, added in suc-
cession to salts of quinidine, produce a permanent bulky precipitate,
whilst the same reagents produce, with salts of quinine, only a red
coloration which quickly disappears (Schwarzer, N. Jahrb. Pharm.
23, 348). Quinidine forms with iodine and sulphuric acid a compound
corresponding to Herapathite (p. 313). Quinidine heated for half an
hour with iodide of ethyl, forms hydriodate of ethyl-quinidine (Sten-
house).
Combinations. With Water. ·A. Hydrated Quinidine. Obtained
from ether or warm alcohol in transparent, clinorhombic crystals,
which turn white and opaque in the air (van Heijningen). Broad dis-
tinct crystals (Stenhouse). White needles (Henry & Delondre).
Remains as a transparent gum (hydrated? Kr.) on evaporating a
solution in chloroform (Herapath).
The crystals effloresce rapidly in the air (Henry & Delondre; Pas-
teur). They lose 10.8 p. c. of water at 110° to 130° (van Heijningen),
5.8 p. c. at 130° (Henry & Delondre).
Crystals.
van Heijningen.
C40N2H2404
4HO
324
90.00
36
10.00
10.8
C40N2H2404,4HO.... 360
100.00
B. Aqueous solution. — Quinidine (crystallised? Kr.) dissolves in
1,500 parts of water at 8°, and in 750 parts of boiling water, from
which the greater part is deposited in crystals on cooling (van Heij-
ningen; De Vrij). This crystallisation was not observed by Delffs
(N. Jahrb. Pharm. 11, 321). The cold aqueous solution becomes milky
on the addition of a large quantity of alkali. It is rendered brown by
tincture of iodine, and is not precipitated by nitrate of silver or mer-
curic nitrate.
With Acids. Quinidine forms mono- and bi-acid salts (van Heij-
ningen), which resemble the salts of quinine, but are, for the most
part, more easily crystallisable (Henry & Delondre). The sulphates,
the mono-acid hydrochlorate, and the oxalate exert a powerful action
on polarised light (Herapath). The salts are in some cases more
QUINIDINE.
299
އ
soluble than the corresponding salts of quinine, so that oxalic, acetic,
and tartaric acids do not precipitate soluble quinidine-salts. The hy
drochlorate and nitrate are less soluble (van Heijningen). With
excess of acid the salts are as highly fluorescent as those of quinine
(Herapath; Stenhouse). The precipitate thrown down by ammonia in
their solutions dissolves far less easily than quinine, but more easily
than cinchonidine, in excess of ammonia (Kerner). Tartaric acid does
not prevent the precipitation of quinidine by bicarbonate of soda (Riegel,
Jahrb. pr. Pharm. 25, 340).
Sulphate of Quinidine. A. Mono-acid. Resembles sulphate of
quinine, but is softer and less woolly to the touch. Gives off its water
of crystallisation at 130° (van Heijningen).
The salt dissolves in 350 parts of water at 10°, and in 32 parts of
absolute alcohol (van Heijningen). It dissolves in cold aqueous solu-
tions of Glauber's salt and Rochelle salt so freely, that the presence
of quinidine is indicated in the filtrate by ammonia, and by chlorine-
water and ammonia (C. Mann). A solution in boiling water is
greenish (Herapath).
at 100°.
van Heijningen.
C40N-H2404
SO3
324
75.88
40
9.37
9.58
HO
9
2.11
6 aq.
54
12.64
12.84
C40N2H240+,HO,SO³ + 6 aq.
427
100.00
-
B. Bi-acid. Crystals, very easily soluble in cold water
(van Heijningen). Circular tufts of fine needles. When one of the
tufts is laid upon a plate of tourmaline covered with selenite, opposite
quarters of the circle appear of the same colour, whilst the inter-
mediate quarters exhibit the complementary colour (green and red or
yellow and blue) (Herapath).
Hydriodate of Quinidine.-A. Mono-acid. Iodide of potassium
throws down from sulphate [or hydrobromate (De Vrij)] of quinidine, a
white granular precipitate, which crystallises from boiling water in
needles (Henry & Delondre). Small, white, very hard and heavy
crystals. Dissolves in 1,250 parts of water at 15°, and crystallises
easily from a boiling saturated solution on cooling (De Vrij).
B. Bi-acid. Fine, pale-yellow salt, soluble in 90 parts of water
at 15° (De Vrij).
Quinidine behaves towards biniodide of potassium in the same manner
as quinine (Bouchardat & Boudet). Iodine dissolved in hydriodic acid.
throws down from all salts of quinidine an abundant red-brown pre-
cipitate (De Vrij).
Hydrobromate of Quinidine. The mono-acid salt resembles the
hydriodate, but dissolves in 200 parts of water at 14°. It is precipi-
tated from the hydrochlorate by bromide of potassium (De Vrij).
—
Hydrochlorate of Quinidine. A. Mono-acid.-Chloride of sodium
throws down from cold saturated aqueous solutions of sulphate of
quinidine, light woolly crystals, resembling hydrochlorate of quinine
(De Vrij). By dissolving quinidine in aqueous bydrochloric acid, fine
300
PRIMARY NUCLEUS C40H25; OXYAZO-NUCLEUS CON³H2O¹.
transparent crystals are obtained, which lose 4.79 p. c. of water at
120°, (2 at. = 49 p. c. HO). Dissolves easily in water and in alcohol
(van Heijningen).
C40N2H2404
HCI
C40N2H2404,HC1
at 130°.
van Heijningen.
324
89 87
36.5
10.13
9.48
360.5
100.00
B. Bi-acid. In a current of hydrochloric acid gas, 100 parts of
quinidine take up 22.52 parts of the acid (calc. for CN2H04,2HC1
21.91 parts); a solution of the compound in water yields large, fine
crystals (van Heijningen).
Nitrate of Quinidine.
When quinidine is added in excess to nitric
acid, and the solution is filtered, large, flat, shining crystals separate
(van Heijningen).
Chloride of Zinc with Mono- and Bi-acid Hydrochlorate of Quinidine.
Slightly acid solutions of chloride of zinc throw down from alcoholic
quinidine a granular powder, slightly soluble in cold and in boiling.
water, but easily soluble in dilute hydrochloric acid.
The easily
formed solution of the precipitate in alcohol of 50 p. c. yields
crystals resembling calcspar, and containing 26-7 p. c. of chlorine
(C40N2H2O4, 2HC1+2ZnCl26.65 p. c. Cl); when re-crystallised, the
compound gives up hydrochloric acid and chloride of zinc, and is ulti-
mately transformed into large hexagonal tables and prisms. The latter
contain 7.44 p. c. of zinc at 100°, and are, therefore, C4°N H²40¹,HCl +
ZnCl (calc. 7-58 p. c. Zn) (Stenhouse).
=
Chloromercurate of Quinidine. - Precipitated as a white powder on
mixing hydrochlorate of quinidine and chloride of mercury, and obtained
in pearly laminæ from a solution in boiling alcohol. Melts under
boiling water. Dissolves slightly in cold, more easily in hot water,
and especially in water containing hydrochloric acid; from the last
solvent it is occasionally deposited in the form of a resin (Stenhouse).
Stenhouse.
C40N2H2404
2H,Hg.......
3 Cl
at 100°.
324
60.84
102
19.15
106.5
20.01
20.01
100.00
C40N2H2404,2HCl,HgCl.... 532.5
Quinidine with Nitrate of Silver. Alcoholic quinidine solidifies on
addition of nitrate of silver, from formation of fine needles, which are
to be washed with cold water and recrystallised from boiling water
containing nitric acid. Fine silky needles, having a silvery lustre
when dry. Decomposes when recrystallised from alcohol, with sepa-
ration of silver (Stenhouse).
C40N2H2404
NO6
Ag
at 100°.
Stenhouse.
324
65.59
62
12.55
108
21.86
21.59
494
100.00
C40N2H2404,AgO,NO5
Chloroaurate of Quinidine. Thrown down from cold hydrochlorate
QUINIDINE.
301
of quinidine by excess of terchloride of gold, as a pale-yellow precipitate,
which is to be dried in a vacuum, and afterwards at 100°. Melts at
115°, or on boiling with water, and turns brown (Stenhouse).
C40N2H2404
2HC1,6C1
2 Au
C40N2H2404,2HCl,2AuCl³
Stenhouse.
at 100°.
324
32.29
286
28.52
393.2
39.19
39.15
1003.2
100.00
Chloroplatinate of Quinidine. Separates immediately in the form of
a precipitate on adding bichloride of platinum to a strong cold solution
of hydrochlorate of quinidine; from hot or dilute solutions crystals are
obtained after some time. When recrystallised from boiling dilute
hydrochloric acid, it forms shining, irregular crystals.- Decomposes
at 200°, with an odour of white-thorn. Dissolves with difficulty in
water either cold or boiling (Stenhouse). Gives off 4.86 p. c. of water
at 100°.
C40N2H2404....
2 H
6 Cl
2 Pt...
4 HO
C40N2H2404,2HC1,2PtCl2 + 4 aq.
Air-dried.
van Heijningen.
324
41.96
42.55
2
0.25
213
27.57
27.85
197.4
25.56
25.65
36
4.66
4.86
772.4
100.00
The salt dried at 150° contains 26 66 p. c. of platinum (Stenhouse) (calc. 26.67
p. c.).
Quinidine is coloured pale-yellow by platinocyanide of potassium
(Delffs).
Acetate of Quinidine. - Crystallises from the syrupy solution on
standing for some days, in fine, transparent crystals (van Heijningen).
Turns blue litmus paper red, and red blue (De Vrij).
-
Oxalate of Quinidine. A. Bibasic. Small brittle crystals, ob-
tained by neutralising oxalic acid with quinidine. Nearly insoluble in
cold, but freely soluble in boiling water (Stenhouse).
at 100°.
Stenhouse.
84 C
504
66.67
66.45
4 N
56
7.41
52 H
52
6.88
7.17
18 O
144
19.04
2C40N2H2404, C4H2O8 + 2 aq.
756
100.00
....
B. Mono-acid.
Obtained by van Heijningen in the same way as
the bibasic salt was obtained by Stenhouse, and not by double decom-
position. Pearly crystals, giving off 4.32 p. c. of water at 120° (van
Heijningen).
Crystals.
van Heijningen.
C40N2H2404
C4H208
324
77.89
74
17.79
2 HO
18
4.32
19.83
4.32
C40N2H2404, C4HºOº + 2 aq.
416
100.00
302 PRIMARY NUCLEUS C40H25; OXYAZO-NUCLEUS CON²H²304.
Succinate of Quinidine forms pearly prisms (Henry & Delondre).
Tartrate of Quinidine. - Pearly crystals, obtained in the same way
as the oxalate (van Heijningen). The dextrotartrate and antitartrate
undergo the same transformation as the quinine-salts when heated
(Pasteur).
Tartrate of Quinidine and Potash? Quinidine and cream of tartar
yield crystals soluble in alcohol (Henry & Delondre).
Tartrate of Antimony and Quinidine. 1. Mono-acid tartrate of
quinidine is boiled for some hours with freshly precipitated oxide of
antimony, and the filtrate is left to evaporate. 2. Powdered quinidine
is added to a cold saturated aqueous solution of tartar-emetic; the
liquid is heated to boiling; and the excess of quinidine, together with
the precipitated oxide of antimony, is separated by filtration from the
solution of the double salt and neutral tartrate of potash. — Long,
slender needles, which, after drying in a vacuum, lose to 1 per cent.
of water at 100°. Dissolves slightly in cold, easily in hot water, and
easily also in boiling alcohol, from which it crystallises (Stenhouse).
Stenhouse.
48 C
2 N
29 H
18 O
Sb
In vacuo.
mean.
at 100°.
288
47.28
47.87
47.51
28
4.59
29
4.76
5.53
4.87
144
23.63
....
120.3
19.74
20.53
19.61
100.00
CN?H*O*,HO,SbO3,CSH*O10.... 6093
Picrate of Quinidine. - A solution of quinidine in boiling picric acid
deposits, on cooling, a resin which does not crystallise from solution
in alcohol on evaporation (Stenhouse).
Aqueous quinidine is precipitated white by tannic acid (van
Heijningen). Quinidine behaves like quinine with oleic acid and olive
oil (Attfield).
Quinidine dissolves in 45 parts of absolute alcohol at 8°, and in 3.7
parts of boiling alcohol (van Heijningen). It is deposited from solu-
tion in alcohol of 15° to 18° Baumé, in crystals, or in the form of a
resin which crystallises when treated with aqueous alcohol (Henry &
Delondre). Dissolves in 90 parts of ether (van Heijningen).
Quinicine.
C'¹ºN²H²404 = C¹¹ºN²H²²04,H².
PASTEUR. Compt. rend. 37, 111, and 166.
On heating a salt of quinine or of quinidine, especially a salt
which melts below the temperature of decomposition, one and the same
isomeric product, quinicine, is formed in both cases. Quinicine exerts
a right-handed rotatory action on polarised light, and resembles cin-
chonicine (p. 230), except in composition; a solution of quinicine in
aqueous racemic acid, however, deposits at first chiefly the dextro-
QUINOÏDINE.
303
tartrate, whilst the antitartrate accumulates in the mother-liquor. -
Quinicine is coloured green by chlorine-water and ammonia, though
less intensely than quinine (Herapath).
Appendix to Quinidine and Quinicine.
Quinoïdine.
SERTÜRNER. Hufel & Osann's Journ. 1829, 95.
THIEL. Mag. Pharm. 2, 83.
BUCHHOLZ. N. Tr. 6, 2, 94.
GRUNER. Br. Arch. 12, 156.
GEIGER. Mag. Pharm. 7, 44; Handb. der Pharm. 4 ed. 1, 1048.
HENRY & DELONDRE. J. Pharm. 16, 144; N. Tr. 22, 1, 244; abstr.
Schw. 60, 343.
GUIBOURT. J. Chim. méd. 6, 357; abstr. Schw. 60, 245.
DUFLOS. Schw. 62, 308.
LIEBIG. Ann. Pharm. 58, 348.
WINCKLER. Jahrb. pr. Pharm. 7, 65; 13, 361; 15, 281; Repert. 98,
391; Jahrb. pr. Pharm. 17, 32; 18, 367; Kopp's Jahresber. 1849,
373.
Sertürner recognised the basic nature of quinoïdine, and distinguished it from
quinine and cinchonine as a peculiar uncrystallisable base. He is, therefore, to be
regarded as the discoverer of amorphous quinine.
Quinoïdine occurs in commerce as a brown resinous mass, which is
obtained in the manufacture of quinine and cinchonine by precipitating
the brown uncrystallisable mother-liquors with ammonia or potash, and
washing and drying the precipitate. Sertürner's quinoïdine was
obtained in a similar manner.
The product obtained by evaporating the mother-liquors of sulphate
of quinine to dryness also occurs in commerce as quinoïdine (Geiger).
Concerning the adulterations of quinoïdine, and the detection thereof, see Walz
(Jahr. pr. Pharm. 19, 270); R. Lehmann (N. Br. Arch. 61, 132); Volland (N. Br.
Arch. 61, 136); Overbeck (N. Br. Arch. 61, 304); Wessel & Wolpert (N. Br. Arch.
61, 306, and 62, 308); Winckler (Jahrb. pr. Pharm. 18, 371).
There appear to be two kinds of quinoïdine, which may be dis-
tinguished as follows:-
a. Containing quinidine, with smaller quantities of quinine, cinchonine,
and resin. Dissolves freely in ether. Obtained from inferior kinds of
cinchona-bark, but not from Cinchona regia or C. flava dura (Winckler).
Commercial quinoïdine was found to contain 72.75 p. c. C., 7.30
H., and 8.68 N., and was separable into 3 p. c. quinine, 6 to 8 p. c.
cinchonine, and 50 to 60 p. c. quinidine. When this body is dis-
solved in dilute sulphuric acid, and the solution is warmed for some
hours, so that it acquires a dark-brown colour, it yields on cooling few
or no crystals of sulphate of quinidine. On pouring the solution thus
treated into a large quantity of water, filtering from the black precipi-
tate which is deposited, precipitating the filtrate with ammonia, and
dissolving the precipitate in sulphuric acid, crystals of sulphate of
304
PRIMARY NUCLEUS C4029; OXYAZO-NUCLEUS C4N2H2O¹.
quinidine are obtained. Quinoïdine contains also amorphous quinine
(van Heijningen).
Duflos and Roder, who believed they had obtained sulphate of
quinine from quinoïdine, appear to have investigated a similar quinoï-
dine, and to have confounded quinine with quinidine.
Roder (J. Chim. med. 25, 184) dissolves quinoïdine in 4 parts of
alcohol, adds gradually 13 parts of chloride of tin dissolved in 2 parts
of water, whereby a resinous precipitate is thrown down, and preci-
pitates the decanted liquid with ammonia. The grey-white precipitate
is washed, again treated in the same way as the original quinoïdine,
and precipitated with ammonia; and the precipitate is dissolved in
alcohol, and combined with sulphuric acid, whereupon the sulphate
crystallises. Winckler did not obtain crystals by this process.
Duflos (Schw. 62, 308) mixes the uncrystallisable mother-liquor
evaporated to a syrup with half its weight of oil of vitriol, with
constant stirring. After standing for some hours, the liquid is diluted
with water, neutralised almost completely with milk of lime, strained,
and pressed; and the filtrate is digested with animal charcoal. The
liquid, again filtered, is precipitated with milk of lime, and the precipi-
tate is collected, dried, and exhausted by boiling with alcohol of 80 p.c.
The tincture distilled to rd of its bulk, deposits crystals of cinchonine
on standing, whilst the mother-liquor, neutralised with sulphuric acid,
diluted with water, and freed from alcohol by distillation, yields
sulphate of quinine [quinidine (Kr.)].
b. Quinoidine consisting chiefly of uncrystallisable transformation-pro-
ducts of the Cinchona-bases. Dissolves to the extent of 20 to 25 p. c.
and often only to 5 or 10 p. c. in pure ether (Winckler).
When true Cinchona regia or Cinchona flava dura is employed in the
preparation of quinine, the brown-red mother-liquor contains neither
quinidine nor cinchonidine, but traces only of amorphous quinine,
cinchonine, and a red-brown resin, insoluble in ether (Winckler).
Quinoïdine is always a transformation-product of the cinchona-
alkaloids, being formed either in their preparation or in the drying of the
cinchona-tree. In the latter case the change is produced especially by
sunlight, since the salts of quinine and cinchonine turn red-brown in
the sun (Pasteur).- Quinoïdine is a mixture of amorphous quinine and
two non-bitter resins, and does not contain any peculiar alkaloïd.
(Winckler).
On treating quinoïdine with commercial ether, evaporating the
solution, and treating the residue with pure ether, a portion only is
dissolved. The undissolved portion behaves exactly like the product
obtained by the action of oil of vitriol on cinchonine (p. 203); it forms
also a yellow, loose, pulverulent platinum-salt, containing 22.5 to
23.5 p. c. of platinum (Winckler).
Quinoïdine neutralises acids, and yields a large quantity of chinoline
when distilled with caustic potash; but its salts are uncrystallisable.
On dissolving it in acids, precipitating the solution by ammonia or
carbonate of soda, agitating the precipitate with ether, which dissolves
it almost completely, and evaporating the ethereal solution, an
amorphous residue, resembling the original quinoïdine, remains. The
same amorphous quinine is obtained also by warming quinoïdine with
aqueous sulphate of copper (which dissolves it, with separation of
oxide of copper), removing the copper by means of hydrosulphuric
QUINOÏDINE.
305
acid, and precipitating the alkaloïd with an alkali. It contains, on the
average, 73.65 p. c. C., 7·63 H., and 8.79 N. It is insoluble in cold,
but slightly soluble in hot water, and neutralises acids, forming
uncrystallisable salts, from which it is precipitated by ammonia and
alkaline carbonates. The platinum-salt resembles the corresponding
quinine-compound, and contains 32.44 p. c. C., 3·86 H., and 26.37 Pt.
This amorphous quinine dissolves in alcohol, from which it is preci-
pitated as a resin by water; it is soluble also in ether (Liebig).
Powerfully antifebrile (Hruschauer, Ann. Pharm. 60, 116).
Winckler's amorphous quinine is obtained from quinoïdine or from
the mother-liquors of the sulphate.
1. From the mother-liquors of Sulphate of Quinine. The mother-
liquors, diluted with hot water, are saturated with sulphate of
soda, and precipitated in portions by carbonate of soda so long
as a dark-brown resin is separated thereby, and till the super-
natant liquid appears of a wine-yellow colour. The precipitated
resin contains only small quantities of cinchonine and amorphous
quinine, which may be extracted by successive treatment with "ether
and alcohol. From the wine-yellow liquid, excess of carbonate of
soda throws down white flocks, running together to a resin, and con-
taining cinchonine and amorphous quinine, the former of which may be
separated by repeatedly dissolving the precipitate in ether-alcohol,
leaving the solution to crystallise, precipitating the alcoholic solution
with a large quantity of ether, and dissolving the precipitate in pure
ether (Winckler).
2. From Quinoïdine. - Quinoïdine is mixed with its own weight of
oil of vitriol and allowed to stand at a temperature not exceeding 37°,
till the syrup becomes perfectly homogeneous, for which purpose several
days are required when large quantities are employed. The liquid is
then diluted and filtered, the hot filtrate is precipitated with carbonate
of soda, and the precipitate washed with hot water. The precipitate is
still coloured: it is therefore suspended in 12 parts of water; acetic
acid is added till solution is nearly complete; the liquid is decolorised.
with animal charcoal and afterwards precipitated by ammonia; these
operations are repeated; and the product is washed and dried. The
pale-yellow resin, easily triturable to an electric powder, still contains
cinchonine, which remains behind on dissolving in ether. The portion
soluble in ether forms with sulphuric acid a salt which is distinguished
from sulphate of quinine by its ready solubility. When this body is
freed from admixed quinine as far as possible by crystallisation, and
then mixed, in neutral solution, with phosphate of soda (whereby only
a very little phosphate of quinine is precipitated on standing for several
days) two layers are formed, from the lower of which ammonia throws
down amorphous quinine.
By the fractional precipitation of its, hydrochloric solution with
carbonate of soda, quinoïdine may be resolved into a resin insoluble in
alcohol, and a pale-yellow portion richer in alkaloïds.
When amorphous quinine is precipitated from the sulphate by car-
bonate of soda, the white flocks immediately run together to a hard
yellow resin, which, after washing with hot water and drying over the
water-bath, dissolves perfectly in ether. The ethereal solution mixed
with th of alcohol, deposits no crystals on spontaneous evaporation,
0
VOL. XVII.
X
306 PRIMARY NUCLEUS C40H28; OXYAZO-NUCLEUS C40N2H22O¹.
excepting a little admixed cinchonine, and after incomplete neutrali-
sation with sulphuric acid, dries up to an amorphous yellow gum,
which may be triturated to a nearly white powder, dissolves easily in
all proportions of cold water, and when dried over the water-bath, con-
tains 10.65 p. c. of sulphuric acid. On dropping alcoholic sulphuric
acid into an ethereal solution of amorphous quinine, the sulphate is
thrown down in the form of a yellow syrup. The hydrochlorate (and
acetate) also is uncrystallisable: it is not affected by hyposulphite of
soda, but is precipitated in loose flocks by chloride of mercury
(Winckler).
Batka (Chem. Centr., 1859, 913; Pharm. Viertelj. 9, 277) describes
as quinio, a yellow resin rich in quinine and resembling quinoïdine,
obtained by exhausting fresh cinchona-bark with alcohol and lime. He
supposes it to be the form in which cinchona-bases are present in the
bark.
Conjugated Compounds of Quinine or Quinidine, and Compounds derived
therefrom.
SCHÜTZENBERGER.
Hydroquinine.
C4CN2H2606 = C4°N2H240°,H².
Compt. rend., 46, 1065; J. pr. Chem. 74, 227
Ann. Pharm. 108, 347; Chem. Centr. 1858, 541; Kopp's Jahresber.
1858, 370.
Hydrate de quinine. Contains H2O2 more than quinine.
Obtained from quinine by the action of zinc and sulphuric acid in
the same manner as hydrocinchonine (p. 231).
Amorphous resin, nearly as bitter as quinine. Softens at 35°, and
melts at 100° (as hydrated hydroquinine? Kr.).— Hydroquinine, dried
at 120°, contains 2 at. of water, one of which is expelled slowly at
140°, and the other at 150°.
Hydroquinine exhibits the same green coloration as quinine with
chlorine-water and ammonia.
It combines with 1 and 2 at. water. (See above.)
at 140°.
Schützenberger.
40 Č
2 N
240
68.37
68.40
28
7.98
27 H
27
7.69
7.53
70
56
15.96
C40N2H2606 + HO
351
100.00
....
at 120°.
Schützenberger.
40 C
240
66.66
66.19
2 N
28
7.78
28 H
28
7.78
7.93
80
64
17.78
C40N2H2606 + 2HO.... 360
100.00
The salts of hydroquinine are more soluble than the corresponding
QUININE-SULPHURIC ACID.
307
quinine-salts. The sulphate crystallises with difficulty. The pla-
tinum-salt contains, at 100°, 26.2 p. c. of platinum (C4°Ñ²H²ºOº,2ÏICI,
2PtCl² = 26·2 p. c. Pt).
Hydroquinine dissolves in alcohol and in ether.
Oxyquinine.
C40N2H2406 C40N2H2206,H2.
SCHÜTZENBERGER. Compt. rend. 47, 81; J. pr. Chem. 75, 124; Ann.
Pharm. 108, 350; Chem. Centr. 1858, 678; Kopp's Jahresber. 1858,
371.
Sulphate of quinine is boiled with aqueous nitrite of potassium, and
after the evolution of nitrogen has ceased, the cooled solution is precipi-
tated by ammonia. The white crystalline precipitate is obtained in the
anhydrous state by dissolving it in alcohol, evaporating the solution
over the water-bath, and drying the residual resin at 130°.
Colourless, transparent resin, which does not melt at 140°. Less
bitter than quinine.
at 150°.
Schützenberger.
40 C .......
240
70.59
70.32
2 N
28
8.23
6.36 (?)
24 H'......
24
7.06
7.40
6 0 ...
48
14.12
1.5.92
100.00
100.00
C40N2H2406 ........ 340
Oxyquinine in contact with water takes up a large quantity thereof
and becomes converted into crystalline granules, which melt at 100°.
It dissolves slightly in water.
The platinum-salt, C40N2H240°,2HCl,2PtC, contains 25.90 p. c. of
platinum (by calc. 25.95 p. c. Pt).
Oxyquinine is soluble in alcohol and in ether.
Quinine-sulphuric Acid.
C40N2H2SO = C40N2H2404,SO³.
SCHÜTZENBERGER. Compt. rend. 47, 236.
Acide sulfoquinique.
Obtained by dissolving quinine in fuming sulphuric acid, in the
same manner as cinchonine-sulphuric acid (p. 232), and resembles the
latter body.
The baryta-salt yields, after drying at 100, 27.02 p. c. sulphate
of baryta (calculation for CN2H23 Ba04,SO requires 26.99 BaO,SO).
Has a bitter taste.
x 2
308
PRIMARY NUCLEUS C402; OYXAZO-NUCLEUS C40N2H22O4.
Methyl-quinine.
C42N2H2604 C40N2H2(CH)04, H².
=
AD. STRECKER. Ann. Pharm. 91, 164.
The addition of 1 at. H. forms the hypothetical methyl-quinium, corresponding to
ammonium. Known only in combination with hydriodic acid.
When iodide of methyl is added to an ethereal solution of quinine,
crystals of hydriodate of methyl-quinine are formed in the liquid after
standing for a while. The compound resembles hydriodate of ethyl-
quinine in its behaviour with ammonia and caustic potash.
Strecker.
40 C
2 N
at 100°.
252
54.08
54.2
28
6.01
27 H
4 O
27
5.79
5.9
32
6.87
I
127
27.25
26.9
C¹¹ºN³H23 (C²H³)O,HI.... 466
100.00
AD. STRECKER.
Ethyl-quinine.
C44N2H2804 = C¹ºN³H²¹(C¹H³)O‘,H².
Ann. Pharm. 91, 163.
With the addition of 1 at. H. it forms the ethyl-quinium of the ammonium-theory.
Known only as hydrate, and in combination with acids.
Iodide of ethyl in contact with alcoholic or ethereal solution of
quinine, forms, after some hours, yellow needles of hydriodate of ethyl-
quinine, an aqueous solution of which is converted by oxide of silver
into iodide of silver and a strongly alkaline solution of ethyl-quinine.
When the latter is evaporated, and the amorphous residue is dissolved
in alcohol and mixed with ether, a syrup is precipitated which is
gradually converted into colourless needles, probably of hydrate of
ethyl-quinine.
M
Tastes caustic and bitter in aqueous solution. When heated to
120°, it evolves an odour of chinoline and decomposes. A strong alco-
holic solution is not altered by iodide of ethyl.
Ethyl-quinine dissolves easily in water. It forms with acids, mono-
and bi-acid salts. Aqueous ethyl-quinine absorbs carbonic acid from
the air, and is converted into an uncrystallisable alkaline salt.
Sulphate of Ethyl-quinine. — A. Mono-acid. Obtained by decompos-
ing hydriodate of ethyl-quinine with sulphate of silver. Crystals which
give off 14.8 p. c. of water at 110° (8 at. = 15·2 p. c. HO).
15.2 p. c. HO). Dissolves
slightly in water, and more easily than B in alcohol.
•
ETHYL-QUININE.
Dried.
ཟླ་༡༠ ཕྱི་- བྲུ
C44N2H2804
352
9
40
87.78
2.24
9.98
HO
SO3
C44N2H2804,HO,SO³.... 401
100.00
Strecker.
10.1
309
B. Bi-acid. Aqueous ethyl-quinine mixed with a quantity of sul-
phuric acid sufficient to produce a strong acid reaction, leaves on eva-
poration a syrup, which, in contact with absolute alcohol, is transformed
into crystals, which may be freed from excess of acid by washing with
alcohol. - Needles, having an acid reaction, and losing 8.2 p. c. of
water at 120° after drying over oil of vitriol (4 at. = 4 p. c. HO). — Dis-
solves very easily in water, without crystallising on evaporation;
caustic potash throws down from the concentrated solution a precipi-
tate soluble in water (probably mono-acid sulphate). The salt dissolves
in alcohol.
C44N2H2804
2 HO.....
2 S03
Dried.
Strecker.
352
78.22
18
4.00
80
17.78
18.2
100.00
C4N2H2804,2HO,2SO³.... 450
Hydriodate of Ethyl-quinine. Purified by washing with water and
recrystallising from ether. Very light, colourless, silky needles,
neutral, unchangeable at 110°, melting at a higher temperature, with-
out loss of weight, and solidifying to a vitreous mass on cooling.
Tastes very bitter. Dissolves freely in water and is not precipitated
by ammonia, but is thrown down in an unaltered state by a large quan-
tity of caustic potash after standing for some time. Dissolves in
alcohol, but not in ether.
Strecker.
at 100°.
mean.
44 C.......
2 N......
29 H
4 O........
264
55.00
54.9
28
5.83
....
29
6.04
6.2
32
6.66
I
127
26.47
26.4
C44N2H2804,HI
480
100.00
....
Hydrochlorate of Ethyl-quinine. Obtained with difficulty from hydro-
chloric acid and ethyl-quinine, or more easily by decomposing nitrate
of ethyl-quinine with chloride of sodium. Slender needles, united in
hemispherical groups. Neutral. Dissolves much more easily in boil-
ing than in cold water.
C44N2H290¹.......
Cl................
at 120°.
353
35.3
Strecker.
90.86
9.14
9.1
100.00
C44N2H204,HCl.... 3885
Nitrate of Ethyl-quinine does not crystallise on evaporation.
Chloroplatinate of Ethyl-quinine. - Yellow precipitate, crystallising
from a solution in boiling water, on cooling, in indistinct crystals.
310
PRIMARY NUCLEUS C40H28; OXYAZO-NUCLEUS C40N2H”Oª.
at 110°.
Strecker.
CªN2H2804,2HCl,4C1 ........ 567·0
74.18
2 Pt
197.4
25.82
25.4
C4N2H04;2HC1;2PtCl2.... 7644
100.00
Hydrate of ethyl-quinine dissolves easily in alcohol.
Ethyl-quinidine.
C44N2H2O = C40N2H2(CH)04,H³.
STENHOUSE. Ann. Pharm. 129, 20.
Known only in combination with water and with acids.
Obtained as hydriodate of ethyl-quinidine by heating quinidine for
half an hour with excess of iodide of ethyl. On separating the
iodine from a solution of this salt by means of oxide of silver, the
filtrate contains aqueous ethyl-quinidine, the alkaline bitter solution of
which absorbs carbonic acid on evaporation, but yields no crystals.
Sulphate of Iodethyl-quinidine is obtained in the same way as the
corresponding quinine-compound (Herapath).
Hydriodate of Ethyl-quinidine. This salt alone, and not a compound of
biethyl-quinidine, is obtained by again treating a strong aqueous solution of ethyl-
quinidine with iodide of ethyl.-Long, silky needles, nearly insoluble in
cold water, crystallising from boiling dilute alcohol.
at 100°.
Stenhouse.
C44N2H2904
353
73.54
I .......
127
26.46
26.39
C44N²H²³ (C+H³)04,HI .... 480
100.00
Chloroplatinate of Ethyl-quinidine. - The hydriodate is decomposed by
chloride of silver, and the filtrate precipitated by bichloride of platinum.
-Pale-yellow powder. Dissolves very slightly in cold or boiling
water, and somewhat more freely in hot dilute hydrochloric acid.
at 100°.
Stenhouse.
C44N2H2804
352
46.02
2 HC1,401
215
28.12
2 Pt....
197.4
25.86
25.61
C40N2H23 (CH)04,2HCl,2PtCl²
764.4
100.00
SCHÜTZENBERGER.
Benzoyl-quinine.
C54N2H2806 C40N2H23(C14H502)04.
=
Compt. rend. 47, 234.
Chloride of benzoyl is poured upon quinine dried at 130°, where-
upon an evolution of beat occurs, and the quinine deliquesces to a
SULPHATE OF IODOQUININE.
311
thick syrup, composed of hydrochlorate of benzoyl-quinine and excess.
of chloride of benzoyl. The syrup is dissolved in water; the base is
precipitated by ammonia; and the white resinous mass is dried at 140°,
at which temperature it gives off a large quantity of water.
54 C
2 N
at 140°.
324
75.70
Schützenberger,
75.76
28
6.54
28 H
28
6.54
6.76
60
48
11.22
C40N*H23 (C¹4H5O²) 04
428
100'00
Benzoyl-quinine is coloured green by chlorine-water and ammonia.-
The platinum-salt contains 23.2 p. c. platinum (cale, for C40N2H23(C¹¹H³Ọ²)O¹,
2HC1,2PtCl² requires 23.5 p. c. Pt).
Compounds of the Cinchona-bases with Iodine and
Sulphuric Acid.
HEKAPATH. 1. Phil. Mag. [4] 3, 161; 4, 186; Chem. Soc. Qu. J. 5, 177 ;
abstr. with remarks by Zamminer; Ann. Pharm. 84, 149; Kopp's
Jahresber. 1852, 148.-2. Phil. Mag. [4] 6, 346; Ann. Pharm. 88,
207; J. pr. Chem. 61, 82; N. Ann. Chim. Phys. 40, 249.—3. Phil.
Mag. [4] 6, 171; J. pr. Chem. 61, 87; 2 and 3 in abstract; Kopp's
Jahresber. 1853, 198.-4. Phil. Mag. [4] 7, 352; Dingl. 134, 570;
J. pr. Chem. 62, 367; Kopp's Jahresber. 1854, 156.—5. Phil. Mag.
[4] 9, 366; J. pr. Chem. 65, 380; Kopp's Jahresber. 1855, 150.
6. Phil. Mag. [4] 14, 224; J. pr. Chem. 72, 104; Kopp's Jahresber.
1857, 405.-7. Chem. Gaz. 1858, 56; J. pr. Chem. 74, 415.-8. Chem.
Gaz. 1858, 70; J. pr. Chem. 74, 411; Complete: Chem. Soc. Qu. J.
11, 130.-9. Chem. Gaz. 1858, 437; abstr. J. pr. Chem. 76, 364;
Rép. Chim. pure 1, 39; 7 to 9; abstr. Kopp's Jahresber. 1858, 364.
HAIDINGER & STOKES. Wien. Acad. Ber. 10, 106; Pogg. 89, 250;
Kopp's Jahresber. 1853, 198.
When the bi-acid sulphate of a cinchona-base is dissolved in a
warm mixture of alcohol and acetic acid, or in dilute sulphuric
acid, and mixed with a warm alcoholic solution of iodine, crystals
separate on cooling, and are to be washed with alcohol and water,
and dried at 93°.
The crystals contain, in all cases, iodine, sulphuric acid, and the
base. They exhibit various colours of body and surface. Even in
extremely thin plates they polarise light very completely, and possess
also, in other respects, the optical properties of the tourmaline or
Nichol's prism, for which they may be used as substitutes.
A solution of the crystals colours starch blue. It precipitates
nitrate of silver, forming iodide of silver and a compound which is
soluble only in strong nitric acid. The crystals, when treated with
nitric acid, evolve iodine-vapour and nitric oxide; they dissolve
quickly in oil of vitriol, turn red in cold strong hydrochloric acid,
and form with the boiling acid a yellow solution, from which dull
312 PRIMARY NUCLEUS C6H33; OXYAZO-NUCLEUS C40N22H204.
yellow needles are deposited. An alcoholic solution of the crystals is
immediately decolorised by hydrosulphuric acid, soluble sulphides, sul-
phurous acid, and chlorine-water: from the solution treated with hydro-
sulphate of ammonia, or sulphide of potassium, alkalis precipitate the
cinchona-base. Aqueous alkalis and alkaline earths abstract the sul-
phuric acid, and leave a yellow residue containing iodine and the
base. The crystals dissolve in ammonia.
The crystals are nearly insoluble in water, but dissolve slightly
in cold dilute acids and in weak alcohol. They dissolve with brown
colour in boiling alcohol, from which they crystallise on cooling;
water throws down from the solution a brown, amorphous precipitate.
The crystals are nearly insoluble in ether and in chloroform.
If a solution contains at the same time quinine, quinidine, cin-
chonine, and cinchonidine, as bi-acid salts, tincture of iodine throws
down first the quinine-salt, then a mixture of cinchonidine- and quinine-
salts, and afterwards quinidine-salt, whilst the more soluble cinchonine-
salt crystallises only (mixed with quinidine-salt) when a large quantity
of cinchonine is present. Thus the presence of cinchonidine in cincho-
nine, or of quinidine in quinine may be easily recognised.
On the
1. Sulphate of Iodoquinine. Herapathite in the more restricted sense.
100 grammes of bi-acid sulphate of quinine, 1,440 grammes of acetic
acid, and 120 grammes of dilute sulphuric acid (containing 10 per
cent. of anhydrous acid) are heated to 100°, and a solution of 30
grammes of iodine in 1,150 grammes of alcohol is added, whereupon,
after prolonged cooling to 4.5°, the mixture deposits an abundance of
crystals, which are to be washed with acetic acid at 4·5°, re-crystallised
repeatedly from boiling alcohol of sp. gr. 0.838, washed with cold
alcohol, and dried at 32°, and at last over oil of vitriol. Subsequently
Herapath recommended 100 grammes of bisulphate of quinine,
1,920 grammes of acetic acid of sp. gr. 1.042, 480 grammes of alcohol
of sp. gr. 0·837, and 60 grammes of alcoholic solution of iodine.
preparation of larger crystals for optical purposes see Herapath (2 and 4). Elon-
gated, rectangular, quadratic, octagonal, and rhombic laminæ, stellate
groups of needles, or large, very thin plates. By reflected light they
exhibit a shining, cantharides-green colour, with metallic lustre; by
transmitted light they appear very pale olive-green or colourless, and
perfectly transparent. The alcoholic solution is orange-coloured. When
polarised at right angles to the axis the lamina appear red, brown-
red, or black. Sp. gr. = 1·895 at 15°.
1.895 at 15°. The salt dissolves in 1,000
parts of boiling water; in 650 parts of boiling alcohol of sp. gr. 0-837
at 13.9°; in 50 parts of boiling alcohol. Dissolves in 750 parts of
acetic acid of sp. gr. 1·042 at 15.5°, and in 60 parts at the boiling heat;
on prolonged boiling iodine is evolved.
The crystals [dried over oil of vitriol (Hauers)] lose 2.49 p. c.
(Herapath), 2-27 to 2:48 p. c. of water at 100° (Hauers). No iodine is
expelled in drying, but the crystals assume a brownish-red colour,
and turn green again only on absorption of water (3 at. : 2.24 p.c. HO)
(Hauers).
SULPHATE OF IODOQUININE.
313
at 100°.
Herapath.
80 C
480
40.81
41.35
4 N
56
4.76
3.54
51 H
51
4.34
4.70
11 O
88
7.48
9.81
3 SO³.....
120
10.19
9.77
3 I.....
381.3
32.42
30.83
2 C40N2H2404,3(HO,SO³),31
1176.3
100.00
100'00
....
Over oil of vitriol.
Hauers.
80 C ....
4 N
54 H
14 O
3 SO3
3 I
2 C40N2H2404,3 (HO,SO³),31 +3 aq.
4.80
39.89
39.39
56
4.64
54
4.48
4.67
112
9.36
120
9.96
9.98
381.3
31.67
31.69
1203.3
100.00
Herapath gave the evidently incorrect formula C57N2H3305 12,2(HO,SO³) + 3 aq.
He formerly found 10.6 p. c. SO³, 32.6 of iodine, 42.7 of quinine, and 141 of water.
Hauers' analysis was made in Kraut's laboratory.
2. Sulphate of Iodethylquinine. - Either thin needles, perfectly
opaque, or thick plates, transparent and purple-coloured in thin films,
and of a shining metallic green colour by reflected light; or dark or
orange-red laminæ, transparent and orange-yellow by transmitted light.
-
3. Sulphate of Iodoquinidine. When a dilute solution of bi-acid
sulphate of quinidine is heated to 70° or 80° with one-third or half its
volume of alcohol, and a little tincture of iodine is added, long four-
sided prisms of a deep garnet-red colour crystallise out. The crystals
are purple-red by reflected, and dark brown-red by transmitted light.
They dissolve in 121 parts of cold, and 31 parts of boiling alcohol,
from which they are precipitated by water in the form of a cinnamon-
brown powder.
The crystals contain 32.76 p. c. C., 4:44 N., 3.98 H., 6-34 SO³, and
39.73 I, corresponding, according to Herapath, to the formula
C35N2H1904I2, SO3,HO + 5 aq.-Other and optically different crystals
are obtained when tincture of iodine is dropped into a strong solution
of bi-acid sulphate of quinidine mixed with 30 or 40 volumes of alcohol,
at a temperature below 70° (Herapath) (9).
4. Sulphate of Iodethylquinidine is obtained in one form only, re-
sembling the dark purple-red ethylquinine-salt.
5. Sulphate of Iodoquinicine. - Obtained in the preparation of 3, as
a dark blood-red resin.
6. Sulphate of Iodocinchonine. - Long, four-sided, purple-black
needles, deep purple-red by transmitted, dark purple-blue by reflected,
light. Thin lamina transmit lemon-yellow light. - Contains, on the
average, 27.70 p. c. C., 3.31 N., 3·49 H., 50·41 I, and 5.23 SO³, and is,
according to Herapath, CN2H190²I³, SO³+6 aq.
7. Sulphate of Iodocinchonidine. Obtained in three different forms,
with varying proportions of water. a. In green lamine having a blue
body-colour and a brass-yellow surface-colour. They contain, on the
average, 35·49 p. c. C., 4·31 H., 8.63 SO³, and 39.22 O., corresponding,
314
APPENDIX TO THE CINCHONA-BASES.
according to Herapath, to the formula C57N2H330513,2(SO³,HO) + 5 aq.
These crystals absorb light as powerfully as the quinine-salt.
b. When a is allowed to remain long in the mother-liquor containing
sulphuric acid, long golden-yellow, silky needles are formed; they
contain 4 at. water more than a, and may be reconverted into a by
crystallisation from alcohol.-c. The needles retain their yellow colour
in the air, but become olive-green over oil of vitriol or at 100°, losing
5.32 p. c. (= 6 at.) of water. The olive-green salt is likewise con-
verted into a by crystallisation from alcohol.
8. Wittstein's cinchonidine yields, with iodine and sulphuric acid, a
salt having a deep bistre-brown body-colour, and a reddish-brown sur-
face-colour. This salt differs from the foregoing. (Herapath.)
APPENDIX TO THE CINCHONA-BASES.
1. Cinchona-yellow. When the ethereal extract of cinchona-bark is
exhausted with cold water, and the solution is evaporated, there remains
a yellow extractive colouring matter, having a harsh taste, and forming
with hydrate of alumina, a lake which is not affected by alcohol, but
from which acids precipitate the colouring matter in a slightly reddened
condition (Henry & Plisson, J. Pharm. 13, 371). The yellow is easily
soluble in water and alcohol, and slightly soluble in ether. It is pre-
cipitated by basic acetate of lead, but not by tartar-emetic or tiucture
of galls (Pelletier & Caventou).
2. Bitter Alkaloid of Carapa-bark. Extracted from the bark by
boiling alcohol, after previous exhaustion with ether and cold alcohol.
The red tincture is evaporated; the residue is exhausted with boiling
water; the solution is boiled with magnesia; and the alkaloïd is ex-
tracted from the precipitate by boiling alcohol. - Yellowish, very
bitter, alkaline mass, whose alcoholic solution is precipitated by tincture
of galls and by oxalate of ammonia, the precipitate with the last reagent
The acetate is not
being soluble in acetic acid and easily in alcohol.
crystallisable (Petroz & Robinet, J. Pharm. 7, 349; N. Tr. 6, 2, 194).
3. Copalche-bark, which, according to Pereira, is obtained from
Croton Pseudochina, contains a bitter organic base, soluble in ether, and
precipitable from its salts by ammonia. It assumes a green colour with
chlorine-water and ammonia, like quinine (Howard, Pharm. J. Trans.
14, 319; Pharm. Viertelj. 4, 458).
Jamaïcine.
HÜTTENSCHMID. Diss. sist. analys. Geoffroya jamaic. et surinam.
Heidelberg 1824; Mag. Pharm. 7, 287.
BUCHNER. Repert. 56, 164.
WINCKLER.
Jahrb. pr. Pharm. 2, 162; Pharm. Centr. 1840, 120.
GASTELL. Schweiz. Pharm. Wochenschr. 1865, 97; N. Repert. 14,
211.
Discovered by Hüttenschmid in 1824, in the bark of Geoffroya jamaicensis. It is
identical with berberine (p. 185), as shown by Gastell, who examined jamaïcine pre-
pared by Hüttenschmid himself.
JAMAÏCINE.
31
Preparation. The bark is repeatedly boiled with alcohol; the
filtrate is distilled to remove the greater part of the alcohol; the
residue is dissolved in water; and the filtered solution is mixed with
basic acetate of lead, and then treated with hydrosulphuric acid, with-
out filtering, till the whole of the lead is precipitated. After filtering
from sulphide of lead, the liquid is mixed with sulphuric acid, which
throws down granules of sulphate of jamaïcine, more of which may be
obtained by evaporating and cooling the remaining liquids. The sul-
phate is collected, pressed, and dissolved in water, and the solution is
digested with carbonate of baryta, filtered, and evaporated to crystal-
lisation (Hüttenschmid). When the solution which has been freed
from lead is evaporated to dryness, and the residue is exhausted with
a little cold alcohol, acetate of jamaicine remains undissolved, whilst a
yellow colouring matter is taken up, though, according to Buchner, this
latter is nothing but impure jamaïcine. Buchner mixes the extract
prepared with hot water, after drying and powdering, with freshly
ignited charcoal, and extracts the jamaïcine from the mixture by re-
peated treatment with warm alcohol.
Properties. Pomegranate-yellow, semi-transparent quadratic tables,
melting below 100° (Hüttenschmid). Yellowish-brown, crystalline
powder, or yellow needles (Gastell). Inodorous and bitter. Neutral
to vegetable colours. Not decolorised by charcoal.
When heated it melts to a brown-red liquid, swells up very much,
and burns, giving off vapours which redden turmeric and smell of
roasted cocoa.
According to Hüttenschmid, jamaïcine dissolves easily, according to
Buchner, with difficulty, in water. The solution in 50 parts of water is
of a fine yellow colour (Winckler). Potash and ammonia colour the
aqueous solution red-brown (Gastell).
The salts of jamaicine are bitter, crystalline, soluble in water and
alcohol, and are not decolorised by animal charcoal. Aqueous jamaï-
cine precipitates most metallic salts. The phosphate forms lemon-
yellow granules; the sulphate sulphur-yellow needles; also the hydro-
chlorate, which melts below 100°. The nitrate forms yellow crystalline
crusts, which dissolve in water and alcohol and melt below 100°.
Aqueous jamaïcine is precipitated in the crystalline form by oxalic acid
after some time, but not by tartaric acid (Hüttenschmid). - Jamaïcine
exhibits the behaviour of berberine towards iodide and biniodide of
potassium, bichromate of potash, nitrate of silver, hyposulphite of soda and
silver-oxide, chloride of gold, and cyanide of potassium: mineral acids in
excess also precipitate aqueous solutions of its salts. Chloroplatinate
of jamaicine is thrown down as a reddish-yellow gelatinous precipitate,
which becomes flocculent on warming, and contains, at 100°, 17.75
p. c. of platinum (calc. for chloroplatinate of berberine requires 18-22
p. c. Pt.) (Gastell).
Acetate of Jamaïcine. If the liquid obtained in the preparation of
jamaïcine, after precipitating the lead by hydrosulphuric acid, be eva-
porated, without addition of sulphuric acid, the remaining granular
extract, exhausted with a little cold alcohol, and the undissolved por-
tion purified by recrystallisation from water, yellow, bitter, four-sided.
tables are obtained. These tables melt below 100°, evolve an odour
316
APPENDIX TO THE CINCHONA-BASES.
of acetic acid when treated with sulphuric acid, and dissolve easily in
water, and less freely in alcohol (Hüttenschmid).
Jamaïcine dissolves in alcohol, but is nearly insoluble in ether. It
is precipitated of a yellow colour by tincture of galls.
5. Surinamine.
HÜTTENSCHMID. Dissert. Heidelberg, 1824.
WINCKLER. Jahrb. pr. Pharm. 2, 159.
Geoffroyine. An alkaloïd from the bark of Geoffroya surinamensis. Recognised
also by Overdun in 1824. Erroneously regarded as alumina by van der Byll
(Mulder's Natuur-en Scheikund. Archief. I, 295; abstr. Ann. Pharm. 7, 265).
Preparation. An alcoholic extract of the bark is exhausted with
water; the filtrate is precipitated by basic acetate of lead and again
filtered; and the liquid is freed from lead by hydrosulphuric acid,
filtered, and evaporated, whereupon a portion of the surinamine is depo-
sited. The remainder is obtained by digesting the liquid with mag-
nesia, filtering, and evaporating further (Hüttenschmid). The surina-
mine thus separated is purified by washing with cold water and
crystallising from boiling water. A pound of the bark yields 30 grains
(Winckler).
Properties. White, very fine, bulky, woolly needles, having a faint
taste. Without action on pigeons, in doses of two grains. Neutral to
litmus and turmeric.
Decompositions. When carefully heated, a portion appears to vola-
tilise unaltered, but the greater part blackens, evolves vapours smelling
like melted quinine, and leaves a combustible charcoal (Winckler).
When heated in a glass vessel, it emits an odour of bruised plum-
kernels, and yields a liquid which reddens turmeric, and leaves char-
coal (Hüttenschmid). With nitric acid containing nitrous acid, it yields
first à violet, then a brilliant prussian-blue-coloured liquid (Hütten-
schmid). Winckler obtained with strong nitric acid a colourless solu-
tion, which evolved nitrogen in abundance over the water-bath, and
left a residue soluble in water with yellow colour. Oil of vitriol
dissolves surinamine, forming a colourless liquid, which turns brown
when heated (Winckler).
Surinamine dissolves very slightly in cold, but easily in boiling
water: the solution is not affected by iodine, ammonia, mercurous
nitrate, or tincture of galls (Hüttenschmid; Winckler).
Surinamine dissolves very easily in dilute sulphuric and hydrochloric
acids. The solution in sulphuric acid yields crystalline lamine on evapo-
ration, the solution in hydrochloric acid, white needles, which turn white
and opaque in water (Hüttenschmid). By evaporating the hydrochloric
acid solution over the water-bath, Winckler obtained a colourless trans-
parent residue, which reddened litmus, precipitated silver-salts, and
turned milk-white when digested in water.
Surinamine dissolves in caustic potash more freely than in water: on
PEREIRINE.
317
evaporating the solution a white pellicle, made up of nodules, remains
(Hüttenschmid).
Surinamine is nearly insoluble in cold, slightly soluble in boiling
alcohol, and insoluble in ether.
6. Pereirine.
Goos. Repert. 76, 32; Pharm. Centr. 1839, 610; Berz. Jahresber. 23,
372.
PERETTI. J. Chem. méd. 26, 162.
An alkaloïd contained in Cortex Pereira from Brazil, which is pro-
bably obtained from a species of Cerbera (Handbuch, viii [2], 57).
First prepared by Blank in Rio Janeiro, then by Dos Santos, and lastly
by Goos.
Preparation. The bark is exhausted with acidulated water, and the
extract precipitated by aqueous ammonia. From the precipitate thus
obtained, the pereirine is extracted by ether, which leaves it on evapora-
tion, and the residue is purified by solution in dilute hydrochloric acid and
precipitation by ammonia (Goos). Yellow, but not colourless, pereirine
is obtained also by decomposing the platinum-salt with hydrosulphuric
acid, and precipitating the acid solution with ammonia (Berzelius).
Properties. Whitish-yellow, amorphous, very bitter powder. Ac-
cording to Peretti, it may be obtained from alcohol or ether in granules.
Has an alkaline reaction.
Pereirine melts, when heated, without loss of water, to a blood-red
mass, emitting an odour of melted quinine, and afterwards puffs up,
blackens, and leaves a porous charcoal. When submitted to dry dis-
tillation, it evolves ammonia. Dissolves in strong nitric acid, with fine
purple-red colour (Pelletier, J. Pharm. 26, 162), with blood-red colour,
which changes to greyish-brown and disappears on diluting the solu-
tion (Goos). A solution of sulphate of pereirine, reddened by nitric
acid, is not precipitated by ammonia or potash; on evaporating the
solution, bitter white granules and needles are obtained, which are
again reddened by nitric acid (Peretti). Oil of vitriol dissolves perei-
rine, with fine violet colour, changing to brown, and on dilution with
water to olive-green, and lastly to grass-green.
Pereirine dissolves very slightly in water, to which it imparts its
bitter taste. It combines with acids to form neutral, amorphous
salts, which are for the most part soluble in water and alcohol. The
solution in dilute sulphuric acid yields indistinct crystalline granules on
evaporation (Peretti). Aqucous solutions of pereirine-salts are pre-
cipitated yellowish-white and pulverulent by oxalate of potash, but not
by free oxalic acid. - Hydrochlorate of pereirine produces with bichloride
of platinum a yellow precipitate, but slightly soluble in water (Berzelius).
Pereirine dissolves in alcohol and ether.
7. Pitoyine. — Occurs, according to Peretti (N. J. Pharm. 21, 515),
in China bicolor (Wigg. 429), which was examined by Peretti as China
318
PRIMARY NUCLEUS C40H30.
pitoya. — An aqueous extract of the bark is treated with alcohol of 34°;
the tincture is diluted and distilled, and the aqueous residue precipitated
by ammonia. The precipitate is treated with ether, which takes up
tannate of pitoyine, and leaves a residue soluble in boiling water.
This solution is mixed with sulphuric acid and purified by animal
charcoal; the excess of acid is removed by means of lime; and the
solution is evaporated. On dissolving the residue in alcohol, and evapo-
rating the filtrate, fan-shaped crystals of sulphate of pitoyine remain.
Pitoyine tastes bitter in solution, though not in the solid state. It
melts above 100°, giving off very bitter vapours, which sublime in
needles, and afterwards empyreumatic products. It is decomposed by
boiling nitric acid. Forms with sulphuric acid a crystallisable, and
with acetic acid an uncrystallisable salt. Dissolves in water and
alcohol, and very easily in ether.
Since Peretti's bark contained, according to Guibourt (Hist. des
drogues, 3, 141), a large quantity of quinine and cinchonine, his pito-
yine cannot be regarded as a distinct substance (Gerhardt, Traité, 4,
105).
Primary Nucleus C40H30.
Sylvic Acid.
C'4013004 = C'40H 30, 04.
UNVERDORBEN. N. Tr. 8, 1, 21; abstr. Pogg. 7, 311.-Pogg. 8, 40, and
407; 11, 28, 230, and 393; 14, 116; 17, 186.
TROMMSDORFF. Ann. Pharm. 13, 169.
ROSE. Pogg. 33, 42; Ann. Pharm. 13, 184. — Pogg. 53, 374.
LAURENT. Ann. Chim. Phys. 65, 324; 68, 395; 72, 459: Ann. Pharm.
34, 272. N. Ann. Chim. Phys. 22, 459; J. pr. Chem. 45, 61.
SIEVERT. Zeitschr. für d. ges. Naturwissenschäften, 14, 311: Kopp's
Jahresber. 1859, 508.
MALY. Wien. Acad. Ber. 44, 121; Krit. Zeitschr. 5, 47; Kopp's
Jahresber. 1861, 389.
Discovered and investigated by Unverdorben, but confounded by him and all
later investigators except Maly, with abietic acid, the acid existing ready formed
in pine-resin. Owing to this confusion, it is not always clear which statements refer
to abietic and which to sylvic acid. Unverdorben, however, seems to have examined
therefore sylvic acid. Laurent's
principally an acid prepared with sulphuric acid
statements apply better to sylvic acid, though his method of preparation must have
yielded abietic acid (Kr.).
Two acids found by Baup (Ann. Chim. Phys. 31, 108) in French colophony, acide
pinique and acide abiétique, as well as Lecanu & Bussy's crystallised acid from tur-
pentine (J. Pharm. 13, 62) appear to belong to this head.
Formation and Preparation. 1. From Abietic acid. An alcoholic
solution of abietic acid is precipitated by dilute sulphuric acid, and the
hardened crystalline precipitate is washed with alcohol, and afterwards
crystallised from that liquid (Maly). - Sylvic acid is obtained also,
together with sylvinolic acid, by passing hydrochloric acid gas into a
solution of abietic acid in alcohol (Maly).
C88H61010 + 2HO
C40H300+ + CH360³ (Kr.).
SYLVIC ACID.
319
2. From White Pitch, Colophony, &c. - White pitch is allowed to
stand, covered with an equal quantity of alcohol, till it is completely
saturated with the liquid, and until the turpentine-like deposit formed
at first has become crystalline. It is collected on a cloth, triturated
with a little alcohol, washed with that liquid on the filter, and after-
wards dissolved in a small quantity of hot absolute alcohol containing
sulphuric acid: the solution cools to a crystalline mass. Purification is
effected by pressing the crystals, and repeatedly subjecting a hot
alcoholic solution to fractional precipitation with hot water, whereby
the less pure portions are thrown down first. The alcoholic solution,
mixed with a quantity of hot water barely sufficient to produce tur-
bidity, yields large crystals on cooling (Trommsdorff).
Ries had previously observed that acids produce large crystals in the alcoholic
solution of white pitch. Unverdorben purified his sylvic acid by dissolving it in
2 parts of absolute alcohol containing th of oil of vitriol: Sievert proceeded in a
similar manner. Rose and Liebig obtained their acid from Trommsdorff.
Laurent boils pine-resin with water to free it from turpentine; extracts the pinic
acid by means of cold alcohol, and dissolves the residue in boiling alcohol. The
solution on cooling yields crystals, which are freed from adhering oil by washing with
cold alcohol, and recrystallisation from boiling alcohol. Unverdorben, and likewise
Trommsdorff and Sievert, employ similar methods. The product thus obtained is
abietic acid (Maly).
Long standing of the alcoholic solution reduces the yield of the crystals (Sievert).
Properties. Colourless, transparent, tabular, rhomboïdal prisms,
with four-sided summits (Unverdorben); indistinctly crystalline masses,
also triangular lamina (Rose; Laurent). Right prismatic? According
to Sievert, they are doubly oblique prismatic (triclinic). The crystals
exhibit the faces u, t, and a (Fig. 66), but with peculiar hemimorphous
development. Of the octahedron a in particular, only the upper left
posterior, and the lower right posterior are developed, so that the left.
half of the prism disappears, and the face appears in the form of a
triangle. Anterior u: posterior u = 96°; u: t = 132°. The remaining
upper octahedral face makes with the anterior face t an angle of 70°;
the lower octahedral face with the posterior t, an angle of 110°. The
plane angles of the triangular faces t are 90°, 45°, and 45°. Vitreous,
very brittle, triturable to a white powder (Sievert). — Does not lose
weight at 100°, or in a vacuum, and melts without loss of weight
(Unverdorben) at 152.5°, but becomes quite fluid at higher temperatures
(Trommsdorff). In a warm tube the crystallised acid, as well as that
which has been previously fused, melts at 162°, but when heated in a
retort it cakes together, partially at 118°, and completely at 150°, and
melts to a thin, clear liquid, which turns thick at 120°, viscid at 110°,
and solidifies to a glassy mass, afterwards melting partially at 135°, and
completely at 155° (Sievert). The lower melting-point of the previously
melted amorphous acid had been previously observed by Wöhler, (Ann. Pharm. 41,
155.) Sylvic acid sublimes partially at 170°, in a thin crust, which,
when dissolved in alcohol, yields crystals of the unchanged acid; the
residue turns dark-red at 240°, but does not boil even at 290° (Sievert).
Distils without much decomposition, yielding a trace of water, and a
colophony-like distillate, an alcoholic solution of which yields crystals
of unchanged sylvic acid, whilst the residue contains a trace of char-
coal (Laurent). Inodorous and tasteless; reddens litmus. Rotates a
ray of polarised light to the left, more powerfully than pimaric acid.
Sp. gr. = 1∙1011 at 18° (Sievert).
320
PRIMARY NUCLEUS C40H30.
Tromms-
dorff.
Rose.
40 C
240
....
30 H
30
40
32
79.47
9.93
10.60
78.90
....
....
9.82
11.28
Liebig.
78.65
9.82
11.53
earlier.
later.
78.07
9.93
12.00
78.54
9.96
....
11.50
....
....
....
C40H3004.... 302
100.00
100.00
100.00
100.00
....
....
....
100.00
Laurent.
Sievert.
Maly.
C ......
H.....
77.39
79.14
79.12
9.90
9.75
10.08
O.......
12.71
11.11
10.80
100.00
100.00
100.00
Abietic acid contains 78.57 p. c. C., and 9·52 H.
Amorphous Sylvic acid? Alcoholic sylvic acid becomes uncrystallisable on stand-
ing (Rose; Sievert); by spontaneous evaporation of the solution in a vacuum there
is obtained a white, brittle mass which melts over the water-bath, losing 2 per cent.
in weight, and then contains, on the average, 74:31 p. c. C., 8.83 H., and 16·86 O.
On one occasion the amorphous mass had the composition of sylvic acid (Rose). See
also Hesse (Ann. Pharm. 29, 141), who examined a similar product with 71.16 p. c.
C. and 8.74 H. as oxysylvic acid.
Decompositions. 1. Sylvic acid submitted to dry distillation (see above)
yields water and empyreumatic oil, then a little gas, followed first by a
thinner and afterwards a thicker oil, containing sylvic and pinic acids
and a large quantity of a neutral resin and oils.-2. Nitric acid slowly
decomposes sylvic acid, and dissolves it only on prolonged boiling;
water throws down from the solution yellow flocks, soluble in ammo-
nia, caustic potash, and alcohol. —3. Oil of vitriol rapidly dissolves
sylvic acid, forming a yellowish-brown solution, from which water
precipitates unchanged sylvic acid and a large quantity of pinic acid
(Unverdorben).
Combinations. Sylvic acid combines with bases, with elimination of
water (Unverdorben; Laurent) (contrary to Rose). It expels the acid
from carbonates, and when melted also from succinates and benzoates
and from chloride of calcium; but salts of sylvic acid, dissolved in
water, are decomposed by boric and acetic, and by stronger acids,
with precipitation of sylvic acid. The salts are obtained-1. By dis-
solving the acid in the aqueous base. 2. By precipitating an acetate
dissolved in alcohol by means of alcoholic sylvic acid, dissolving the
precipitate in ether, and re-precipitating by alcohol, which retains in
solution the excess of sylvic acid.-3. By double decomposition. -
Some of the sylvates are crystallisable; a few of them are soluble in
water and alcohol, and all of them in ether (Unverdorben).
Sylvate of Ammonia. The easily formed syrupy solution of the acid
in aqueous ammonia becomes turbid on evaporation, and deposits the
acid when boiled. The white semi-fluid precipitate thrown down by
sal-ammoniac from sylvate of potash is, according to Unverdorben,
monosylvate of ammonia, soluble in 200 parts of water.
Sylvate of Potash. a. Basic ? Caustic potash dissolves sylvic
acid precipitated by water, but the addition of more acid throws down
a difficultly soluble salt (Rose). From sylvic acid dissolved in ether and car-
bonate of potash a colourless amorphous salt is obtained (Unverdorben).
SYLVIC ACID.
321
b. Mono-acid. When sylvic acid is boiled with 6 parts of alcohol and
with carbonate of potash, the filtrate on cooling deposits delicate,
white needles, which may also be obtained by mixing the salt a with
alcoholic sylvic acid (Unverdorben; Sievert). Melts to a resin when
heated; dissolves very slightly in water, slowly in 20 parts of alcohol,
more freely in hot alcohol. Dissolves abundantly in warm ether and
oil of turpentine, and to a less extent in olive-oil (Unverdorben).
Needles.
Sievert.
40 C
240
70.55
(69.67)
29 H ......
29
8.52
8.45
30
24
7.05
8.29
ΚΟ
47.2
13.88
13.59
C40H29KO+
340.2
100.00
100.00
c. Quadracid. Boiling alcoholic potash, neutralised with sylvic
acid and cooled, solidifies to a crystalline mass, which may be purified
by recrystallising and pressing. The same salt is precipitated front
alcoholic sylvic acid by an alcoholic solution of acetate of potash..
Fine, silky tufts of delicate needles. Decomposes when boiled with
water, ths of the acid being precipitated, whilst the mono-acid salt
remains in solution (Sievert).
160 C
119 H .......
15 O
ΚΟ
C40H29K04,3C403004
Needles.
Sievert.
960
77.03
76.95
119
9.55
9.58
120
9.63
9.51
47.2
3.79
3.96
....
1246.2
100.00
100.00
The soda-salt is obtained in crystals by boiling alcoholic sylvic acid
with excess of carbonate of soda and cooling the filtrate (Unverdorben).
-The baryta-salt dissolves in 3,000 parts of water, in 6 parts of cold,
and less of boiling absolute alcohol, from which it is deposited in
microscopic crystalline flocks on cooling (Unverdorben).
Sylvate of Lime. The solution of the salt in cold absolute alcohol
deposits colourless, shining, crystalline granules on spontaneous evapo-
ration (Unverdorben). The mono-acid salt is obtained by the double
decomposition of sylvate of potash and chloride of calcium, and a salt
containing a smaller proportion of lime, by precipitating alcoholic
sylvic acid with an alcoholic solution of acetate of lime (Sievert).
Sievert.
40 C............
240
74.76
74.45
29 H.....
29
9.03
8.78
3 0......
24
7.48
8.36
Cao......
28
8.73
8.41
C40H29CaO4
321
100.00
100.00
Sylvate of Magnesia dissolves in all proportions in alcohol of 65
per cent. and in absolute alcohol; from the latter solution a double
volume of water throws down a colourless semi-fluid salt, which dries
up to a transparent resin in the air, and dissolves in ether and in rock-
oil. -The sylvates of manganese and zinc are soluble in absolute
alcohol.
VOL. XVII.
Y
322
PRIMARY NUCLEUS C40H30.
=
Sylvate of Lead. The acid loses 3.02 p. c. of water when heated
to 168° with oxide of lead (1 at. 2.97) (Sievert). The precipitate
thrown down by an alcoholic solution of sylvic acid from alcoholic
neutral acetate of lead is a white, amorphous powder, easily fusible,
and containing, on an average, 26.94 p. c. of oxide of lead (1 at. = 26·17 p.c.
Pbo) (Rose).
The ferrous and ferric salts dissolve slightly in alcohol and easily in
ether (Unverdorben).
Sylvate of Copper. — Dissolves in ether and crystallises from absolute alcohol
in shining granules (Unverdorben).-a. Alcoholic sylvic acid is precipitated
by an alcoholic solution of acetate of copper; the pale blue flocks thus
obtained run together when warmed. The precipitate is powdered
and repeatedly exhausted with alcohol. From the filtrate from a,
water throws down the pale blue precipitate b.-c. When a boiling
alcoholic solution of sylvic acid is precipitated with alcoholic acetate
of copper, aqueous ammonia added till the precipitate is dissolved,
and the solution then cooled or mixed with water, a dark blue pre-
cipitate is produced, which is triturable to a pale blue powder after
drying (Sievert). Trommsdorff drops alcoholic sylvic acid into excess
of alcoholic acetate of copper, and washes the precipitate with water.
The pale blue precipitate contains 11.38 p. c. of oxide of copper at
109°, and is, therefore, the mono-acid salt.
Sievert.
al.
b.
C.
40 C
29 H
30
Cu O
240
72.14
71.52
67.66
71.64
29
8.72
8.61
7.82
8.72
24
7.21
9.37
8.81
7.38
39.8
11.93
10.50
15.71
12.26
C10H29 CuO4.... 332.8
100.00
100.00
100.00
100.00
Sylvate of Silver. Crystallises from alcohol in shining granules on
spontaneous evaporation. When boiled with potash and oil of turpen-
tine, it behaves like pinate of silver. Dissolves in 15 parts of cold,
and in a smaller quantity of boiling alcohol, and instantaneously in
ether, which takes it up from water when suspended therein (Unver-
dorben). — The precipitate produced by alcoholic nitrate of silver in
alcoholic sylvic acid on addition of ammonia, contains 26.01 p. c. of
silver (1 at. = 26.4 p. c. Ag.) (Rose). The silver-salt prepared with
sylvic acid obtained by the first method (p. 318), contains 25.88 p. c.
silver (Maly).
25
Sylvic acid dissolves in acetic acid. It dissolves very slightly in
cold alcohol of 65 p. c., and in about 3 parts of the boiling liquid, from
which it crystallises on cooling, about th only remaining in solution.
It dissolves in about 3 parts of cold, and 1 part of boiling absolute
alcohol or ether, and is thrown down from the former solution by an
equal quantity of water, as a semi-transparent oil, which hardens to a
crystalline solid on addition of more water, or on exposure to the air
(Unverdorben). Sylvic acid dissolves in 10 parts of cold, and in 4ths
of boiling alcohol of 92 p. c.; more freely, therefore, than pimaric
acid (Sievert). It dissolves in acetic ether, rock-oil, and oil of turpen-
tine, without crystallising therefrom (Unverdorben).
PIMARIC ACID.
323
Pimaric Acid.
C40H3004 C40H30,04.
=
LAURENT. Ann. Chim. Phys. 72, 384; Ann. Pharm. 34, 272. — N. Ann.
Chim. Phys. 22, 459; Compt. rend. 21, 858; J. pr. Chem. 45, 61.
SIEVERT. Zeitschr. für die gesammt. Naturwissensch. 14, 311.
Occurs in the turpentine of Pinus maritima, which hardens to galipot in the air,
and also in colophony from Bordeaux. Compare p. 319, and Abietic acid.
Preparation. Galipot, which occurs in commerce, mixed with tur-
pentine, is freed from the latter body, broken up, and digested with
a mixture of 1 part of ether and 6 parts of alcohol, which is poured off
after standing for a short time. The undissolved portion is again
treated twice in the same way, and then dissolved in boiling alcohol;
on standing for some days the solution deposits crystalline crusts,
which are removed from time to time, and purified by recrystallisation
from boiling alcohol (Laurent). Or, Bordeaux colophony is washed
with cold alcohol, and the residue is dissolved in boiling alcohol and
allowed to crystallise (Laurent).
Properties. White, nodular crystalline crusts, consisting of micro-
scopic, rectangular, or sometimes six-sided prisms (Laurent). Thin
laminæ, derived from a quadratic prism, often truncated at the edges or
acuminated (Sievert). Melts about 125°, and solidifies only at 68° to a
transparent, or sometimes granulo-crystalline mass. The acid dried
in a vacuum loses 4ths p. c. of water when melted (Laurent). Runs
together at 120° to 135°, and at 158° melts completely to a clear
liquid, from which some of the acid sublimes unchanged at 120°.
a narrow tube the crystallised acid, as well as that which has pre-
viously melted, melts at 155° (Sievert). Sp. gr. 1·1047 at 18°. Exerts
a left-handed action on polarised light, less powerful than sylvic acid
(Sievert).
In
Laurent.
Sievert.
40 C
240
79.47
78.18
79.02
30 H
30
9.94
9.74
9.87
40
32
10.59
12.08
11.11
C40H3004
302
100.00
100.00
100.00
Isomeric with sylvic acid. — Maly is inclined to regard pimaric acid as abietic
acid, C88H64010, in which I agree with him (Kr.).
Amorphous Pimaric acid. Crystallised pimaric acid becomes amorphous on
keeping. White crystalline crusts of pimaric acid lost their transparency in three
months and became yellow and friable. When dissolved in boiling alcohol, they
yielded, on cooling and evaporating, an amorphous syrup free from crystals. The
acid thus altered dissolves in its own weight of alcohol, from which it does not
crystallise. It is thrown down from the solution by water as a soft mass, but still
possesses the composition of the crystallised acid (78-45 p. c. C., 9.63 H., 11·92 O.).
This alteration does not occur with the fused acid, nor with that dissolved in alcohol
(Laurent). Laurent afterwards regarded amorphous pimaric acid as identical with
pinic acid (see below).
Decompositions. 1. Pimaric acid assumes a yellow-brown colour on
Y 2
324
PRIMARY NUCLEUS C40H80.
prolonged melting. On distilling 10 grammes in a vacuum, there pass
over first traces of water, and then a liquid, Laurent's pyromaric acid
(p. 325), which solidifies, for the most part, in the neck of the retort,
the contents of the retort remaining of a transparent yellow to near
the end of the process, and leaving only a trace of charcoal. When
the acid is distilled in larger quantity in vessels containing air, pimarone
is also obtained (Laurent).
When the viscid distillate is saponified by caustic potash, the
pimarone is taken up by the soap, and on drying and powdering the
soap, and afterwards shaking it with ether, the pimarone is dissolved
by that liquid, together with a little potash-salt, which is removed by
water. The remaining pimarone is washed with aqueous potash and
with water, and dried in a vacuum. Thus obtained it is yellowish,
resembles a fatty oil, and is soluble in ether and alcohol. It hardens
almost completely in the air. Contains 84.20 p. c. C., 10·32 H., and
5.48 O., corresponding to the formula C40H2802 (calc. 84.5 C., 9.85 H.)
(Laurent).
=
2. By the action of boiling nitric acid on pimaric acid, nitromaric
acid is produced (Laurent).-3. On adding powdered pimaric acid
gradually to oil of vitriol, a brown-red solution is obtained, which,
after standing for 24 hours, deposits grey flocks when poured into
water. These flocks are rendered nearly colourless by washing with
water; they do not crystallise from alcohol, and yield no pyromaric acid
when submitted to dry distillation: they contain, at 100°, 76.69 p. c. C.,
9.68 II., and 13.69 0. (Laurent).
Combinations. Pimaric acid is insoluble in water. It forms soluble
salts with ammonia and the alkalis. Its alcoholic solution does not
precipitate alcoholic solutions of chloride of barium (?), strontium, cal-
cium, or magnesium, but on addition of ammonia an abundant white
precipitate is produced in the lime-solution, whilst in the other solutions.
a smaller precipitate is formed, or precipitation takes place only on
cooling; the baryta solution does not yield any precipitate. An alcoholic
solution of the acid, mixed boiling with alcoholic acetate of lead,
copper, or silver, throws down amorphous salts after some time
(Laurent).
Lead-salt. The acid heated with oxide of lead loses 2.8 to
3.4 p. c. water (1 at. 2.98 p. c. HO.).— The lead-salt obtained
by precipitating boiling alcoholic neutral acetate of lead with the alco-
holic acid, contains, after drying in a vacuum, 26.5 p. c. oxide of
lead (CIPbO27-65 p. c. PbO). This white lead-salt, when
heated, melts to a resin, cooling to a yellow transparent mass, which,
when subjected to dry distillation, yields water and a thick oil soluble
in caustic potash, and leaves charcoal and lead (Laurent).
—
Pimaric acid dissolves in 10 parts of alcohol at 18°, and in its own
weight of boiling alcohol; it is precipitated from the solution by water
in flocks which do not cake together (Laurent). The acid dissolves in
13 parts of alcohol of 92 p. c. (Richter); in 2 parts of boiling alcohol
(Sievert). Fused pimaric acid dissolves rapidly when triturated with
its own weight of cold alcohol, but the solution solidifies almost im-
mediately, from separation of crystals. When the fused acid has
again become crystalline, it requires as much alcohol to dissolve it as
NITROMARIC ACID.
325
the crystallised acid (Laurent). Crytals are still obtained from the
alcoholic solution, even after long standing (Sievert).
Laurent's Pyromaric acid. Obtained by the dry distillation of
pimaric acid. When the colophony-like distillate is triturated with
twice its weight of alcohol, the solution produced at first quickly
becomes turbid, from separation of crystals of pyromaric acid, which
are purified by washing and recrystallisation. Triangular tables,
melting at 125°, volatile without decomposition. Contains 78.27
p. c. C., and 9.90 H., or the same proportions as pimaric acid, from
which it differs by the fact that when its boiling dilute alcoholic solu-
tion is mixed with neutral acetate of lead, it produces no precipitate at
first, and after some time only, long needles of a lead-salt containing
26.52 p. c. oxide of lead, at 100°. The acid dissolves in 8 or 10
parts of alcohol, and very easily in ether. This acid, which Laurent
found also in Paris colophony, was afterwards regarded by him as
identical with sylvic acid. On the other hand, Sievert, who found
pimaric acid volatile without decomposition (and susceptible of distilla-
tion? Kr.), seems to consider pyromaric acid as identical with pimaric
acid, and different from sylvic acid.
Nitromaric Acid.
C40N2H26016 = C40X2H260²,06.
LAURENT. Ann. Chim. Phys. 72, 397; Ann. Pharm. 34, 282.— N、
Ann. Chim. Phys. 22, 461; J. pr. Chem. 45, 61.
Azomarsäure. Acide azomarique.
Preparation. Pimaric acid is boiled with a large excess of nitric
acid till a yellow, friable resinous mass forms on the surface of the
liquid. This mass is boiled repeatedly with water, powdered, and
slowly dried, at last at 100°; or it is dissolved in alcohol and pre-
cipitated by water.
Yellow, amorphous resin. Its alcoholic solution reddens litmus.
Laurent.
earlier.
later.
40 C
240
56.87
56.72
57.0
2 N
28
6.60
7.20
7.1
26 H
26
6.15
5.60
5.9
......
16 O
128
30.38
30.48
30.0
C40X2H2608 ....
422
100.00
100.00
100.0
—
Nitromaric acid decomposes when melted, leaving a bulky char-
coal; it does not glow or explode, even when rapidly heated. Burns
like a resin. When submitted to dry distillation, it yields a very
little oil.
The acid is insoluble in water. It dissolves in oil of vitriol, from
which it is precipitated by water.
Those of the
The salts of nitromaric acid are reddish-yellow.
alkalis are soluble in water; the baryta-salt is insoluble. A solution
326
PRIMARY NUCLEUS C40H30.
of the very easily soluble ammonia-salt dries up to a reddish-yellow
transparent mass.
An alcoholic solution of nitromaric acid forms yellowish pre-
cipitates with alcoholic neutral acetate of lead and nitrate of silver. The
lead-salt explodes slightly when heated; it contains 32.8 to 33.4 p. c.
lead, and dissolves to a slight extent in alcohol (C40X2H2Pb²0° = 33·12
p. c. Pb).
Nitromaric acid dissolves easily in alcohol and ether.
Copaivic Acid.
C'40H3004 = C40H30,04.
SCHWEITZER. Pogg. 17, 488; 21, 172.
H. ROSE. Pogg. 33, 35; 53, 372.
HESS. Pogg. 46, 324; Ann. Pharm. 29, 140.
Copabavinsäure. Occurs, together with copaiba-oil, in balsam of co-
paiba. See below.
-
Nine parts of copaiba balsam are mixed with two or more parts of
aqueous ammonia of sp. gr. 0·95, and placed in the cold in closed vessels,
when, after some weeks at 10°, or in the course of a day at — 12.5°,
white shining needles are formed. The solidified mixture is thrown upon
a cloth; the crystals remaining are shaken with a little ether, which
dissolves the copaiba balsam; and the crystals are then pressed and re-
crystallised from absolute alcohol, from which they separate free from
ammonia (Schweitzer).
Properties. Transparent or translucent, colourless crystals, 4 to 6
lines long (Schweitzer). According to G. Rose, rhombic prisms
without cleavage. The angles of the obtuse lateral edges = 90° 46';
the acute lateral edges frequently truncated; two bevelling faces
inclined to one another at 126° 50' rest upon the obtuse edges. — The
acid has a bitter taste, like the balsam, and a faint odour. It is heavier
than water; has an acid reaction (Schweitzer; Rose).
Rose.
Hess.
earlier.
later.
40 C
240
79.48
78.17
79.29
78.02
...
30 H
30
9.93
10.15
10.31
10.01
4 O
32
10.59
11.68
10.40
11.97
C40H3004
302
100.00
100.00
100.00
100.00
Isomeric with sylvic and pimaric acids.
Copaivic acid dissolves in oil of vitriol with red-brown colour, and
carbonises when the solution is heated. It dissolves in hot strong
nitric acid, from which it is precipitated in white flocks by water
(Schweitzer).
The acid is insoluble in water. It is not precipitated from an
alcoholic solution by aqueous ammonia; the acid thrown down from its
alcoholic solution by water dissolves in ammonia. Alcoholic potash
COPAIVIC ACID.
327
or strong aqueous potash does not precipitate the alcoholic solution of
the acid, but dilute potash throws down the potash-salt.
Lime-salt. Alcoholic copaivic acid is mixed with excess of chloride
of calcium; ammonia is added; and the resulting precipitate is collected
without access of air (Rose).
C40H2903
CaO
C40H29 CaO4
Rose.
293
91.28
28
8.72
8.32
321
100.00
Lead-salt. -The acid gives off water when heated with oxide of lead
(Schweitzer). Alcoholic neutral acetate of lead throws down from an
alcoholic solution of the acid, an abundant slightly crystalline precipi-
tate. Easily fusible (Rose).
C40 H2903
РЬО
C40H29PbO4........
Rose.
293
72.34
112
27.66
27.53
405
100.60
Silver-salt. Nitrate of silver in alcoholic solution mixed with
alcoholic copaivic acid, forms a crystalline precipitate on addition of
ammonia. The salt turns brown in the light. It is easily fusible,
and dissolves in aqueous ammonia, and with difficulty in alcohol
(H. Rose).
Rose.
40 C...........
240
58.68
57.75
29 H....
29
7.09
7.55
3 O........
24
5.87
AgO.....
116
28.36
27.41 to 28.25
C40H29 AgO4.... 409
100'00
Copaivic acid is easily soluble in absolute alcohol; less freely in
dilute alcohol, and in ether.
(Schweitzer).
It dissolves in volatile and fat oils
Copaiba Balsam. From various species of Copaïfera. 1. Brazilian
balsam, containing volatile oil (xiv, 286) and copaivic acid. — Pale
yellow transparent oil, at first fluid, like thick oil, afterwards of the
consistence of honey. Sp. gr. 0.95 (Schönberg), 0.966 (Stoltze),
0.9925 (Brandes & Reiche), 0.997 (Martins), 0-916 to 0.986
(Procter). Has a peculiar balsamic odour and a burning bitter taste.
When mixed with alcohol it reddens litmus (Martins). Rotates a ray
of polarised light generally to the left in varying degrees (Buignet).
When distilled with water, it yields volatile oil. With fresh balsam
the remaining resin is brittle only after boiling for 20 to 24 hours, but
with old balsam after 8 or 10 hours (Schweitzer). A solution of the
resin in warm alcohol of 75 p. c. deposits on cooling, a brown, greasy,
soft resin, which forms a milky solution with ammonia and caustic
potash, dissolves in ether and alcohol (in 75 p. c. alcohol only when
warmed), and in volatile and fat oils. There remains in solution a
brittle, pale-yellow resin-copaivic acid. This splitting up is effected
also by strong rock-oil, which dissolves the copaivic acid and leaves
the soft resin un dissolved (Gerber; Stoltze).
328
PRIMARY NUCLEUS C40H30.
The bottom of a bottle containing copaiba balsam was found, after
standing for many years, to be covered with a transparent resinous.
layer, together with six-sided tables and prisms (Pelletier, J. Pharm.
6, 315). — When heated alone to 125°, the balsam gives off only traces
of oil and water; at 262° it begins to boil and yield oil, with forma-
tion of gas; and at 287° there pass over, first colourless, then yellow
and dark-brown oil, whilst gases are evolved and charcoal remains
(Schönberg, A. Gehl, 6, 493). The balsam dissolves phosphorus
easily, and, when hot, also sulphur (Gerber).
Copaiba balsam forms with a small quantity of aqueous ammonia
of sp. gr. 0.95 to 0.96, a turbid mixture, but with th of ammonia a
perfectly clear solution, which again becomes turbid with more than
1th of ammonia, and gradually deposits the soap of the balsam, the
supernatant liquid consisting of excess of ammonia with traces of
balsam. Under these circumstances a rise of temperature of about
15° takes place. If the balsam contains fat oil, or more than 4th of
castor-oil, it does not become clear with 4th of ammonia at 15°. The
clear mixture of balsam and ammonia may be mixed with a little
water without turbidity, but with more than an equal quantity of water
it becomes milky (Stoltze; Planche; Schweitzer). The balsam is
rendered turbid by dropping into it a solution containing 4rd of hydrate
of potash, but becomes perfectly clear, with rise of temperature,
when 3rd of its volume of the solution is added, and is again rendered
turbid by a larger quantity, after which two layers are formed on
standing. The soap of copaiba balsam dissolves perfectly in alcohol of
75 to 90 p. c.; when fatty oils are present, the solution deposits white
flocks in a few hours (Stoltze): the soap of a balsam thus adulterated
is rendered turbid by a much smaller quantity of water than that of
pure balsam (Müller, Br. Arch. 8, 74). See also Anthon (Repert. 52, 331).
When an alcoholic solution of the balsam is shaken with solution of
caustic soda, the oil (xiv, 286) which rises to the surface removed, the
soapy liquid beneath evaporated to the consistence of honey, and the
soap freed from excess of alkali by means of chloride of sodium, the pro-
duct, on being washed with a little water, dissolved in alcohol, and evapo-
rated, forms a yellow, transparent soap, which dissolves in 12 parts of
cold, and in 3 parts of boiling water (Ader, J. Pharm. 15, 95).
parts of the balsam dissolve 3.1 parts of magnesia alba (Brandes &
Gruner, Br. Arch. 23, 277). 8 parts of the balsam solidify to a plastic.
mass with 1 part of calcined magnesia (Mialbe). The compound
dissolves in ether and alcohol (Gerber). The balsam hardens more
rapidly with th of hydrate of lime than with magnesia (Thierry,
N. J. Pharm. 1, 310). The presence of water, either in the balsam
or in the lime or magnesia, is necessary for solidification; anhydrous
balsam mixed with quick lime remains unchanged for a long time, but
hardens in a few hours on addition of th of water. A homogeneous
mass is produced only when water is added to the balsam or to the
mixture of lime and balsam; by shaking the balsam with hydrate of
lime, a granular crystalline mass is formed, on which floats the volatile
oil (Roussin, N. J. Pharm. (4) 1, 321).
5
36
10
100
Copaiba balsam mixes with absolute alcohol; and it dissolves freely
in 90 p. c. alcohol, but only to the extent of th or 4th in alcohol of
75 p. c. (Gerber). It mixes with volatile and fatty oils in all propor-
tions, and the mixture may be added without turbidity to 2 parts of
alcohol of 90 p. c., or to absolute alcohol, ether, or acetate of ethyl,
COPAIVIC ACID.
329
but with a larger quantity (about 8 parts) of alcohol or ether, the fatty
oil is partially separated (Stoltze, Berl. Jahrb. 27, 2, 179). On copaiba
balsam see further; Martins (Repert. 26, 306), Gerber (Br. Arch. 30, 147; 37, 36),
Brandes (Br. Arch. 36, 351), Oberdörffer (N. Br. Arch. 45, 172), Stöckhardt (N. Br.
Arch. 72, 14), Guibourt (N. J. Pharm. 23, 321), Procter (Pharm. J. Trans. 10, 603 ;
Pharm. Centr. 1851, 590). Lowe's statements (Pharm. J. Trans. 14, 65; Pharm.
Centr. 1854, 653) seem to refer to Gurgun balsam.
2. Thinner Copaiba Balsam. - Thinner, and of a paler yellow than the
former, Sp. gr. = 0·94.
0.94. Remains turbid when mixed with aqueous
caustic potash or ammonia, does not form a soap, and separates in a dis-
tinct layer on standing. Forms a milky solution with alcohol. - Con-
tains 82 p. c. of paracopaiba oil, and 18 p. c. of neutral resin (Posselt).
If the residue which remains on distilling the balsam with water
be boiled with water till all the volatile oils are driven off, there re-
mains a light-brown, friable resin, a portion of which is taken up by
alcohol, while another portion, nearly insoluble even in hot absolute
alcohol, remains behind.a. The soluble resin is pale-yellow, friable,
and softens when warmed; at a higher temperature it assumes a
darker colour, becomes tough, and decomposes. Neutral. Insoluble in
ammonia and caustic potash, and does not precipitate acetate of copper.
It is deposited from a solution in weak boiling alcohol, on cooling, in
white flocks, and from strong alcohol, on evaporation only, in drops.
Dissolves in ether and rock-oil. Contains, on the average, 60·62 p. c.
C., 8.37 H., and 31.61 0.-b. The insoluble resin, purified by boiling
with alcohol (whereby its bulk is diminished) and by dissolving in
ether, is pale-yellow, difficultly fusible, insoluble in ammonia or caustic
potash, and in weak alcohol. It is deposited in great part from a
solution in a large quantity of boiling absolute alcohol on cooling, but
dissolves easily in ether and rock-oil. Contains, on the average,
81.94 p. c. C., 10·52 H., and 7·54 O. (Posselt, Ann. Pharm. 69, 71).
Resin of the Copaiba-balsam of Para. Deposited, on standing, from
a balsam imported in 1839, as a white, crystalline sediment, which
was purified by pressing between blotting-paper, dissolving in alcohol,
and allowing the solution to evaporate spontaneously. Rhombic
prisms, truncated at the acute angles, triturable to a highly electric
powder. Melts at about 120°. An alcoholic solution reddens litmus.
The crystals contain, on an average, 74.83 p. c. C., 8.83 H., and
16.34 O., corresponding to the formula CH2O (75.95 p. c. C., 8.86 H.);
but when a solution of the impure resin (not of the pure) in ether-
alcohol is rapidly evaporated, with constant stirring, a white amorphous
powder is obtained, which is nearly opaque, softens in boiling water,
and contains, on the average, 71.15 p. c. C., 9.04 H., and 19.81 O., and is,
therefore, a hydrate of the resin, CHOº,2HO (calc. 71.85 p. c. C.,
9.00 H.).
The resin is decomposed by cold strong nitric acid, and by the
dilute acid when warm, with formation of carbonic acid, nitric oxide,
and two solid products, one of which is an acid free from nitrogen,
soluble in water and alcohol, and forming a lead-salt which contains
approximately C30H18014,4PbO, while the other is a nitrogenous, very
bitter, amorphous substance, the lead-salt of which contains about
C30H18013,3PbО. On evaporating the resin with nitric acid, a black
pitch containing humic acid is produced.
330
PRIMARY NUCLEUS C40H0; OXYGEN-NUCLEUS CHOS.
The resin forms, with soda and potash, soaps soluble in water. It
remains behind unchanged on evaporating its solution in ammonia-
water. Alcoholic neutral acetate of lead throws down from an alco-
holic solution of the resin mixed with a little ammonia, a white pre-
cipitate, which when washed with a little alcohol, strongly pressed,
and again washed with a little alcohol, exhibits the following mean
composition; but if it be washed with a large quantity of water or
alcohol, the percentage of lead is altered. The silver-salt is obtained
in like manner.
Lead-salt.
Fehling.
40 C...............
27 H
240
57.28
56.23
27
6.44
6.43
5 O.......
40
9.55
11.03
Pbo.....
112
26.73
26.31
С40Н27РЬО6 ........ 419
100.00
100.00
Silver-salt.
Fehling.
40 C.......
240
56.74
56.27
44...
27 H
27
6.39
6.43
5 O......
40
9.46
10.47
AgO.......
116
27.41
26.83
100.00
100.00
C¹ºH27 Agoº........ 423
The resin dissolves in alcohol and more freely in ether (Fehling,
Ann. Pharm. 40, 110).
Oxygen-nucleus C40H22O8.
Mangostin.
C40H22O10 C40H2208,02.
=
W. SCHMID. Ann. Pharm. 93, 83; abstr. Pharm. Centr. 1855, 182;
J. pr. Chem. 64, 254; Chem. Soc. Q. J., 8, 190; Kopp's Jahresber.
1855, 726.
Occurs in the husks of the fruit of Garcinia Mangostana (Handbuch,
viii, [2], 35).
Preparation. The husks are exhausted with hot water and boiled
with alcohol; the tincture is evaporated till an amorphous, yellow
mass of resin and mangostin is deposited; and this mass is dissolved
in alcohol, heated to boiling, and mixed with small quantities of water
till it becomes turbid. On cooling, the resin is deposited at the bottom
of the vessel; and on decanting the liquid and allowing it to stand, it
deposits mangostin, which, for complete purification, must be dissolved in
alcohol and precipitated with basic acetate of lead. The precipitate is
washed and decomposed under alcohol with hydrosulphuric acid; the
filtrate, mixed with water, is set aside to crystallise; and the producț
is finally recrystallised from dilute alcohol.
MANGOSTIN.
331
Properties. Fine golden-yellow, thin lamina, melting at 190°,
without loss, to a thick yellow liquid which solidifies to a brittle, amor-
phous mass. When heated above its melting-point, it sublimes partly
unaltered. Heavier than water; inodorous and tasteless; neutral.
at 100°.
240
22
40 C.......
22 H........
10 O......
80
C40H22O10......
342
Schmid.
mean.
44
70.17
69.67
6.43
6.49
23.40
23.84
100.00
100.00
Decompositions. Mangostin burns on platinum-foil, without leaving
a residue. — It dissolves in cold oil of vitriol with yellowish-red colour,
and carbonises in the hot liquid. Warm nitric acid converts it into
oxalic acid. It reduces the oxides of the noble metals.
Mangostin is insoluble in water, but soluble with yellowish-brown
colour in alkalis. It produces with aqueous sesquichloride of iron, a dark
green-black coloration, which disappears on the addition of acids. It
is precipitated by basic acetate of lead, but not by any other metallic
salts.
Mangostin with Lead-oxide. An excess of alcoholic mangostin,
mixed with alcoholic neutral acetate of lead and a little ammonia,
yields as yellow, gelatinous precipitate, triturable to a light yellowish-
green powder after drying at 100°. Insoluble in water, but slightly
soluble in alcohol, and (with decomposition) in acids.
Calculation according to Schmid.
80 C
45 H
21 O
5 PbO
2C40H22O10,5Pьо + Hо
....
Schmid.
480
38.37
38.67
45
3.59
3.45
168
13.46
13.74
560
44.58
44.14
1253
100.00
100.00
Another time, when prepared in apparently the same manner, it contained 37.65
p. c. of oxide of lead.
Mangostin dissolves easily in alcohol and ether.
Resin of Garcinia Mangostana. Exudes in small quantity from
the tree. Fine lemon-yellow tears, of the size of peas, inodorous and
tasteless. Easily pulverisable. Does not form sugar when digested
with sulphuric acid. When treated with 90 p. c. alcohol, it gives up
88 p. c., which remains on evaporation as a clear amorphous mass,
easily soluble in alcohol and ether, fusible at 110°, but not in boiling
water. This purified resin contains 67.92 p. c. C., 6·81 H., and 25·27 0.,
corresponding to the formula C6H22020. It is decomposed by aqueous
ammonia into alpha- and beta-resin.
a. The deep-yellow ammoniacal solution throws down, on addition
of hydrochloric acid, yellow flocks of the alpha-resin which melt at
80°, and, like the purified resin, contain 67.71 p. c. C., 6.84 H., and
25.45 0. When the ammoniacal solution is precipitated by neutral
acetate of lead, the yellow gummy precipitate (which is decomposible
by acetic acid) contains 63 42 p. c. PbO., 24.68 C., 2·50 H., and 9′40 O.,
corresponding to the formula C36H22O10,5PbO.
B. The beta-resin, insoluble in ammonia, is a pale-yellow, loose
332
PRIMARY NUCLEUS C40H32.
powder, melting at 115°, only partially soluble in caustic potash, but
easily soluble in alcohol and ether. After drying at 100° it contains,
on the average, 52.92 p. c. C., 7.88 H., and 39.20 O., corresponding to
the formula CH22O10 + 10H0 (Reitler, Pharm. Viertelj. 7, 170).
Primary Nucleus C40H32.
BRANDES. Br. Arch. 30, 1.
BILTZ. N. Tr. 20, 1, 37.
DULK. J. pr. Chem. 45, 36.
resin.
Dammaryl.
C40H32.
Probably identical with Brandes' dammarin and Biltz's difficultly soluble hard
Recognised as a non-oxygenised compound and investigated by Dulk.-
Occurs in East Indian and probably also in Australian dammar-resin. (See below.)
Powdered dammar-resin is exhausted with warm alcohol of 82 p. c.,
which takes up soluble resins; the insoluble portion is treated with
ether; the ethereal solution is concentrated; and the residue thrown
into boiling water for a few seconds, after which the product is col-
lected and dried, as quickly as possible in a vacuum (Dulk).
Properties. White, highly lustrous, amorphous powder, resembling
magnesia; not electric when rubbed. Softens at 145°, and melts at
190° to a clear yellow oil (Dulk).
at 100º.
Dulk.
mean (7).
40 C
32 H......
240
88.23
88.28
32
11.77
11.97
C40H 32
272
100.00
100.25
Dulk's formula, C45H36, is also a multiple of CH4. Isomeric with gutta-percha
and caoutchouc.
Decompositions. 1. Dammaryl when submitted to dry distillation
yields an empyreumatic oil (and acetic acid) (Biltz). 2. When heated
it melts, burns for a long time with flame, turns brown, and burns away
without leaving a residue (Brandes). 3. It is not perceptibly acted on
by cold nitric acid, but is converted into a yellow acid resin by the hot
acid (Brandes). Strong nitric acid dissolves it, forming a reddish
solution, from which water precipitates a resin, soluble, with brown-
red colour, in ammonia and potash (Biltz). -4. It is not altered by
cold oil of vitriol at first, but afterwards turns yellow, and, when
warmed, brown-red, and dissolves partially, so that water throws
down white flocks from the liquid (Brandes; Biltz). - 5. When boiled
with chlorate of potash and hydrochloric acid, it takes up chlorine; after
8 hours it contains 27 p. c., after 16 hours, at 110°, 33.38 p. c., and
after longer treatment very little more (33.73 p. c.) chlorine (C40H29C13
= 28-3; C40H28C14 34.6 p. c. chlorine). The latter product gives off
DAMMARYL.
333
water at 120°, and when further heated, hydrochloric acid [chlorous
acid (Dulk)], and at 130° loses 6 to 7 p. c. of its chlorine: it turns
yellow at 160°, and burns at 185° (Dulk).
With Water ?
Combinations.
Dammaryl is found to contain
oxygen even after short contact with air, and still more after exposure
to aqueous vapour at 110°, or to warm moist air, and retains oxygen
even after drying at 100° (Dulk). Dulk regards this change as an
oxidation, or, as a conversion into dammarylic acid and hydrate of
dammaryl: he did not, however, investigate the behaviour of the pro-
ducts with solvents (Kr).
Dulk.
With 1 at. water.
Cl..
b.
C.
40 C .......
240
85.41
85.51
83.29
82.4
33 H....
33
11.74
11.77
11.11
11.5
O......
8
2.85
2.72
5.60
6.1
C40 H32,HO
281
100.00
100.00
100.00
100.0
With 2 at. water.
40 C........
34 H
240
82.75
34
11.72
2 O......
16
5.53
C40H32,2HO..........
290
100.00
...
Dammaryl is not perceptibly soluble in hot aqueous phosphoric
acid, or in acetic acid, ammonia-water, or boiling solution of caustic
potash.
Dammary is insoluble in boiling alcohol (Dulk): according to
Brandes, it dissolves in 500 parts of boiling absolute alcohol. - It
dissolves easily in cold ether (Dulk), in volatile oils, in fat oils when
warm, and in warm copaiba balsam (Brandes; Biltz).
BILTZ.
Appendix to Dammaryl.
1. Semihydrate of Dammaryl.
C80H650 = 2040H2, HO.
N. Tr. 20, 1, 52.
DULK, J. pr. Chem. 45, 41.
When dammar-resin is exhausted with alcohol and ether, this body
remains behind as a grey pasty mass which persistently retains the
ether, and, after drying, is shining, brittle, and easily pulverisable.
It softens at 205°, and melts to a clear brown liquid at 215°. - In-
soluble in alcohol, ether, acetic acid, ammonia, and potash. It
dissolves slowly in hot oil of vitriol, from which it is precipitated by
water as a white resin, and is completely soluble in hot oil of tur-
pentine, more quickly in rock-oil, and slightly in oil of almonds and
olive-oil (Biltz; Dulk).
334
PRIMARY NUCLEUS C4032.
at 180°.
Dulk.
mean (2).
80 C
65 H....
4,80
86.82
86.52
...
65
11.75
11.75
О
8
1.43
1.73
2CH* HỌ ....... 553
100.00
100.00
According to Dulk, C⁹0H73O.
2. Dammar-resins soluble in alcohol. When powdered dammar-
resin is treated with weak and with absolute alcohol in succession,
two different resins are dissolved (Dulk's hydrate of dammarylic acid
and anhydrous dammarylic acid), whilst dammaryl and semihydrate of
dammaryl remain undissolved.
ɑ. The resin extracted by weak alco-
hol, when freed from adhering alcohol by boiling with water and dried, is
a white, soft, very electric powder, melting at 56° to a deep-yellow
oil, which floats on water, and does not absorb oxygen from the air at
45°. In alcoholic solution it reddens litmus slightly. b. The resin
extracted by absolute alcohol resembles a, but is whiter, melts at 60°,
and reddens litmus strongly. c. Hot alcohol of 65 p. c., used for
extracting dammar, deposits c in the form of a white powder on
cooling (Dulk).
C
H
0
J
Analyses by Dulk, at a mean temperature of 50°.
a.
b.
C.
79.45
81.81
80.19
10.75
11.10
10.95
9.80
7.09
8.86
100.00
100.00
100.00
a is hydrate of dammarylic acid, C45H³7O4, b dammarylic acid C45H36O³, and c a
mixture of the two (Dulk).
a and b form with bases corresponding salts, which, however, are
not obtained in the crystalline state, and contain very varying pro-
portions of base. The potash-salt is brown, soluble in alcohol and
ether, and contains 2·03 and also 4.38 and 6.15 p. c. KO. a does not
precipitate either neutral or ammoniacal nitrate of silver; but nitrate
of silver produces in a strong warm alcoholic solution of b, a whitish-
yellow precipitate containing, at 100°, 16-38 p. c. AgO: the alcoholic
washings deposit a pure yellow silver-salt containing 14.64 p.c.
AgO. Other silver-salts contained only 10.73 and 7.86 p. c. AgO
(Dulk).
3. Dammar-resin.
LUCANUS.
Schw. 56, 60.
BRANDES. Br. Arch. 30, 1.
BILTZ. N. Tr. 20, 1, 37.
GIESEKE. N. Br. Arch. 18, 189.
THOMPSON. N. Ann. Chim. Phys. 9, 499; Phil. Mag. 23, 81; Ann.
Pharm. 47, 351.
SCHRÖTTER. Pogg. 59, 72.
A. DULK. J. pr. Chem. 45, 16.
The dammar-resin occurring in commerce is of various sorts,
DAMMAR-RESIN.
335
the East Indian and Australian being the most abundant. See Guibourt
(Rev. Scient. 16, 177). The East Indian, or Dammar-puti, from Pinus
Dammara, Lamb., occurs in pieces varying from the size of a pea to
that of the fist: it is whitish-yellow, clear and translucent, some-
times covered with a white dust. It is easily broken, and exhibits
a shining conchoïdal fracture. Nearly inodorous and tasteless, and
does not soften between the teeth. Sp. gr. 1.04 to 1.05 (Biltz),
1.06 (Lucanus), 1.097 to 1.123 (Brandes). Melts at 73° (Dulk):
becomes viscid at 100°, and melts at a higher temperature, more
easily than mastic, less easily than colophony (Biltz). Softens at
75°, forms a thick liquid at 100°, and is clear and limpid at 150°
(Schrötter.) Its alcoholic solution reddens litmus (Lucanus). —
Australian or New Zealand dammar-resin, from Dammara Australis,
occurs in masses of the size of the fist or larger, composed of an
internal milk-white portion covered with a transparent layer, which
is again covered with an opaque outer layer. It is of a pale amber-
yellow colour, exhibits a conchoïdal fracture, and softens somewhat
between the teeth. Melts under hot water to a viscid mass.
Emits an odour of turpentine when rubbed (Guibourt).
Analyses of the entire resin.
Schrötter.
Thompson.
Dulk.
mean, at 100°.
a.
b.
mean, at 50°.
C
81.96
74.45
75.46
82.53
H
11.18
10.28
9.76
11.29
O
6.86
15.27
14.78
6.18
100.00
100.00
100.00
100.00
Thompson's analyses appear to differ from the others, not so much from his having
investigated Australian, and the others East Indian dammar, as because his analyses
were made with oxide of copper, without oxygen. Moreover, the resin b, melted at
176°, was doubtless decomposed.
Dammar-resin, subjected to dry distillation, yields [no umbelliferous
(Sommer), and no hydrosulphuric acid (Bandrimont)] acetic acid, vola-
tile oil, and a yellowish resinous sublimate, leaving a residue of charcoal
(Lucanus). Thompson obtained, by dry distillation, an empyreumatic
oil (his dammaröl) containing 82-22 p. c. C., 11-14 H., and 6.64 O., cor-
responding to the formula, CH2803; by dry distillation with 6 parts of
lime, a thick oil boiling at 132°, called dammarone is obtained; it con-
tains 86.22 p. c. C., 11·53 H., and 2.25 0., corresponding to the formula,
C38H300.- Water takes up from dammar small quantities of vegetable
acids and sulphate of lime (Biltz). - Oil of vitriol dissolves it com-
pletely, forming a yellow, or purple-red, or with more dammar, a black
solution, from which water throws down a whitish-yellow mass, some-
what less easily fusible than dammar, but behaving in the same way
with ether and alcohol (Dulk). Dammar-resin is dissolved and de-
composed by nitric acid. The resin, suspended in boiling water
and treated for several hours with chlorine, is converted into a
whitish-yellow frothy mass containing 26 p. c. chlorine, and does not
undergo further change. When heated with soda-lime, at last to
320°, dammar evolves hydrogen and hydrocarbons: the resin separated
from the residue by hydrochloric acid is more difficultly fusible than
before; insoluble in potash and ammonia, but almost entirely soluble
in absolute alcohol. An odour of valerianic acid is evolved in the
336
PRIMARY NUCLEUS CH3.
process (Dulk). Dammar-resin is not attacked by warm acetic acid,
hydrochloric acid, ammonia-water, or caustic potash, though, according
to Lucanus, it increases in weight in the last-named liquid, and after
the solution has been poured off, is found to be partially soluble in
water.
Besides 0.2 p. c. of mineral substances, and 0.1 p. c. of gum,
dammar contains the following bodies: a, a hydrocarbon, viz., dammaryl
(p. 332); b and c, resins soluble in alcohol, hydrated and anhydrous
dammarylic acid; and d, semi-hydrate of dammaryl (p. 333).
these constituents, d (amounting to 6 or 8 per cent.), is insoluble in
ether and absolute alcohol; b is dissolved by the first treatment with
weak alcohol, together with portions of c, which is completely extracted
by absolute alcohol, whilst a mixture of a and d, separable by ether,
remains behind. As, however, dammaryl takes up oxygen and water
from the air (becoming insoluble?) different quantities of it are obtained
according to the method of treatment adopted (Dulk). a. Cold ether
dissolves 98 p. c. of the powdered resin, leaving d.-B. Boiling abso-
lute alcohol takes up 80 to 84 p. c. 9. The powdered resin, treated
with weak alcohol, gives up to that liquid 36 p. c. of dammarylic acid;
absolute alcohol then takes up 43 p. c. of anhydrous dammarylic acid,
leaving a mixture of 13 p. c. of dammaryl soluble in ether, and 8 p. c.
of semi-hydrate of dammaryl insoluble in ether.. Alcohol of 65
or 82 degrees dissolves the hydrated together with a portion of the
anhydrous acid; when employed boiling, it deposits a mixture of the
two on cooling (Dulk).
Lucanus found dammar soluble to the extent of one-half in abso-
lute alcohol, whilst with alcohol of 80 p. c., 4th was soluble in the cold,
and 4th in the hot liquid. Brandes obtained from dammar 83.1 p. c.,
easily soluble in alcohol, and 168 p. c. of a difficultly soluble resin.
Biltz obtained 72.5 p. c., easily soluble in 80 p. c. alcohol, 22.5 p. c.,
difficultly soluble in hot absolute alcohol and ether, and 5 p. c. of inso-
luble resin. Thompson separated Australian dammar-resin, by boiling
it with weak alcohol, into dammaran, which remained behind, and
dammaric acid, which dissolved and was precipitated from the solution
by water. The latter body separates from alcohol in crystalline
granules, reddens litmus, and contains, at 100°, 76-29 p. c. C., 9.31 H.,
and 18:00 O., corresponding to the formula, C40H8107. It dissolves in
ammonia, and forms a silver-salt (which may be precipitated from the
ammoniacal solution by nitrate of silver) containing 64.78 p. c. C.,
9.01 H., 11.61 O., and 14.60 AgO.- Dammaran is a white brittle
resin, containing, at 100°, 75·02 p. c. C., 9.60 H., 15.38 O., correspond-
ing to the formula, C40H³¹06; it absorbs oxygen when heated to 150°
175°. Forms colourless solutions with absolute alcohol and oil of tur-
pentine (Thompson). These analyses and statements do not appear to be very
trustworthy (Kr.).
Dammar dissolves very slightly in acetone (Wiederhold), completely
in volatile and fat oils (Dulk), but, according to Stickel, not perceptibly
in castor-oil. According to Guibourt, oil of turpentine does not dissolve
East Indian dammar completely (contrary to Brandes and Lucanus),
and leaves 80 p. c. of Australian dammar undissolved.
GUTTA (GUTTA-PERCHA).
337
Gutta (Gutta-percha).
C40H 32
SOUBÉIRAN. N. J. Pharm. 11, 17; J. pr. Chem. 39, 373; Dingl. Polyt. J.
103, 415; Ann. Pharm. 64, 380; Kopp's Jahresber. 1847 and 1848,
743.'
KENT. Sill. Am. J. (3), 6, 246; Kopp's Jahresber. 1847 and 1848,
744.
ADRIANI. Kopp's Jahresber. 1850, 519; Pharm. Centr. 1851, 17; abstr.
from Verhandl. over de Gutta Percha en Caoutchouc. Utrecht, 1850.
Chem. News, 2, 277, 289, and 318; Kopp's Jahresber. 1860, 496.
D. MACLAGAN. N. Ed. Phil. J., 39, 238.
ARPPE. J. pr. Chem. 53, 171; Kopp's Jahresber. 1851, 530.
PAYEN. Compt. rend. 35, 109; J. pr. Chem. 57, 152; Kopp's Jahresber
1852, 637. — Rép. Chim. appliquée. 1, 517; Kopp's Jahresber. 1859,
519.
BAUMHAUER.
J. pr. Chem. 78, 277; Chem. Centr. 1860, 186; Kopp's
Jahresber. 1859, 518.
A. W. HOFMANN. Ann. Pharm. 115, 297; Kopp's Jahresber. 1859,
517.
OUDEMANNS. Scheik. Onderz. 2 Deel, 3 Stuk, Onderz. 291; Kopp's
Jahresber. 1859, 517.
W. A. MILLER. Chem. Soc. Qu. J. [2], 3, 273.
The hydrocarbon C40H32 (or C40H30, according to Miller), the pure
gutta, forms the principal constituent of the hardened sap of Isonandra
Gutta, which occurs in commerce as gutta-percha.
Separation from Gutta-percha. Gutta-percha, purified by treating it
with water and hydrochloric acid, is dissolved in boiling ether; the
mass which separates on cooling is quickly pressed, and dissolved in
boiling ether; and the portion again deposited is washed with cold
ether and alcohol: it then becomes gelatinous. The expressed mass
is at once melted by heating to 100°, to prevent oxidation, and dried
(Baumhauer).
The following methods also seem to yield pure gutta, although the
products investigated were already changed by oxidation.
1. Comminuted gutta-percha is treated with cold ether, or with
boiling absolute alcohol, so long as these liquids take up anything: the
residue is pure gutta: the filtrate deposits alban, whilst fuavil remains
in solution (Payen). 2. Gutta-percha is treated in succession with
boiling water, which takes up acids and a brown extract, with boiling
alcohol, which extracts a soft resin, and with ether, which dissolves a
yellowish-white resin; the residue is dissolved in oil of turpentine, and
precipitated with alcohol, and the precipitate is washed with boiling
alcohol (Soubeiran. Adriani and Geiseler adopt a similar process. 3. Gutta-
percha, previously treated with water, alcohol and ether, is dissolved
in chloroform and precipitated by alcohol (Adriani). As the solution.
cannot be filtered when it contains, more than 1 part of gutta-percha in
40 parts of chloroform, and as the strong solution clarifies very slowly
by standing, Maschke (N. Br. Arch. 89, 31) shakes the solution with
VOL. XVII.
Ꮓ
338
PRIMARY NUCLEUS C40H32.
a little water, which takes up the impurities, and, after allowing it to
stand for 14 days, draws off the clear lower layer. The solution may be
decolorised with animal charcoal; alcohol and ether also extract the
brown colour from gutta-percha which has been dissolved in alcohol
and recovered from the solution by distillation, taking up at the same
time alban and fluavil (Maschke).
Properties. White, fine powder, becoming transparent at 100°,
melting to a viscid mass at 150°, and decomposing at higher tempera-
tures (Baumhauer). The residue which remains on exhausting gutta-
percha with boiling alcohol, or with ether, is white and opaque, or semi-
translucent in the cold, and translucent at 100°, at which temperature
it runs together; at 10° to 30° it is soft, tough, ductile, and slightly
elastic. After the removal of air-bubbles, it is heavier than water
(Payen).
Baum-
40 C
32 H....
240
32
....
88.23
11.77
hauer. Hofmann. Adriani.
88.02 88.12 87.91
11.88 12.49 11.94
....
Mac-
lagan. Soubeiran.
86.36 83.47
12.15 11:47
....
C40H32
272
AR
...
100.00 .... 99.90
100.61 ... 99.85.... 98.51 .... 94.94
Miller.
Or: 40 C
240
88.88
88.96
30 H
30
11.12
11.04
C40H30
270
100.00
100.00
Isomeric with dammaryl (p. 332) and caoutchouc (p. 343).
Decompositions. 1. Gutta very readily absorbs oxygen, especially
when in powder, whether in the pure state or as a constituent of com-
mercial gutta-percha, formic acid being thereby produced (Baumhauer).
a. Gutta prepared as above and dried in powder, whereby it be-
comes transparent, exhibits the composition a. b. Gutta prepared in a
similar manner was almost entirely soluble in cold ether after drying (b).
When gutta-percha, purified by kneading with water, washing
with hydrochloric acid, and drying in the air or over oil of vitriol, is
powdered, exhausted with cold alcohol, and dissolved in chloroform,
alcohol throws down from the solution a fine powder, which, when
exhausted with cold alcohol and dried in a vacuum, exhibits the com-
position c. When again exhausted with alcohol it gives up to that
liquid a pale-brown resin, which may be obtained by recrystallisation
in the form of a white, somewhat crystalline mass (e): d remains un-
dissolved (Baumhauer).
a.
C
86.80
b.
83.49
C.
d.
e.
68.81
67.71
83.19
H
11.72
11.25
9.16
1:48
5.26
21.73
9.17
23.12
10.34
6.47
100·00
100.00
100.00
100.00
100.00
!
Baumhauer gives for b the formula C20H160.
To such an oxidation is owing the brittleness of manufactured
GUTTA (GUTTA-PERCHA).
339
gutta-percha, which thereby loses its cohesion and exhibits an altered
behaviour with ether and alcohol. a. Cold alcohol takes up from the
altered gutta-percha a brown resin, triturable to a powder after drying
over oil of vitriol and at 100° (at which temperature it melts), and con-
taining, on an average, 62.79 p. c. C., 9.29 H., and 27.92 0. — b. From
the residue freed from a, boiling alcohol takes up a similar resin, con-
taining 67.72 p. c. C., 10.09 H., and 22.19 0. -c. The residue ex-
hibits the composition of pure gutta (given above), and dissolves in
ether, chloroform, and benzene (A. W. Hofmann).
When thin sheets of white, flexible, gutta-percha, perfectly soluble
in bisulphide of carbon, are frequently moistened and dried, and ex-
posed to temperatures varying between 10° and 50°, the gutta-percha
hardens to a yellow brittle substance, which dissolves partially in
alcohol and ether, and has become partially insoluble in bisulphide of
carbon. The portion taken up by alcohol resembles fluavil; that
soluble in ether is granular, yellow, and scarcely fusible at 100°; the
portion dissolved by bisulphide of carbon is soft, white, and ductile,
like gutta-percha. The portion remaining undissolved is yellow and
brittle; it swells in chloroform, benzene, and oil of turpentine, and
shrinks in ammonia-water and acetic acid (Payen).
¶ From Miller's experiments it appears that gutta-percha may be
preserved for months and even years with little change, either in air
or water, provided light be excluded; sea-water appears to be particu-
larly well adapted for its preservation. But alternate exposure to
moisture and dryness, especially if the sun's light has also access to it,
rapidly destroys gutta-percha, rendering it brittle, friable, and resinous.
A gradual absorption of oxygen takes place, and the gutta-percha
slowly increases in weight, becoming at the same time proportionately
soluble in alcohol and in dilute solutions of the alkalis. Some portion
of the gutta, however, always remains unchanged. ¶
Pure gutta is violently acted on by ozone. It decomposes at a
temperature of 180°, evolves bubbles of vapour at 210°, and begins to
froth up at 280° (Baumhauer). By dry distillation gaseous and liquid
hydrocarbons are produced (Payen). - Nitric acid forms hydrocyanic
and formic acids (Oudemanns). In hydrochloric acid gas gutta assumes
a brown-black colour, melts superficially, and takes up hydrochloric
acid. When dry hydrochloric acid gas is passed over gutta-percha
previously purified with water and hydrochloric acid, and the brown
mass thereby formed is boiled with ether, which dissolves the greater
part, the brown portion remaining undissolved contains, at 100°,
72.98 p. c. C., 9.05 H., 3.86 Cl., and 14.11 O. On evaporating the
ethereal solution, exhausting the residue with cold alcohol, evapo-
rating, again dissolving in boiling alcohol, and cooling the solution, a
brown, elastic, sticky mass is thrown down, containing 83.54 p. c. C.,
11.49 H., and 5.26 Cl., corresponding to the formula C1008º.HCÍ
(Baumhauer). Gutta turns brown in oil of vitriol, evolving sulphurous
acid (Payen).
Gutta is insoluble in alcohol and cold ether (see above), but easily
-soluble in bisulphide of carbon and chloroform. It dissolves very slightly
in benzene at 0°, but more freely at 25°: the solution saturated at 30°
solidifies to a semi-transparent mass on cooling. It is scarcely soluble
in oil of turpentine at 0°, but becomes suspended in the liquid, and
dissolves on warming (Payen). See also Gutta-percha.
z 2
340
PRIMARY NULLEUS C40H.
Gutta-percha of Commerce.
10
The hardened sap of Isonandra Gutta, an East Indian tree of the
sapotaceous order. Sapota Muelleri also yields gutta-percha (Bleck-
rode). The sap, which is fluid at first, solidifies to a yellow spongy
mass on boiling (Oxley, N. Ed. Phil. J. 44, 286), or even when kept in
bottles (Baumhauer). A sap of this kind, altered a little by transport,
but otherwise in a natural state, yielded, on addition of ths of
alcohol, 143 p. c. of pure white gutta-percha, the colouring matter
remaining dissolved in the alcohol (Blcekrode). The sap is dried in
thin layers; or the imported gutta-percha is purified by rasping it in
cold water, whereby the organic matters and salts are removed, and
the separation of pieces of wood and earthy impurities is facilitated.
It is finally washed in warm water, dried in vessels heated to 110°,
and kneaded together (Payen).
Getah Malabeoya is a sap resembling gutta-percha, obtained from
Palembang. It melts at 170°, and forms, with boiling water, a neutral
milky liquid, precipitable by alcohol. It is soluble in chloroform
(Adriani, Kopp's Jahresber. 1850, 522). Concerning the Getah Lahoe of
İndia, see under Wax.
Gutta-percha is pale-yellow or grey-white, or is coloured reddish-
brown by pieces of bark falling into the sap. It is nearly as hard as
wood, and tough and flexible between 0° and 25°. At 48° it becomes
pasty, and at 45° to 60° may be drawn out into sheets, threads, and
tubes, whereby it becomes fibrous, but not so elastic as caoutchouc;
on cooling it again becomes hard. Softens in hot water, and may be
moulded into forms which it retains in the cold. Strongly electric
when rubbed. Sp. gr. 0.9795 (Soubeiran), 0·966 to 0.999 (Adriani),
0.979, but heavier than water when completely freed from air (Payen).
Nearly inodorous.
The gutta-percha of commerce is a mixture of pure gutta, casein, a
vegetable acid, a resin soluble in ether and oil of turpentine, and
another resin soluble in alcohol (Soubeiran). It contains 5.18 p. c. of
ash (Adriani). Contains 75 to 82 p. c. of pure gutta, 16 to 14 p. c. of
alban, and tó 6 to 4 p. c. of fluavil, besides small quantities of salts,
fat, volatile oil, colouring matter, and nitrogenous vegetable substances
(Payen).
Miller found in a sample of good commercial gutta-percha
taken from a new cable, pure gutta 79.70 p. c., soft resin 15.10,
vegetable fibre 2.18, moisture 2.50, and ash 0:52. The moisture was
mechanically diffused through the mass, and seems to have some in-
fluence on its pliability and toughness. 100 pts. of the commercial
sample, dried at 100° till it ceased to lose weight, contained (deducting
the ash) 8+66 p. c. C., 11-15 H., and 4:19 0. This gutta-percha
softens and liquefies at 100°. It is soluble, with the exception of a few
flocks of fibrous matter, in benzene, bisulphide of carbon and ether.
Alcohol dissolves none of the pure gutta, but extracts a portion of the
soft resin. This resin is an oxidised compound, probably in a transi-
tional state to a higher degree of oxidation. It was found to contain
76.65 p. c. C., 11∙16 H., and 12.69 O. The true gutta was extracted
nearly pure from the above-mentioned commercial sample by dissolving
it in benzene, filtering, and adding alcohol, whereby a coagulum of
GUTTA-PERCHA OF COMMERCE.
341
nearly pure gutta was separated, containing 87-22 p. c. C., 12.04 II.,
and 0.74 0., the small quantity of oxygen being probably due to a
small portion of the resin precipitated at the same time. T
According to Arppe (J. pr. Chem. 53, 171; Kopp's Jahresb. 1851,
530, gutta-percha contains chips, sand, and similar bodies, salts of
apocrenic acid, and six different resins, which may be separated as fol-
lows: Gutta-percha is purified by softening it in boiling water, digest-
ing it repeatedly with alcohol of sp. gr. 0.81, and evaporating the
solution. The residue consists of a mixture of resins, which are dis-
solved by ether, with the exception of alpha-resin. The ethereal
solution is evaporated; the semifluid, sticky residue is boiled with
alcohol; and the solution is filtered from the undissolved portion,
which appears to be a compound of delta-resin with lime. The ethereal
solution leaves on evaporation a mixture of sticky gamma-resin and
crystalline beta-resin, separable by cold absolute alcohol, which leaves
the latter undissolved. The gutta-percha exhausted by boiling
alcohol of sp. gr. 0.81 gives up to alcohol of sp. gr. 0.83 a further
portion of delta-resin, while there remains undissolved a mixture of
epsilon- and eta-resin, the former of which is more easily soluble than
the latter in ether. Alpha-resin is white, difficultly fusible, and may
be obtained from alcohol in indistinct crystals. Beta-resin, C4H626,
forms long needles, melting at 125°, and solidifying on cooling to a
colourless glass, soluble in alcohol. Gamma-resin, C40H6203, is pale-
brown, sticky, and fusible at 50°; in water it is converted into white
flocks, which are difficultly soluble in alcohol. Its solution is precipi-
tated by neutral acetate of lead. Delta-resin, C40II4808, forms colour-
less granules, melting at 175°, easily soluble in ether, difficultly soluble
in absolute alcohol, and not precipitable by neutral acetate of lead.
Epsilon-resin, C40H48010, is a white powder, melting at 55°, precipitable
from its ethereal solution by alcohol. Eta-resin, C40H620, is white and
soft, ropy at 40°, brown at 110°, and brick-red after cooling. It is
nearly insoluble in cold ether, and very slightly soluble in boiling
alcohol: it forms the principal part of gutta-percha. Epsilon- and
eta-resins are inflamed by strong nitric acid, and oxidised by weaker
acid, with formation of picric acid. Thus, according to Arppe, whose work
is before me only in extracts (Kr.).
-
Gutta-percha yields by dry distillation, first a clear yellow, then a
dark oil, of variable boiling-point and sp. gr. 0.909, amounting alto-
gether to 57.66 per cent. (Adriani). The oil contains 10 at. C. to
8 at. H. (Maclagan). The dry distillation of gutta-percha proceeds in
the same way as that of caoutchouc, yielding a little acid water, vola-
tile bases, hevene (sce under Caoutchouc), and a little isoprene and caout-
chin, together with an empyreumatic product, which may be removed
by rectifying the distillate over caustic potash (Williams). - Gutta-
percha is very inflammable, and burns with a bright flame (Oxley).
Oil of vitriol carbonises and corrodes gutta-percha, evolving sulphurous
acid-Nitric acid softens gutta-percha and dissolves it on boiling,
whereupon water throws down a soft yellow resin; ultimately cam-
phretic acid and the decomposition-products of albumin are formed.
(Schwanert, Ann. Pharm. 128, 124). Strong hydrochloric acid attacks
gutta-percha slowly at 20°, rendering it brown and brittle (Payen).
Gutta-percha is insoluble in water, though boiling water takes up
from it an acid (Adriani) and a brown extract (Soubeiran). It is in-
soluble in acids and alkalis. Liquid carbonic acid extracts brown
-
342
PRIMARY NUCLEUS CHOHS.
colouring matter, and leaves the undissolved portion white as before
(Gore, Chim. pure. 3, 214).- Bisulphide of carbon dissolves gutta-
percha even in the cold, with the exception of a brown substance
(Payen), and leaves it unchanged and not viscid on evaporation. The
solution can be filtered only when not more than 1 part of gutta-percha
is dissolved in 12 parts of the bisulphide (Gieseler, N. Br. Arch. 83, 9).
The pale-brown solution renders paper and wood water-proof (Vogel,
Repert. 98, 402). — Gutta-percha does not dissolve, or dissolves only to
the extent of 22 per cent. (Payen) in absolute alcohol; moreover,
alcohol precipitates most of the other solutions. See above. It is
insoluble in nitrous ether (J. Chim. méd. 24, 436) and in acetic acid.
Ether softens it in the cold, and dissolves it on warming (Soubeiran).
Vogel found gutta-percha insoluble; Kent found it slightly soluble;
Payen, soluble to the extent of 22 p. c. only, in ether; Schwerdtfeger
found it only partially soluble even in boiling ether; Maclagan and
Hofmann, on the contrary, found it soluble in ether. Gutta-percha
purified by kneading with water and washing with hydrochloric acid,
and dried, dissolves, with the exception of brown flocks, in boiling
ether, the solution solidifying to a jelly on cooling (Baumhauer).
Gutta-percha dissolves easily in chloroform; the solution cannot be
filtered when it contains more than 1 part of gutta-percha in 16 parts
of chloroform. The solution, mixed with 3 parts of ether and kept for
some time below 15°, deposits the gutta-percha in the form of a white
powder (Kent). The solution in chloroform is precipitable by alcohol,
but not by ether (Schwerdtfeger). Glycerin containing acetic acid or
tartaric acid dissolves gutta-percha when heated over the water-bath
(Dullo, Polyt. Notizbl. 20, 91).
Gutta-percha dissolves in benzene (Mansfield); it dissolves only par-
tially in benzene and oil of turpentine in the cold, but almost completely
on warming (Payen). Rock oil, coal-tar oil, resin oil, the empyreumatic
oils of caoutchouc and gutta-percha, terebene, and hydrochlorate of terebene
dissolve gutta-percha, and leave it unchanged on evaporation, but if
oil of turpentine containing resins is employed, it remains in a sticky
state. Olive oil is without action on gutta-percha in the cold; the hot
oil dissolves a little, and deposits it again on cooling (Payen).
On exposing samples of sheet gutta-percha for nine months to the
action of linseed oil, boiled and unboiled Stockholm tar, and coal-tar, it
was found that these liquids had not exerted any perceptible solvent
action upon the gutta, which retained its texture and tenacity in all those
portions which had been fairly submerged in the liquid, and protected
from the light and atmospheric air; but in those portions which had
projected into the atmospheric air contained in the jar, where it was
also exposed to the effects of diffused daylight, the texture had
become rotten, and the material more or less brittle and resinous.
These liquids exclude oxygen from the gutta-percha, and are thus
enabled to exert a preservative influence upon it, without, however, in
any degree softening or dissolving its texture. Hence they are likely
to be highly valuable agents in coating the insulating material of tele-
graphic cables (Miller). ¶
Alban. Light, pulverulent mass, made up of microscopic, transparent
lamina (Payen). At ordinary temperatures its composition agrees
with the formula C201602; at 130° it is represented by the formula
C20H150 (Oudemanns). - Melts at 140° (Oudemanns), at 160° to 180°,
CAOUTCHOUC.
343
J
to a transparent oil, which remains transparent on cooling, and solidi-
fies to a cracked mass a little heavier than water (Payen). It is not
attacked by cold or boiling water, or by caustic potash or dilute acids.
Strong sulphuric and nitric acids act violently upon it, as upon gutta-
percha; hydrochloric acid is without action. Alban dissolves very
easily in bisulphide of carbon, chloroform, benzene, oil of turpentine,
and ether, crystallising from the latter on evaporation in long, pearly
laminæ. It dissolves freely in warm absolute alcohol, crystallising
from the solution on cooling, and also on evaporation (Payen).
According to Oudemanns, it dissolves in 196 parts of cold, and 19 parts
of boiling alcohol.
Fluavil. When freed from alcohol, which it obstinately retains,
by heating to 100° in a vacuum till frothing ceases, it is a lemon-
yellow, amorphous mass, solid and brittle at 0°, pasty at 50°, melting
at 100° to 110° (Payen). According to Oudemanns, it is C20H16O.
Boils when strongly heated, undergoing decomposition. Violently
attacked by oil of vitriol and strong nitric acid, but not decomposed by
hydrochloric acid, ammonia, or alkalis. Dissolves in cold bisulphide
of carbon, chloroform, alcohol, ether, benzene, and oil of turpentine,
and is left in an amorphous state on evaporation; under favourable
conditions, however, it appears to crystallise (Payen).
Caoutchouc.
C40H92.
ACHARD.
MACQUER. Mém de l'Acad. des Sc. de Paris, 1768, 209.
Chem. Phys. Schriften, 211. JULIAANS. Diss. de res. elast. Traj. ad.
Rh. 1780. BERNIARD. J. Phys. 18, 265. TROMMSDORFF. Crell.
Ann. 1792, 1, 524. - GROSSART. Ann. Chim. 11, 253. FOURCROY.
Ann. Chim. 11, 225. — FOURCROY & VAUQUELIN. Ann. Chim.
55, 296. — A. Gehl. 6, 673. CADET DE GASSICOURT. J. Pharm.
11, 343.
FARADAY. Quart. J. of Sc. 21, 19; Dingl. 20, 411; Berzel. Jahresber.
7, 245.
NEES V. ESENBECK. Repert. 22, 46. — NEES v. ESENBECK & MARQUART.
Ann. Pharm. 14, 43.
ADRIANI.
Verhand. over de Gutta-percha en Caoutchouc, Utrecht.
1850; abstr. Pharm. Centr. 1851, 17; Kopp's Jahresber. 1850, 519.
Chem. News 2, 277, 289, and 313; Kopp's Jahresber. 1860, 496.
PAYEN. Compt. rend. 34, 2; J. pr. Chem. 55, 273; Pharm. Centr. 1852,
81; N. J. Pharm. 22, 172. Compt. rend. 34, 353; J. pr. Chem.
56, 196; Kopp's Jahresber. 1852, 637.
TRAUN. Vers. einer Monographie des Kautschuks. Göttingen, 1859.
W. A. MILLER. Chem. Soc. J. [2] 3, 280.
On the products of distillation of caoutchouc :
BEALE & ENDERLEY. L'Instit. 69, 290.
CHEVALLIER. J. Chim. méd. 11, 80; abstr. Repert. 52, 394.
TROMMSDORFF. Repert. 53, 145; Pharm. Centr. 1853, 834.
GREGORY. Ann. Pharm. 16, 61. - Phil. Mag. 9, 321; J. pr. Chem.
9, 387; J. Pharm. 22, 382; N. Br. Arch. 10, 64.
344
PRIMARY NUCLEUS CHOH32.
ПIMLY. Dissert. de Caoutchouc ejusdem destill. sicc. productis. Göttingen
1835, abstr. Ann. Pharm. 27, 40.
DALTON. Rhil. Mag. 9, 479; J. pr. Chem. 10, 120.
BOUCHARDAT. J. Pharm. 23, 454; J.pr. Chem. 36, 313; Ann. Pharm.
27, 30.
GR. WILLIAMS. Phil. Trans. 10, 516; Phil. Mag. [4] 21, 463; J. pr.
73, 188; Rép. Chim. pure 3, 200; Complete: Chem. Soc. Qu. J.
15, 110; abstr. Chem. Centr. 1862, 833; Kopp's Jahresber. 1860,
494.
Federharz. Gummi elasticum. India-rubber. First made known in
Europe by Bouguer and Condamine in 1736. The milky juices of
the most various plants, according to Schleiden all milky saps, contain
caoutchouc. The inspissated sap of the following plants forms the
caoutchouc of commerce, which comes from the northern part of South
America, from the East Indies and the Sunda Islands, as well as from
Madagascar. A. America. The Euphorbiaceae: Siphonia elastica, S.
lutea, and S. brevifolia; the Apocynacee: Hancornia speciosa; the Arto-
carpaceæ: Artocarpus integrifolia, Castilleja elastica, Cecropia peltata, also
Polletri Sapotea Mülleriana.-B. India.
B. India. The Apocynaceæ: Urceola
elastica; Artocarpacea: Ficus elastica, F. indica, and F. religiosa.-
C. Madagascar. Vahea gummifera, of the apocynaceous order.
The caoutchouc of opium possesses the same properties as com-
mercial caoutchouc, but dissolves more easily in ether and in volatile
and fixed oils, probably on account of its finer state of division. It
contains 87.89 p. c. C., and 12:11 II. (Pelletier, Ann. Chim. Phys.
50, 277; Ann. Pharm. 5, 177). See also Buchholz (N. Tr. 8, 1, 37).
The dried saps of Ficus Carica, Euphorbia Cyparissias and E. off,
Papaver somniferum, Asclepias syriaca, A. gigantea, Lactuca sativa,
Cichorium Intybus, several species of Sonchus and other plants, yield
caoutchouc-like substances, which remain on exhausting the dried sap
with water and alcohol, or may be precipitated from an ethereal solution
by alcohol: Native Caoutchouc. See Carradori (Ann. Chim. Phys. 26,
58), Ricord Madiana (J. Pharm. 16, 107). The substance obtained from
Ficus Carica appears, according to Bizio (Brugn. Giorn. 20, 41), to be
identical with viscin.
The sap of the Ficus elastica cultivated in Germany contained in
1827, a colourless, soft resin, gum, and visciu; the same substances
were found also in 1835 in the sap which exuded from the cut ends of
young green twigs of the same tree; but the less fluid sap flowing
from incisions made in the stem of the tree dried up quickly to caout-
chouc (Nesenbeck & Marquart). The sap of Ficus elastica contains a
larger quantity of water, the farther from the root it is extracted. The
sap of the terminal buds contained 17·7 p. c., that of the parts immediately
below 20.98 p. c., and that from still lower 25.15 p. c. of solid con-
stituents, 9.57, p. c. of those from the sap of the terminal buds con
sisting of caoutchouc (Adriani).
The sap of Siphonia elastica conveyed in a nearly unaltered condition,
in closed vessels, from South America to England contained 31·7 p. c. of
caoutchouc, besides wax, bitter substance, gum, albumin, and 56.4
p. c. of water, with salts and acetic acid. It formed a pale-yellow, thick,
homogeneous cream, of sp. gr. 1·012, having an acid odour like that of
spoilt milk. When left at rest, it separated into a lower dark-brown
transparent liquid, and an upper white, opaque, creamy portion. In
CAOUTCHOUC.
345
thin layers it dried up to ordinary caoutchouc in the air. When heated
it curdled instantaneously from separation of caoutchouc; the addition
of a large quantity of alcohol, but not of water or aqueous alkalis,
also threw down the caoutchouc (Faraday). Fresh caoutchouc-sap
curdles in the air, like milk turning sour; the separation being hastened
by the addition of hydrochloric acid or chloride of sodium. It may be
preserved, mixed with th of ammonia-water, in air-tight vessels filled
with the liquid (Johnson, Dingl. 130, 156) Boussingault & Rivero (Ann.
Chim. Phys. 23, 220), examined a sap from Mexico, the caoutchouc of
which was completely precipitable by ammonia. The reddish-white
caoutchouc-sap kept in bottles turns brown-red in the air (Baumhauer).
On fig-tree sap, see Bizio (Br. Arch. 22, 158), Trémolière (Bull. Pharm. 6, 316),
Landerer (Repert. 72, 353; 84, 70): on the sap of Ficus sylvestris and F. doliaria,
Peckolt (N. Br. Arch. 105, 31); on a sap from Guiana, Hancock (Ed. N. Phil. J. 1,
240). Some other saps are described in the Appendix (p. 351).
If the exuding sap of the stem of Ficus religiosa be received in
ether, a colourless syrup is obtained, which when diluted with more
ether throws down a deposit. On evaporating the solution, the caout-
chouc remains as an elastic mass, which may be freed from adhering
wax by boiling with alcohol (Nesenbeck & Marquart). The sap of
Siphonia elastica diluted with 4 parts of water, and allowed to stand
for twenty-four hours, deposits the caoutchouc in the form of a creamy
layer, to be purified by repeated washing with water. This very
finely divided caoutchouc, intimately mixed with water, is converted
into a soft curdy mass on removing the water by evaporation or by the
action of drying substances, and when further evaporated or pressed,
passes into a close elastic condition, after which it is no longer miscible
to a cream with water (Faraday).
The caoutchouc of commerce is made by drying successive layers
of the sap on clay over a fire, or by evaporating it in the sun.
It may
also be obtained by allowing the sap to curdle in the air, and then
removing the upper solid elastic portion from the whey beneath. --
Pure caoutchouc is obtained by dissolving the crude product in chloro-
form and precipitating with alcohol (Adriani).
Pure caoutchouc appears white and opaque so long as it contains
water between its particles, but after long drying in the air, it becomes
colourless and transparent, and only slightly coloured in large masses.
It possesses the elasticity of ordinary caoutchouc, has a silky lustre
and a fibrous appearance when stretched, and exhibits no trace of tex-
ture (Faraday). According to Payen, however, thin sheets of crude
caoutchouc exhibit irregular rounded pores, and under a magnifying
power of 300 diameters a reticulated texture. See also Page (Repert. Pat.
Invent. 1858). Common caoutchouc is generally black outside, pale-
yellow within, and opaque; the lighter cut surfaces soon turn brown
on exposure to the air. Sp. gr. of pure caoutchouc = 0·925 (Faraday),
of commercial 0.9335 (Brisson), of the bottle India-rubber 0.9454; of
the so-called Speckgummi 0.9628 at 20° (Adriani), varying in different
kinds between 0.919 and 0.943 (Ure). The specific gravity is not in-
creased by pressure (Faraday). At ordinary temperatures caoutchouc
is soft, tough, and highly elastic; freshly cut surfaces remain for a long
time sticky, and may be united together so that the connection is as
perfect at the joint as at any other part. Below 0° it is hard, slightly
flexible, no longer adhesive on freshly cut surfaces, and but slightly
346
PRIMARY NUCLEUS C40H32.
clastic. It evolves heat when stretched; a string of caoutchouc by which
a weight is suspended contracts when warmed and expands on cooling
(Gough, N. Gehl. 9, 217).-Caoutchouc is a non-conductor of electricity
(Faraday); and becomes highly electric when rubbed. Has a faint
odour. Tasteless. It is not quite impervious to water, since under
water it gradually absorbs the liquid and becomes opaque (Faraday).
According to Chevreul and Peyron, it is not quite impermeable by gases;
Berzelius, however, found the barometric pressure, under the receiver of
an air pump with india-rubber joint, unchanged after twenty-four
hours.
Faraday. Ure.
Purified.
Williams.
Brown.
Yellow.
40 C
32 H
240
32
88.24
11.76
87.2
12.8
90.00
86.1
87.2
9.11
12.3
12.8
....
....
....
....
272
100.00
100.0
99.11
98.4
100.0
....
....
....
C40H32
The following formulæ have been proposed for the composition of caoutchouc :
C3H2 (Ure), CH7 (Faraday; Payen & Pelletier) C12H10 (Soubeiran). The above
formula of Williams agrees with the composition of the oil of caoutchouc. - Isomeric
with dammaryl and gutta-percha.
¶ Pure unmanufactured or virgin Para caoutchouc and good sheet
masticated or manufactured caoutchouc were found by Miller to con-
tain:
Masticated.
Pure caoutchouc
Moisture......
Resin
Ash...
Virgin.
96.6
96.64
1.3
0.82
1.8
2.06
0.3
0.48
100.0
100.00
On deducting moisture and ash, the elementary composition is :-
Carbon
Hydrogen
Oxygen
Virgin.
Masticated.
85.82
85.53
11.11
12.06
3:07
2.41
100.00
100.00
T
Crude caoutchouc contains a nearly insoluble ingredient, tough,
elastic, and slightly sticky, which is the pure caoutchouc, or caoutchouc
proper, together with a soluble, ductile, sticky body, fat, volatile oil,
nitrogenous matters, one of which is extracted, together with the fat,
by alcohol and water (Payen). It contains sulphuretted, nitrogenous,
and chlorinated substances, which pass over, more or less decomposed
on dry distillation (Cloez & Girard, Compt. rend. 50, 874).
Caoutchouc oxidises slowly at ordinary temperatures, and becomes
brittle. When dried over oil of vitriol for a month, it contains 78.25
p. c. C., 11.34 H., and 11:40 O. (Adriani).
¶ 500 grains of pale-brown virgin Para caoutchouc in a narrow
tape-like strip, exposed in netting in the open air to sun and rain for
nine months, became blackened and rotten, but was neither sticky nor
crumbled, and increased in weight 34-5 grains or 7 p. c. Another
similar piece cxposed to air and light for the same time in a dry bottle
placed with its mouth downwards, gained, by absorption of oxygen,
CAOUTCHOUC.
347
14 grains or 2.8 p. c., and became brown, soft, and sticky, especially
in the parts most exposed to light. It gave up to alcohol, 11.81 p. c.
of an oxidised soft viscous resin, containing 67.23 p. c. carbon, 9.34
hydrogen, and 23.23 oxygen. A similar sample of masticated sheet
caoutchouc exposed to sun and rain collected into a sticky mass which
had lost its tenacity and elasticity. Another sample of the same
exposed in the inverted bottle to diffused light and air, gained 8 grains
or 1.6 p. c., and collected into a lump which was viscous and had lost
its elasticity, especially in the parts most exposed to light. Alcohol
extracted from it 12.64 p. c. of resinous matter. A third sample
exposed freely to the air in a glass bottle, but kept in the dark,
gained only 0.6 p. c., showed no alteration in tenacity or elasticity, and
yielded to alcohol only 2 p. c. of resin (Miller). ¶
From calico which had been saturated with a solution of caoutchouc
in naphtha, and had been left to itself for six years, benzene extracted
a brownish-yellow resin, fusible below 100°, and containing 64.00 p. c.
C., 8.46 H., and 27.54 0. The resin closely resembled shellac, dis-
solved in alkalis, and was precipitated from the solution by acids,
and was easily soluble in alcohol, benzene, and chloroform, but in-
soluble in sulphide of carbon and oil of turpentine (Spiller, Chem. Soc.
J. [2] 3, 44; Chem. Centr. 1865, 495).
Caoutchouc when heated in the air burns with a bright white,
smoky flame, emitting a disagreeable odour. According to Achard it
melts at about 125° [160° (Himly)], giving off aromatic odours, and
remains of a tarry consistence on cooling; but after longer melting, it
cools to a black, brittle mass. When pure caoutchouc is gently heated
in a glass tube, it volatilises in a decomposed state, leaving only a
trace of charcoal (Faraday).
The products of the dry distillation of ordinary caoutchouc are car-
bonic acid, hydrocarbons, ammoniacal water, and empyreumatic oils,
the last of which are yellow and fluid when distilled at a low tempera-
ture, but brown and thick and have a stronger smell at high tempera-
tures (Achard). There remains a little porous charcoal, together with
ash.
The empyreumatic caoutchouc oil, purified [from volatile bases
(Williams)] by treating it with dilute sulphuric acid, water, and solid
caustic potash, is a mixture of hydrocarbons of various boiling-points.
By submitting it to fractional distillation, at last over sodium, the
following products are obtained. 1. A very easily volatile liquid,
consisting, according to Himly, of eupione (xv, 152), boiling at 33° to
44° [see on the contrary, Liebig, Ann. Pharm. 16, 61]; according to Bouchardat
butylene (x, 66), boiling at 10°, and cautchene (x, 21), boiling at
14.5°; according to Williams isoprene, CH, boiling at 37° to 40°.-
2. A body boiling at 171.5°, caoutchin (xiv, 326), Č20H16.-3. Hevene,
or Heveene, the least volatile of the oils, having an amber-yellow colour,
of sp. gr. 0.921 at 21°, boiling at about 315°, and remaining fluid in
the cold. This body has a faint empyreumatic odour, and a harsh
taste, and is without action on polarised light it contains 86·11
p. c. C., and 14·02 H., or equal numbers of atoms of carbon and hydro-
gen. Hevene is inflammable and not completely volatile without de-
composition it absorbs chlorine abundantly, giving off hydrochloric
acid, and is converted into a black resin. Hevene forms with oil of
vitriol a viscid mass, from which there separates a colourless oil boiling
at 228° (Bouchardat).
:
348
PRIMARY NUCLEUS C10H32.
Nitric acid colours caoutchouc yellow, evolving nitrogen, carbonic
acid, and hydrocyanic acid, and producing oxalic acid and a fatty body.
Six parts of fuming nitric acid dissolve 1 part of caoutchouc completely,
with effervescence, forming a dark-brown solution, from which water
throws down yellow flocks, soluble in alcohol, acids, and alkalis, and
inflammable at 100° (Achard). Melted caoutchouc takes fire when
strong nitric acid is poured upon it (Hare). When digested for 12
hours with nitric acid, caoutchouc is converted into a soft, yellow,
non-elastic mass (Roxburgh). Caoutchouc is dissolved by boiling nitric
acid of sp. gr. 135, without any violent action, forming camphretic
acid and a small quantity of resin precipitable by water (Schwanert,
Ann. Pharm. 128, 123).- Oil of vitriol converts moderately thin
pieces of caoutchouc, after some days only, into a black friable sub-
stance without dissolving it (Roxburgh): when heated, it produces a
turpentine-like mass, from which water separates a black brittle resin
(Achard). — The dark-brown solution of caoutchouc in bisulphide of
carbon is decolorised by passing chlorine-gas into it, and on subsequent
addition of water, deposits a white, non-elastic mass. Sulphurous acid
acts in the same manner (Traun). When thrown upon melted chlorate
of potash, caoutchouc burns with a very bright flame, evolving a large
quantity of heat, so that the bottom of the glass tube containing it is
melted (Böttger, N. Repert. 6, 247).
Combinations. Caoutchouc does not dissolve in water at any tem-
perature, but swells up and becomes sticky in boiling water; after
cooling it remains softer and more bulky than before, and is found to
have taken up water. Thin strips of caoutchouc kept in water for 30
days take up from 18.7 to 26.4 p. c., and increase in length and thick-
ness (Payen). Boiling water sometimes takes up a little resin from
commercial caoutchouc.
A narrow strip of virgin Para caoutchouc, weighing 500 grains,
exposed to diffused light in fresh water in an open bottle, became white
and opaque from absorption of moisture, and increased by 86 grains, or
17 per cent., but experienced no other alteration in chemical properties,
and resumed its original characters when dried. A similar sample ex-
posed in sea-water, in an open bottle to diffused light, absorbed 3.6
per cent. of its weight of water, but was only a little altered in
appearance, not in chemical composition. A sheet of masticated
caoutchouc immersed in fresh water, open to the air and diffused light,
increased 87 per cent. by absorption of water, that is to say, it nearly
doubled its weight. It became white, opaque, slimy, and sticky when
pressed, and allowed water to be squeezed out by pressure. It lost
weight rapidly by drying when exposed to the air. - Another sample
similar to the last, but exposed in sea-water, became slightly opaque
and slimy, but increased only 5 per cent. in weight by absorption. A
second sample, in sea-water in a closed bottle, emitted a smell of sul-
phuretted hydrogen, and gained 5.6 per cent. in weight by absorption.
Its elasticity and tenacity were not impaired. A quantity of acetate of
potash having been enclosed in bags made of sheet rubber and accu-
rately sealed, and the bags immersed in water, the salt in each of the
bags was found at the end of nine months to have become liquefied by
the water which it had absorbed, and the bags had in each case gained
in weight several grains (Miller). T
Caoutchouc is insoluble in aqueous hydrochloric acid, and is not acted
CAOUTCHOUC.
349
upon by dilute sulphuric acid. Aqueous potash, even in very strong
solution (Faraday), and alcoholic potash are without action on caout-
chouc, even when heated (Bernard; Achard). Contrary to Thorey and
Thomson, who found it softened and dissolved thereby. Caoutchouc is not
acted on by ammonia-gas: when digested for some months in solution
of ammonia, it colours the liquid brown, assumes a silky lustre, and
swells up, and when shaken with oil of turpentine, dissolves to an emul-
sion, from which the greater part of the caoutchouc separates in the
form of a cream on standing (Ann. Pharm. 23, 359). See also Sumers
(Dingl. 64, 77; 69, 158). - Caoutchouc is apparently not altered in liquid
carbonic acid, but when taken out of the liquid, it swells up to six or
eight times its volume and afterwards contracts again, having become
white throughout the entire mass (Gore, Rép. Chim. pure, 3, 214).
By contact with sulphur, under favourable conditions, caoutchouc is
converted into vulcanised caoutchouc, further into vulcanised caoutchouc
less rich in sulphur, and hardened caoutchouc.
a. When sheets of caoutchouc, 2 or 3 millimetres thick, are im-
mersed for two or three hours in melted sulphur, at a temperature of
112° to 116°, the sulphur permeates the pores of the caoutchouc more
quickly than water or alcohol would do, and increases its weight from
10 to 15 p. c. without altering its behaviour towards solvents. If it
be now heated from 135° to 160° for a few minutes, combination with the
sulphur takes place and it is converted into vulcanised caoutchouc.
Hancock's process (Lond. Journal of Arts, 1845, 178).
Vulcanised caoutchouc remains equally elastic and soft at tempe-
ratures varying between-20° and +50°, and does not soften to any
great extent even at 100° or higher. Under water it takes up a much
smaller quantity of the liquid than crude caoutchouc, and permits the
evaporation of water from vessels made of it to a much less extent.
The combination with sulphur does not alter the proportion of carbon
to hydrogen, which corresponds, as in crude caoutchouc, to the formula.
CH (Payen). Vulcanised caoutchouc is much less easily attacked
by solvents than crude caoutchouc; but, according to Baumhauer, it
is rendered porous by the action of ozone.
Miller found that a sheet of vulcanised caoutchouc exposed in
netting to the sun and rain, lost 2 p. c. in weight, and was scarcely
less tenacious than at first. A similar sheet immersed in fresh water
absorbed 19 p. c., but was not otherwise altered. A similar sheet in sea-
water became rather more slimy, but gained only 1.6 p. c. in weight. ¶
Vulcanised caoutchouc may also be obtained by mixing crude caout-
chouc with finely-powdered sulphur and heating to 135° to 160° (Good-
year's method), and probably also by kneading it with sulphide of lead or
mineral kermes. It is formed by dipping crude caoutchouc into a
mixture of bisulphide of carbon and chloride of sulphur (Parkes), or by
heating it to 140° for some hours with polysulphide of potassium
(Gerard).
b. Vulcanised caoutchouc contains 1 to 2 per cent. of combined
sulphur, the remainder being enclosed mechanically in the pores. This
excess is gradually separated by the stretching and contracting of the
caoutchouc during some months, and may be more quickly and com-
pletely removed by means of hot caustic potash. The caoutchouc less
rich in sulphur thus obtained still retains its elasticity at various tem-
peratures and its indifference towards solvents.
c. When subjected to prolonged heating, especially in melted sulphur,
350
PRIMARY NUCLEUS C40H32.
vulcanised caoutchouc becomes hard and horny, and susceptible of
polish, these properties increasing with the proportion of sulphur and
the duration of heating. Hydrosulphuric acid is evolved in the re-
action, especially when the temperature exceeds 160°, part of the gas
remaining dissolved in the excess of sulphur and escaping only as the
sulphur crystallises. Goodyear heats 1 part of caoutchouc with
part of sulphur to 100° for 2 hours, and afterwards to 151° for 4 hours.
Hardened caoutchouc is still less soluble than the vulcanised, and
scarcely swells even in bisulphide of carbon. Ebermayer found in
the hardened caoutchouc of commerce 12 to 28 p. c. of sulphur.
Caoutchouc dissolves partially in bisulphide of carbon (Lampadius).
It swells up in that liquid to a spongy mixture of a dissolved and an
undissolved body, and dissolves to the extent of 30 to 70 per cent.
(Payen). Caoutchouc in pieces, digested with six parts of bisulphide
of carbon, swells up over night to a soft unctuous mass (Dullo). ~ The
solution may be accelerated by agitation with shot (Anthon, Repert.
52, 372). If the bisulphide contains free sulphur, the caoutchouc takes
up that body and remains as vulcanised caoutchouc on evaporation
(Dullo).
Caoutchouc swells up in cold, and still more in boiling alcohol, with-
out dissolving. Boiling alcohol takes up from crude caoutchouc a
bitter, sticky resin, amounting in some cases to 4 p. c. (Adriani);
sometimes also a little wax (Nesenbeck). Thin sheets of caoutchouc
become opaque and sticky by absorption of alcohol (Payen). - Anhy-
drous ether decomposes caoutchouc in the same manner as bisulphide
of carbon, forming a colourless solution and leaving 34 p. c. of a
coloured substance undissolved (Payen). Macquer found it completely
soluble; Berniard and Roxburgh quite insoluble, in ether. Pure caout-
chouc swells up very much in ether, but dissolves very slightly
(Nees v. Esenbeck and Marquart). The addition of a little sulphuric
acid (van Gears, Repert. 52, 392), or previous boiling with water
(Stratingh), greatly promotes the solubility in ether. The presence
of alcohol in the ether prevents the swelling of india-rubber bags
(Mohr, Ann. Pharm. 22, 184), though according to Payen, caout-
chouc swells to 4 times its volume in a mixture of 1 volume of
absolute alcohol and 6 volumes of ether. The solution in ether is
precipitated by alcohol; it leaves unchanged caoutchouc on evapo-
ration. See also Juch. (A. Gehl. 4, 226); Pfaff (Schw. 61,384). A mixture of
100 pts. bisulphide of carbon and 6 or 8 pts. absolute alcohol dis-
solves caoutchouc very easily when one volume of the solution is
mixed with 2 vols. absolute alcohol, the whole of the caoutchouc is
precipitated. whilst fat and colouring matter remain in solution. The
viscid precipitate, saturated with bisulphide and alcohol, dissolves easily
in a larger quantity of bisulphide to a clear liquid (Payen). Caoutchouc
swells up in chloride of ethyl and nitric ether, turning white and dis-
solving (Achard; Pfaff, N. Gehl. 5, 335). It is scarcely soluble in
acetone (Wiederhold), but swells up therein to a jelly (Trommsdorff).
:
Caoutchouc dissolves in chloroform much more easily than in other
liquids, and remains unchanged on evaporating the solution (Cloez, N.
J. Pharm. 14, 382). Solution is effected only on triturating the jelly
first formed. Alcohol precipitates the caoutchouc in a coherent, elastic
mass (Schwerdtfeger, N. Jahrb. Pharm. 1, 100). When pieces of
caoutchouc are heated to 100° in a sealed tube, with more than twice
their bulk of chloroform, a jelly is produced which is fluid when
CAOUTCHOUC.
351
heated, and mixes with bisulphide of carbon without precipitation
(Traun).
Caoutchouc swells up in fusel oil, amyl-aldehyde, valerianate of amyl,
and valerianic acid (Trautwein, Repert. 91, 29).
Caoutchouc swells up very much in the rectified empyreumatic oils of
caoutchouc (xiv, 326) in the light oils of coal-tar, rock oil, oil of turpentine
freed from resin and rectified, in the light resin-oils, cupione, oil of cajeput,
oil of lavender, and in many other volatile oils, dissolving in these liquids
in the same manner as in ether. It does not swell in creosote, and
softens only on long boiling therein, without dissolving (Reichenbach).
Fatty oils also, and hog's lard and spermaceti dissolve caoutchouc on
heating, or mix with it when melted. See Reichenbach (J. pr. Chem.
1, 388), Märker (Jahrb. pr. Pharm. 2, 226), Mohr (Ann. Pharm. 21, 342;
22, 184), Martin (Ann. Pharm. 22, 99), Roxburgh (Repert. 35, 349),
Dullo (Polyt. Notizbl. 20, 90).
¶ Virgin Para caoutchouc resists the action of linseed oil, whether
boiled or unboiled, and of Stockholm tar almost perfectly, retaining its
toughness, excepting in those parts which are above the surface of the
liquid and exposed to light. In the tar it contracts spontaneously, but
still remains strong and elastic. Masticated caoutchouc, exposed to
the action of the same liquids, becomes greatly swollen and gelatinized,
and in the case of the unboiled oil is completely dissolved. Vulcanized
caoutchouc similarly treated loses its tenacity, and becomes swollen
and gelatinous, but retains its form and a certain degree of elasticity
(Miller). ¶
Appendix to Caoutchouc.
1. Milky sap of Tabernamontana utilis, from Guiana. Contains
water, sugar, gum, salts, a resin melting at 170° and brittle at 160°,
and represented by the formula CH2402 (81.47 p. c. C., 11·14 H.,
7.39 0), a second resin melting at 140° to 150°, and softening at 60°,
represented by the formula C30H2602 (81.22 p. c. C., 11.51 H., 7·27 0.),
and caoutchouc. To obtain this last substance, the sap is curdled by
alcohol, and the curdled mass is washed and exhausted with cold and
boiling absolute alcohol in succession, whereby the resins are dissolved,
and the caoutchouc left behind. It is elastic, soluble in boiling ether to a
milky liquid, and contains 82.85 p. c. C., 11.68 H., and 5:47 O., cor-
responding to the formula C¹ºH³¹O (Heintz, Pogg. 65, 260). To this
place belongs also a sap investigated by Marchand (J. pr. Chem. 21,48)
as the milk of the cow-tree, in which he found two resins, together
with caoutchouc containing 81.10 p. c. C., 11.02 H., and 7.98 O., cor-
responding to the formula C40H3303. See also Christison (Ed. N. Phil.
J. 9, 32).
2. Resins from the milk of the Cow-tree (Galactodendron utile). The
milk preserved by addition of alcohol contains a resin soluble in cold
and in boiling alcohol, and very easily also in ether, not decomposible
by digestion with strong caustic potash, and not precipitable by
alcoholic neutral acetate of lead or nitrate of silver. It contains, on
the average, 82-27 p. c. C., 11:40 H., and 6.33 0., corresponding to the
formula C7H5804, and forms 31.4 p. c. of the milk. The milk imported.
352
PRIMARY NUCLEUS C40H32.
without addition of alcohol contains altered resins (Heintz, Pogg.
65, 240). See also Boussingault & Rivero (Ann. Chim. Phys. 23, 219), Solly (Phil.
Mag. 11, 452).
3. Resin from the milk of Hura crepitans, a Brazilian tree. The
yellowish inodorous, milky sap, tastes weak at first, but afterwards ex-
tremely irritating in the throat; its vapour produces violent inflammation.
-On boiling with alcohol the sap evaporated to an extract, evaporating
the filtrate, and exhausting the residue, first with boiling water and then
with ether, the ether takes up resin and leaves undissolved an oil,
which, when freed from adhering ether by evaporation, solidifies to a
crystalline mass, having a burning, acrid taste, and the property of
reddening turmeric. The resin is yellow, sticky, inodorous, tasteless
at first, but afterwards acrid; it produces blisters on the skin. At a
little over 100° it is fluid, and boils and volatilises undecomposed in
open vessels, more especially with vapour of water or alcohol; the
vapours blister the face and cause inflammation. It is easily soluble in
alcohol, ether, and oil of turpentine, but nearly insoluble in aqueous
ammonia or potash (Boussingault & Rivero, Ann. Chim. Phys. 28, 430;
Repert. 23, 189). See also Merat & Gilbert (Pharm. Centr. 1849, 30).
4. Chinese India-rubber. - Probably formed by the desiccation of
drying oil. Yellow (also red or blue); slightly elastic; lighter than
water. Burns with a bright flame, even on water, leaving a little ash.
Softens when boiled with water, and melts to a black, brittle mass
when heated. Dissolves completely in warm aqueous carbonate of
potash, forming a soap. Alcohol takes up a portion when warmed
with it, and leaves the rest in the form of a white mass. It is insoluble
in volatile oils (Thorey, Crell. Chem. J. 2, 107.)
5. Viscin.
P. REINSCH. N. J. Pharm. 14, 129; abstr. Chem. Centr. 1861, 145;
Kopp's Jahresber. 1860, 541.
The white, semi-elastic substance, extremely sticky and viscid
when warmed, which exudes from the disc and floral envelopes of
Atractylis gummifera, was termed viscin by Macaire-Princep (Bibl. univ.
54, 19; J. pr. Chem. 1, 415; Ann. Pharm. 12, 261), and recognised by
him as identical with the essential constituent of bird-lime. It is in-
soluble in water and alcohol, but dissolves in ether and oil of turpentine,
and remains sticky and viscid on evaporating the solution, without
drying up in the air. Macaire's supposition that this viscin does not
exist in the fresh berries and husks of the mistletoe, or in the bark of
holly, but is produced only in the process of making bird-lime, appears
to be erroneous.
Bird-lime is obtained from the bark, leaves, or berries of mistletoe
(Viscum album) by boiling, or better by crushing and washing with
water. Or the inner peel of the twigs of Ilex aquifolium is cut in
pieces and softened by boiling with water, and then buried in the
earth in a closed vessel and allowed to remain for some weeks, after
which the mass may be kneaded into a semi-transparent green paste.
VISCIN.
353
The same or similar substances occur in the epidermis of young
twigs of Robinia viscosa (Vauquelin, Scher. J. 3, 120), in the bark of
Ilex aquifolium (Bouillon Lagrange; Henry, N. Tr. 3, 2, 289), in the
root of Gentiana lutea, together with soft resin (N. E. Henry, J. Pharm.
5, 97; 7, 175; Leconte, J. Pharm. 23, 474), in the sticky coatings of
Lychnis Viscaria and Saxifraga tridactylites. The sap of the young
twigs of Ficus elastica, and of other species of Ficus, contains viscin,
in the form of a white body, which may be drawn out in long threads,
and is insoluble in alcohol, but soluble in ether; the sap of the stem,
however, contains caoutchouc (Nees v. Esenbeck & Marquart, Ann.
Pharm. 14, 43). Concerning the viscin of Atractilis, see also Geiger
(Mag. Pharm. 24, 23), Landerer (Repert. 63, 192).
Preparation. Bird-lime is prepared from the white berries of the
mistletoe by grinding them with water and straining off the skins, or
from the finely-scraped bark by kneading it with water till all soluble
matters are removed, and a mixture of bird-lime and woody fibre re-
mains. This mass is kept under water for some days, the water being
frequently renewed, and is then digested with 90 p. c. alcohol so long
as it colours that liquid yellow, after which it is boiled repeatedly with
alcohol, whereby wax is removed. The remaining yellowish-brown
mass, when treated five or six times with ether, gives up viscin, whilst
viscaoutchin and woody fibre remain undissolved. The ethereal solu-
tion is evaporated; the residue is warmed to drive off the last portions
of ether; and the viscid yellowish mass is kneaded with alcohol so
long as it gives off colouring matter. It is then kneaded under water,
and heated to 120°, without access of air, till the whole of the water
is expelled (Reinsch).
Properties. Clear transparent mass, of the consistence of honey at
ordinary temperatures, and capable of being drawn out into long
threads; fluid at 100°, like oil of almonds. Produces a greasy stain
on paper. Sp. gr. = 1. Nearly inodorous and tasteless. Has an acid
reaction.
Reinsch.
mean.
40 C......
48 H
240
57.69
57.52
48
11.54
11.52
16 0.......
128
30.77
30.96
C40H 48016........
416
100.00
100.00
Reinsch's formula is C20H2308; from that given above, viscin may be regarded as
a hydrate of caoutchouc (Kr.).
Viscin begins to boil at 210°, and yields at 235° a thin yellow oil,
Reinsch's viscene, of sp. gr. 0.856, boiling at 227-229°; and at tem-
peratures gradually rising to 275°, a buttery distillate, whilst a little
carbon remains behind. On shaking the distillate with caustic soda, it
solidifies to a crystalline pulp, from which an oil is volatilised by boil-
ing; the remaining soda-salt, distilled with phosphoric acid, yields the
acid (Reinsch's viscic acid), though with difficulty, in the form of a
yellow acid oil, the soda-salt of which is soluble in alcohol, but in-
soluble in water (Reinsch).
Viscaoutchin
VOL. XVII.
This substance remains behind, together with woody
2 A
351
PRIMARY NUCLEUS CHH34; OXYGEN-NUCLEUS C40H2806,
fibre, after the extraction of viscin by ether as above, and is taken up
by oil of turpentine. After distilling off the turpentine, the yellowish
mass is dissolved in ether, in which it has now become soluble; the
ethereal solution is evaporated; and the residue is washed with alcohol
and water, and dried at 120°. At ordinary temperatures it is viscid,
and resembles vegetable wax; at 120° it is of the consistence of olive
oil. Very elastic, and may be drawn out into long threads. Sp. gr.
=0·978. Tasteless; of faint odour and neutral reaction. Contains,
on the average, 75.56 p. c. C., 11.91 H., and 12.53 O., corresponding to
the formula CHO (Reinsch). C40H3706 = C40H32,5HO requires 75-71
p. c. C., and 11·67 H. (Kr.).
Primary Nucleus C40H34; Oxygen-nucleus C¹ºH28O6.
Wormwood-bitter or Absynthiin.
C40H2808 = C'40H2808,02.
LEONARDI. Br. Arch. 28, 211.
Caventou. Br. Arch. 29, 157.
MEIN. Ann. Pharm. 8, 61.
RIGHINI. J. Chim. méd. 19, 383.
LUCK. Ann. Pharm. 54, 112; 78, 87.
KROMAYER. N. Br. Arch. 108, 129; Chem. Centr. 1862, 49; Kopp's
Jahresber. 1861, 745.
The bitter principle of Artemisia Absynthium (Handbuch, viii, [2],
67). Investigated chiefly by Mein, Luck, and Kromayer, but with
somewhat discordant results.
Frickhinger (Repert. 101, 365) and Landerer (Repert. 105, 316) de-
scribed crystals deposited from Tinctura Absynth on standing. - Bra-
connot's absynthic acid (J. Phys. 84, 341) is, according to Zwenger
(Ann. Pharm. 48, 122), succinic acid; Tichanowitsch also found the
latter acid, but Luck denies its existence in wormwood. Mein's worm-
wood-bitter may likewise, according to Zwenger, be succinic acid with
adhering bitter substance; the properties of the body, however, do
not accord with such a supposition (Kr.).
a. According to Mein. Freshly dried flowering twigs of worm-
wood are digested in warm water, and after standing for twenty-four
hours, pressed, and again treated once or twice in the same manner.
The infusions are filtered and evaporated to an extract, which is
exhausted with alcohol of 36° B.; the alcohol is distilled off; the
residue is again evaporated; and the portion soluble in water is
separated. The undissolved portion is freed from adhering extractive
by dissolving it in 3 parts of alcohol and precipitating the filtrate by
water, and this process is repeated until the filtrate is no longer
coloured green by sesquichloride of iron. The resinous bitter principle
thus obtained resembles jalap-resin, and has an acid reaction and
very bitter taste. When its solution in 24 parts of alcohol of 80 p. c.
is shaken up with 96 parts of 30 p. c. alcohol, filtered after twenty-four
hours from the flocks which are deposited, precipitated with neutral
acetate of lead, mixed with water, and heated till the whole of the
WORMWOOD-BITTER OR ABSYNTHIIN.
355
alcohol is driven off, and the aqueous liquid filtered, freed from lead
by hydrosulphuric acid, and concentrated at 60°, the liquid becomes
covered with a colourless pellicle and deposits small white prisms.
These prisms, which Mein regards as pure absynthiin, and classes with
the crystalline resins, colour oil of vitriol an intense yellow, gradually
changing to dark purple. They dissolve in 1,000 parts of water,
forming a solution which reddens litmus and is precipitated by
tincture of galls, but not by metallic salts. They dissolve in dilute
caustic alkalis and their carbonates, and easily in acetic acid, from
which they are precipitated by water; they are most easily soluble in
alcohol and less freely in ether (Mein). According to Geiger, this
absynthiin is a substance closely related to santonin.
b. According to Luck. An alcoholic tincture of the dried herb is
evaporated to a syrup, from which the wormwood-bitter and acid resin
are extracted by repeated shaking with ether. The ethereal solution is
distilled, and the residue treated with ammoniacal water, which takes
up resin and leaves the bitter for the most part undissolved, in the form
of a powder. This powder is digested with dilute hydrochloric acid to
remove ammonia, washed with water, dissolved in alcohol, and pre-
cipitated with neutral acetate of lead. The filtrate is freed from Ïead
by hydrosulphuric acid, mixed with a little water, and evaporated in a
warm place, whereupon the bitter is deposited in yellow resinous drops,
which become crystalline after some days or weeks. They are acid
and very bitter, slightly soluble in cold, and fusible in boiling water.
The red-yellow solution in cold oil of vitriol quickly turns indigo-blue
in the air and then yields with water, greyish green not bitter flocks,
whilst the solution remains of a rose-red colour. The solution in
hydrochloric acid is yellow, but when slightly warmed, becomes red and
deposits brown clots. The bitter dissolves slightly in ammonia with
wine-yellow colour, and more easily in potash, forming a golden-yellow
solution. When an alcoholic solution is mixed with caustic potash and
treated with carbonic acid so long as carbonate of potash is deposited,
the filtrate yields, with neutral acetate of lead, fine yellow flocks of
absynthiin and lead-oxide, which, after a few minutes, turn white and
undergo decomposition. To obtain the lead-compound, Luck mixes
the alcoholic solution of the bitter with ammonia and basic acetate of
lead, evaporates in a vacuum over oil of vitriol, triturates the residue
and washes it with water, ether, and alcohol. Thus obtained it con-
tains 55.25 p. c. of oxide of lead. This wormwood-bitter dissolves
easily in alcohol, less freely in ether, and also in acetic acid, from
which it is precipitated by water. After drying in a vacuum, it has
the following composition:-
Calculation, according to Ludwig.
40 C.
Luck.
mean.
240
65.93
65.18
28 H.....
28
7.69
7.62
12 O.......
96
26.38
27.20
100.00
100.00
C4023012........ 364
According to Luck, C16H1105. According to Ludwig's formula, Luck's absynthiin
contains 4 at. of oxygen more than Kromayer's.
c. According to Kromayer. An infusion of wormwood prepared with
hot water is precipitated with infusion of galls, and the precipitate is
2 A 2
356 PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS CH2806.
collected, washed, and decomposed while still moist by desiccation with
oxide of lead. From the dry mass alcohol takes up the absynthiin,
which is purified by treating its hot alcoholic solution with animal char-
coal, and afterwards dissolving it in ether. — Or, instead of the infusion,
the sap of the fresh plant, previously freed from albumin by heating,
may be employed. The absynthiin thus obtained may be purified
by precipitating an aqueous solution with basic acetate of lead, and
removing the lead which remains in solution by hydrosulphuric acid.
On agitating an aqueous extract of the herb with animal charcoal,
the absynthiin is taken up thereby, and may be extracted by alcohol,
but still requires purification. Righini had previously obtained worm-
wood-bitter by the same process.
Properties. Absynthiin is obtained by the slow evaporation of its.
alcoholic solution, in faintly-yellow, oily drops, which solidify to a hard,
indistinctly crystalline mass. The ethereal solution leaves a nearly
colourless, transparent mass, triturable to a powder, which is perma-
nent in the air. Neutral. Has an aromatic odour and very bitter taste.
Melts at 120° to 125°. Free from nitrogen.
Kromayer.
Over oil of vitriol.
40 C.......
240
70.38
70.47
....
29 H.....
29
8.50
8.78
9 O.......
C40H2OS,HO?
72
21.12
20.75
341
100.00
100.00
The above is the formula given by Ludwig & Kromayer, which, however, derives
but little support from the analysis of tannate of absyntliiin (Kr.).
Decompositions. 1. Absynthiin decomposes when heated, emitting
acrid, irritating vapours. 2. It reduces the metal from ammoniacal
nitrate of silver.-3. It is decomposed by nitric acid only when hot. -
4. The brown solution in oil of vitriol quickly turns greenish-blue, or
when water is dropped into it, dark-blue; with a larger quantity of
water it deposits grey flocks. Dilute sulphuric and strong hydrochloric
acids produce brown resins, but no sugar. - Absynthiin does not reduce
an alkaline solution of cupric oxide.
Absynthiin is nearly insoluble in cold, and but slightly soluble in
hot water; the excess melts in the liquid to transparent oily drops. The
solution does not precipitate metallic salts.
Absynthiin dissolves in caustic potash, with brown-red colour, and is
not precipitated from the solution by hydrochloric acid. Hydrochloric
acid throws down part of the absynthiin from its solution in aqueous
ammonia, the precipitate dissolving in excess of the acid with rose-red
colour.
Tannate of Absynthiin. - Alcoholic absynthiin, to which water is
added till cloudiness is produced, forms with aqueous tannic acid a
white, plaster-like precipitate, which, after washing with water and
weak alcohol and drying at 100°, may be triturated to a grey
powder.
Calc. according to Ludwig & Kromayer.
Kromayer.
at 100°.
58 C
39 H.....
23 O..
348
60.94
61.03
•
39
184
6.83
32.23
7.20
31.77
C40H2SOS, C18H8O2 + 3HO?
571
100.00
100.00
.
ASARONE.
357
Absynthiin dissolves easily in alcohol and ether.
When the alcoholic tincture of wormwood is precipitated with alco-
holic neutral acetate of lead, and the precipitate is dried, triturated, and
washed with water, acetate and succinate of lead are dissolved. From
the dried residue, ether takes up resin of wormwood and a little worm-
wood-bitter, the latter of which is removed by repeated boiling with
water. The resin is yellowish, scarcely acid in alcoholic solution, and
fusible in water to an oil, which floats on the surface. It dissolves in
oil of vitriol, from which it is precipitated by ammonia, and is easily
soluble also in boiling caustic potash and in ammonia, whereupon
excess of ammonia throws down a precipitate. It does not affect
acetate of copper or nitrate of silver, and dissolves easily in alcohol
and ether (Tichanowitsch, Zeitschr. Ch. Pharm. 6, 197; Chem. Centr.
1863, 908).
Oxygen-nucleus C40 H2O.
Asarone.
C40H26010 C402608,0².
=
GÖRZ. Pfaffs System der Materia med. 3, 229.
LASSAIGNE & FENEULLE. J. Pharm. 6, 561; N. Tr. 5, 2, 72.
GRÄGER. Dissert. de Asara europ. Göttingen 1830.
SELL & BLANCHET. Ann. Pharm. 6, 296.
K. SCHMIDT. Ann. Pharm. 53, 156; J. pr. Chem. 33, 221.
Asarabacca-camphor. Haselwurz-campher.—Discovered by Görz.
Occurs in
the root of Asarum europæum, which, according to Lassaigne & Feneulle, contains
also a bitter substance. Gräger further distinguishes as Asarite, crystals obtained
in the same way as asarabacca-camphor, and apparently identical therewith.
Preparation. When the dried root is distilled with 8 parts of water
till 3 parts have passed over, one portion of the asarone collects in
white granules in the neck of the retort and below the distillate, while
another portion is deposited from the distillate in the cold (Görz).
Gräger purifies the product by dissolving it in alcohol and precipi-
tating with water, and frees it from admixed asarum-oil (xiv, 359) by
fusion.
Properties. Transparent, pearly, four-sided tables (Lassaigne &
Feneulle). Crystals of the oblique prismatic system, occurring in
various forms (Schmidt). See the description (loc. cit.). Sp. gr. 9.95
(Gräger). Melts at 40° (Blanchet & Sell), 70° (Gräger), and solidifies
at 27° (Blanchet & Sell) in a radiated crystalline mass. Sublimes in
small quantities between two watch-glasses, but a portion is easily
rendered brown and empyreumatic. The strongly smelling vapour ex-
cites coughing. Inodorous and tasteless (Gräger); according to Görz
it smells and tastes like camphor and acts as an emetic.
Schmidt.
Blanchet & Sell.
mean.
mean.
40 C......
26 H....
10 O
210
69.37
68.66
69.37
26
7.51
7.74
7.66
80
23.12
23.60
22.97
C4026010
346
AAAAAAA
100·00
100.00
100.00
358
OXYNITROAZO-NUCLEUS C40N2XH20010.
According to Blanchet & Sell, C16H1104; according to Schmidt C20H1305.
Decompositions. 1. When asarone is heated above 100° in a
sealed glass tube, the fused mass crystallises on cooling the more.
slowly in proportion as it has been longer and more strongly heated;
if heated to 210° for half an hour, it crystallises completely only after
three days (Schmidt).-2. It begins to boil at 280°, but decomposes
without distilling, the temperature rising to 300° (Blanchet & Sell):
the residue forms a red viscid mass, from which the asarone crystal-
lises after some days (Schmidt).-3. The easily formed solution of
asarone in strong warm alcohol, when boiled for 10 or 15 minutes,
assumes at last a deep blood-red colour and deposits only a part of the
asarone in crystals on cooling, the mother-liquor drying up to a red,
tough resin, which carbonises without subliming when heated, and is
precipitated from its alcoholic solution by water in amorphous globules,
containing 69.03 p. c. C., 7.65 H., and 23.32 0. This resin (amor-
phous asarone) yields the original crystals when distilled with water
(Schmidt).-4. Asarone burns with a bright smoky flame (Gräger).
5. It dissolves in strong nitric acid, forming oxalic acid (Schmidt),
and leaving a tough yellow resin (Görz).-6. When heated with
bichromate of potash and sulphuric acid it yields an amorphous red
resin, neutral, precipitable from its alcoholic solution by water, and
containing 66.0 p. c. C., 6·89 H., and 27.11 0. Oxide of manganese and
sulphuric acid act in a similar manner, but the resin is not altered by peroxide of
lead or by melting in hydrochloric or sulphurous acid gases (Schmidt). The
crystals do not melt in the vapour of anhydrous sulphuric acid, and
are only partially attacked, the edges assuming red, black, and other
colours. A conjugated compound of sulphuric acid appears to be
formed (Schmidt).The crystals dissolve in cold oil of vitriol with
yellow, and in the hot liquid with brown-red colour: from the former
solution water throws down unchanged asarone, from the latter a
brown resin (Gräger; Schmidt). — 8. Asarone is not attacked by
chlorine in a freezing mixture, but at ordinary temperatures it melts,
with considerable evolution of heat, to a deep blood-red mass, which
afterwards gives off hydrochloric acid and turns green, and then
absorbs chlorine quietly. When 100 parts of asarone have taken
up 46 parts of chlorine, the green, non-volatile, resinous residue con-
tains 47.16 p. c. C. and 4.41 H., and has, therefore, exchanged hydrogen
for chlorine (Schmidt).
Asarone dissolves slightly in hot water (Görz), and easily in
alcohol, precipitable therefrom by water in the form of an oil, which
crystallises. It dissolves in ether and volatile oils (Gräger).
Oxynitroazo-nucleus CN2XH20010.
Cacotheline.
C40N4H22016 C40N2XH20010, H2.
GERHARDT. Compt. rend. 19, 1105; Compt. chim. 1845, 112; J. pr.
Chem. 36, 11.. N. J. Pharm. 9, 817; 13, 232 and 14, 212.
LAURENT. Compt. rend. 22, 633; N. Ann. Chim. Phys. 22, 463; J. pr.
CACOTHELINE.
359
Chem. 45, 378.-N. Ann. Chim. Phys. 24, 314; Ann. Pharm. 69,
15; J. pr. Chem. 46, 32.
ROSENGARTEN. Ann. Pharm. 65, 111; Pharm. Centr. 1848, 199; N. J.
Pharm. 13, 232; Kopp's Jahresber. 1847-48, p. 632.
A. STRECKer. Ann. Pharm. 91, 76; J. pr. Chem. 62, 437; Pharm.
Centr. 1854, 652; Compt. rend. 39, 54; N. Ann. Chim. Phys. 42,
366; Kopp's Jahresber. 1854, 520.
Kakothelin. Discovered by Gerhardt and Laurent; investigated chiefly by
Strecker. —— Formed, together with nitrite of methyl, carbonic acid, and oxalic acid,
by the action of nitric acid on brucine (See BRUCINE).
Preparation. When nitric acid of sp. gr. 14 is poured upon melted
brucine in a retort, a violent action occurs, attended with evolution of
gases and red vapours: if necessary, the retort may be placed in cold
water to moderate the action. The contents of the retort are diluted
with water, and the precipitated yellow flocks are collected and washed
with water. The mother-liquor, when concentrated, freed from crystals
of oxalic acid, and diluted with water, yields an additional quantity of
the product. The flocks may be crystallised from water containing
nitric or hydrochloric acid (Strecker).
Properties. The yellow or orange-yellow crystals lose their water
at 100°, becoming at the same time darker in colour if they have been
crystallised from hydrochloric acid (Strecker). They assume a dark-
brown colour in sunlight (Laurent), and explode when heated
(Gerhardt).
Laurent.
Rosengarten. Strecker.
mean.
mean.
mean.
40 C.......
4 N
240
51.95
51.34
51.67
52.1
56
12.12
11.20
12.70
12.6
22 H
22
4.76
4.40
5.06
4.9
18 O....
144
31.17
33.06
30.57
30.4
C40N2X2H22O10…...
462
100.00
100.00
100.00
100.0
The above is Strecker's formula: Laurent proposed CªN¹H²²O²º0. For Stahl-
schmidt's views on the formula of cathoteline, see Pogg. 108, 542.
Combinations. A. With Water. Cacotheline crystallised from
water containing nitric acid lost 4.1 p. c. of water at 100° (2 at. 3.8
p. c.), but when crystallised from water containing hydrochloric acid, it
lost 1.9 p. c. (1 at. = 1.9 p. c. HO) (Strecker).
·
Cacotheline is nearly insoluble in water, either cold or boiling.
B. With Acids. Cacotheline dissolves in acids and combines with
them like a base, forming salts, which are easily decomposed, even by
water. From its solution in strong hydrochloric acid, water throws
down orange-yellow laminæ, free from hydrochloric acid after slight
washing; the crystals obtained from a solution in nitric acid are also
free from acid when thoroughly washed (Strecker).
Sulphate of Cacotheline. A solution of cacotheline in sulphuric acid
deposits yellow crystals, which retain sulphuric acid after washing with
alcohol (Strecker).
Chloroplatinate of Cacotheline, From a solution of cacotheline in
-
360
OXYNITROAZO-NUCLEUS CON²X²HO10.
strong hydrochloric acid, bichloride of platinum throws down, after long
standing, yellow needles, to which the solution afterwards solidifies.
The crystals are washed with water and ether-alcohol. - Lemon-yellow:
stable at 100°; explodes when cautiously heated (Strecker).
Strecker.
C4º¸²X²H²²O¹º,HC1,2CI .... 569-5
85.18
Pt
98.7
14.82
144-148
100.00
C40N2X2H22O10,HCl,PtCP³.... 668.2
C. With Oxides. Cacotheline dissolves easily in aqueous ammonia,
potash, or baryta; the ammoniacal solution throws down a flocculent
precipitate from neutral acetate of lead and silver-salts (Strecker).
The solution in ammonia-water turns green, and ultimately brown,
when warmed (Laurent; Strecker). After the free ammonia, alcohol
throws down from the solution, blackish-green flocks, the green aqueous
solution of which is precipitated green by acetic acid and by neutral
acetate of lead or nitric acid (Gerhardt). On one occasion the ammo-
niacal solution deposited a base containing hyponitric acid, insoluble
in water and alcohol, but easily soluble in hydrochloric acid, and pre-
cipitated from the solution by ammonia as a yellow jelly, and by bichlo-
ride of platinum as a reddish-yellow double salt. This double salt,
when dried, turns black, with a golden-green reflex, but when
moistened with a drop of alcohol, it again becomes reddish-yellow;
when very highly dried, it appears of a bluish-red colour, which is
changed to orange-red by a drop of water. It dissolves in oil of
vitriol with fine rose-red colour, changing to lilac when strongly heated.
It explodes when heated alone, leaving 23 p. c. of platinum (Laurent).
The solution of cacotheline in caustic potash is brownish-yellow
(Gerhardt).
Cacotheline-Baryta.
When cacotheline is boiled with water and
carbonate of baryta, carbonic acid is evolved, and a deep-brown solu-
tion formed, from which an amorphous brown powder is deposited on
standing, and more on the addition of alcohol. The powder is soluble
in water with brown colour. - After drying in a vacuum, it loses 10·5
p. c. of water at 120° (7 at. : 10.5 p. c. HO) (Strecker).
C40N2X2H22O10
BaO
Dried.
462
Strecker.
76.5
85.78
14.22
14.1
100.00
CN2X*HO,BaO.... 538 5
Cacotheline with Lead-oxide.
From a solution of neutral acetate of
lead, mixed with nitrate of cacotheline, ammonia throws down yellow
flocks, which, after drying at 100°, contain 57.6 p. c. lead-oxide, or
about 6 at. to 1 at. of cacotheline (Strecker).
Cacotheline with Silver-oxide. —Obtained in the same way as the lead-
compound, nitrate of silver being substituted for acetate of lead.
Yellow precipitate, containing 21.6 p. c. of silver, or 1 at. to 1 at. of
cacotheline (Strecker).
Cacotheline dissolves slightly in alcohol, according to Laurent. It
is easily soluble in boiling alcohol and ether, before drying, but nearly
insoluble after drying (Gerhardt). ·
ARNICIN.
361
Primary Nucleus C40H36; Oxygen-nucleus C4H³O².
Ursone.
C403404 = C40H340²,0².
H. TROMMSDORFF. N. Br. Arch. 80, 273; Chem. Centr. 1855, 115.
HLASIWETZ. Wien. Acad. Ber. 16, 293; N. Br. Arch. 85, 15; J. pr.
Chem. 66, 123.
Source.—In the leaves of Arbutus Uva Ursi (Trommsdorff).
Preparation. The coarsely-powdered leaves are exhausted with
ether, and the crystalline deposit which forms in the extract is washed
with ether and crystallised from alcohol. In the preparation of
arbutin (xv, 419) ursone remains in that portion of the alcoholic extract
which is insoluble in water, and may be obtained by washing with
ether and boiling with alcohol. In the latter case it is to be purified
by washing with ether and recrystallising from alcohol, with the help
of animal charcoal (Trommsdorff).
Properties. Colourless, silky needles (Trommsdorff), which melt at
198°-200°, and solidify to a crystalline mass, or when heated above
their melting-point, to an amorphous, fissured mass (Hlasiwetz). Boils
at a higher temperature, and sublimes apparently unaltered (Tromms-
dorff).
Hlasiwetz.
at 100°.
mean.
40 C
240
78.43
78.40
34 H
34
11.11
11.17
4 0.....
32
10.46
10.43
C40H3404
306
100.00
......
100.00
According to Hlasiwetz, it has the formula C20H¹702 and is allied to hartin.
Ursone burns with a yellow smoky flame, without leaving charcoal.
It dissolves partially, with orange colour in cold oil of vitriol, and car-
bonises when heated therewith, evolving sulphurous acid. With
fuming nitric acid it evolves a little nitric oxide, and forms a yellow solu-
tion, precipitable by water (Trommsdorff).
Ursone is insoluble in water and in dilute acids and alkalis, and but
slightly soluble in alcohol and ether (Trommsdorff).
Oxygen-nucleus C40H3000.
Arnicin.
? C40H3008 = C40H³90º,0².
LEBOURDAIS. N. Ann. Chim. Phys. 24, 63; Ann. Pharm. 67, 251;
J. pr. Chem. 45, 363.
362 PRIMARY NUCLEUS CH36; OXYGEN-NUCLEUS CHO.
WALZ. N. Jahrb. Pharm. 13, 175; 14, 79; Pharm. Viertelj. 10, 188;
Kopp's Jahresber. 1860, 544. - N. Jahrb. Pharm. 15, 329; N. Br.
Arch. 108, 1; Pharm. Viertelj. 11, 1; Kopp's Jahresber. 1861, 752.
The bitter principle of Arnica montana (Handbuch, viii. [2], 66). From this
plant, Pfaff (Syst. der Mat. med. 3, 209), and Chevallier & Lassaigne (Taschenbuch,
1821, 91) obtained resins, Bastick an amorphous alkaloid, Pavesi a resin allied to
santonin. Peretti, by distilling arnica-flowers with solution of caustic potash,
obtained a volatile base, which O. Hesse (Ann. Pharm. 129, 254) recognised as
ammonia with traces of trimethylamine. Arnicin occurs more abundantly in the
flowers than in the root (Walz).
Preparation. A. From the root. Arnica-root is freed from volatile
oil by distillation with water; the residue is pressed and exhausted
with alcohol; the tincture is digested with oxide of lead; and the dis-
solved lead is removed by means of hydrosulphuric acid. The alcohol
is then distilled off, and the residue evaporated to dryness, after which
the arnicin is extracted by ether. The ethereal solution is shaken
with solution of caustic potash, to which it gives up fat and colouring
matter, and after separation from the alkaline liquid, it is treated with
animal charcoal and evaporated to dryness. The residue is dissolved
in weak alcohol, and the filtrate evaporated or precipitated with water.
In this way 13 pounds of the root yield about an ounce of arnicin
(Walz).
-
B. From Arnica flowers. 1. The flowers are exhausted with ether;
the ether is distilled off; and the arnicin is extracted from the residual
fatty mass by alcohol of sp. gr. 0·85. A little fat which is taken up
at the same time may be separated by repeated solution in weak
alcohol. Purification is effected by animal charcoal. 2. The alcoholic
tincture of the flowers is treated with animal charcoal to remove
chlorophyll; the filtrate is evaporated, and the residue exhausted with
ether; the fat and arnicin taken up thereby are separated as in 1.
3. An aqueous decoction of the flowers is precipitated by tannic
acid, and the precipitate is washed (not too long), dried, triturated,
and exhausted with alcohol. The solution is agitated with levigated
oxide of lead to remove tannic acid, filtered, treated with hydrosul-
phuric acid, and freed from alcohol by distillation, whereupon fat is
deposited, to remove which the arnicin is precipitated by water. The
precipitate is purified by washing it with water, dissolving in alcohol,
digesting the solution with animal charcoal, and precipitating with
It is then dissolved in ether and left to evaporate (Walz).
Lebourdais allows a strong aqueous infusion of the flowers to run
slowly through a thick layer of purified animal charcoal, which takes
up colouring matter and the bitter principle. He then washes the
charcoal with water, dries, and exhausts it with hot alcohol. On
evaporating the filtrate, the arnicin remains as a neutral turpentine-
like mass, very slightly soluble in water, but soluble in all proportions
in alcohol. On attempting to precipitate the colouring matter with
neutral acetate of lead, before treating with animal charcoal, the
greater part of the arnicin is thrown down at the same time (Lebour-
dais).
water.
Bastick's alkaline arnicin is extracted from the flowers by alcohol
containing sulphuric acid. The tincture is digested with a slight
excess of lime and filtered; the filtrate is saturated with dilute sul-
ARNICIN.
363
phuric acid, again filtered, and evaporated; the resin thereby thrown.
down is removed, and the liquid is exactly neutralised with carbonate
of potash and separated from the resulting precipitate. The filtrate is
then shaken with a large excess of carbonate of potash and ether, to
which it gives up the arnicin. Thus obtained, arnicin is bitter, alkaline,
soluble in water, alcohol, and ether, and combines with acids to form
crystallisable salts, which are precipitated in dense flocks by tincture
of galls (Bastick, Pharm. Journ. 3, 386; Jahrb. pr. Pharm. 24, 44;
N. J. Pharm. 19, 454).
Pavesi (J. Médic. de Bruxelles, 1859, 61; abstr. Pharm. Viertelj. 9,
290) prepares arnicin in the same manner as santonin (xvi, 249) by
extraction with lime and alcohol. He thus obtains a dark-yellow,
viscid, nauseously bitter resin, insoluble in water, but soluble in alkalis,
and precipitable therefrom by acids. It dissolves slightly in alcohol
and ether.
Properties. Walz's arnicin forms a golden-yellow, amorphous
mass, free from nitrogen.
Walz.
mean. at 100°.
40 C.....
240
71.85
30 H
30
8.99
8 0.....
64
19.16
C40H3008
334
100.00
...
71.78
9.19
19.03
100.00
Walz's earlier formula, C70H54014, agrees very nearly with these numbers.
Arnicin is decomposed by boiling with acids, with separation of
dark flocks. It is, however, not a glucoside. It hardens with
nitric acid, and assumes a yellowish-brown colour with oil of vitriol,
without undergoing solution. When alcoholic arnicin is heated for
some time to 100° with caustic potash, and the residue is distilled with
dilute sulphuric acid, a large quantity of resinous flocks is deposited,
whilst oil and acid water, containing valerianic or butyric acid, pass
over (Walz).
Arnicin dissolves only slightly in water, but is soluble in aqueous
ammonia and in alkalis. Its alcoholic solution forms crystals with
caustic baryta. It forms a white precipitate with basic acetate of lead,
also with solutions of silver-oxide, mercurous oxide, and platinic
oxide. Arnicin is soluble in ether (Walz).
Resins of Arnica-root. A. Resin soluble in ether. When an alcoholic
tincture of the root, previously exhausted with water, is freed from
substances precipitable by oxide of lead and from oxide of lead taken
up at the same time, then evaporated and exhausted with ether, this
liquid takes up the arnicin. The portion remaining undissolved, when
mixed with an acid, yields flocks of the resin, which is purified by dis-
solving in alcohol, digesting with animal charcoal, and precipitating
with water. — It forms a clear, yellowish-brown mass, which is soft
and pasty at 100°. Has a peculiar odour, and a somewhat acrid taste.
Contains 65.72 p. c. C., 8.50 H., and 25.78 O., corresponding to the
formula C40H30012 (65.57 C., 8.19 H.) (Walz).
B. Resin insoluble in ether. When the portion of the alcoholic
cxtract insoluble in ether is treated with water, the yellow colouring
364
PRIMARY NUCLEUS C40H36; OXYGEN-NUCLEUS CH2808.
matter is dissolved, whilst this resin remains behind. It is purified by
dissolving it in alcohol and precipitating with water. Dark-brown,
easily pulverisable mass, having a harsh taste. Contains 51.81 p. c. C.,
6.5 H., and 41.69 O., corresponding to the formula C40H3002 (51.5 C.,
6·45 H.) (Walz).
Arnica yellow. - Amorphous yellow mass, soluble in water. The
lead-compound contains 30.0 p. c. C., 3.9 H., 21-0 O., and 45'0 PbO.
= CH30024, 3PbO. (Walz).
Oxygen-nucleus C40H2808.
Elaterin.
C40H28010 = C¹ºH2808,0².
HENNEL. J. Royal Inst. 1, 532.
MORRIES. Edin. Med. and Surg. Journ. No. 107, 339; Repert. 39,
134.
CL. MARQUART.
Repert. 46, 8.
GOLDING BIRD. Repert. 73, 222.
ZWENGER. Ann. Pharm, 43, 359.
WALZ. N. Jahrb. Pharm. 11, 21, and 178.
Braconnot (J. Phys. 84, 294) described a bitter substance, Paris (Répert. 13, 270)
a soft resin, from ecbalium, as Elaterin.
Source. In the fruit of Ecbalium Elaterium (Handbuch, viii, 37) and
in the powder which is deposited from the sap, the officinal Elatérium
album and nigrum. The fruit collected in autumn contains no elaterin,
but only chlorophyll (Marquart), or at least the elaterin is less easily
prepared from it, and is obtained only in small quantity (Walz).
Elaterium album contains 15 to 26 p. c. (Morries), 40 p. c. (Hennel),
50 p. c. (Walz) of elaterin.
Preparation. 1. White elaterium is exhausted with boiling alcohol;
the tincture is evaporated to half its bulk, and the elaterin is precipi-
tated by boiling water. It still requires to be purified by washing
with ether and crystallising from absolute alcohol (Zwenger).-2. The
portion of elaterium insoluble in water is exhausted with alcohol, and
the tincture is evaporated to an oil, aud poured while still warm into
boiling caustic potash. The chlorophyll is thereby retained in solution,
whilst the elaterin is gradually thrown down as a crystalline precipitate,
which is purified by washing with water (Morries).
3. The expressed juice of the fruit is evaporated to an extract,
which is exhausted with alcohol; the solution is precipitated with
alcoholic neutral acetate of lead; the filtrate is freed from lead by
hydrosulphuric acid, and evaporated; the residue is exhausted with
ether; the undissolved portion taken up by alcohol; and the
elaterin precipitated from the alcoholic solution by water. The ether
dissolves a little elaterin, which remains behind on evaporating the
ethereal extract and exhausting the residue, first with water and then
PROPHETIN.
365
with ether.
obtained by extraction with alcohol (Walz).
The pressed fruit still contains elaterin, which may be
Properties. Colourless, shining, six-sided tables (Zwenger); rhombic
needles striated on the sides (Morries). Melts [between 100° and
150° (Hennel); a little over 100° (Morries)] exactly at 200°, first
becoming yellow, to a transparent yellowish amorphous mass, which
cracks on cooling (Zwenger). Tastes very bitter (Hennel), bitter
and styptic (Morries), very slightly acrid alone, and extremely bitter
when dissolved in alcohol (Marquart). - 4th of a grain kills a dog
in a day or two (Morries). Its acts as an extremely powerful cathartic
and emetic (Marquart). — Neutral. Free from nitrogen (Zwenger).
Zwenger.
at 100".
mean.
40 C.....
28 H
240
68.96
68.46
28
8.04
8.22
10 0......
80
23.00
23.32
C40H28010
......
348
100.00
100.00
According to Zwenger the formula is C201405.
Decompositions. Elaterin decomposes when strongly heated, evolving
white fumes having a somewhat suffocating odour, and burns with a
smoky flame (Zwenger). — It dissolves in oil of vitriol with dark-red
colour, and is precipitated from the solution as a brown substance by
water (Zwenger; Morries). The solution is rendered pale red by
permanganate of potash (Guy).- Elaterin is decomposed by nitric acid,
forming a transparent gum (Morries). See below.
Elaterin is insoluble in water. - It dissolves in fuming nitric acid,
from which it is precipitated unaltered by water (Zwenger). It is
insoluble in dilute acids and alkalis, and does not precipitate alcoholic
solutions of metallic salts. Aqueous solutions of metallic salts pre-
cipitate elaterin from its alcoholic solution in the same manner as
water (Zwenger).
Elaterin dissolves in 15 parts of cold, and 2 parts of hot alcohol,
and in 290 parts of ether (Hennel). It is slightly soluble in cold, and
easily soluble in hot oil of turpentine (Marquart), and in hot olive oil
(Morries).
Appendix to Elaterin.
1. Prophetin.
? C46H 36014.
WALZ & WINCKLER. N. Jahrb. Pharm. 11, 31.
WALZ.
N. Jahrb. Pharm. 11, 178.
Source. In Cucumis Prophetarum and in Ecbalium Elaterium.
Preparation. A. From the fruit of Cucumis Prophetarum. — The
juice of the fruit, clarified by standing and boiling, is evaporated over
366 PRIMARY NUCLEUS CH36; OXYGEN-NUCLEUS C40H2SO³,
the water-bath to a syrup, and, after cooling, mixed with 4 times its
volume of 80 p. c. alcohol and filtered. The alcohol is separated by
distillation, and the residue, evaporated to a thin syrup, is shaken
with ether so long as it gives up a bitter substance. The ethereal
solution leaves, on evaporation, a turpentine-like residue, which
dries up over the water-bath to a white, resinous, friable mass
(Winckler).
B. From Ecbalium Elaterium. Together with ecbalin, hydro-
elaterin, and elateride. The entire plant, dried and coarsely pow-
dered, is exhausted with boiling alcohol; the extract is mixed with
water, and the alcohol distilled off; and the aqueous liquid, filtered
from the resin which is deposited, is employed for the preparation of
prophetin, hydro-elaterin, and elateride. The resin is used for the
preparation of ecbalin.
a. Preparation of Prophetin.-The solution is precipitated with
neutral acetate of lead, filtered, and again precipitated with basic
acetate of lead; this second precipitate is likewise removed or is redis-
solved in a large quantity of water [the precipitate contains prophetin and
elateride it is doubtful to me which process Walz intends to indicate (Kr.)]; the
dissolved lead is removed by the addition, first of an insufficient quantity
of sulphuric acid and then of carbonate of soda; the slightly alkaline
solution is precipitated by aqueous tannic acid (an excess of which
redissolves the precipitate); the precipitate is washed slightly,
pressed, and digested in alcohol; and the filtered alcoholic solution is
shaken up with hydrated oxide of lead, filtered, and concentrated,
whereupon the prophetin is slowly deposited in the form of a white
powder. This and the quantity subsequently obtained is washed with
water, dissolved in alcohol, and crystallised by adding water till
cloudiness is produced, and leaving it at rest.
-
b. Preparation of Hydro-elaterin and Elateride. The mother-liquor
from which prophetin has been separated is evaporated to dryness; the
residue is redissolved in water and evaporated; and the hydro-elaterin is
extracted from the residue by ether, whilst elateride remains undis-
solved. The latter body is purified by dissolving it in absolute alcohol,
and evaporating the filtered solution.
c. Preparation of Ecbalin. -The resin obtained as above is dissolved
in ether; the solution is digested with animal charcoal and filtered;
the ether is distilled off; and the residue, after drying completely at
100°, is again dissolved in ether, and digested with animal charcoal.
The filtered solution is then evaporated, or precipitated with water.
Properties. Prophetin forms a yellowish-white powder, seen under
the microscope to consist of resinous granules. It loses 2.5 p. c. in
weight over the water-bath. Free from nitrogen. Tastes very
bitter.
Walz.
b.
Walz.
C.
Dried?
mean.
46 C
276
65.09
64.91
to
65.75
64.80
36 H
36
8.49
14 O
112
26.42
8.39
26.70
>>
8.48
25.77
7.57
27.63
C46H36014 424
100.00
100.00
100.00
100.00
....
23
PROPHETIN.
367
Walz calculates his analyses incorrectly (Kr.).—a was obtained from Cucumis, b
from Ecbalium.
Decompositions. Prophetin dissolves in oil of vitriol with red-brown
colour. When boiled with hydrochloric acid, it breaks up into sugar
and propheretin, which separates in the form of a resin, and after wash-
ing and dissolving in ether, remains as an amorphous resin (Walz sub-
sequently obtained crystals), containing, on the average (from
Cucumis), 71.11 p. c. C., 9.12 H., and 19.77 0. From these numbers
Walz calculates the formula C40H008 (71.85 p. c. C., 9.00 H.), and
represents the decomposition by the equation—
C46H36014
=
C40H3008 + C¹²2012.
On one occasion he obtained from prophetin 78.5 p. c. of propheretin
and 19.5 p. c. of sugar, on another occasion 34 p. c. of sugar.
Combinations. Prophetin dissolves slightly in cold, and in 200 parts
of boiling water. It dissolves in alcohol of 80 p. c., and in nearly all
proportions of absolute alcohol, from which it is precipitated by water.
It is freely soluble in ether. It is precipitated by aqueous tannic acid
in white flocks.
2. Ecbalin or Elateric acid.-Preparation see above. Yellow, soft
resin. Very bitter and acrid. It is converted by chlorine-water into a
white friable substance, and is decomposed by nitric acid, with deep red
coloration, and also by oil of vitriol. It dissolves in 20 parts of water,
and is soluble in aqueous alkalis, from which it is precipitated by acids,
and in alcohol and ether.
Lead-salts precipitate ecbalin (Walz).
Walz.
Calculation according to Walz.
mean.
40 C
34 H
240
71.01
71.44
34
10.06
10.48
8 O...
64
18.93
18.08
C40H3+08
338
100.00
100.00
3. Hydroelaterin. - Yellow, amorphous, friable mass, soluble in
water, alcohol, and ether. Does not yield sugar with acids. The
solution in caustic potash is precipitated by acids.
Calculation according to Walz.
Walz.
40 C
240
65.57
64.81
65.38
30 H
30
8.19
8.01
8.06
12 O
96
26.24
27.18
26.56
C40H30012
366
100.00
100.00
100.00
-
4. Elateride. Intensely bitter substance, precipitated, unaltered
from its solution in strong acids by water, without forming sugar. In-
soluble in water and ether, but soluble in alcohol and alkalis, from the
latter of which it is precipitated by acids.
Calculation according to Walz.
Walz.
at 100°.
40 C
240
51.72
52.66
52.09
32 H
32
6.89
6.89
6.76
24 O
192
41.39
40.45
41.15
C40H32024
264
100.00
100·00
100.00
Walz calculates all these analyses incorrectly (Kr.).
368
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS CH³¹O¹.
Oxygen-nucleus C4ºH24012.
Coriamyrtin.
C40H24014 = C40 H24012, 02.
RIBAN. Par. Soc. Bull. 6, 87; N. J. Pharm. 45, 487; abstr. Compt.
rend. 57, 798; Chem. Centr. 1864, 367; Pharm. Viertelj. 14, 93.
A glucoside contained in the leaves and fruit of Coriaria myrtifolia.
Preparation. The sap of the fresh plant, or the aqueous decoc-
tion of the dried plant, is precipitated by basic acetate of lead, and
filtered; and the liquid, freed from excess of lead by hydrosulphuric acid,
is evaporated to a syrup. When shaken with ether, the syrup gives
up to that liquid the coriamyrtin, which remains on evaporation, and is
purified by crystallisation from alcohol. 100 pounds of the young
shoots yield 7.5 grammes of impure crystals.
White, inodorous four- or six-sided prisms, apparently monoclinic.
Very bitter and poisonous. Exerts a right-handed action on polarised
light. Does not lose weight at 200°; melts at 220° to a colourless
liquid, which solidifies in a crystalline mass. Neutral. Free from
nitrogen.
at 100°.
Riban.
40 C
240
63.86
63.69
63.90
24 H
24
6.38
6.56
6.49
14 O
112
29.76
29.75
29.61
C40H24014
376
100.00
100.00
100.00
Coriamyrtin turns brown on prolonged fusion, and afterwards car-
bonises.It is rapidly decomposed by warming with nitric acid, form-
ing a clear solution. Other acids, including acetic and oxalic, decom-
pose it, with formation of sugar and resin. Emulsin does not act
upon it.
Coriamyrtin dissolves in 70 parts of water at 22°, and slightly in
boiling water. The solution is not precipitated by chloride of platinum
or phosphomolybdic acid.
Nearly insoluble in bisulphide of carbon. Dissolves in 49.7 parts of
86 p. c. alcohol at 22°, and very freely in boiling alcohol, crystallising
on cooling. Dissolves in ether, chloroform, and benzene.
Primary Nucleus C40H38; Oxygen-nucleus C¹H¾40*.
Asclepione.
C40H3406 C40H3404,02.
=
C. LIST. Ann. Pharm. 69, 125; abstr. Pharm. Centr. 1849, 283.
Discovered by List in the milk-sap of Asclepias syriaca (Hand-
buch viii, [2], 57), John (Chem. Schr. 2, 26) having previously described
a resin obtainable therefrom.
A resinous substance and a bitter principle (Asclepiadin, Asclepin)
XANTHOXYLIN.
369
from Asclepias Vincetoxicum have been described by Feneulle (J. Pharm.
11, 305).
The sap which flows from incisions in Asclepias syriaca curdles when
warmed, from coagulation of albumin, which encloses the asclepione.
The coagulum is exhausted with ether to remove the asclepione, which,
after evaporating the ether, crystallises on further concentration of the
remaining clear liquid. The product is purified by dissolving it in an-
hydrous ether, a foreign substance then remaining undissolved.
White, cauliflower-like mass, forming when slowly evaporated,
delicate radiated tufts. Inodorous and tasteless. Melts at 104°, and
solidifies on cooling to an amorphous, transparent mass.
List.
mean.
40 C......
240
74.54
74.68
34 H
34
10.56
10.61
60
48
14.90
14.71
C40H3406
322
100.00
100.00
Asclepione, when heated above its melting-point, assumes a yellow
colour, and evolves an odour of caoutchouc.
hot strong caustic potash.
It dissolves unaltered in
Insoluble in water and alcohol, but easily soluble in ether, and less
freely in acetic acid, rock-oil, and oil of turpentine.
STENHOUSE.
Oxygen-nucleus CH24014.)
Xanthoxylin.
C40H24016 = C40H24014,03.
N. Phil. Mag. 7, 28; Ann. Pharm. 89, 251; J. pr. Chem.
61, 497; Kopp's Jahresber. 1854, 639.— Ann. Pharm. 104, 326;
Pharm. Journ. 17, 19; J. pr. Chem. 73, 179; Kopp's Jahresber. 1857,
482.
Occurs in Japan pepper, the fruit of Xanthoxylum piperatum or
alatum (Handbuch, viii [2], 21). On distilling the ground pepper with
water, a floating oil is obtained, from which the xanthoxylin separates
on cooling; it remains behind when the oil is freed from xanthoxylene
(xiv, 315) by distillation at 130°.-Xanthoxylin crystallises also on
concentrating the alcoholic tincture, and may be freed from resin by
washing it with cold aqueous ammonia. It is purified by recrystal-
lisation from ether or alcohol.
Large, colourless crystals of the oblique prismatic system, having
a silky lustre. Fig. 85 without f. Angle i: t = 90° ; a :t
a: t = 142°50';
a : i = 127° 10′; u : t = 121° 10'; u in front: i 96° 30'. The crys-
tals are tabular in form from predominance of i; a and u imperfectly
formed. Cleavable parallel to t and i (Miller).-Xanthoxylin is sus-
ceptible of distillation. It melts at 80° and solidifies at 78°. Has a
faint odour like stearin and an aromatic taste. Neutral.
VOL. XVII.
2 B
370
PRIMARY NUCLEUS C40H10.
Stenhouse.
40 C .......
240
61.22
61.09
60.97
24 H
24
6.12
6.62
6.14
16 O
128
32.66
32.29
32.89
C40H24016
392
100.00
100.00
100.00
Xanthoxylin is converted by nitric acid into oxalic acid. It is in-
soluble in water, but easily soluble in alcohol and ether. The alcoholic
solution is not precipitated by alcoholic neutral acetate of lead or
nitrate of silver, even with addition of ammonia (Stenhouse).
HEINTZ. Pogg. 90, 146.
Primary Nucleus C4040.
Arachidic Acid.
C40H4004 = C40H40,04.
GÖSSMANN. Ann. Pharm. 89, 1; J. pr. Chem. 61, 336.
SCHEVEN & GÖSSMANN. Ann. Pharm. 97, 257; J. pr. Chem. 68, 179.
CALDWELL. Ann. Pharm. 101, 97; J. pr. Chem. 71, 192.
Butic acid. Discovered by Heintz in butter, and afterwards by
Gossman in earth-nut oil.
Preparation. From Earth-nut oil. — The solid fatty acids obtained
by saponifying the oil and decomposing the soap, are macerated with
five or six times their volume of alcohol. The liquid is filtered, and
the residue is pressed, and afterwards dissolved in 20 times its weight
of boiling alcohol, whereupon, on cooling, impure arachidic acid sepa-
rates in laminæ, which are purified by repeated recrystallisation from
absolute alcohol till they melt at 75°, and freed from adhering green
resin by solution in warm ether (Gössmann).
A further portion of the acid may be obtained by partial precipita-
tion of the alcoholic mother-liquors with acetate of magnesia (some-
what in the manner described at p. 355, vol. xvi), the arachidic acid
going down with the first portions of the precipitate (Gössmann).
Ou submitting the solid fatty acids of butter to fractional precipita-
tion, the arachidic acid is thrown down in the first portions of the pre-
cipitate, but cannot be completely separated from stearic acid, even
when four pounds of butter are employed (Heintz). See xvi, 210, 354.
Properties. Very small, shining laminæ, having a pearly lustre after
pressing. Melts at 75°, and solidifies in a radiated mass at 73.5°.
When kept it turns white and porcelain-like.
Gössmann.
Heintz.
mean.
mean.
40 C
240
76.92
76.84
76.55
40 H
40
12.82
12.86
12.80
40
32
10.26
10.30
10.65
C40H4004
312
100.00
100.00
100.00
Heintz's acid melting at 60·75° still contained stearic acid.
ARACHIDIC ACID.
371
Arachidic acids forms with glycerin, mono-, di-, and triarachin (see ix,
490; xvi, 358; and xvii, 373). Scheven & Gössmann described as arachin a pro-
duct melting at 70°, and containing, on the average, 76 21 p. c. C., and 12:57 H.,
obtained by heating arachidic acid to 210° with excess of glycerin: according to them,
the body is represented by the formula C126H124014 (= 304040O4 + CH8O6 4HO).
According to Berthelot, this product is a mixture of diarachin and free arachidic
acid.
-
The salts of arachidic acid resemble the stearates and palmitates.
They are, for the most part, difficultly soluble.
Arachidate of Ammonia. A warm alcoholic solution of the acid,
mixed with excess of aminonia, deposits the salt on cooling, in needles,
which, after drying, crumble to a loose white powder and give up
ammonia.
Arachidate of Potash. Mono-acid. Arachidic acid is boiled with a
strong solution of caustic potash for several days, or until combination
is complete; the solution is evaporated to dryness; and the residue is
exposed for some time to air containing carbonic acid, and afterwards
exhausted with alcohol. The salt is deposited from a strong alcoholic
solution in the form of a jelly, which falls to a loose crystalline powder
on the filter, and from a more dilute solution in distinct crystals.
With 15 or 20 times its weight of boiling water, it forms a clear
solution which, when largely diluted, deposits shining laminæ of a
bi-acid salt.
C40390 3........ 303
ΚΟ
Scheven & Gössmann.
86.52
47.2
13.48
13.01
C40H39 KO¹
350-2
100.00
Arachidate of Baryta.
soluble in water, but soluble in a large quantity of boiling alcohol.
White, light, crystalline powder, in-
C40H3903
BaO
Scheven & Gössmann. Heintz.
303
76.5
79.85
79.73
20.15
19.72
20.27
100.00
100.00
CH3BaO* ........ 8795
Arachidate of Strontia. Dissolves more easily than the baryta-
salt in boiling alcohol, from which it is deposited in the form of a
crystalline powder on cooling.
Scheven & Gössmann.
C40H 3903
Sro
303
52
44
85.36
14.64
C40H39SrO
355
100.00
14.0
Arachidate of Lime is a loose, lustrous powder.
Arachidate of Magnesia. On mixing alcoholic arachidate of
ammonia with an alcoholic solution of acetate of magnesia, this salt
is deposited as an amorphous precipitate, which dissolves on boiling
and crystallises from the solution as it cools. White, loose,
crystalline powder, insoluble in water but slightly soluble in
alcohol.
2 B 2
372
PRIMARY NUCLEUS C40H40.
Scheven & Gössmann.
C40H3903
303
93.81
MgO
20
6.19
6.27
C40H39 MgO¹
323
100.00
Arachidate of Copper. Alcoholic acetate of copper throws down
from arachidate of ammonia, a blue-green amorphous precipitate,
which turns crystalline on standing and crystallises from alcohol in
needles. Melts when heated.
Scheven & Gössmann.
mean.
40 C
39 H.....
3 0.....
CuO
240
70.03
70.55
.......
39
11.38
11.58
24
7.01
6.46
40
11.58
11.41
C40H 39 CuO¹
343
100.00
100.00
Arachidate of Silver. Obtained by double decomposition as an
amorphous precipitate, which crystallises from alcohol in white needles,
not altered by exposure to light.
C40H3904
Ag
C40H39 AgO4......
Scheven & Gössmann.
311
74.22
108
25.78
25'4
419
100.00
Arachidic acid is nearly insoluble in cold, but easily soluble in
hot alcohol. It dissolves very easily in ether (Gössmann).
Arachamide.
39
C40NH4¹0² = C¹ºAdH⁹9,0².
SCHEVEN & GÖSSMANN. Ann. Pharm. 97, 262.
A mixture of earth-nut oil with excess of strong alcoholic
ammonia is allowed to stand for several weeks; the liquid is satu-
rated afresh with ammonia; and when no further change is per-
ceptible, the alcohol and excess of ammonia are removed by warm
water. The product is allowed to cool, and the more solid portion is
collected, freed from adhering oil by pressing, and repeatedly crystal-
lised from alcohol.
Stellate groups of prisms, melting at 98 to 99°.
Scheven & Gössmann.
mean.
77.08
4.27
40 C.......
240
......
N.....
14
41 H.
41
2 O.......
16
77.17
4.50
13.18
5.15
13.11
5.54
...
C40NH402
311
100.00
100.00
Arachamide is insoluble in water, but easily soluble in hot alcohol
of 95 p. c. from which it crystallises on cooling.
MONOARACHIN.
373
Arachidate of Methyl.
C42H4204 = C²H³O, C40H3903.
CALDWELL. Ann. Pharm. 101, 98.
Arachinsaures Methyloxyd.
Formed by passing hydrochloric acid gas into a solution of
arachidic acid in wood-spirit, and purified by crystallisation from
alcohol.
White, pearly scales. Melts at 54 to 54.5°, and solidifies to a
semi-transparent, crystalline mass. Not volatile without decompo-
sition. Easily soluble in alcohol and ether.
Caldwell.
42 C......
42 H.....
252
77.30
77.47
42
12.88
12.82
4 O......
32
9.82
9.71
C2H30,C40H3908.... 326
100.00
100'00
GÖSSMANN.
Arachidate of Ethyl.
CH**O* = C*H*O,CH3O®.
Ann. Pharm. 89, 9.
SCHEVEN & GÖSSMANN. Ann. Pharm. 97, 261.
Arachinsaures Aethyloxyd.
Formed by saturating a solution of arachidic acid in absolute
alcohol at 80° or 90° with hydrochloric acid gas, heating for 12 hours,
at last to boiling, and precipitating with water. The free arachidic
acid is removed by heating the alcoholic solution with aqueous car-
bonate of soda. The ether is also formed by boiling arachidic acid
with alcohol, especially in presence of acetic acid.
Tough, translucent crystalline mass, having a lamellar fracture.
Melts at 50°.
Gössmann.
44 C.......
264
77.64
77.60
Want
44 H.....
44
12.94
12.88
4 O......
32
9.42
9.52
C4H5O,C40H3903
340
100.00
100.00
Arachidate of ethyl is not affected by ammonia gas at 60°, nor by
alcoholic ammonia at 100°.
Monoarachin.
C46H4608 = C6H˜О³,C¹ºH³⁹O³.
BERTHELOT. Chim. organ. 2, 78; N. Ann. Chim. Phys. 47, 355.
374
PRIMARY NUCLEUS C40H40.
Obtained by heating arachidic acid with glycerin for eight hours to
a temperature not exceeding 180°. It is purified with ether and lime
(xvi, 359).
Fine granules, melting to a wax. White. Neutral.
Nearly insoluble in cold, and but slightly soluble in boiling ether.
Berthelot.
46 C
46 H
276
71.50
71.7
46
11.92
12.0
80
64
16.58
16.3
C6H705, C40H3903
386
100.00
100.0
BERTHELOT.
Diarachin.
C*HOL = (*HO®,2CH3O®.
Chim. organ. 2, 78; N. Ann. Chim. Phys. 47, 357.
Concerning Gössmann's Arachin, see p. 371.
Formed by heating monoarachin to 200° or 230° for 8 hours with
arachidic acid and a trace of water, or by heating arachidic acid to
200° or 230° for 6 hours with glycerin. It is purified by lime and
ether (xvi, 359).
Very fine, indistinctly crystalline granules, melting at 75°. White.
Neutral.
Almost completely volatile on platinum-foil. Burns with white
flame. Decomposed completely by lime at 100° in 70 hours.
Nearly insoluble in cold, and very slightly soluble in hot ether;
more freely soluble in bisulphide of carbon.
Berthelot.
mean.
86 C.......
516
73.92
73.93
A
86 H.....
12 O.......
86
12.33
12.53
96
13.75
13.54
C6H8O6,2C40H3903
698
100.00
100.00
....
....
Triarachin.
C'126H122012 = C6H5O3,3C40H3903.
BERTHELOT. Chim. organ. 2, 79; N. Ann. Chim. Phys. 47, 359.
Obtained by heating a perfectly dry mixture of diarachin within 15
or 20 times its weight of arachidic acid to 200° or 220° for 8 or 10
hours, and purifying the product with lime and ether (xvi, 359).
Neutral mass, very slightly soluble in ether.
Berthelot.
126 C........
756
112 H
122
77.62
12.53
77.1
...
12.6
...
12 O.......
96
9.85
10.3
C6H503,3C03903.... 964
100.00
100.0
LITHOFELLIC ACID.
375
Arachidate of Amyl.
С50H500¹ = C¹¹ºH¹¹O,C¹ºH³⁹O³.
CALDWELL. Ann. Pharm. 101, 99.
Arachinmylester.
Obtained in the same way as arachidate of methyl, by employing
amyl-alcohol instead of wood-spirit.
Shining scales, melting at 44.9° and solidifying at 44° to a semi-
transparent crystalline mass. Decomposes when heated. Dissolves
easily in hot alcohol and ether.
50 C...............
50 H
Caldwell.
300
78.53
78.42
50
13.09
13.25
4 0......
32
8.38
8.33
C10H¹¹O,C40H3903
382
100.00
100.00
....
·
Oil of earth-nuts. From the seeds of Arachis hypogaa (Handbuch,
viii, [2] 8). Colourless or faintly coloured oil, thinner than olive oil.
Sp. gr. 0.9163. Deposits a large quantity of tallow at 3°, and soli-
difies to a soft mass at — 3° to 4° (Payen & O. Henry). Solidifies
completely at -7° (Gössmann). Has an agreeable taste, resembling
that of almond oil, and an odour like olive oil at 50° to 75° only. — It
does not easily turn acid and is non-drying. It yields a very white
and hard soap (Bouillon-Lagrange, J. Pharm. &, 231). Absorbs
oxygen more slowly than almond-oil. Does not solidify with mer-
curous nitrate. Dissolves very slightly in alcohol, but easily in
ether (Payen & O. Henry, J. Chim. méd. 1, 437; Ostermaier, Repert.
98, 243; J. A. Buchner, Repert. 98, 251). Contains the glycerides of
arachidic, palmitic, and physetoleic acids, but no stearin (Gössmann ;
Caldwell, Ann. Pharm. 101, 97).
Oxygen-nucleus C403604.
Lithofellic Acid.
C40H3608 = C40H3604,04.
FR. GÖBEL. Ann. Pharm. 39, 237.
ETTLING & WILL. Ann. Pharm. 39, 242.
WÖHLER. Ann. Pharm. 41, 150; J. pr. Chem. 25, 50; Pogg. 54, 255.
HEUMANN. Ann. Pharm. 41, 303; Repert. 75, 226.
MALAGUTI & SARZEAU. Compt. rend. 15, 518; Ann. Pharm. 44, 289.
WINCKLER. Jahrb. pr. Pharm. 18, 376.
TAYLOR. Phil. Mag. 28, 192.
LUDWIG. N. Br. Arch. 85, 141.
Bezoardic acid, which name has also been given to ellagic acid
Discovered by Göbel, and investigated chiefly by him and Wöhler.
(xvi, 183). –
Occurs in one
376
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS CH¾O¹.
:
of the varieties of Oriental bezoars, the gall-stones of an antelope, which consist
almost entirely of this acid. Bezoars containing lithofellic acid melt when heated
and dissolve in hot alcohol. Concerning these bezoars, see F. Göbell, Taylor, and
Ludwig (loc. cit.); further Guibourt (Rev. scient. 14, 17.-N. J. Pharm. 3, 125);
Hankel (Pogg. 55, 481).
Preparation. The bezoars are dissolved in boiling alcohol, and the
crystals which form slowly on cooling the solution and concentrating
the mother-liquor, are purified by recrystallisation, with the help of
animal charcoal (Wöhler; Göbel). Or, the bezoars, after being
exhausted with water, are treated for 24 hours with cold dilute
ammonia; the filtrate is decolorised with animal charcoal; and the
lithofellic acid is precipitated by dilute sulphuric acid and washed
(Winckler). The acid precipitated from alkaline solutions requires
still to be purified by crystallisation from boiling alcohol (Heumann).
Properties. Very small, clear, short six-sided prisms with end-
faces at right angles to the sides. Rhombic prisms with oblique end-
faces (Göbel). Hard and easily pulverisable. Melts at 204° (Göbel),
205° (Wöhler), and solidifies, when not heated above its melting-point,
to an opaque crystalline mass. When heated a few degrees above
its melting-point, it solidifies to a clear amorphous glass, which be-
comes electric when rubbed and melts at 105° to 110° to a viscid
mass. Alcohol poured upon this amorphous acid produces a large
number of fine cracks, and the acid when left in contact with a little
alcohol, again becomes crystalline (Wöhler).
a bitter taste in the mouth (Winckler).
(Wöhler).
The acid slowly excites.
Has an acid reaction
Ettling & Will.
Wöhler.
Taylor.
Crystals.
mean.
mean.
40 C
36 H
80
240
70.59
70.39
70.39
70.18
36
10.59
10.86
10.60
10.71
64
18.82
18.75
19.01
19.11
C40H36OS
340
100.00
100.00
100.00
100.00
10.4
My Trad
Ettling & Will proposed the formula C42H380³. The acid is allied to gallic acid
(Göbel; Wöhler). Identical with the fellanic acid of Berzelius (Berz. Lehrb. 3
Aufl. 9, 273) (Heumann).
Decompositions. 1. Lithofellic acid boils when heated, evolving
white fumes having a faint aromatic odour, yielding a distillate of
acid oil and water, and leaving a carbonaceous residue (Göbel;
Heumann). The distillate forms with potash a soap, from which
hydrochloric again sets free the empyreumatic acid (Göbel). By the
dry distillation of the soap, pyrolithofellic acid, CH3406, is obtained
(Malaguti & Sarzeau).-2. The acid burns with a luminous smoky
flame (Wöhler). — 3. It dissolves in nitric acid when heated [with fine
red, afterwards yellow, colour (Taylor)], frothing up and evolving
nitric oxide, and remains on evaporation as a lemon-yellow mass,
which dissolves in caustic potash, and is precipitated from the solution
by acids in the form of a brown friable mass (Göbel). A nitrogenous
acid Acide lithazofellique, C40H28014, 2NO4, is produced in the reaction.
(Malaguti & Sarzeau). 4. The acid produces a violet-red colora-
tion with oil of vitriol and sugar, like bile (Strecker, Ann. Pharm.
67, 53)
LITHOFELLIC ACID.
377
Lithofellic acid is insoluble in water. It dissolves in oil of vitriol,
from which it is precipitated by water (Wöhler) unaltered and amor-
phous (Taylor).
It dissolves easily in caustic ammonia and its carbonate, also in
dilute aqueous alkalis, and is thrown down by acids as an amorphous
precipitate, melting at 105° (Wöhler). The alkaline solution is ren-
dered milky by sal-ammoniac (Wöhler). The ammoniacal solution
leaves the acid free from ammonia on evaporation (Göbel; Wöhler).
A saturated solution of the acid in caustic potash has a slightly alka-
line reaction, and leaves on evaporation a clear gum, which dissolves
in water, but not in caustic potash (Wöhler). When heated with a
strong solution of caustic potash, lithofellic acid forms a limpid yellowish
soap, which floats on the surface of the lye, and forms on cooling a
solid mass resembling colophony, and easily soluble in water, alcohol,
and ether (Göbel).
Lithofellate of soda, prepared by saponifying the acid with caustic
soda, and washing the soap repeatedly with a saturated solution of
salt, yields, when decomposed by hydrochloric acid, 10-4 parts of
soda to 100 parts of lithofellic acid (Göbel). -Amorphous gum
(Heumann).
Baryta-salt. A solution of the acid in ammonia or fixed alkalis
precipitates salts of baryta (Göbel; Wöhler). An alcoholic solution of
the acid, mixed with water till the cloudiness at first produced disap-
pears, does not precipitate chloride of barium or calcium (Ludwig). —
On heating the acid with carbonate of baryta and evaporating, crystals
are obtained, which dissolve in alcohol and separate therefrom as an oil,
afterwards solidifying in a crystalline mass (Heumann).
Lithofellate of soda precipitates salts of baryta, iron, lead, mercury,
silver, and platinum (Göbel). The ammonia-salt precipitates baryta-
salts (Wöhler).
Lead-salt. Lithofellate of potash produces with neutral lead-salts
a plaster-like precipitate, containing 32 p. c. of oxide of lead (Wöhler).
Aqueous ammoniacal lithofellic acid throws down from neutral
acetate of lead, a precipitate containing 41-45 p. c. of oxide of lead
(Wöhler). The dazzling white precipitate thrown down by an ammo-
niacal alcoholic solution of the acid from neutral acetate of lead, dissolves
with difficulty in water, but somewhat more freely in alcohol, and con-
tains 49 p. c. of lead-oxide (Ettling & Will).
Silver-salt. — Ammoniacal nitrate of silver throws down from alco-
holic lithofellic acid, bulky flocks, which disappear on addition of
alcohol. By evaporating the solution, long light needles are obtained,
which blacken on exposure to light, and contain, like the flocks, 25.43
p. c. of silver-oxide (Ettling & Will). Wöhler obtained from a solu-
tion of the silver-salt, a creamy non-crystalline pellicle containing 25
p. c. of oxide of silver.
Lithofellic acid dissolves freely in strong acetic acid, and crystallises
on evaporating the solution (Wöhler). It dissolves in 6.5 parts of
boiling 90 p. c. alcohol and in 29-4 parts at 20° (Göbel), from which it
is precipitated by water. It is soluble in 47 parts of boiling, and 444
parts of cold absolute ether (Göbel).
378
PRIMARY NUCLEUS CH0; OXYGEN-NUCLEUS C40H¹0".
Oxygen-nucleus C40H3406.
Flocks from Rottlera tinctoria.
C40H3408 = C40H340,0².
When the hairs and glands which cover the fruit of Rottlera tinctoria
(the kamala of commerce) are exhausted with boiling alcohol, the tinc-
ture, on cooling, deposits flocks, which may be obtained nearly colour-
less by repeated crystallisation. The mother-liquor retains in solution
a resinous colouring matter.
Granular, non-crystalline flocks, not precipitable by salts of lead or
silver. Insoluble in water, but slightly soluble in ether and cold
alcohol (Anderson, Pharm. Centr. 1855, 373).
Anderson.
mean.
40 C.......
240
71.00
70.78
34 H
34
10.05
10.45
8 O.....
64
18.95
....
18.77
C40H3408
338
100.00
100.00
Resinous colouring matter of Rottlera. Remains on evaporating the
mother-liquor of the flocks just described, as a dark-red resin melting
at 100°, purified by solution in ether. It is insoluble in water,
but soluble in all proportions in alcohol and ether, and is thrown
down by neutral acetate of lead as a deep orange-red precipitate. A
solution in aqueous carbonate of soda dyes silk a fine permanent orange
(Anderson).
Anderson.
mean.
60 C ......
30 H
360
71.71
71.35
30
5.97
6.29
14 O
112
22.32
22.36
100.00
100.00
C603014 502
Resins from Rottlera tinctoria (Kamala). See xiv, 520. Leube did not
succeed in preparing Anderson's rottlerin. The extract of kamala prepared
by extraction with ether, breaks up when heated with cold alcohol, after
previous boiling with water, into an easily soluble and a sparingly
soluble resin, both of which are brittle and reddish-yellow, the easily
soluble melting at 80°, and the sparingly soluble at 191°. Both resins
dissolve in caustic potash with fine red colour, and in ammonia and
carbonate of ammonia, from which they are precipitated by acids.
They form oxalic acid with nitric acid, and do not yield sugar with
dilute sulphuric acid. The easily soluble resin contains at 60°, on the
average, 68.53 p. c. C., 6·97 H., and 24.50 0. (=C30H1808); the sparingly
soluble, at 150°, 51.18 p. c. C., 6.21 H., and 42.61 0. ( C16H12Ŏ10)
O.
(Leube, Pharm. Viertelj. 9, 321).
EMETINE.
379
+
Oxyazo-nucleus C40N2H28010.
Emetine.
? C40N2H30010 C40N2H28010,H2.
PELLETIER & MAGENDIE. Ann. Chim. Phys. 4, 172; Schw. 19, 440;
Complete: J. Pharm. 3, 145.
PELLETIER & DUMAS.
Ann. Chim. Phys. 24, 180.
PELLETIER. J. Pharm. 14, 200.
MERCK. N. Tr. 20, 1, 134.
LANDERER. Repert. 52, 211.
REICH. N. Br. Arch. 113, 193.
Prepared by Pelletier in 1816 in an impure, and in 1821 in the pure
state. Occurs in the Ipecacuanha roots of Cephaëlis Ipecacuanha,
Richardsonia scabra; also of Psychatria emetica, Jonidium Ipecacuanha,
and Euphorbium Ipecacuanha. - Pleischl (Das chem. Labor. zu Prag,
1820) and Buchholz (Taschenb. 1818, 97) describe a soft resin of Ipe-
cacuanha.
Preparation. The root-bark is exhausted with ether to remove
soft resin, and then boiled with alcohol; the tincture is evaporated,
and the residue dissolved in water, whereupon wax separates.
The
aqueous solution is freed from gallic acid (ipecacuanhic acid, xv, 523)
by digesting it with carbonate of baryta; the emetine is precipitated
with basic acetate lead; the precipitate is washed, and decomposed
under water by hydrosulphuric acid; and the liquid is filtered and
evaporated. The impure emetine thus obtained is boiled with water
and excess of calcined magnesia; the precipitate is washed with a very
little cold water to remove colouring matter, then dried and boiled
with alcohol; the solution is filtered and evaporated; and the residue
is dissolved in aqueous acid and decolorised by animal charcoal, after
which the emetine is precipitated by magnesia and again extracted by
alcohol (Pelletier). The water with which the magnesian precipitate
is washed, and probably also the filtrate from the lead-precipitate, still
contain a little emetine (Pelletier). See below.
2. The bruised root is boiled with water; the extract is evaporated
to dryness, and the residue exhausted with alcohol. The tincture is
filtered, freed from alcohol by distillation, and again evaporated to
dryness; and the residue is exhausted with dilute hydrochloric acid.
The solution thus obtained is precipitated with chloride of mercury;
the precipitate is washed with cold water and dissolved in alcohol; and
the mercury is thrown down by the addition of sulphide of barium.
Excess of baryta is then removed by sulphuric acid; the solution is
diluted with water and distilled to remove alcohol; and the emetine is
precipitated by ammonia and washed with cold water (Merck).
Landerer precipitates the acetic extract of ipecacuanha with mag-
nesia, and after washing and drying the precipitate, exhausts it with
alcohol. The emetine which remains on evaporating the alcohol is
purified by dissolving it repeatedly in acetic acid, decolorising the
380 PRIMARY NUCLEUS CH; OXYAZO-NUCLEUS CNH28010.
solution with animal charcoal, and precipitating with magnesia.
Reich exhausts the coarsely powdered root with warm alcohol, mixes
the tincture with neutral acetate and basic acetate of lead in succes-
sion, whereby ipecacuanhic acid is thrown down; then filters the solu-
tion, distils off the greater part of the alcohol, and dilutes the residue
with water, which precipitates resin. After removing the resin, and
also the lead, by means of hydrosulphuric acid, the emetine is precipi-
tated by tannic acid; the precipitate is triturated with oxide of lead,
dried, and boiled with alcohol, which takes up the emetine and leaves
it behind on evaporation. The product may be purified by again pre-
cipitating it with tannic acid and decomposing the precipitate, and
lastly by exhausting it with ether. The yield is 4th to rd per cent.
(Pelletier).
Properties. White, inodorous powder, having a slightly bitter taste
(Pelletier). According to Landerer, cubic crystals. Has a strongly acid re-
action according to Pelletier, but according to Landerer, turmeric is not
affected by it, and litmus only slightly. Melts at 50° (Pelletier). It
acts as an emetic, and is poisonous in large doses. Without action on
polarised light (Buignet, Compt. rend. 52, 1085).
Dumas & Pelletier.
Reich.
40 C
2 N
240
63.49
64.57
63.11
28
7.40
4.30
6.11
30 H…......
30
7.93
7.77
7.99
10 O
80
21.18
23.36
...
22.79
100.00
100.00
100.00
C40N2H30010.... 378
The above is Reich's formula. According to Pelletier & Dumas, it is C35NH2509;
according to Fehling (Handwörterb. 2, 2, 3, 777) probably C3NH25010. The above
formula requires verification.
Decompositions. 1. Emetine melts when heated, like wax, takes
fire at a stronger heat, evolving dense fumes, and burns (Merck;
Reich). 2. Its salts are violently decomposed by the electric current
(Hlasiwetz & Rochleder, Wien. Akad. Ber. 5, 447).-3. A solution in
400 parts of acidulated water assumed a saffron-yellow colour on
passing chlorine into it for ten minutes, and deposited a slight precipi-
tate; the emetine, however, was not quite pure (Lepage, J. Pharm.
26, 140). — 4. Emetine acquires a brownish-yellow colour in vapour of
iodine, and a greenish-yellow brown in vapour of bromine or chloride of
iodine (Donné). — 5. According to Guy, oil of vitriol does not colour
emetine, but according to Merck, it produces a dirty olive-green colora-
tion. 6. Nitric acid colours it yellowish-brown (Guy); brown-red, and
resinises it (Merck).-7. Strong hydrochloric acid, boiled with emetine,
does not produce a splitting up, and does not form any substance
having a reducing action on an alkaline solution of copper; neither
does unchanged emetine cause a separation of cuprous oxide
(Reich).
Combinations. Air-dried emetine loses 2.4 p. c. of water at 100°
(Reich). It dissolves with difficulty in cold, and somewhat more
freely in hot water (Pelletier). It is insoluble in ammonia-water
(Merck).
EMETINE.
381
With Acids. Emetine dissolves in all acids [including acetic acid
(Merck)], which it neutralises. The salts are not susceptible of
crystallisation, with some exceptions in presence of excess of acid
(Pelletier). According to Landerer, the phosphate crystallises.-They
are precipitated by ammonia and carbonate of ammonia, and by caustic
alkalis and their carbonates and bicarbonates, also by magnesia,
the precipitates not being soluble in excess of the precipitants (Planta).
In the pure state they are not precipitated by basic acetate of lead
(Pelletier).
Phosphate of soda does not precipitate hydrochlorate of emetine.
Tincture of iodine produces a carmine-red, iodic acid a yellow, iodide of
potassium a yellowish-white precipitate (Planta). Phosphomolybdic acid
throws down pale-yellow flocks (Sonnenschein), iodhydrargyrate of potas-
sium, a yellowish-white [amorphous (Dellfs)] powder, insoluble in hydro-
chloric acid, mercuric chloride, a white powder sparingly soluble in hydro-
chloric acid, and insoluble in sal-ammoniac; terchloride of gold, a flesh-
coloured, bichloride of platinum, a yellowish-white, chloride of iridium
and sodium, an ochre-yellow precipitate. Sulphocyanide of potassium
produces a pulverulent, yellowish-white precipitate (Lepage; v.
Planta). Oxalates and tartrates of the alkalis do not precipitate salts
of emetine (Pelletier). Croconate of emetine is yellow, indistinctly
crystalline, and soluble in water and alcohol; the rhodizonate is hyacinth-
red (Heller). - Hydrochlorate of emetine yields with picric acid a
sulphur-yellow powder (Merck; v. Planta). It is rendered turbid by a
little tincture of galls, whereupon a drop of hydrochloric acid produces
a dense, whitish precipitate, which dissolves in more hydrochloric acid
(v. Planta). The precipitate produced by infusion of galls does not
act as an emetic; it is nearly insoluble in water, but soluble in aqueous
alkalis (Pelletier).
Emetine dissolves very easily in dilute and in absolute alcohol, but
is insoluble in ether and in oils (Pelletier; Merck).
-
Appendix to Emetine.
Violine. Violenemetine. Occurs, according to Boullay, in all parts
of the Viola odorata. An alcoholic extract of the dried root is freed
from chlorophyll and fat by means of ether, and the residue is boiled
with dilute sulphuric acid (whereby acetic acid is volatilised), evapo-
rated to dryness with excess of hydrated oxide of lead, and exhausted
with alcohol of 40°. The alcoholic solution, when evaporated, leaves.
violine, from which a little colouring matter may be extracted by a
small quantity of strong alcohol. Violine forms a pale-yellow, bitter
powder, which melts when heated, and burns like resin; it is more
soluble in water, but less soluble in alcohol than emetine, and insoluble
in ether. It combines with acids, without forming distinct salts there-
with (Boullay, Mem. de l'Acad. de Méd. 1828, 1, 417; abstr. Repert. 31,
37).
Torosiewicz distinguishes as melonenemetine, an aqueous extract of
melon root, which has been but little investigated.
"
382 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
APPENDIX TO COMPOUNDS CONTAINING 40 ATOMS OF CARBON.
1. Resins.
On Resins in general.
The older chemists distinguished by the general name resin, sub-
stances insoluble in water, generally soluble in alcohol, for the most
part uncrystallisable, and softening or melting when warmed, such
substances being either:
a. Secretions of Plants, generally exuding from the plant, and
hardening in the air. They are, as a rule, mixtures, sometimes con-
taining considerable quantities of gum, mucus, or volatile oil, and in such
cases distinguished as Gum-resins, or as natural Balsams. Related to
the resins separated from living plants are the Fossil or Earth resins.
Or b. Substances extracted from plants with help of alcohol, not
separable into simpler constituents, and therefore regarded as simple
organic compounds.
The uncrystallisable coloured products obtained by the decompo-
sition of volatile oils in the air, or by nitric acid; by the drying up of
drying fatty oils; by the decomposition of alcohol, aldehyde, and other
organic compounds by potash; and by the dry distillation of many
organic compounds, are also designated as resins.
Volatile oil, when mixed with resin, is removed by exposure to the
air, by boiling with water, or by melting the resin.
- Hot alcohol or
ether extracts the resin from vegetable organs; the solutions deposit
most of the wax or fat on cooling, and, when mixed with water and
distilled, leave the resin as residue.
The products thus obtained frequently contain also acid, fat, vola-
tile oil, or colouring matter, &c.; some of them are further decom-
posible into resins of different properties.
Resins are transparent or translucent, colourless, yellow, brown, or
otherwise coloured, either hard and brittle, and in that case sometimes
crystalline (hard resins), or greasy (soft resins), or elastic (caoutchouc).
When warmed they soften or melt, generally without decomposition,
to a thick viscid liquid, usually thicker than melted fat. They are
inodorous, sometimes tasteless, sometimes having a bitter or acrid
taste (mild or acrid resins). When dissolved in alcohol, they in some
cases redden litmus, without yielding a peculiar acid (acid resins), and
in other cases are without action upon it (neutral resins). They are
more easily inflammable than fats, and burn with a bright, very smoky
flame. They are insoluble in water. They are mostly capable of
combining with salifiable bases. Their solutions in caustic potash or
soda leave on evaporation, amorphous masses, the resin-soaps, frequently
precipitable from their aqueous solutions by excess of potash. The
compounds with metallic oxides, obtained by double decomposition, are
generally insoluble in water. Neutral resins are insoluble, or nearly
so, in alkalis.
Most resins are freely soluble in cold alcohol, but a few are nearly
insoluble, or soluble only in the hot liquid; caoutchouc is insoluble.
RESINS (BENZOïn).
383
i
The alcoholic solutions are turned milky by water, and precipitated
more completely by mineral acids. On exposure to the air, they leave
the resins behind: Spirit-varnish. Most resins are soluble in ether;
volatile oils also dissolve them, and on exposure to air leave first a
balsam-like mass, and then the resins: Turpentine varnish. Resin may
be melted together with fat; the solution in drying-fat hardens in the
air: Fatty varnish.
{
Unverdorben has attempted a classification of the resins. See also Johnston on
the formula of the resins, and Heldt on the laws of the formation of resins.
HATCHETT. N. Gehl. 1, 555.
BOUILLON-LAGRANGE & VÖGEL. Ann. Chim. 72, 72.
PELLETIER. J. Phys. 79, 275. — Ann. Chim. 79, 90; 80, 38. — Bull.
Pharm. 3, 381; 4, 502.
BRACONNOT. Ann. Chim. 68, 19 and 66.
BONASTRE. J. Pharm. 9, 178; 10, 1; 12, 492.
UNVERDORBEN. N. Tr. 8, 1, 21; Pogg. 7, 311; 8, 40 and 407; 11, 28,
230 and 393; 14, 116.
BERZELIUS. Pogg. 10, 252; 12, 419; 13, 78.
DEVILLE. N. Ann. Chim. Phys. 3, 151.
JOHNSTON. Lond. Edinb. Phil. Mag. 13, 474; 14, 95 and 340; J. pr.
Chem. 17, 157.
ROSE. Pogg. 53, 384.
HELDT.
Ann. Pharm. 63, 50.
The following pages contain, generally in alphabetical order, first
the resins and balsams containing benzoic and cinnammic acids, which
exude from living plants; then the resins free from benzoic acid, and
the earth-resins; and lastly those extracted from plants. The list
includes also a few of the bodies allied to resins.
A. Resins containing Benzoic or Cinnamic acid.
1. BENZOÏN. Asa dulcis. From Styrax Benzoin. Irregular gra-
nules or tears of a reddish-yellow colour without, and milk-white
within; brittle, with conchoïdal fracture and fatty lustre; also irre-
gular porous masses, of a dirty red-grey to brown colour, and slightly
shining fracture, in which the white granules are disseminated in
greater or lesser number. Sp. gr. 1.003 (Pfaff), 1·092 (Brisson). It
lias an agreeable odour, especially when warmed or rubbed, and a
sweetish-acrid balsamic taste.
Benzoin contains traces of volatile oil [sometimes an oil which
when treated with chlorine yields chloride of benzoyl (Frémy)], benzoic
acid varying in amount from 12.5 to 19.8 p.c., a resin soluble in ether,
and a second resin insoluble in that liquid (Buchholz; Stoltze). The
white granules consist almost exclusively of the resin soluble in ether,
whilst the brown benzoïn consists chiefly of the insoluble resin
(Stoltze, Berl. Jahrb. 25, 1, 55). See below. Some varieties of benzoïn,
especially an almond benzoin frora Sumatra, contain cinnamic and
benzoic acids (Kolbe and Lautemann, Ann. Pharm. 119, 136); such resin
384 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
of the first quality contains only cinnamic acid: the brown Sumatra
resin contains only benzoic acid (Aschoff, N. Br. Arch. 107, 153; Chem.
Centr. 1861, 650).
The resins of benzoïn contain a group of substances belonging to
the benzoyl series, and a second belonging to the phenyl series, the
derivatives of which occur in the products of decomposition. 1. In
the dry distillation of benzoïn free from benzoic acid, a fatty unctuous
body, probably the odorous principle, is obtained, together with benzoic
and carbolic acids (E. Kopp). Cahours (N. Ann. Chim. Phys. 3, 192)
obtained by the dry distillation of benzoïn free from acid, an oil,
C36H1804, resembling benzoate of ethyl, which was completely con-
verted into benzoic acid by hydrate of potash. Umbelliferone is not
formed in the dry distillation (Sommer).-2. Chromic acid forms oil
of bitter almonds and benzoic acid, together with carbonic and formic
acids. 3. Nitric acid produces a violent frothing, with evolution of
red fumes, and forms a brittle, porous, very bitter, orange-yellow
mass, from which picric and benzoic acids are produced by the con-
tinued action of the nitric acid, whilst hydrocyanic acid, oil of bitter
almonds, and benzoic acid distil off. 4. Oil of vitriol dissolves the
resins of benzoïn with carmine-red colour, forming a solution from
which water throws down a copious violet precipitate; it yields a
soluble lime-salt when saturated with that base (E. Kopp, Compt.
rend. 19, 1269).
Benzoin, purified by boiling with carbonate of potash, dissolving
the residue in alcohol, distilling, and precipitating with water, yields
when melted with hydrate of potash, benzoic acid, paraoxybenzoic
acid, CHO, protocatechuic acid, C4H608, (also a compound of these
two acids in equal numbers of atoms), pyrocatechin, acetic acid, pro-
pionic acid, and butyric acid. Small quantities of a crystallisable
acid (probably C18H8O10) which dissolves with difficulty in dilute
alcohol and assumes a fine red colour with sesquichloride of iron, are
also obtained (Hlasiwetz and Barth, Ann. Pharm. 134, 265).
See
Benzoïn is slightly soluble in ammonia, but more freely soluble in
boiling caustic potash, with brown colour. -Boiling water, milk of lime,
and aqueous alkaline carbonates extract benzoic acid from it.
below. It is soluble in cold acetic acid. Alcohol forms a reddish-brown
solution, precipitable by acids and water: ether also dissolves it
(Brande) (See above). Cold creosote dissolves it completely (Reichen-
bach).
The yellowish-white almonds of benzoïn melt at about 93°, and
solidify on cooling to a colourless, transparent, brittle resin, which
turns brown when more strongly heated, with liberation of benzoic acid.
After being kept in a semi-fluid state for 20 hours at 93°, it contains
72.01 p. c. C., 6·67 H.; and 21.32 O. (deducting 0.23 p. c. of ash)
(Johnston, Phil. Trans. 1840, 369). — White benzoïn soluble in ether
without residue, and melting at 95°, contains 72-23 p. c. C., 6.80 H., and
20.97 0. (Schrötter, Pogg. 59, 71).
Separation of the resins of Benzoin. — A. According to Stoltze. --An
alcoholic solution of benzoin is neutralised with carbonate of soda and
evaporated with water, the separation of the resin being promoted by
the addition of carbonate of soda. The precipitate is washed with
water and treated with ether, which dissolves one resin and leaves the
other undissolved.
RESINS (BENZOïn).
385
a. The resin soluble in ether is pale-yellow, friable, neutral, easily
fusible, with agreeable odour, and does not yield benzoic acid when
decomposed at a higher temperature. It dissolves in oil of vitriol,
with dark-red colour. When precipitated from an alcoholic solution
by water and diluted, it remains suspended, as a milky liquid, which
becomes clear only when left at rest for several days, but immediately
on addition of mineral acids, acetic acid, or Glauber's salt. The resin
dissolves in warm caustic potash: it is precipitated from its alcoholic
solution by neutral acetate of lead: easily soluble in strong acetic
acid, from which it is precipitated by water. b. The resin insoluble
in ether is brown, friable, easily fusible, and insoluble in volatile and
fatty oils (Stoltze).
B. According to Unverdorben and van der Vliet. Benzoin boiled
with aqueous carbonate of soda gives up to that liquid benzoic acid
and a little gamma-resin: from the residue ether extracts alpha-resin,
whilst beta-resin soluble in alcohol remains behind. These three resins
yield the same products when heated with hydrate of potash (Hlasi-
wetz & Barth).
Its
a. Alpha-resin. - Freed from volatile constituents by warming.
Pale-brown. Insoluble in aqueous ammonia or carbonate of soda, but
easily soluble in caustic potash, alcohol, and oil of cumin.
alcoholic solution precipitates alcoholic neutral acetate of lead, but not
alcoholic acetate of copper (Unverdorben). It contains, on an average,
71.85 p. c. C., 7-19 H., 20-96 O. [72.74 C., 7.33 H., 19.93 O (Mulder)];
in the lead-salt 16·44 p. c. of oxide of lead, the residue consisting of
71.90 p. c. C., 7.08 H., and 21.02 O., (van der Vliet).
b. Beta-resin. - After the extraction of the alpha-resin the residue
contains beta-resin, a compound of alpha-resin with carbonate of soda,
and the impurities of the benzoïn. Its solution in boiling alcohol
deposits the compound of alpha-resin with carbonate of soda on cool-
ing; the filtrate yields on evaporation the beta-resin, which is boiled
with water containing hydrochloric acid (van der Vliet). The beta-
resin is insoluble in ether, but easily soluble in caustic potash, from which
it is precipitated by a large quantity of potash. It behaves in other
respects like the alpha-resin (Unverdorben).-Contains, on an average,
70.43 p. c. C., 6·70 H., 22.87 O. (van der Vliet); 71·41 p. c. C., 6·88
H., and 21·71 O. (Mulder); in the lead-salt, 25.46 p. c. of oxide of lead,
the residue containing 71.74 p. c. C., 6-28 H., and 21.98 0. (van der
Vliet).
c. Gamma-resin. Extracted from benzoïn by boiling with carbonate
of soda, precipitated from the solution by hydrochloric acid, and
purified by boiling with water. The gamma-resin is formed from the
alpha and beta-resins in moist air, inasmuch as these latter become
thereby soluble in aqueous carbonate of soda.
It dissolves in aqueous
ammonia, in caustic potash, from which it is precipitated by further
addition of potash, in alcohol, and with difficulty in ether and oil of cumin.
It behaves in the same manner as the a-resin towards neutral acetate
of lead and acetate of copper. Contains 74.44 p. c. C., 8·49 H., and
17.07 0., (van der Vliet); 73-76 C., 8.67 H., 17.67 0., (Mulder); in the
lead-salt 31.28 p. c. of oxide of lead (van der Vliet, J. pr. Chem. 18, 411;
Ann. Pharm. 34, 177; Unverdorben, Pogg. 17, 179). See also Frémy
VOL. XVII,
2 C
11
386 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
(Ann. Chim. Phys. 70, 203); Dulong (J. Pharm. 12, 33). On the
formulæ of the resins of benzoïn, see also Ludwig (N. Br. Arch.
123, 21).
C. According to Johnston. a. When picked benzoin is freed from
benzoic acid by repeated boiling with water and with dilute and strong
carbonate of potash, a red-brown residue is left, which is completely
soluble in alcohol and ether, and yields no sublimate of benzoic acid
when heated in a narrow tube. It contains, on an average, 71.61 p. c. C.,
7.49 H., and 20.90 O., corresponding to the formula C402408.b. A
similar red-brown resin is obtained by boiling benzoïn with milk of lime,
washing with a large quantity of boiling water, decomposing the un-
dissolved compound of resin and lime with boiling hydrochloric acid,
dissolving the precipitated resinous acid in alcohol, and evaporating.
It evolves a volatile oil when heated to about 120°, and contains 70·00
to 72-23 p. c. C., 7.38 to 7.63 H., 22.62 tc 20·14 O., corresponding to
the formula C40H2408 or C40H240° (Johnston). c. When the last wash-
waters of the lime-compound are precipitated by hydrochloric acid,
grey-white flocks are obtained, which contain 73.11 p. c. C., 9.21 H.,
and 17.68 0., corresponding to the formula C40H3007 (Johnston).
d. Strong solution of caustic potash, added to the cold alco-
holic solution of benzoïn, turns the liquid darker, and throws down
a grey precipitate, which dissolves in a larger quantity of caustic
potash, and is again precipitated by tincture of benzoïn. If the precipi-
tates are collected, washed with boiling water, which takes up but little,
again dissolved in caustic potash, precipitated by hydrochloric acid,
and washed with hot water, a grey resinous powder is obtained, which
is deposited almost entirely from its solution in boiling alcohol or
ether on cooling. It is still a mixed substance, from which alcohol
takes up a portion containing 71.73 p. c. C., 7.33 H., and 20.94 O.,
corresponding to the formula C40H2408, after which ether extracts a
second portion containing 71.00 p. c. C., 6·77 H., and 22:23 O., cor-
responding to the formula C40H22O⁹. e. The solution which has been
precipitated by potash throws down, on dilution with water, a slight
precipitate, after the removal of which the filtrate is to be precipi-
tated by hydrochloric acid. The precipitate thus obtained is washed
with hot water, dissolved in alcohol, and recovered from the solution.
by evaporation. After drying for a short time at 93°, it contains
73·02 p. c. C., 9·16 H., and 17·82 O.; on more prolonged drying the
percentage of carbon decreases to 69.77.
Alcoholic neutral acetate of lead throws down from an alcoholic
solution of benzoïn, a slight precipitate, containing 24.86 p. c. of lead-
oxide: the filtrate yields, on addition of ammonia, a further precipi-
tate containing 41·41 p. c. This last, when boiled with hydrochloric
acid, furnishes a resin, which, after solution in alcohol and evaporation,
contains 69.17 p. c. C., 7·60 H., and 23.23 0., corresponding to the
formula C4H26010 (Johnston, Phil. Trans. 1840, 369). According to
Unverdorben, neutral acetate of lead does not precipitate alcoholic
benzoïn.
2. YELLOW RESIN FROM BOTANY BAY. - From Xanthorrhoea hastilis:
Of a darker reddish-yellow than gamboge, frequently covered with a
greenish-grey crust. Brittle, of shining fracture, triturable to a
greenish-yellow powder. Does not stick to the teeth. Tastes sour and
RESINS (DRAGON'S BLOOD).
387
aromatic, and has an agreeable balsamic odour. Contains a very
small quantity of an agreeably-smelling volatile oil; a resin soluble in
alcohol and ether, and also in alkalis and baryta- and lime-water; a
little benzoic acid, and bassorin (Laugier, Ann. Chim. 76, 265). Tromms-
dorff (Taschenb. 1826, 1) distinguishes two, Widmann (Repert. 22, 198) three
resins. Its solution in ether or alcohol leaves on evaporation a dark
resin, containing, at 120°, 66.98 p. c. C., 5·73 H., and 27.29 O., corre-
sponding to the formula C40H20012, and almost entirely precipitable from
its alcoholic solution by water, even in presence of a large quantity of
ammonia (Johnston, Phil. Trans. 1839, 292).
The resin melts at a moderate heat, and afterwards burns with
smoky flame and an odour of storax. When submitted to dry distilla-
tion, it yields a large quantity of carbolic acid in the form of an acid
heavy oil, and a little light oil, having the odour of a mixture of ben-
zene and cinnamene [no umbelliferone (Sommer)]. - Nitric acid acts
violently upon the resin, even in the cold, and dissolves it with dark-
red colour; the further action of the acid produces a large quantity of
picric acid (xi, 211), together with a little nitrobenzoic acid and oxalic
acid (Stenhouse). The brown-red solution of the resin in aqueous alkalis
throws down, when neutralised with hydrochloric acid, a dark brown
brittle mass, whilst the acid liquid retains in solution cinnamic acid and
a little benzoic acid (Stenhouse, Phil. Mag. 28, 440; Ann. Pharm. 57, 84).
The resin gives up to boiling water benzoic acid and gum. It dis-
solves in oil of vitriol, forming a pale brown solution, which is precipi-
tated of a violet-red by water. It colours acetic acid yellow, without
dissolving in it to any great extent, and dissolves easily in alcohol,
ether, some volatile oils, and partially in fatty oils, forming in all cases
fine yellow solutions (Widmann; Lichtenstein).
3. DRAGON'S BLOOD. - Occurs in commerce in three different varieties,
namely, Oriental (from Calamus Draco and other species), Canary (from
Dracaena Draco), and American (from Pterocarpus Draco. Handbuch, viii
[2], 12), the first of which is further distinguished as Sanguis Draconis
in baculis, in lacrymis, and in massis. The resin is reddish-brown in
mass, blood-red in powder, opaque, brittle, of dull fracture. Sp. gr.
1, 196. Inodorous and tasteless. Has an odour of benzoïn when
heated. Contains fat, benzoic acid [Hempel (Ann. Pharm, 59, 321) found
neither benzoic nor cinnamic acid], oxalic acid, phosphate of lime, and
90 p. c. of colouring matter, which is precipitated from the alcoholic
solution by sulphuric acid (Melandri's Dracin; Herberger's Drachen-
blutstoff). According to Melandri (Br. Arch. 25, 193), dragon's
blood dissolves gradually in warm water. It dissolves, for the
most part, in alkalis (Herberger), and slightly in lime-water, the
fine red solutions being precipitated of a yellow colour by acids. — It
dissolves easily with purple colour in alcohol, in acetic acid, less easily
in ether, and in fatty and volatile oils [not in castor oil (Stickel)]
(Herberger, Repert. 37, 17), easily in fusel oil, less freely in valerianic
aldehyde, and still less in valerianic acid and valerate of amyl (Traut-
wein, Repert. 91, 29).
Dragon's blood, when submitted to dry distillation, melts, gives off
acid water together with acetone and benzoic acid up to 210°, swells up,
evolves carbonic acid and carbonic oxide with dense white fumes, and
yields a distillate of black-red oil, whilst a large quantity of carbon
remains behind. The oil contains dracyl (toluol, iv, 226) and draconyl
A
2c2
388 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
[styrol, which is transformed into metastyrol (xiii, 6) by rectification
(Hofmann & Blyth), and probably occurs as metastyrol in dragon's blood
(Kovalewsky, Ann. Pharm. 126, 69)]. After distilling off these two sub-
stances at a temperature below 180°, there passes over an oily mixture
of benzoic acid with an oxygenated oil heavier than water, and turning
red and black in the air, from formation of benzoic acid and a peculiar
liquid (Glenard & Boudault, Compt. rend. 17, 503 ; N. J. Pharm. 4, 274;
Ann. Pharm. 48, 343. Compt. rend. 19, 505; N. J. Pharm. 6, 250).
-
Dragon's blood is violently acted upon by nitric acid of sp. gr. 1·34
when warmed therewith, becoming very hot, and dissolving completely
in 6 or 8 parts of the liquid, with formation of oxalic acid, and perhaps
a trace of picric acid. Nitric acid, diluted with an equal volume of
water, dissolves dragon's blood gradually on boiling, vapours smelling
of nitrobenzene and hydrocyanic acid passing over, and a non-volatile,
pulverulent acid, together with a sublimable acid, probably nitrobenzoic
acid, being formed (Blumenau, Ann. Pharm. 67, 127). Böttger &
Will (Ann. Pharm. 58, 274) likewise obtained only benzoic acid (no
styphnic acid) by the action of nitric acid. Alcoholic dragon's blood
reduces nitrate of silver on standing (Johnston). - Dragon's blood
melted with caustic potash, yields phloroglucin and protocatechuic acid
(Hlasiwetz & Pfaundler, Wien. Acad. Ber. 50, 52). Hlasiwetz &
Barth afterwards obtained the following results: dragon's blood, puri-
fied by dissolving it in alcohol, distilling off the alcohol, and precipi-
tating the residue with water, yields, when melted with caustic
potash, (1) acetic acid (or butyric or propionic acid); (2) benzoic acid;
(3) paraoxybenzoic acid; CHO', (4) a˜compound of paraoxybenzoic
with protocatechuic acid in equal numbers of atoms; (5) phloroglucin;
(6) a difficultly soluble acid, CisH8O10, which is also obtained from ben-
zoïn (p. 385); (7) oxalic acid; and (8) a small quantity of microscopic
needles, corresponding to the formula C18H1008. Dragon's blood in
tears and that in sticks yield the same products, but in different propor-
tions, in the one case a large quantity of phloroglucin and but little
paroxybenzoic acid being produced, and in the other case a small
quantity of phloroglucin, but a large quantity of paraoxybenzoic acid,
either free or combined with protocatechuic acid (Hlasiwetz & Barth,
Ann. Pharm. 134, 283).
Johnston (Phil. Trans. 1839, 134; 1840, 384) examined two varie-
ties of dragon's blood, one comparatively pure, the other mixed with
vegetable remains.
a. When the purer dragon's blood, occurring in commerce in sticks,
is digested with alcohol, and the filtered liquid is evaporated over
the water-bath, there remains a nearly black residue, of a splendid
red colour, translucent in thin layers, and triturable to a dark red
powder. After evaporating the solution at 82°, the residue swells up
when heated to 100°, giving off astringent vapours; at a temperature
of 93° it loses the whole of the alcohol or ether in 12 hours, and dis-
solves completely in alcohol, even after drying at 138° (analyses a c).
B. When the same dragon's blood is dissolved in ether, and the
filtrate is evaporated, the residue exhibits a like composition, d, whether
dried for 12 hours at 66° or 88°, or for 6 hours at 100°. y. The dragon's
blood occurring in larger pieces, mixed with vegetable remains, but pro-
bably less altered by artificial processes, gives up to alcohol the resin e,
to ether the resin f, both of which were analysed after drying for
12 hours at 88°. These resins are C40H2108 or C40H2008.
RESINS (PERU BALSAM).
389
a.
at 100°.
....
b.
Analyses by Johnston.
at 104°.
70.80
6.11
23.09
....
C.
at 138°.
72.35
6.21
21.44
d.
e.
f.
C
H
O
70.93
5.98
23.09
****
72.15
6.10
21.75
....
***
73.16
6.40
20.44
72.91
....
6.66
20.43
..
100.00
100.00
100.00
100.00
100.00
100.00
....
4440
*
4. PERU BALSAM. From Myroxylon peruiferum. Occurs in com-
merce in the solid and in the fluid state. It is dark red-brown, trans-
parent, and of spongy consistence. Sp. gr. 1·15 (Lichtenberg; Stoltze),
1.1475 (Brandes & Reiche). It smells like vanilla, and tastes at first
mild, afterwards bitter and aromatic, producing a pricking sensa-
tion on the tongue and throat. When taken internally, it occasions
the formation of hippuric acid, and the urine acquires a blood-red
colour on being heated with hydrochloric acid (Wöhler & Frerichs,
Ann. Pharm. 65, 339).
Peru balsam contains cinnameïn (xiii, 283) and frequently also
styracin (xiii, 286), cinnamic acid (xiii, 268), a resin easily soluble, a
second resin difficultly soluble in alcohol, and extractive matter soluble
in water.
The balsam deposits crystals of cinnamic acid (xiii, 269) on pro-
longed standing. When distilled with water it yields little or no
volatile oil (Lichtenberg). When it is heated to 100° a trace only of
oil and acid are obtained; at 287° the balsam boils and yields first a
yellow, then a brown oil, together with a little acid, water, carbonic
acid, and combustible gas (Lichtenberg). By dry distillation, water,
oil, and a large quantity of cinnamic acid are obtained (Scharling).
Without a wick, the balsam burns only at a high temperature, but with
a wick it burns easily, with bright smoky flame. Nitric acid dis-
solves it with violent action and formation of hydrocyanic acid
(Hatchett). When mixed with cold oil of vitriol, the balsam becomes
hot and evolves sulphurous acid, forming a dark-brown mixture, which
yields a sublimate of benzoic acid when heated (Stoltze; Hatchett).
On dropping the balsam into boiling concentrated solution of chlo-
ride of zinc, water and a little cinnamic acid pass over, together with
a light and a heavy brown empyreumatic oil, which give up cinnamic
acid to water (Scharling).
When Peru balsam is shaken with strong caustic potash, a solid
soap is obtained, a solution of which in water separates into two
layers; the upper brownish-yellow layer, the Perubalsamöl of Stoltze,
containing cinnameïn (and styracin), the lower, the potash-salt of cin-
namic acid and resin (Plantamour and others). On distilling the sub-
jacent aqueous liquid, a little more volatile oil is obtained (Šcharling).
A mixture of 1 part of Peru balsam with 2 or 3 parts of solution
of caustic potash of sp. gr. 1-3, allowed to stand for twenty-four hours
and then distilled, yields water, a heavy oil, and a light oil.
a. The
heavy oil, having a sp. gr. of 1.03 at 14°, boils with decomposition at
205°, and does not solidify at 15°. It has a faint odour, aromatic
after long standing. It solidifies in contact with bisulphide of carbon
and caustic potash, and according to Scharling, is to be regarded as
cinnamate of ethyl, but according to Kraut (Ann. Pharm. 107, 208), as
benzylic alcohol. — b. The light oil, boiling at 180°, smells of anise,
tastes sweet and aromatic, and does not solidify at 15°. It solidifies
390 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
with caustic potash and bisulphide of carbon, probably on account of
admixture with a (Scharling, Ann. Pharm. 74, 230). Aqueous alkaline
carbonates extract cinnamic acid from Peru balsam.
The balsam mixes with absolute alcohol in all proportions (Pfaff),
traces only of the sparingly soluble resin and extractive being de-
posited. It dissolves in weaker alcohol, with separation of the
sparingly soluble resin (Stoltze). Alcoholic potash throws down
resinate of potash from the alcoholic solution, whilst cinnamate of
potash and cinnameïn precipitable by water remain dissolved (Frémy).
Absolute ether takes up cinnamic acid, cinnameïn, and an easily soluble
resin (Stoltze). Fusel-oil and valerianic aldehyde dissolve the balsam
completely; valerianic acid and valerate of amyl dissolve it with
turbidity (Trautwein, Repert. 91, 29). Rock-oil extracts impure cinna-
meïn (Frémy). — The balsam mixes with th of oil of turpentine; with
a larger quantity the mixture separates into two layers (Stoltze).- Oil
of almonds dissolves half of the balsam (Pfaff). — Štoltze (Berl. Jahrb.
25, 2, 24); Plantamour (Ann. Pharm. 27, 329; 30, 341); Frémy (Ann.
Chim. Phys. 70, 180); Scharling (Ann. Pharm. 74, 230; 97, 168). The
eight substances obtained by Richter (J. pr. Chem. 13, 167) from Peru
balsam appear to be either identical with known bodies, or mixtures.
The resin of Peru balsam is identical with that of Tolu balsam and
benzoïn (xiii, 290) (Frémy). When mixed with pumice-stone and sub-
mitted to dry distillation, it yields benzoic acid, water, and an oil con-
sisting of styrol or a similar body (xiii, 2), benzoate of methyl, and
carbolic acid (Scharling).
The sparingly soluble resin remains behind when the balsam is
repeatedly treated with cold alcohol of 75 p. c. It is black-brown,
friable, inodorous, and tasteless, neutral, and fusible at a moderate.
heat, emitting an odour of benzoïn. It dissolves in oil of vitriol with
carmine-red colour, and in hot strong caustic potash, from which it is
precipitated by acids. Its hot alcoholic solution throws down from
neutral acetate of lead, a precipitate soluble in acetic acid. The resin
dissolves slightly in hot strong acetic acid, but is insoluble in ether, oil
of turpentine, and olive-oil (Stoltze).
The easily soluble resin is obtained by neutralising the solution of
the balsam in 6 parts of alcohol with carbonate of soda, diluting the
solution with water and concentrating, whereupon the liquid separates
into three layers. The upper aqueous layer is removed; the lower
layers are dissolved in alcohol, the solution is again evaporated, and
the residue is dissolved in 12 parts of warm olive-oil, which retains the
oil of the balsam in solution, but deposits the resin in flocks on cooling.
The flocks are purified by solution in alcohol. Dark-brown, inodorous
and tasteless mass, transparent in thin layers, melting below 100°. It
dissolves in cold oil of vitriol with dark-violet colour. The alcoholic
solution is precipitated of a grey colour by neutral acetate of lead, the
precipitate dissolving in acetic acid, and is coloured dark-green by
sesquichloride of iron. The resin dissolves easily in strong acetic acid
and in strong alcohol, but not in ether, cold oil of turpentine, or olive
acid oil. It is thrown down from the alcoholic solution in grey flocks
by gelatin (Stoltze).
The dried Peru balsam imported in gourds is reddish-yellow and
friable, and contains volatile oil, benzoic acid, and a resin soluble in
hot dilute caustic potash, and in alcohol and ether (Trommsdorff, N. Tr.
2, 1, 80).
RESINS (STORAX).
391
The gum-resin which exudes from the Peru balsam tree contains
77.4 p. c. resin, and 17.1 p. c. gum, besides woody fibre, water, and
a little volatile oil. The resin is uncrystallisable, and reddens litmus
slightly in alcoholic solution (Attfield, Pharm. Trans. (2) 5, 241; Kopp's
Jahresber. 1863, 557).
5. LIQUID STORAX. The American variety is obtained from Li-
quidambar styraciflua, the Oriental from Liquidambar Altingia. -Green-
grey, of an agreeable odour and the consistence of honey. Hardens
in the air. When distilled, it yields carbonic acid and combustible gas,
acid water, benzoic acid (or cinnamic acid?), a coloured oil which
solidifies, and carbon. It gives up benzoic (cinnamic?) acid to water
or milk of lime. Dissolves in oil of vitriol with brown colour, and is
precipitated from the solution in white flocks by water (Dulong). —
With excess of nitric acid of sp. gr. 1-2 it yields a large quantity of
benzoic acid and a little picric acid (Böttger & Will, Ann. Pharm. 58,
274). It dissolves, with the exception of impurities, in 4 parts of
alcohol, forming a brown solution (Bouillon-Lagrange).
Liquid storax is a mixture of styrol (xiii, 1), cinnamic acid (xiii, 268),
resins, and styracin (xiii, 286), which occurs in storax partly as acid
cinnamate of styracin. a. The styrol is obtained by distilling storax
with water and carbonate of soda, but in varying quantities, as it
becomes converted into a non-volatile body by keeping (Simon). -
b. The liquid which remains after distilling with water (without car-
bonate of soda) deposits acid cinnamate of styracin when concentrated.
c. The resin remaining on distilling storax with aqueous carbonate
of soda, dissolves partly in alcohol and partly in ether; the alcoholic
solution deposits styracin. If the solution be distilled with caustic
soda and water before the styracin separates, styracone (xiii, 256) is
obtained (Simon).
Storax contains metastyrol (Kovalewsky). When the styrol is
removed by distillation with water, the cinnamic acid by treating
the residue with caustic soda, and the undissolved portion is then re-
peatedly washed with alcohol, there remains a solid black resin, which
on distillation yields styrol, formed from the metastyrol, and amounting
to 1.6 to 2.8 p. c. of the liquid storax (Kovalewsky, Ann. Pharm.
120, 66).
Fresh liquid storax is yellow, of the consistence of copaiba balsam
at 15°, thicker in the cold, heavier than water, and reddens litmus
slightly. It dissolves to the extent of 3ths in alcohol, leaving crystals,
and in all proportions in ether. It contains volatile oil, a waxy sub-
stance which passes over with the water and is taken up from the
water by ether, benzoic acid, styracin, a soft resin, yellow colouring
matter, and a crystalline substance different from styracin. When
storax is submitted to prolonged boiling with water and the residual
liquid is filtered from resin and evaporated, crystalline granules are
deposited, which are to be washed with cold water and triturated with
12 parts of cold water. The undissolved portion, dissolved in boiling
water, deposits on cooling nearly colourless crystals, which are rendered
quite white by treatment with animal charcoal. They form microscopic
four-sided pyramids, neutral, white and shining, having an odour
of melilotene, and volatilising on glowing charcoal, therefore pro-
bably allied to coumarin (Bonastre, J. Pharm. 17, 345; N. Tr. 24, 2,
236).
2
392 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
6. SOLID STORAX. From Styrax officinalis. Occurs either in yellow
translucent granules of the size of peas and the hardness of wax
(Storax in granis), or in brown, yellow, or white coherent pieces, sticky
when warmed (Storax in massis); or in brown cakes made up of
storax, sawdust, and other impurities (Scobs storacina, Storax cala-
mita). Has a very agreeable odour and a burning taste. When
distilled with water, it gives off its oil only after all the water has
passed over. The oil is at first limpid and afterwards buttery; it is
empyreumatic and contains benzoic acid (Neumann). It forms with
oil of vitriol a red solution from which water throws down red flocks
(Dulong). It is soluble in alcohol. - Contains styracin, uncrystal-
lisable soft resin, colouring matter, and benzoic acid, the last of which
may be extracted by boiling with lime, but not by boiling water:
neither does the aqueous decoction redden litmus (Lepage, J. Chim.
méd. 18, 727).
The solid Storax from Bogota contains easily soluble resin, benzoic
acid, bitter extractive, and 40 p. c. of woody fibre (Bonastre, J. Pharm.
16, 88; N. Tr. 21, 2, 242).
The Storax calamita of 1785 was very light, crumbly between the
fingers, had an odour of benzoin, and appeared to consist almost
entirely of needles of benzoic acid and yellow pieces of resin. When
heated, it yields a sublimate of benzoic acid, and when distilled with
water, a milky distillate from which ether extracts a stearoptene. The
residual water deposits crystals on evaporation, and leaves a dark-
yellow gum. The undissolved portion forms with alcohol a brown-
red tincture containing benzoic acid (cinnamic acid?) and resins,
while woody fibre remains undissolved. The same constituents,
together with ammonia and caoutchouc, are present in the reddish
heavy, and the brown granular Storax calamita of commerce, and
are therefore not to be regarded as artificial products (Reinsch, Repert.
63, 289).
7. TOLU BALSAM. From Myrospermum toluiferum or frutescens.
Yellowish to pale red-brown, and of the consistence of turpentine
in the fresh state (white Tolu balsam). Becomes hard and reddish-
brown on keeping (black Tolu balsam), and dries up in the air to a
brittle solid resinous mass (dry Tolu balsam). The following varie-
ties are to be distinguished: a. The ordinary balsam from Carthagena;
reddish-yellow, not quite transparent, granular, or crystalline, brittle
in the cold, softening in the mouth. b. The turpentine-like balsam
from Brazil, which becomes harder than the preceding when exposed
to the air. It yields cinnamic acid to warm water (St. Martin, Pharm.
Viertelj. 14, 110). Tolu balsam from Santa Fe de Bogota is very
soft, contains a little benzoic acid, and yields by distillation a fluid
balsamic oil, in part lighter than water (Bonastre, J. Pharm. 19, 676;
Ann. Pharm. 10, 128).
Tolu balsam has an agreeable odour and a warm, sweetish,
biting taste. When exposed to the air on a plate, it gradually dries,
becoming crystalline and richer in acid (Guibourt; Scharling). It
dissolves in oil of vitriol with red colour, and in nitric acid with evolu-
tion of hydrocyanic acid, and when distilled with the latter acid
yields benzoic acid, together with Hatchett's artificial tannin.
When boiled or digested with aqueous carbonate of soda, it forms a
brittle mass, which turns red in the air. It does not dissolve com-
RESINS (MECCA-BALSAM).
393
pletely in caustic potash of sp. gr. 1·06, even when warmed, but is
soluble in a solution of sp. gr. 1·17, without separation of oil (or cinna-
meïn). Caustic potash of sp. gr. 1.27 forms with it a clear solution,
which afterwards solidifies (Scharling). It dissolves in 6 parts of
alcohol (Planche), less easily in ether and volatile oils, not completely
in fat oils.
Tolu balsam is a mixture of a little volatile oil, free acid, and resin.
a. The volatile oil obtained by distillation with water contains tolene
(xiv. 312), benzoic acid, and cinnameïn (xiii, 28), also a body boiling at
180°, and containing 84.9 p. c. C., 11.83 H., and 3.27 0., probably a
hydrate of tolene (Deville). By dissolving the balsam in dilute caustic
potash, Frémy obtained also cinnameïn, which separated in the form
of an oil; Scharling, however, denies its existence in Tolu balsam.
—b. The acid of the balsam is cinnamic acid (Frémy), a mixture of cin-
namic and benzoic acids (Deville); the benzoic acid is not formed, as
Kopp imagines, by the action of alkalis on the resins, but may be ex-
tracted by carbonate of soda or distilled off with vapour of water at
170° (Scharling).
c. On the resins of Tolu balsam see xiii, 290. Kopp's alpha-resin ap-
pears not to be a peculiar body, but if the residue which is left on dis-
tilling Tolu balsam in a current of superheated steam be treated with
weak and with strong alcohol, there remains a portion nearly insoluble
in alcohol, ether, bisulphide of carbon, and oil of turpentine, but soluble
for the most part in caustic potash, and precipitable by hydrochloric
acid from the alkaline solution in the form of a jelly having the same
composition as the beta-resin (xiii, 291) (Scharling).
When Tolu balsam, freed from volatile oil and dehydrated by
heat, is subjected to dry distillation, a colourless viscid distillate which
afterwards crystallises is obtained, containing toluene (xii, 226),
benzoate of methyl [according to Scharling; but according to Deville,
benzoate of ethyl (xii, 60)], benzoic acid, and a little cinnamic acid:
on continuing the distillation, a violent frothing takes place for some
time, after which the mass boils quietly, yielding a distillate of water
and a heavy, limpid oil, carbonic oxide and carbonic acid being evolved,
whilst charcoal remains behind (Deville). The balsam freed from acid
by carbonate of soda dissolves in boiling strong caustic potash, forming
a brown liquid which solidifies on cooling in a granular mass, com-
pletely soluble in water, and yielding toluol on distillation (Kopp).
When the resin of Tolu balsam is distilled with coarsely powdered
pumice, 31 p. c. of an acid brown oil is obtained, consisting of a mixture
of methylic benzoate, toluol, and carbolic acid (Scharling). - Frémy
(Ann. Chim. Phys. 70, 201); H. Deville (N. Ann. Chim. Phys. 3, 151);
È. Kopp (Compt. Chim. 1849, 145); Scharling (Ann. Pharm. 97, 88).
8. MECCA BALSAM. Source, xiv, 383.- Limpid, pale-yellow, of
sp. gr. 0.95. Smells fragrant, or, after standing for some time in the
air, like turpentine; tastes bitter and warm. When exposed to the
air, it rapidly becomes thick, viscid, and specifically heavier. It dis-
solves easily in alcohol and ether.
Mecca balsam distilled with water yields volatile oil (xiv, 383), a
very bitter aqueous decoction, a resin soluble in cold alcohol, and
a second resin insoluble in that liquid. Much of the balsam also
contains gum. The soluble resin is soft, of acid reaction, insoluble in
aqueous ammonia, and soluble in small quantity only in boiling nitric
394
APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
acid: it does not combine completely with an equal quantity of caustic
potash and water. - The insoluble resin is moderately hard, of a
whitish-grey colour, inodorous and tasteless, and softens with difficulty
when warmed. It dissolves very slightly in boiling alcohol, from which
it is thrown down in white flocks on cooling, but is easily soluble in
ether (Bonastre, J. Pharm. 18, 98; Ann. Pharm. 3, 147). Trommsdorff
(N. Tr. 16, 1, 76), by boiling the balsam first with water and then with
absolute alcohol, obtained a yellowish-brown, soft, viscid residue, with-
out smell or taste, which dried up gradually when warmed, melted at
100° to 110°, and at a higher temperature evolved acid and aromatic
vapours, and burnt with a bright flame. It swelled up in cold strong
nitric acid and also in the hot dilute acid, was insoluble in ammonia and
in boiling caustic potash, but easily soluble in warm volatile and fat oils,
and became suspended in boiling absolute alcohol without dissolving.
The portion of Mecca balsam taken up by absolute alcohol remains
on evaporation as a friable, transparent, honey-yellow mass of sp. gr.
1.33, which softens at 44° and becomes limpid at 92°. It yields by
distillation a yellow oil, a little water, and a little combustible gas,
whilst a dark brittle resin remains behind. It forms with nitric acid
of sp. gr. 1·55, oxalic acid and yellow products, and with cold oil of
vitriol, a brown-red solution. It is insoluble in ammonia and caustic
potash, slightly soluble in absolute alcohol and cold ether, but more
easily soluble in these liquids when warm, and in warm volatile and
fatty oils (Trommsdorff; Vauquelin, Ann. Chim. 69, 221).
Mecca balsam from an Egyptian tomb was solid, fusible, and con-
tained an admixture of crystals. When distilled with water, it yielded
acetic acid, but no volatile oil or benzoic acid. The balsam exhausted
with boiling water is decomposible by alcohol into two resins: the
crystals also dissolve in alcohol. The crystals are cauliflower-like,
slightly acid, nearly tasteless, fusible only above 90°, and not susceptible
of sublimation (Bonastre, J. Pharm. 18, 336).
Lançon or Landsome, a balsam obtained from the Philippines, sepa-
rates, on standing, into an upper yellow and a lower turbid layer,
which are not miscible. It is less fluid than balsam of copaiba, more fluid
than Venice turpentine, and dissolves in cold alcohol with the exception
of a white residue. When distilled with water, it yields 20 p. c. of
volatile oil (xiv, 373) and a soft residue, from which cold alcohol of
36° takes up a resin, the rest remaining undissolved. - The soluble
resin is transparent, difficultly saponifiable, and slowly decomposed
by nitric acid, which colours it reddish-violet. The insoluble resin,
obtained by dissolving in alcohol and evaporating the solution, is
amorphous, inodorous, tasteless, and insoluble in alkalis. When warmed
with nitric acid it assumes a faint rose-red colour, arising from the
presence of volatile oil (Bonastre, J. Pharm. 15, 662; N. Tr. 21, 2, 215).
The balsam of Hedwigia balsamifera or Bursera balsamifera exudes
from the inner bark of the tree. The balsam 30 years old is dark-red,
soft, viscid, and sticks to the fingers: it has an odour of turpentine
and a burning bitter taste. It contains a soft resin easily soluble in
alcohol, a hard resin insoluble in cold alcohol, volatile oil (xiv, 371),
bitter principle, sugar, lime, and potash-salts (Bonastre, J. Pharm. 12,
485; Repert. 26, 134).
Concerning the balsam of Terminalia vernix (Vernis de la Chine),
which contains benzoic acid, see Macaire-Princep (J. Pharm. 15, 525;
N. Tr. 21, 1, 107).
STEAROPTENE FROM OIL OF CASSIA.
395
دا
Stearoptene from Oil of Cassia.
ROCHLEDER & SCHWARZ. Wien. Akad. Ber. 5, 77; J. pr. Chem. 51,
432; Kopp's Jahresber. 1850, 509.— Wien. Akad. Ber. 12, 192; J.
pr. Chem. 63, 129; Pharm. Centr. 1854, 701; Kopp's Jahresber. 1854,
590.
The partly colourless, partly yellow crystalline masses deposited
from oil of cinnamon (xiii, 258) are obtained by recrystallisation from a
small quantity of alcohol, in colourless, inodorous, shining, brittle
prisms, which melt to a colourless, highly refractive oil when heated,
volatilise at a higher temperature, and solidify to a yellow lamellar
mass on cooling.
The crystals contain, on the average, 75.20 p. c. C., 6·83 H., and
17.97 0., from which numbers Rochleder deduced the formula C28H¹505,
and afterwards C56H290¹0. — They are converted by nitric acid into a
nitrogenous acid exhibiting the behaviour of nitrobenzoic acid, but con-
taining 45-48 p. c. C., and 3.95 H. (probably CH'XO). The stearop-
tene forms with ammonia a nitrogenous product, and with caustic
potash, when distilled therewith, a volatile oil containing 69.63 p. c. C.,
6.18 H., and 24.29 O., together with a little brown resin.
When the stearoptene is boiled with aqueous bisulphite of soda for
five minutes, it melts to an oil, colours the solution yellow, and dissolves
on cooling with the exception of admixed resin. The filtrate deposits
crystals of benzhydrolic acid, after the removal of which, the filtrate
yields benzhydrol; (a) on boiling the solution, as a floating oil which
afterwards solidifies; (b) on addition of dilute sulphuric acid.
Benzhydrolic acid, purified by dissolving it in lime-water and preci-
pitating with hydrochloric acid, forms colourless or yellowish crystal-
line flocks which lose water in a vacuum. Benzhydrol (differing from
Linnemann's benzhydrol, a product obtained by treating benzophenone
with sodium-amalgam), has the composition a and b [when obtained
according to a and b (above)]: when melted for several hours at 110°
and then cooled, it solidifies to a crystalline mass c. It assumes a yellow
to black colour in the air.
Analyses by Rochleder & Schwarz.
Benzhydrolic acid.
Benzhydrol.
Air-dried (a). In vacuo (b).
a.
b.
C.
C
71.28
72.84
74.63
75.66
72.57
H
6.23
6.25
6.45
6.45
6.34
****
O
22.49
20.91
18.92
17.89
21.09
100.00
100.00
100.00
100.00
100.00
Rochleder gives the following formula: for benzhydrolic acid a and benzhydrol
c, C42H2¹09; for the acid b, C12H22O10; for benzhydrol a and b, C42H2¹OS and
C28H1405.
When a solution of benzhydrolic acid in lime-water is neutralised
with nitric acid and precipitated with nitrate of silver, white flocks of a
silver-salt are obtained, containing 55.14 p. c. C., 4·58 H., 17·50 O., and
22.78 AgO. — Benzhydrol forms also with bisulphite of soda a compound
containing 20.13 p. c. soda and 32.42 p. c. carbon.
396 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
B. Resins free from Benzoic Acid.
1. ALOUCHI RESIN. From a tree growing in Madagascar. Dirty-
white externally, blackish and marbled within, opaque, solid, and
friable. Has a strongly aromatic odour, resembling pepper, and a
bitter taste. Contains volatile oil, a resin easily soluble in alcohol, a
second resin sparingly soluble in alcohol, free acid, ammonia-salt,
bitter extractive and impurities.
The sparingly soluble resin occurs to the extent of 20.45 p. c. in the
crude resin. To obtain it the resin is washed repeatedly with cold
alcohol, the residue is boiled with alcohol, and the solution filtered,
whereupon the sparingly soluble resin separates from the filtrate in
flocks. It forms very fine, light, pearly, radiated groups of needles,
harsh to the touch and phosphorescent. It melts when heated and
volatilises with resinous odour, subliming in small laminæ : if the heat
has been cautiously applied, the residue is not coloured. It is insoluble
in boiling caustic soda, slightly soluble in boiling alcohol, and more
casily in ether (Bonastre, J. Pharm. 9, 180; 10, 1). See also Vauquelin
(Ann. Chim. 72, 299).
From Dorema armeniacuт.
Yellowish-
2. GUM AMMONIACUM.
white, translucent pieces, friable in the cold, having a conchoïdal frac-
ture and a fatty lustre on the fractured surface. Has a repulsive odour,
and a slightly bitter and acrid taste. Its alcoholic solution reddens
litmus. It contains a brittle resin soluble in alkalis and alcohol, also
guin, bassorin, and a transparent light oil, besides woody fibre and
sand. It forms a milk with water. When submitted to dry distilla-
tion, it does not melt, and yields no umbelliferone (Sommer), but
according to Braconnot (Ann. Chim. 68, 69) ammoniacal products.-
With nitric acid of sp. gr. 1.2, it forms styphnic acid (xi, 228), but no
other acid (Böttger & Will). Nitric acid of sp. gr. 1·35 dissolves it after
boiling for a short time: the solution deposits a soft yellow resin when
mixed with water, and more when concentrated and again diluted,
whilst camphretic acid CHO remains in solution (Schwanert, Ann.
Pharm. 128, 123). Gum ammoniacum melted with caustic potash
yields protocatechuic acid and resorcin (xvii, 240) (Hlasiwetz & Barth).
Commercial gum ammoniacum increases but little in volume when
digested with cold alcohol of sp. gr. 0.83, but yields a pale-yellow
solution, which leaves on evaporation a clear, nearly colourless resin,
having the odour of the gum, and assuming a yellow colour, with par-
tial loss of odour at 100°. It is easily fusible, precipitable from the
alcoholic solution by neutral acetate of lead as a white precipitate, and
contains, on the average, 70.95 p. c. C., 7.59 H., and 21:46 O., corre-
sponding to the formula, CH250°. When heated to 131° it becomes
thicker and darker, without frothing or giving off visible vapours, and
then contains about 1 p. c. more of carbon (Johnston, Phil. Trans. 1840,
350.)
3. GUM ANIME. That obtained from the locust-tree Hymenea Courbaril
is yellow, translucent, of sp. gr. 1.028 to 1.03, and softens in the
mouth. It tastes like mastic, and emits a peculiar odour when warmed.
Its alcoholic solution reddens litmus. It does not yield umbelliferone
by dry distillation (Sommer). Contains volatile oil (xiv, 358), an easily
soluble and a difficultly soluble resin, the latter of which remains behind
RESIN FROM ARBOL-A-BREA.
397
on treating the gum with alcohol. It dissolves in warm aqueous am-
monia (Paoli, Brugn. Giorn. 16, 187 and 325; N. Tr. 9, 1, 40 and 61).
Cold alcohol takes up from gum anime, oil and an amorphous resin,
probably pinic acid: the residue, dissolved in boiling alcohol, deposits
on cooling, very delicate needles in the form of light flocks, containing
83.02 p. c. C., 11.50 H., and 5·48 O., corresponding to the formula
C40H390 (Laurent, Ann. Chim. Phys. 66, 314). Gum anime dissolves in
benzene (Mansfield) and partially in creosote (Reichenbach). Concern-
ing other varieties of anime, see Paoli, Manzini (J. Pharm. 27, 752),
Hancock (Ed. N. J. of Sc. 1, 240), Guibourt (Rév. scient. 16, 177).
4. Resin from Arbol-a-Brea.
MAUJEAN. J. Pharm. 9, 45.
BONASTRE. J. Pharm. 10, 199.
DUMAS. J. Chim. méd. 21, 309; J. Pharm. 21, 193; Ann. Pharm. 15,
160; J. pr. Chem. 4, 436.
BAUP. N. J. Pharm. 20, 321; Ann. Pharm. 80, 312; J. pr. Chem. 55,
83.
Obtained from incisions in a tree [probably Canarium album (Baup)]
growing in Manilla.—Soft, greyish-green, sticky resin, having a power-
ful odour of turpentine, cubebs, and fennel, and behaving towards
alcohol and volatile and fatty oils in the same manner as elemi
(Maujean).
According to Bonastre, it contains a light greenish-yellow volatile
oil, an easily soluble and a difficultly soluble resin, the latter of which
forms radiated groups of white shining crystals, containing, according
to Dumas, 85.3 p. c. C., 11.7 H., and 3.0 0.
On treating the resin with cold alcohol of 85 p. c. volatile oil, breïn,
bryoïdin, and breïdin are dissolved, whilst amyrin remains behind.
The solution is evaporated, whereby the volatile oil is driven off, and
the residue is treated with water and with alcohol of 50 p. c. in succes-
sion, which take up the bryoïdin and breïdin, but leave the breïn un-
dissolved. On evaporating the mixed solutions, the bryoïdin is obtained
in drops, which afterwards become solid, whilst the breïdin remains in
the mother-liquor.
a. Amyrin.—Purified by solution in boiling alcohol of 90 to 95 p. c.
and recrystallisation. Identical with Bonastre's difficultly soluble resin
and with the amyrin of elemi resin. Silky fibres, melting at 174°,
soluble in ether.
b. Brein. This body is purified by dissolving it in 85 p. c. alcohol
and evaporating the solution slowly, whereupon it crystallises in
transparent rhombic prisms of 110 and 70°, having two bevelling faces
inclined to one another at an angle of 80°. It melts at 187°, is
insoluble in water, but soluble in 70 parts of 85 p. c. alcohol at 20°,
and easily in ether.
c. Bryoïdin. Crystallises from hot water, and likewise from
aqueous alkalis or dilute acetic acid, in white silky fibres having a biting,
slightly bitter taste. It melts at 135°, and solidifies suddenly, on
398 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
cooling, to a nodular, fibrous mass. Volatilises below its melting-point
without leaving a residue. Neutral. Dissolves in 350 parts of water
at 10°, and in a smaller quantity of hot water: the solutions are pre-
cipitated by neutral acetate of lead and more abundantly by the
basic acetic. Dissolves easily in alcohol, ether, oil of turpentine, and
fat oils.
d. Breidin. Transparent rhombic prisms of 102° and 78°, with
four-sided summits. Becomes opaque when warmed, melts a little
above 100°, and sublimes without residue. Dissolves in 260 parts of
water at 10°, and more easily in hot water. Soluble in alcohol, and
less freely in ether (Baup).
5. Asafoetida.
TROMMSDORFF. N. Tr. 1, 2, 137.
PELLETIER. Bull. Pharm. 3, 556.
BRANDES. Repert. 7, 1.
ANGELINI. Brugn. Gion. 19, 174; Kastn. Arch. 9, 101.
ZEISE. Schw. 46, 324,
REIGEL, Jahrb. pr. Pharm. 4, 348.
REINSCH. Jahrb. pr. Pharm. 12, 362.
JOHNSTON. Phil. Trans. 1840, 354.
STENHOUSE. Phil. Mag. 20, 575; Mem. Chem. Soc. 1, 43; J. pr. Chem.
27, 255; Ann. Pharm. 44, 309.
IILASIWETZ. Ann. Pharm. 71, 23,
Stinkasant. Devil's dung. Teufelsdreck. From Ferula Asafætida
(IIandbuch, viii [2], 45) and other species. White masses turning
rose-red, violet, and brown in the air; friable in the cold, tough when
warmed, having a fetid odour of garlic, and an acrid bitter taste.
Asafoetida contains volatile oil, gum (according to Brandes and
Pelletier, also bassorin), a resin soluble in alcohol and ether, and a
second resin insoluble in ether (Brandes). Asafoetida frequently exhi-
bits needles of gypsum when broken (Riegel). Its alcoholic extract
submitted to dry distillation yields a colourless oil, then acid water,
a green, and lastly, a blue oil having an odour of creosote, together
with umbelliferone. When asafoetida is digested with oil of vitriol of
sp. gr. 1·75, the resulting black-red pulp boiled with water, and
the extract neutralised with carbonate of lime, the filtrate likewise
contains umbelliferone (Sommer). With nitric acid of sp. gr. 1·2
asafoetida forms styphnic acid (xi, 228) (Böttger & Will). - Asafoetida.
treated with caustic potash and then with acid, evolves hydrosulphuric
acid; when treated with nitric acid, it also yields sulphuric acid, and
the sulphuretted oil contained in it (Zeise). When distilled with an
equal quantity of hydrate of lime and a little water, it yields a colour-
less oil, having a burning taste and an odour different from that of
asafoetida. The residue contains resins in combination with lime
(Reinsch). When asafoetida is melted with caustic potash, an acid is
formed resembling that produced by the similar treatment of guaiacum
(Hlasiwetz & Barth).
Commercial asafoetida increases but little in bulk when digested
with cold alcohol of sp. gr. 0·83: the pale-yellow solution formed
RESINS (ASAFŒTIDA).
399
leaves on evaporation a pale-yellow resin, which quickly assumes a
purple colour in sunshine. It dissolves easily in cold alcohol and
ether, and produces with alcoholic neutral acetate of lead, a dense
white precipitate, and according to Johnston, does not yield sulphuric
acid when decomposed by nitric acid, or when deflagrated with chlorate
of potash and chloride of sodium. When heated above 100° it froths
up for a while, giving off a powerful odour of garlic, after which it
flows tranquilly, and after cooling is darker, less odorous, and brittle,
but still perfectly soluble in alcohol. It contains, at 100°, on the
average, 68.65 p. c. C., 7·56 H., and 23.79 O.; and after melting till it
becomes inodorous, 70-18 p. c. C., 7·63 H., and 22.21 0.- When the
alcoholic tincture of asafoetida is poured into a large quantity of boiling
water and boiled (whereby volatile oil is driven off), and the yellow
powder which is deposited on cooling is again dissolved in alcohol,
evaporated, and dried at 100°, the residue contains 70-44 p. c. C., 7·68
H., and 21.88 0. (Johnston). Johnston appears to have overlooked the sulphur
here (Kr.).
When an alcoholic tincture of asafoetida is freed from volatile oil
by distillation, and the residue is precipitated by water, the resin is
obtained as a yellowish-white, nearly inodorous precipitate, which
rapidly turns rose-red in the air. It dissolves in oil of vitriol with
green colour, and is precipitated from the solution in rose-red flocks
by water. On dry distillation, the resin first froths up and gives off
water, hydrosulphuric acid, and asafoetida oil, and then boils quietly,
yielding aromatic oils of a green, blue, violet, and red colour. These
oils, when shaken with caustic potash, colour it yellow, and be-
come turbid. The violet portion of the oils becomes deep-red on ex-
posure to the air. The yellow alkaline solution distilled with sulphuric
acid evolves hydrosulphuric acid, and yields an acid distillate, which is
turbid from the presence of heavy oily drops: the distillate contains
formic acid and a trace of acetic acid, and after neutralisation with
carbonate of soda, reduces nitrate of silver (Hlasiwetz).
The volatile oil of asafœtida, when gradually heated to redness with
potassium, yields a mixture of carbon and sulphide of potassium (Zeise).
It is free from nitrogen (Will; Stenhouse). When obtained by dis-
tilling the powdered resin with powdered glass and water, it is of a
yellowish colour, of sp. gr. 0.943 at 15.5°, tastes mild, and afterwards
acrid, and resinises in the air. After being twice rectified, it begins to
boil at 163°, the boiling-point rising to 188°. The oil dissolves iodine
easily, without explosion. It does not combine with ammonia, and is
but little affected by aqueous or alcoholic potash. Nitric acid resinises
it, with abundant evolution of nitric oxide and formation of sulphuric
acid. Oil of vitriol turns it red, and carbonises it when heated. The
oil precipitates salts of lead, mercurous oxide, and silver black, solution
of sublimate white, and when dropped into melted caustic potash, gives
up a portion, but not the whole, of its sulphur (Stenhouse).
Analyses by Stenhouse.
Oil at 163°.
at 172°.
Distillate.
at 188°.
Ċ ......
H...
65.97
62.57
58.23
9.73
9.25
9.10
S
22.74
20.06
16.31
O........
1.56
8.12
16.36
100.00
100'00
100.00
400
APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
1
3 2
When asafoetida is distilled with water in a flask placed in a bath
of chloride of sodium, volatile oil amounting to nd of the asafoetida
is obtained, a part of which is dissolved, together with valerianic and
propionic acids, in the water which passes over at the same time. If
a copper vessel be employed, the sides become coated with sulphide of
copper. The oil is pale-yellow, limpid, and neutral, has à pene-
trating odour of asafoetida, and a mild, afterwards harsh taste. It
does not redden the skin, does not solidify in a freezing mixture, and
boils at 130° to 140°, with evolution of hydrosulphuric acid. It is a
mixture, in varying proportions, of two sulphuretted oils free from
oxygen, probably CIIS and C2H10S2 (Hlasiwetz).
Calculation.
12 C
72
72.73
12 C
72
63.16
11 H
11
11.11
10 H ......
10
8.77
S
16
16.16
2 S
32
28.07
CHUS
99
100.00
C12H10S2.......
114
100.00
Analyses.
a.
b.
C.
d.
C
H
67.13
65.24
65.46
69.27
10.48
9.55
9.09
10.42
S....
22.37
25.37
25.43
20.17
99.98
100.16
99.98
99.86
a and b were distilled from copper vessels; c from a glass flask; d was evaporated
at 120-130°, without boiling the liquid. Gmelin regarded as probable the formulæ
C10H882 (60 p. c. C., 8 H., and 32 S.) and C¹ºH'S (70·59 p. c. C., 10.59 H., and 18.82 S.)
The oil evolves hydrosulphuric acid on standing, and when kept in
vessels containing air, acquires a different odour, and becomes slightly
acid. Strong nitric acid acts violently upon it, even causing inflam-
mation when cautiously oxidised, the oil yields acetic, propionic, and
a large quantity of oxalic acid.When heated with chromic acid, it
yields acetopropionic and probably also formic acid.
:
Many desulphuretting agents, when brought in contact with asafoetida
oil, form metallic sulphides, and separate an oil which is richer in
sulphur than the original oil (probably CHS), volatile acids being
produced at the same time: a. On shaking the crude oil with caustic
potash saturated with oxide of lead so long as sulphide of lead is
formed, rectifying the remaining portion, and drying it over chloride of
calcium, the product is but slightly coloured, and has an odour of
lavender and rosemary. —b. A similar oil is obtained by digesting the
crude oil with hydrated oxide of lead. c. On passing sulphurous
acid gas for some time through the crude oil mixed with water, a
dingy-coloured resin is deposited: the decanted oil, when washed with
d. By
carbonate of soda and water, and rectified, resembles a and b.
passing the vapour of the crude oil over heated soda-lime, or by
dropping the oil on soda-lime at 200°, 1th of the oil distils as a clear
liquid, which has an odour of lavender, and gives up a little hydrosul-
phuric acid to caustic potash. In this reaction, propio-valerianic and
acetic acids are produced. e. Solution of caustic soda and hydrate of
soda heated to 120°, produce formic acid and a little acetic acid, but
no propionic or valerianic acid. With hydrate of soda the oil swells
RESINS (ASAFŒTIDA).
401
up to a green-brown, thick mass, which dissolves in water when heated
therewith for an hour and a half, giving off an odour of lavender.
f. With excess of silver-oxide, a black mixture containing sulphide of
silver and metallic silver is obtained, from which an oil having the
composition of the oil employed is expelled by heat, together with a
little hydrosulphuric acid. Oxide of silver, therefore, oxidises one part
of the oil, leaving the other part unaltered.
a.-d. according to Hlasiwetz.
a.
b.
48 C ........ 288.... 6050.... 60·16 .... 60·76 ...
44 H
9 S
C.
60·49 ....
d.
e.
f.
44
144
9.25
30.25
9.43
29.85
....
9.52 ..
....
9.36
31.08
60.52.... 76.89 ....
10.13
65 66
....
29.77
11·36 ....
11.62
10·14
24.81
....
....
1448
C48H4S9.... 476 .... 100·00 .... 99'44 ....
....
100·93 .... 100·42 .... 99·87 .... 100·61
The oil C10H9S, therefore, is oxidised, whilst C10HSS remains (Gmelin).
Asafoetida oil, treated with hydrochloric acid gas, acquires a red,
violet, and black colour, and becomes thick. Chlorine acts in a similar
manner, hydrochloric acid and chloride of sulphur being evolved, and a
black stinking tar remaining. With monosulphide of potassium at
150°, and with the pentasulphide at 185°, a turbulent evolution of
hydrosulphuric acid takes place, the oil becoming darker and passing
over undecomposed in very small quantity only.
Potassium pro-
duces a copious evolution of gas, becoming covered with sulphide,
and decomposes the whole of the oil, with the exception of a small
portion still containing sulphur. The sulphide of potassium produced,
when treated with an acid, evolves a powerful odour of cinnamon after
the greater part of the hydrosulphuric acid is given off. Oil of
asafoetida, heated in ammonia-gas, yields an abundant sublimate of
sulphide of ammonium. The oil is scarcely altered by sulphocyanide
of potassium in a sealed tube at 160-200°, and does not form oil of
mustard.
Oil of asafoetida is moderately soluble in water.
Mercury-compound. The white flocks which are produced on
mixing strong alcoholic solutions of the crude oil and of mercuric
chloride acquire a grey colour when allowed to stand under the liquid,
from admixture with sulphide of mercury. If it be collected at once
and boiled with alcohol, a small portion dissolves and crystallises from
the filtrate in delicate white needles, the greater part remaining behind
as a grey-white powder, which turns black with caustic potash, and
contains only 1-72 p. c. of carbon, but behaves towards sulphocyanide
of potassium in the same manner as the crystals. After drying, the
crystals are insoluble in water, very slightly soluble in alcohol, and
soluble in nitric acid only after addition of a drop of hydrochloric acid.
They turn yellow with caustic potash, and give off an odour of oil of
mustard when triturated with sulphocyanide of potassium: when
heated with the latter reagent, they yield drops of oil of mustard,
which forms, with ammonia, crystals of thiosinnamine, a large quan-
tity of the oil, however, remaining fluid. The crystals contain
14-03 p. c. C., 2.39 II., 61.19 Hg., 10-93 Cl., besides sulphur, and ac-
cording to Hlasiwetz, are represented by the formula C¹H¹S2,5 HgS
+ C¹²¹ºS²,HgCl.
Platinum-compound.a. Alcoholic solution of bichloride of pla-
VOL. XVII.
2 D
402 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARbon.
tinum mixed with alcoholic oil of asafoetida throws down, first a pale-
yellow precipitate, which increases in bulk and becomes darker and at
last red-brown, from admixture of sulphide of platinum. - b. On
heating the mixed solutions containing excess of platinum, to boiling,
and filtering, there remains on the filter a dark-brown powder (b): the
filtrate deposits on cooling pale-yellow flocks (c), which are insoluble in
water, dilute acids, and alcohol.
Hlasiwetz.
b.
Calculation according to Gmelin.
A.
e.
20 C
120
25.66
18.83
17.31
24.90
***
....
18 II
18
3.85
3.19
2 Pt
198
42.35
47.48
3:03
52.11
3.87
44.17
6 S
96
20.54
17.53
18.87
20.26
....
....
Cl
35.5
7.60
13.54
100.00
100.57
C20H18S+,PtS2 PtCl.... 467.5
No calculation is possible for a and b, on account of the admixture of sulphide of
platinum.
Oil of asafoetida dissolves very easily in alcohol and ether (Hlasi-
wetz).
6. BDELLIUM. From various species of Balsamodendron (Perottet,
N. J. Pharm. 1, 408; Richard, Ann. Pharm. 7, 321; Handbuch, viii
[2], 19). Reddish-brown and yellow, flexible, softening between the
teeth. Has a bitter taste, and an odour of myrrh. Sticks to the
fingers (Bley & Diesel). Contains 59 p. c. of resin, gum, bassorin, and
heavy volatile oil. When subjected to dry distillation, it yields a
stinking oil and acetate of ammonia (Pelletier, Bull. Pharm. 4, 52).
Bdellium turns
The aqueous extract does not precipitate lead-salts.
soft, white, and opaque in nitric acid (Bley & Diesel, N. Br. Arch. 43,
304).
The resin of bdellium is transparent, and melts at 55° to 60°. It
becomes white and opaque by boiling with water (Pelletier).
On digesting bdellium with cold alcohol of sp. gr. 0.83, evaporating
the pale-yellow tincture, and boiling the residue repeatedly with
water (which thereby acquires a yellowish colour), and drying it at
82° to 93°, it appears as a yellow transparent mass, softening at 100°,
and
with faint resinous odour. It contains 75.50 p. c. C., 9.87 H.,
13·80 to 14·63 0. (Johnston, Phil. Trans. 1840, 368).
9
7. Betulin or Birch-camphor.
LOWITZ.
Crell. Ann. 1788, 2, 312.
JOHN. Dessen Chem. Schriften. 5, 93.
OWEN MASON. Sill. Amer. J. 20, 282; Berz. Jahresber. 12,
IIÜNEFELD. J. pr. Chem. 7, 53.
242.
HESS. Ann. Pharm. 29, 135; J. pr. Chem. 16, 161; Pogg. 46, 312.
Occurs in the outer bark of the birch tree, from which it is expelled
in woolly flocks when birch-wood is heated over a clear fire till the
bark becomes dry and brown. John obtained it also in small quantity
by distilling the outer bark with dilute sulphuric acid.
BETULORETIC ACID.
403
Preparation. Dried and comminuted birch-bark is exhausted with
boiling water. It is then dried, and the betulin is extracted with
boiling alcohol. The tincture on cooling deposits the betulin, which is
collected, pressed, allowed to dry perfectly, and crystallised repeatedly
from ether (Hess). Mason adopts a similar process. Hünefeld boils
the bark with the strongest alcohol, distils the alcohol completely from
the tincture, collects the residual yellowish-white betulin on a strainer,
then presses, dries, and dissolves it in ether-alcohol. He then adds to
the solution, first levigated neutral acetate of lead, which produces a
yellowish precipitate, then animal charcoal; digests; filters the liquid;
and throws down the lead from the filtrate by means of strong aqueous
carbonate of ammonia. The liquid, again filtered and mixed with
water, deposits the betulin, which is purified from small quantities of
resin by again precipitating its solution in ether-alcohol with not too
great an excess of water. The bark when thus treated yields 10 to
12 p. c. of betulin (Hünefeld).
When the red-brown bark of Betula alba is exhausted with ether,
the ethereal solution evaporated, and the amorphous yellow residue
repeatedly boiled with water, there remains a brittle, yellowish-white,
granular mass, which dissolves easily in ether, with difficulty in alcohol,
and is insoluble in alkalis. It is inodorous and tasteless, melts
slowly to a yellow oil, burns with an aromatic odour, and contains
80.00 p. c. C., 10.24 H., and 9.76 0. (Stähelin & Hofstetter, Ann.
Pharm. 51. 79).
Properties. Very light white flocks, or crystalline nodules. Melts
at about 200° (Hess), at 235° (Mason) to a colourless, transparent
mass, with an odour like that of the heated bark. It sublimes in a
current of air (Hess; Mason).
Betulin contains, on the average, 80.37 p. c. C., 10.98 H., and
8.65 0., from which numbers Hess calculates the formula C40H³³0³,
Limpricht (Lehrbuch, 1037), the formula C4H3204. The formula
CH¹Ò¹ or C¹8H30* (calc. 80.9 p. c. C., 10.2 H.) agrees better with the
analysis (Kr.). See also Heldt (Ann. Pharm. 63, 65).
Decompositions. Betulin volatilises on glowing charcoal in agreeably
smelling vapours, and yields by dry distillation, first a white sublimate,
then colourless water, a very viscid oil, resin, and charcoal. It burns
in a candle with white flame. - It dissolves rapidly but quietly in oil
of vitriol, forming a solution which solidifies and turns white with
water (Lowitz).
Betulin is insoluble in water. It does not combine either with
alkalis (Lowitz; Hess) or with acids. According to Mason, it dissolves.
in aqueous alkalis, from which it is precipitated by acids.
It dissolves in 120 parts of cold, and 80 parts of hot alcohol, from
which one-third is deposited on cooling (Lowitz). It is soluble in
ether (Mason), and easily in acetate of ethyl, oil of turpentine, and almond
oil (Lowitz).
Betuloretic Acid.
C. KÖSSMANN. N. J. Pharm. 26, 197; abstr. Kopp's Jahresber. 1854,
613.
2 D 2
404 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
Occurs as a white resinous meal covering the young shoots of the
birch-tree, as well as the upper side of the young leaves, and is
obtained therefrom by scraping. It is purified by dissolving it in
boiling alcohol, evaporating the solution, exhausting the residue with
ether, which leaves a black mass undissolved, evaporating the ethereal
solution, dissolving the residue in carbonate of soda, and precipitating
with an acid.
White flocks, or white friable mass, softening in the mouth, and
melting perfectly at 94°. In alcoholic solution it is very bitter, and
has an acid reaction. The soda-salt acts as a purgative. — It contains,
at 100°, 74-43 p. c. C., 11:53 H., and 14.04 O., corresponding to the
formula C72H66010 (by calc. 74.57 C., 11.42 H. (Kössmann).
Betuloretic acid is coloured a fine red by oil of vitriol, and forms a
solution of the same colour: it does not form sugar even on prolonged
digestion. When boiled with excess of nitric acid, it yields nitric
oxide and picric acid.
The acid is insoluble in water. It dissolves in aqueous ammonia
and potash, and expels carbonic acid from alkaline carbonates. The
precipitates obtained by double decomposition with metallic salts are
insoluble.
Soda-salt. Straw-yellow resin, soluble in water and alcohol. The
aqueous solution is very bitter, and froths strongly.
Lead-salt. White curdy precipitate, drying up to a yellow
powder. It is decomposed by boiling with alcohol, a basic salt being
formed.
Silver-salt. Thrown down from the soda-salt in white flocks by
nitrate of silver. It contains, at 100°, 16.56 p. c. AgO. (calc. for
C72H65 Ago¹º requires 16.97 p. c. AgO).
Morphine-salt. The soda-salt precipitates acetate of morphine in
the cold, and the hydrochlorate on boiling only. The latter precipitate
is converted, on washing, into needles, from which sulphuric acid
separates betuloretic acid.
Quinine-salt. The soda-salt forms with sulphate of quinine a
white precipitate, which is purified by dissolving it in boiling alcohol
and evaporating the solution at 40°. It forms an amorphous mass,
soluble in alcohol and ether, and decomposible by dilute sulphuric acid,
with separation of betuloretic acid.
The acid dissolves in alcohol and ether.
Concerning Gummi Caja see Peckolt (N. Br. Arch. 110, 44).
8. Caranna. From Amyris Caranna, Bursera gummifera, or B.
acuminata. Dark-brown and green-brown, translucent at the edges;
at first tough, afterwards hard and brittle. Sp. gr. 1124. It is
easily fusible; has a faint odour of gum ammoniacum in the cold, and
an agreeable balsamic odour when heated; tastes bitter and resinous.
By distillation it yields a red, agreeably smelling oil. It contains
96 p. c. of a resin easily soluble in alcohol, ether, and potash. When
submitted to dry distillation, it yields a pomegranate-yellow empyreu-
matic oil (Pelletier, Bull. Pharm. 4, 241).
9. Resin of Ceradia furcata. Imported from Africa. - Amber-
COPAL.
405
yellow; smells like elemi. Sp. gr. 1.197. It dissolves in alcohol,
forming a slightly acid solution, which is precipitated by water, but
not by ammonia or nitrate of silver. - At 100° it emits a peculiar
odour, softens, loses 10.6 p. c. in weight in a few days, and then con-
tains 80.11 p. c. C., 9.79 H., and 10.00 O. (= Č402804) (Robert
Thomson, Phil. Mag. 28, 422).
10. Resin of Ceroxylon Andicola. The Cera de Palma occurring in
small yellowish-white pieces, obtained by boiling the shavings of the
stem with water, contains a peculiar wax and a crystalline resiu, separ-
able by dissolving them in a large quantity of boiling alcohol, which
deposits the wax first on cooling. The white resin which crystallises
from the mother-liquor melts only above 100°, solidifying on cooling
to a fissured amber-like mass, which dissolves slightly in cold, and
easily in hot alcohol, also in ether and volatile oils. It contains
81.8 p. c. C., 11.5 H., and 5.1 O., corresponding to the formula
C40H2O2 (Boussingault, Ann. Chim. 29, 330; 59, 19).
11. Copal.
BERZELIUS. Pogg. 10, 254; Lehrb. 3 ed. 7, 53.
UNVERDORBEN. Schw. 59, 460.
FILHOL. N. J. Pharm. 1, 301 and 507; abstr. Ann. Pharm. 44, 323.
A. VOGEL, JUN. N. Jahrb. Pharm. 7, 370; Kopp's Jahresber. 1857,
484.
SCHILLER. Ann. Pharm. 113, 338; Zeitschr. Ch. Pharm. 3, 126; Chem.
Centr. 1860, 414; Kopp's Jahresber. 1859, 515.
The Brazilian and West Indian copal is obtained from Hymenea
Courbaril, the African and East Indian from Hymenea verrucosa, or from
Elaeocarpus copaliferus, the North American from Rhus copallina.
Copal occurs as a hard and as a soft resin, exhibiting, according to
Werlé (Pharm. Viertelj. 14, 86), the following varieties:-
A. Hard kinds. 1. Copal from Zanguebar. The so-called East
Indian, Bombay, or Salem copal of commerce. It is dug up from the
earth in Eastern Africa, and transported across Zanguebar. In the
crude state it usually occurs in dull flat pieces, from the size of a bean
to that of the hand, covered with sand and earth. After proper wash-
ing, it forms colourless or brownish-red, clear and transparent pieces,
having elevations of the size of pins' heads on the surface. It has a
partly dull, partly glassy fracture, splinters when cut, and is suscepti-
ble of being ground and polished. It is nearly as hard as amber.
2. Copal from Sierra Leone. Either perfectly clear globules or
drops, seldom larger than a nut (glass copal), or flat, conchoïdal,
colourless, glassy pieces, often covered with earth, and having vegeta-
ble remains imbedded in them. Nearly as hard as 1.
3. Copal from Benguela.- Clear, pale-yellow, seldom colourless
pieces, of all sizes and thicknesses, generally conchoïdal, and never
globular or disc-shaped. Has a glassy fracture. In the crude state it
is covered with a whitish-yellow crust of lime.
406 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
4. Copal from Angola. -Regular, reddish golden-yellow pieces,
generally globular in form, having warts on the surface larger than in
the first variety. Much softer than 1, and covered, in the rough state,
with a thick red crust.
B. Soft kinds. 5. West Indian or Ball copal. Mostly from the
west coast of Africa, more rarely from the West Indies, Brazil, and
Central America. Tears and conglomerated pieces from the size of a
bean to that of the fist, generally covered with a film of lime. Milky,
or oftener clear and colourless. Very soft, so that when rubbed on
wool, it wears off and becomes sticky. More easily fusible than the
previous kinds. Occurs in commerce in several varieties.
6. Kaurie copal. From New Zealand. In masses weighing as
much as 100 pounds, with grey calcareous crust, opaque within; in
thin splinters, transparent with grey or brown colour. Harder than 5 ;
easily fusible.
7. Manilla copal. From living plants. A hard and a soft variety
occur in commerce. The hard variety resembles 6, but is darker, of a
yellow to brown colour, harder and less easily fusible. The soft
variety forms conglomerated masses of tears or blocks, frequently
mixed with vegetable remains and earth, of a dirty to pure yellow
colour, pulverisable between the fingers in small pieces. It dissolves
in alcohol before melting.
On the varieties of copal see further Martius (Repert. 26, 295); Schindler (J. pr.
Chem. 4, 149); Giseke (Ñ. Br. Arch. 18, 180); Perottet (N. J. Pharm. 1, 406);
Guibourt (Rev. Scient. 16, 177); Batka (N. Tr. 23, 2, 83).
Sp. gr. 1.069 (Thomson), 1.045 to 1.139 (Boisson). Tasteless ;
emits a faint odour when rubbed.
Calcutta.
Filhol.
Bombay.
Schibler.
C .......
80.66
79.7
Madagascar.
79.80
Manilla.
Africa.
H..
10.57
9.9
10.78
79.35
10.27
79.62
$9 19
10.32
O....
8.77
10.4
9.42
10.38
10.06
100.00
100.0
100'00
100.00
100.00
....
Filhol dried his copal at 100° in a current of hydrogen.
Copal absorbs oxygen rapidly from the air, and afterwards contains
a smaller per-centage of carbon, and is more soluble in alcohol, ether,
and oil of turpentine than before. Pulverised Calcutta copal con-
taining 80.4 p. c. of carbon, after being heated to 100° for three days
in a current of air, contains 76.54 p. c. of carbon; the powder, after
keeping for a mouth, is almost entirely soluble in alcohol, and then
contains 73 p. c. of carbon. Durozier's soluble copal is a product of
this kind, obtained by triturating hard Indian copal with water, and
preserving it in contact with air; it contains 71.38 p. c. C., 9.23 H.,
and 19.47 0., is perfectly soluble in alcohol, ether, and oil of turpen-
tine, but still consists of a mixture of several resins (Filhol). — Copal
melts when heated, evolving an aromatic odour, and giving off water
and a little volatile oil, after which it does not undergo much alteration,
a small quantity only of a resin soluble in potash and oil of turpentine,
and insoluble in alcohol. being produced (Unverdorben). IIard copal
COPAL.
407
melts at 340', that of medium hardness at 180° (Violette). When
more strongly heated it froths up for a while, giving off an oil (A), and
afterwards flows quietly; it still, however, contains a large quantity of
undecomposed copal (Unverdorben), and is not yet soluble in cold or
hot oil of turpentine, in which it dissolves only when 20 to 25 p. c. has
been distilled off at a temperature of 360°. Turpentine which has
become thickened by exposure to air and light, however, dissolves
copal which has lost 10 p. c. by distillation (Violette, Repert. Chim.
appl. 1862, 329; Chem. Centr. 1863, 639). —Copal which has been
heated till it has become soluble in oil of turpentine consists of (1)
unchanged alpha- and beta-resin; (2) a small quantity of a resin re-
sembling beta-resin, easily soluble in ether and oil of turpentine, but
soluble only in 50 parts of boiling alcohol, and deposited from the
latter solution, on cooling, in the form of a tarry alcoholate; (3) two
newly-formed resins, one of which resembles the delta-resin, but is
soluble in oil of turpentine, whilst the other dissolves also in aqueous
ammonia, and in absolute and 80 p. c. alcohol, ether, and fatty oils.
If the melted copal be distilled till only 8 p. c. remains, the oil B passes
over, the residue consisting of a mixture of various resins (Unver-
dorben). The two oils of copal, A and B, contain: A. Easily volatile
and difficultly volatile oil, acetic acid, empyreumatic acid (Brandsäure),
and a large quantity of resin soluble in alcohol and potash.
B. Easily and difficultly volatile oil, acetic acid, and two resins, one of
which is soluble in ether and alcohol, the other (the Brandsäure of
Unverdorben) being white, oily, of penetrating empyreumatic odour,
acid, and precipitable from its alkaline solution by excess of caustic
potash, and from the alcoholic solution by acetate of copper, the latter
precipitate dissolving in ether (Unverdorben).
16
The oil obtained by the distillation of Manilla copal on the large
scale is dark-brown; that distilled from African copal at a higher
temperature in copper vessels is coloured green by the copper. When
the oil is rectified, a black pitch remains behind; the distillate, shaken
with caustic potash (which takes up copallic acid), subjected to frac-
tional distillation, and set aside for a month with pieces of caustic
potash in the separate portions, is resolved into three products: a, a
hydrocarbon of the formula C20H¹6 and sp. gr. 0.951 at 10°; b, a por-
tion distilling at 165° to 215°, and containing 84-53 p. c. C., 11-32 H.,
and 4.15 0.; and c, a thick yellow oil boiling at 215° to 260°, and con-
taining, on the average, 74.18 p. c. C., 10.23 H., and 15.59 0. Besides
these the distillate contains an acid which is removed by shaking with
water (Schibler's copalic acid), and, when combined with oxide of lead
and again separated by means of hydrosulphuric acid, dries up to a
red-brown mass containing needles. The baryta-salt forms a reddish-
brown syrup (Schibler).
No hydrosulphuric acid (Baudrimont) or umbelliferone (Sommer) is
obtained by the dry distillation of copal.
Oil of vitriol dissolves copal, forming Hatchett's artificial tannin :
nitric acid also dissolves and decomposes it.
Copal is not dissolved by trituration with water, but its oxidation is
promoted thereby (Filhol). When it is distilled with water, a very
small quantity only of a volatile oil having a smell of copal is obtained
(Unverdorben).Copal is not soluble in liquid carbonic acid (Gore),
and only partially soluble, with evident alteration, in bisulphide of carbon
(Lampadius).
408 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
Powdered copal, moistened with aqueous ammonia, and set aside
in a closed vessel in a warm place, swells up to a clear jelly, which
yields with a little water, a turbid, viscid, slimy mass, and with a large
quantity a milky liquid. On evaporation there remains, first a white tough
elastic mass, and on further drying at 40° to 60°, a yellowish fused
mass, which remains soft at this temperature for some weeks, but is
hard and brittle in the cold, and dissolves very slightly in boiling
alcohol. On the other hand, the jelly produced by ammonia mixes
directly with alcohol to a clear liquid, with the exception of the not
sufficiently swelled copal, which remains behind and cannot be dissolved
by a larger quantity of ammonia. The alcoholic solution of the jelly
leaves on evaporation a white earthy pellicle, which softens to a trans-
parent varnish at 40°. From the solution of copal in aqueous potash
sal-ammoniac throws down white flocks, which do not dissolve in boil-
ing alcohol, even on addition of ammonia (Berzelius).
East Indian copal moistened with ammonia and set aside, accord-
ing to the method of Berzelius, remains pulverulent for several days,
but swells up, on addition of hot alcohol, to a translucent jelly, which
yields a clear filtrate when thrown on a filter, but does not itself dissolve
(Filhol).
Copal dissolves in hot caustic potash (Hatchett) emitting an aro-
matic odour, but being first converted into a clear ropy mass. The
clear yellowish solution becomes turbid and white on cooling and after-
wards curdles, with separation of a little yellowish liquid, which con-
tains one resin, whilst the jelly contains another resin in combination
with potash. If the resin be separated from the jelly by means of an
acid, white flocks are obtained, which do not cohere on heating the
liquid to 40°: the yellowish liquid yields with acids a resin which
cakes together in the cold (Berzelius). East Indian copal does not
dissolve in cold caustic potash, and floats on the boiling liquid as a
spongy curdled mass, which does not dissolve for some hours: from
the alkaline liquid acids throw down only a few flocks, whether weak
or strong caustic potash has been employed (Filhol). - Copal powder
moistened with alcoholic potash assumes a dark-red colour in the air
(Filhol). — Copal boiled with aqueous carbonate of potash softens with-
out dissolving (Berzelius).
The solution of copal-potash precipitates the salts of the earths and
alkaline earths: the precipitates are white or yellowish, hard and
earthy after drying. The salts of the heavy metals are likewise pre-
cipitated (Berzelius).
Copal dissolves freely in chloroform (Cloëz). It dissolves but
slightly in absolute alcohol, and is nearly insoluble in weaker spirit:
according to some authorities, it dissolves more freely when lumps of the
copal are suspended in alcohol-vapour, or when camphor is added to the
alcohol, a statement which was not confirmed for all kinds of copal by the
experiments of Berzelius. Copal swells up to a tough elastic body in
boiling absolute alcohol. According to Unverdorben, copal dissolves
completely when digested with 1 parts of alcohol for 24 hours, the
solution first formed acting as a solvent of the portion insoluble in alcohol
alone. According to Filhol, East Indian copal does not dissolve in
this way.
Copal powder swells up in ether to a bulky jelly, which, according
to Bonastre and Filhol, dissolves slightly, but according to Pfaff and
Berzelius, completely, in excess of ether When ether containing gela-
COPAL.
409
tinous copal is heated to boiling and shaken with a small quantity of
warm alcohol, a transparent liquid is obtained, which may be diluted
at pleasure, whilst a large quantity of cold alcohol added at once
causes the solution to curdle (Berzelius). Ether containing iodine
dissolves copal completely after some time (Vogel).- Powdered copal
heated till it begins to melt, dissolves in about 2.8 parts of anhydrous
acetone, forming a solution from which a part may be distilled, leaving
a syrupy liquid: on complete evaporation a brittle varnish remains
(Wiederhold, Polyt. Notizbl. 19, 214).- Valerianic acid, fusel oil, valerianic
aldehyde, and valerate of amyl cause East Indian copal to swell up to a
translucent mass (Trautwein). With a little carbolic acid, copal deli-
quiesces at 18° to an elastic varnish, which dissolves almost completely
in a larger quantity of the acid, forming a solution which mixes with
warm alcohol (Runge, Pogg. 32, 322).
Copal dissolves slowly in benzene, better when it is suspended in the
vapour of the boiling liquid, the solution then running off in drops of
colourless varnish (Mansfield). Rock oil dissolves scarcely 1 p. c. of
copal (Saussure). Oil of turpentine acts in a similar manner, but dis-
solves a larger quantity when it is made to act in the state of vapour,
or when it is heated above its boiling-point with the copal in closed
vessels, or when aqueous ammonia is added; the last process, how-
ever, yields a varnish which dries with difficulty. - Volatile oils cause
copal to swell, and dissolve a portion, but never the whole (Filhol).
Cold oil of cajeput dissolves copal; the solution leaves a shining varnish
on evaporation (Draper, Chem. News, 1862, 184; Palm, Pharm. Viertelj.
11, 555). The oil obtained by the dry distillation of copal dissolves
soft and semi-hard copal (Violette).
Copal dissolves in the mixture of oleic and stearic acids separated
from soap by acids (Hausmann, Ann. Chim. 18, 185). It appears to
dissolve in fatty oils, such as linseed oil, only after it has been melted
till it no longer evolves acid aromatic vapours. It dissolves in castor
oil to a yellow liquid, which mixes with hot alcohol, and deposits a part
of the copal on cooling: the mixture with ether also deposits copal
after some time (Stickel, J. pr. Chem. 9, 166). On the preparation of
copal-varnish see Giseke (N. Br. Arch. 18, 186), Böttger (J. pr. Chem.
12, 253).
Separation of the Resins of Copal. A. According to Unverdorben.
Powdered African copal is exhausted with the following liquids in
succession: 1. Alcohol of 67 p. c.; 2. absolute alcohol; 3. boiling
alcohol of 77 p. c., with the addition of half the weight of the residue
of caustic potash; 4. alcohol of 25 p. c.
1. The solution in 67 p. c. alcohol contains alpha- and beta-resin.
It is precipitated by alcoholic acetate of copper, and the precipitate is
treated with ether, which dissolves the copper-compound of the alpha-
resin, but leaves that of the beta-resin as a green powder. The
resins are separated from oxide of copper by dissolving the compounds
in alcohol containing hydrochloric acid, and precipitating with water.
Alpha-resin. Soft and flexible from the presence of volatile oil,
which may be removed by fusion at a gentle heat. White and shining;
softens in the mouth; melts at 100°. Dissolves to a slimy liquid in
ammonia, and is not completely precipitated by boiling for a short time.
It dissolves in caustic potash without coloration; excess of potash
410 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
throws down a tarry precipitate, difficultly soluble in cold, but easily
soluble in boiling water. The potash-salt produces with chloride of
barium a precipitate, which is insoluble in alcohol and ether, and cakes
together in a resinous mass on boiling. It precipitates the salts of the
earths and heavy metals. The copper-salt dissolves easily in ether,
and is decomposed by acetic acid. From the alcoholic solution of the
resin, water throws down a transparent oil, which gives up its alcohol
when boiled with caustic potash, but not on boiling for a short time
alone.
Beta-resin. Resembles the alpha-resin, but dissolves only in abso-
lute alcohol, and forms with baryta, sesquioxide of iron, and copper
salts insoluble in ether. It forms with alcohol of 67 p. c. a white oily
alcoholate, which loses its alcohol when boiled with water, remaining
porous and brittle: with ammonia it forms a thick clear solution, which
loses its ammonia by boiling. The ammoniacal solution dries up in the
air to a fissured ammoniacal resin. The beta-resin dissolves easily in
caustic potash, an excess of potash throwing down a precipitate, which
is soluble in water and alcohol, but insoluble in ether. — It dissolves in
ether, but not in oil of turpentine or fat oils.
2. The solution obtained with absolute alcohol contains alpha-,
beta-, and gamma-resin, the last two precipitable by excess of alcoholic
caustic potash. On dissolving the precipitate in water, decomposing
it with hot dilute sulphuric acid, and treating the separated resin with
cold absolute alcohol, the gamma-resin remains behind undissolved.
The same gamma-resin occurs in the solution prepared with 77 p. c.
alcohol and caustic potash, and is precipitated therefrom by sulphuric
acid.
Gamma-resin. —White meal, which cakes together when heated,
melts only at 350° in closed vessels, frothing up strongly, and being
converted into a resin soluble in oil of turpentine. It is insoluble in
ammonia-water, except on addition of alcohol. The concentrated solu-
tion in caustic potash is a thick liquid, which leaves on evaporation a
transparent gum, soluble in water only after addition of alcohol, and
precipitable from the solution by excess of potash. The potash-com-
pound of the resin dissolves in absolute alcohol; it throws down from
metallic salts gelatinous precipitates, which are insoluble in alcohol,
ether, and oils.—The gamma-resin does not dissolve in absolute alcohol,
but converts it into a transparent, tarry alcoholate. It dissolves easily
in ether, and in oil of cajeput and other oils, but not in oil of turpen-
tine.
3. The extract of the copal-residue obtained with alcohol of 25 p. c.
deposits, when mixed with hydrochloric acid, a jelly of the delta-resin,
which is converted into a white mealy hydrate by boiling.
Delta-resin. Loses a little water at 100°, and more at 300°, runs
together without melting, and carbonises when more strongly heated.
By prolonged heating, a resin soluble in oil of turpentine is obtained. -
The delta-resin does not dissolve in aqueous or alcoholic ammonia, if
other resins are not present. Aqueous potash converts it into a potash-
compound, which is insoluble in water, but soluble in weak alcohol.
The copper-salt is insoluble in ether and oils, and the resin itself is
insoluble in absolute alcohol, ether, and oil of turpentine.
COPAL.
411
4. The portion of copal remaining undissolved after the whole of
the foregoing treatment, amounts to about 8 per cent., consisting of
epsilon-resin. It behaves like the delta-resin when heated, giving off
its water, and caking together in a dense mass. It is insoluble in ether,
alcohol, and oils. When the delta- and epsilon-resins are kept under
alcohol in a flask containing air, they are converted for the most part
into soluble resins. This conversion seems to take place also in copal
when kept (Unverdorben).
B. According to Filhol. Filhol, by treating East Indian copal
according to Unverdorben's method, also obtained five resins, which,
however, only partially correspond with those obtained by Unver-
dorben.
1. When the solution obtained with boiling alcohol of 67 p. c. is
precipitated by alcoholic acetate of copper, and the precipitate is
collected and dried, first at 40° to 50°, and afterwards at 100°, without
access of air, it gives off water and a volatile oil, becoming translu-
cent and friable. On treating it with cold ether, a compound of alpha-
resin with oxide of copper, which forms the chief part of the preci-
pitate, is dissolved; the insoluble residue contaius several resins, but
is of very small amount. The alcoholic solution from which the
alpha-resin has been precipitated by acetate of copper contains the
copper-compound of Filhol's beta-resin, which differs therefore from
Unverdorben's beta-resin.
Alpha-resin. Separated from the copper-compound by Unver-
dorben's method. Or the solution in alcoliol containing hydrochloric
acid is precipitated with excess of hydrosulphuric acid, the filtrato
evaporated, and the remaining resin purified by again dissolving it in
cold weak spirit and drying it at 100°, whereby a volatile oil is ex-
pelled. The resin thus obtained is brittle, translucent, of lemon-
yellow colour, fusible at 100°, completely soluble in alcohol of 72 p. c.,
also in absolute alcohol, ether, and oil of turpentine. Its salts dissolve
in ether but not in alcohol, with the exception of the ammonia-salt,
which dissolves easily in alcohol, and gives off the whole of its ammonia.
only on long boiling. The potash-salt is insoluble in alcohol containing
potash, and is precipitated from its aqueous solution by the slightest
excess of potash. The alcoholic solution of the resin throws down
gelatinous precipitates from salts of the heavy metals; the copper-
salt is blue and insoluble in alcohol. The lead-salt, precipitated from
the alcoholic resin by an insufficient quantity of alcoholic neutral
acetate of lead, contains 26-24 p. c. of oxide of lead.
Filhol.
In the
Uncombined, lead-compound.
Calculation according to Filhol.
40 C
31 H
240
77.17
76.87
76.87
31
994
10-16
1011
50
40
12 80
12.07
13:02
C40H3105
311
100.00
100·00
100·00
On the formula of this and the other re-ins of copal, see Heldt (Ann. Pharm. 63,
68).
Beta-resin. Obtained by precipitating the alcoholic solution of its
copper-salt with hydrosulphuric acid, filtering, and evaporating. Or
412 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
the alcoholic solution is mixed with hydrochloric acid, and the resin
precipitated by a large quantity of water; in this way, however, an
emulsion is easily formed, from which the resin separates only on
boiling off the alcohol. In either case the resin is washed with boiling
water and again dissolved in cold weak spirit. It still contains volatile
oil, which is removed by prolonged boiling with water, or by drying at
100° in a current of hydrogen. It resembles the alpha-resin, and,
like it, contains 76.95 p. c. C., 10'05 H., and 13.00 O., but forms with
bases compounds soluble in alcohol and ether. The ammonia and
potash-salts are viscid and sticky; the latter is insoluble in alcohol
containing potash. Since alcoholic neutral acetate of lead does not
precipitate solutions of the resin, the lead-salt is obtained by pro-
longed fusion of the resin with excess of lead-oxide, extraction with
alcohol, and evaporation. It is transparent and fusible, and contains
25 to 28 p. c. of oxide of lead. The copper-salt is of a fine green
colour, melts about 100°, and remains transparent on cooling.
2. The copal which has been exhausted with 67 p. c. alcohol gives
up to boiling absolute alcohol a further quantity of alpha- and beta-
resin, and also gamma-resin. The solution is precipitated by alcoholic
acetate of lead, and the precipitate, which contains alpha- and
gamma-resin, is dried and exhausted with ether, which leaves the
copper-compound of the gamma-resin undissolved.
Gamma-resin. White, very light powder, which melts with diffi-
culty, undergoing decomposition. It remains behind as a transparent
slightly coloured resin on evaporating its alcoholic solution. Oxidises
in the air. The potash-salt is sticky, slightly soluble in water,
moderately soluble in alcohol, soluble also in alcohol containing
potash. The salts of the metals are insoluble in alcohol and ether.
The lead-salt is a heavy, fusible, white powder; the copper-salt is
blue, resembling the acetate.
Calculation according to Filhol.
Filhol.
40 C
240
31 H.
31
3 0.......
24
C403104 ........ 295
mean.
81.35
80.62
10.50
10.54
8.15
8.84
100.00
100.00
3. The soft elastic residue remaining from the previous treatment
of copal dissolves partially in alcoholic potash; from the filtrate dilute
sulphuric acid throws down a large quantity of gamma-resin with a
little delta-resin. Alcohol of 25 p. c. then dissolves the remainder of
the delta-resin as a potash-compound, leaving the indifferent and
insoluble epsilon-resin. To separate the gamma- and delta-resins
they are treated, after drying, with anhydrous alcohol containing ether,
which dissolves only the gamma-resin.
Delta-resin. Present in small quantity only. Gelatinous, or
after drying, a white powder. Melts only when strongly heated,
undergoing decomposition. It is soluble in alcoholic potash, but not
in alcohol or ether.
Epsilon-resin. Transparent gelatinous mass, drying up to small
hard granules, insoluble in all liquids.
RESINS (ELEMI-RESIN).
413
Calculation according to Filhol.
Filhol.
mean.
40 C
31 H....
2 O......
240
31
16
287
83.62
81.42
10.81
10.48
5.57
8.10
100.00
100.00
C40H3102........
C. According to Vogel.
copal, the one soluble, the
Vogel distinguishes only two resins in
other insoluble, in alcohol. Transparent
copal containing 78.13 p. c. C., 10:46 H., and 11:41 0., gave up to
90 p. c. alcohol, 38 p. c. of soluble resin containing 77.70 p. c. C.,
10.72 H., and 11.58 0. The insoluble resin contained 78.59 p. c. C.,
10.08 H., and 11:33 0., and from another copal, 76.12 p. c. C.,
11.11 H., and 12.77 O.; it was not altered or blackened by digestion
with oil of vitriol for 24 hours. It dissolves in ether, the solution
yielding, on evaporation, a varnish which is insoluble in alcohol, but
becomes soluble in that liquid when exposed to the air for some
months.
12. Elemi-resin.
JOHN. Berl. Jahrb. 1819, 356.
BONNASTRE. J. Pharm. 8, 388; N. Tr. 7, 1, 368. — J. Pharm. 8, 574;
9, 179; 10, 198.
H. ROSE. Pogg. 33, 49; 48, 61; also J. pr. Chem. 18, 321.- Pogg.
53, 364.
JOHNSTON. Phil. Trans. 1840, 361.
HESS. Ann. Pharm. 29, 137; J. pr. Chem. 16, 162; Pogg. 46, 320.
J. pr. Chem. 19, 508; Pogg. 49, 219.
SCHRÖTTER. Pogg. 59, 68.
BAUP. N. J. Pharm. 20, 321; Ann. Pharm. 80, 312; J. pr. Chem. 55,
83.
Obtained from various species of Amyris or Icica (Handbuch, viii,
[2], 19). Occurs in commerce as West Indian and East Indian elemi.
The West Indian resin forms brittle, opaque masses of lemon-yellow
or greenish colour, softening between the fingers, and easily fusible.
Sp. gr. 1.018 (Brisson), 1.083 (Pfaff). Its alcoholic solution reddens
litmus (Bouillon-Lagrange & Vogel). Elemi does not yield umbellife-
rone by dry distillation (Sommer), and when it is melted with hydrate
of potash, neither phloroglucin nor protocatechuic acid is formed
(Hlasiwetz & Barth). It softens when warmed with nitric acid, and
dissolves on boiling, forming camphretic acid and the decomposition-
products of gum and albumin (Schwanert, Ann. Pharm. 128, 124). It
dissolves in hot alcohol, with the exception of impurities, and partly in
creosote (Reichenbach). - Yellowish-white, dull, brittle pieces had a
sp. gr. of 1·055 at 208, became soft at 80°, melted to a limpid yellow
oil at 120°, and contained 78.72 p. c. C., 10.71 H., and 10.57 0.
(Schrötter).
Elemi contains a volatile oil (xiv, 289), a resin easily soluble in cold
alcohol, and a resin soluble only in hot alcohol, besides extractive
matters (Bonastre). Johnston and Rose also found only two resins in
elemi, whereas John and Baup seem to have distinguished three resins.
414 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
John found a soft resin, a second resin soluble only in ether, and a third
soluble in hot alcohol and crystallising on cooling. According to Baup
the portion insoluble in cold alcohol is amyrin (p. 397); the soluble
portion contains an amorphous resin and Elemin, which latter body forms
six-sided prisms, melting about 200°, and soluble in 20 parts of cold
88 p. c. alcohol (Baup).
a. Sparingly soluble Resin of Elemi. Obtained by exhausting elemi
repeatedly with cold alcohol and dissolving the residue in boiling
alcohol, from which the resin is deposited on cooling (Bonastre; Rose).
-- Pure white, indistinctly crystalline flocks (Rose). Stellate groups of
crystals, especially fine from alcohol containing volatile oil of elemi
(Bonastre). Colourless crystals, melting at 149° to a colourless oil,
which solidifies to a brittle resin on cooling (Johnston). Neutral.
Johnston.
Rose.
Hess.
mean.
at 93°.
40 C
33 H
О
240
85.41
84.45
84.20
84.01
33
11.74
11.77
11.53
11.87
8
2.85
3.78
4.27
4.02
C40H330 281
100.00
100.00
100.00
100.00
....
Probably identical with the crystals of animé resin (Hess).
Elemi-resin burns with flame when heated, evolving a resinous
odour. When submitted to dry distillation, it yields an acid thick
distillate (Rose). It does not alter when hydrochloric acid gas is
passed over it (Rose).
Combinations. With Water? When crystallised elemi is dissolved
in so much alcohol that nothing is deposited on cooling, and the solu-
tion is evaporated in a vacuum or at a very gentle heat, the liquid
deposits, besides the needles, amorphous, glassy, often yellowish-
coloured masses, which scarcely lose weight over the water-bath.
These masses, not completely separated from the crystalline resin,
were analysed by Rose, who found them to contain much less carbon
than the crystals (frequently not more than 80 p. c., and sometimes only
76 to 40 p. c.); according to him, they are formed by the combination
of the crystals with water. Other glassy masses, however, contained
82 p. c. of carbon, so that the existence of a hydrate appears doubtful.
Elemi is insoluble in water and does not combine with bases. The
alcoholic solution forms a jelly with ammonia; it is not rendered turbid
by caustic potash. Alcoholic neutral acetate of lead and nitrate of silver
produce no precipitate, even on addition of a little ammonia (Rose).
Elemi dissolves in boiling alcohol, and is deposited from the solution
on cooling in the form of a jelly or a spongy mass (Bonastre). The
alcoholic solution turns milky on cooling and afterwards deposits
crystals (Rose). It dissolves easily in ether, from which it crystallises;
also in oil of turpentine; less easily in oil of almonds (Bonastre).
b. The portion of elemi-resin soluble in cold alcohol is brownish-
yellow, brittle, and transparent, and has a smell of lemons. It becomes
white and opaque when boiled with water, but does not colour the
water. It combines with bases (Johnston).Contains, at 100°,
77·57 p. c. C., 10·43 H., and 12:00 O. (Johnston). Contains 75.39 p. c. C.,
RESINS (IVY-RESIN-EUPHORBIUM).
415
11.89 H., and 12.72 O. (Rose). According to Johnston it is represented
by the formula C¹³204.
13. IVY-RESIN. From Hedera Helix. Red-brown or greenish, trans-
parent, brittle pieces, of sp. gr. 1.294 according to Brisson. Has a
faint aromatic smell and an aromatic acrid taste. Contains 23 p. c. of
resin, 7 of gum, and 70 of woody fibre, together with malic acid and
salts (Pelletier, Bull. Pharm. 4, 504). It burns with a bright flame,
emitting an agreeable odour. When subjected to dry distillation, it
yields, first acid, then ammoniacal water, and a yellow and red oil
(Geoffroy). No umbelliferone is obtained thereby, or when the resin is
carbonised by oil of vitriol and boiled (Sommer, N. Br. Arch. 98, 11).
14. EUPHORBIUM.From Euphorbia officinarum, E. antiquorum, and
E. canariensis. Yellowish or brownish externally and whitish within;
brittle, often hollow pieces, softening when warmed. The resin is
without smell, but the dust excites sneezing; when chewed it has an
acrid and persistent burning taste. It does not yield umbelliferone by
dry distillation (Sommer). It contains a brittle, poisonous resin, soluble
in alcohol, ether, and oil of turpentine, and slightly soluble in ammonia-
water and warm caustic potash (Braconnot; Brandes), besides gum,
wax, caoutchouc, and malic acid and its salts. See Braconnot (Ann. Chim.
68, 44), Pelletier (Bull. Pharm. 4, 502), Brandes (Repert. 6, 145), Buchner & Her-
berger (Repert. 37, 213).
The easily soluble portion of euphorbium resin is obtained as a brown-
yellow resin by extracting with cold alcohol and evaporating the pale-
yellow solution. When boiled with water, it turns pale-yellow and
opaque, and colours the water pale-yellow. When dried at 100°, it
again becomes transparent, brown-red, and semi-fluid, cooling to a
brittle mass.
It contains 74.03 to 75·26 p. c. C., 9.83 to 10:20 H., and
15·14 to 14.54 O., but probably still contains some of the sparingly
soluble resin (Johnston, Phil. Trans. 1840, 364).
The sparingly soluble resin crystallises in radiated hemispherical
tufts, becomes luminous when rubbed, but loses this property after
being rubbed for some time, and does not again crystallise from alcohol
(Bonastre). According to Rose, on the contrary, the sparingly soluble
resin is deposited from the hot alcoholic solution, on cooling, in amor-
phous starchy masses, which contained on one occasion 80-20 p. c. C.,
11.12 H., and 8'68 O., and on another occasion 78.55 p. c. C., 10·96 H.,
and 10:49 0. The alcoholic solution reddens litmus and has a faintly
acrid taste; it is not precipitated by alcoholic potash, neutral acetate of
lead, or nitrate of silver, even after addition of a little ammonia.
Aqueous potash turns it turbid, and aqueous ammonia throws down a
white precipitate without forming a jelly. When euphorbium is
boiled for a long time in alcohol, no deposit takes place on cooling;
the solution, evaporated in a vacuum, leaves a transparent turpentine,
in which opaque white masses, less rich in carbon (77.29 and 78 64 p. c.)
than the sparingly soluble resin, are formed on standing (Rose, Pogg.
33, 52; 53, 369).
See John on the resin of Euphorbia Cyparissias, and Ricord Madianna
on the milky juice of Euphorbia myrtifolia (J. Pharm. 18, 589),
15. GOMART-RESIN from Bursera gummifera. Solid dry resin, white
and of crystalline texture, somewhat soft within, and exhibiting hol-
lows lined with shining crystalline nodules. It melts with difficulty,
and
416 APPENDIX TO COMPOUNDS CONTAINING 40 at. carbon.
breaks up into sticky granules in boiling water. It has an odour be-
tween those of elemi and turpentine. When distilled with water it
yields a volatile oil (xiv, 291).
3
4
16. GAMBOGE. Gummigutt. That obtained from Hebradendron co-
chinchinense alone occurs in commerce in pipes, cakes, and as ordinary
gamboge. [See Hanbury (N. Repert. 14, 1)]. Cylindrical masses to
3 inches in diameter, or thick cakes a pound in weight. It is of a dirty
yellowish-brown colour, dusty on the surface, and has a smooth, shin-
ing, conchoïdal fracture. Brittle, and triturable to a fine yellow powder.
Inodorous, tastes slight at first, and afterwards harsh and acrid; colours
the saliva yellow. Softens when heated, without melting. It kindles.
in a flame, and burns with a smoky flame. Forms with water a fine
yellow emulsion, and dissolves in alcohol and ether, leaving gum.
Gamboge, melted with hydrate of potash, yields protocatechuic
acid and phloroglucin (Hlasiwetz & Pfaundler, Wien. Acad. Ber. 50,
52), together with acetic acid (propionic and butyric acids), and a
sparingly soluble resin resembling that obtained from benzoïn (p. 383)
(Hlasiwetz & Barth, Ann. Pharm. 134, 281). It does not yield umbel-
liferone by dry distillation (Sommer).
Pipe gamboge contains 72 p. c. of gamboge-yellow, 23 p. c. of gum,
and 5 of water: the other kinds generally contain less yellow, and also
starch and woody fibre (Christison). See the analyses of Braconnot (Ann.
Chim. 68, 33), John (Chem. Schriften, 4, 190), Christison (Ann. Pharm. 19, 221;
complete: 23, 172; abstr. 76, 343), Büchner (Ann. Pharm. 45, 72).
Gamboge-yellow.
BRACONNOT. Ann. Chim. 68, 36.
JOHN.
Chem. Schriften, 4, 193.
UNVERDORBEN. N. Tr. 8, 1, 60.
CHRISTISON. Ann. Pharm. 23, 185.
JOHNSTON. Phil. Trans. 1839, 281.
PH. BÜCHNER. Ann. Pharm. 45, 72.
Resinous Gamboge-yellow. Gambodic acid (Johnston). — Chiefly investigated by
Johnston and Büchner, but with not perfectly concordant results.
Preparation. 1. Gamboge is exhausted with absolute ether, the
dark-yellow solution is evaporated, and the remaining hyacinth-red
transparent mass, which gives off the last portions of ether only at a
high temperature, is heated till it becomes hard and brittle (Christison;
Johnston). — Gamboge is exhausted with alcohol and the solution pre-
cipitated by water. 3. Gamboge is exhausted with potash and the
solution precipitated by hydrochloric acid (Johnston). The yellow
extracted by ether contains a little lime: if it be dissolved in potash and
precipitated by hydrochloric acid, it takes up a little potash which
cannot be removed by washing. The yellow precipitated from an am-
moniacal solution by hydrochloric acid is free from ash, but contains
water (Buchner).
Properties. Cherry-red or nearly opaque mass, triturable to a fine.
yellow powder. Inodorous; tasteless; has an acid reaction. The
yellow precipitated from an ammoniacal solution, when kept for some
RESINS (GAMBOGE-Yellow).
417
time at 100°, melts to an opaque viscid mass, which loses a large
quantity of water at a higher temperature, becoming thinner, and is
cracked and brittle after cooling (Büchner). — It does not undergo
any alteration at 177° (Johnston).
Calculation according to Johnston.
40 C
24 H
80
C40 H2408
Büchner.
Johnston.
mean, at 100°.
mean.
240
73.17
71.53
72.05
24
7.32
7.29
7.23
64
19.51
21.18
20.72
328
100.00
100'00
100.00
Johnston gives also the formula C40H2409. Büchner gives for the yellow in the
salts the formula C60H35O12: he seems to take 6·12 as the atomic weight of carbon.
Decompositions. Gamboge-yellow gives off white vapours at 204°,
turning darker, and afterwards contains 72.79 p. c. C., 6·60 H., and
22.61 0. When this body is treated with alcohol, about half remains
undissolved in the form of a yellow powder, which contains 70·70
p. c. C., 7·03 H., and 22.27 O., and is unalterable at 204°, but decom-
poses at 260°, without melting (Johnston). The yellow is only
partially soluble in nitric acid (Büchner). On heating it with 8 parts
of nitric acid and evaporating the solution to a syrup, a bitter substance
separates out, whilst the solution contains oxalic acid (and malic acid)
(Braconnot). Gamboge-yellow yields with strong nitric acid crystals
somewhat resembling those of mangostin (p. 330) (Schmid, Ann.
Pharm. 93, 87). — It dissolves in oil of vitriol with red colour, and is
precipitated in an altered state by water (Büchner). Gamboge-
yellow suspended in water is decolorised by chlorine: on evaporating
the product to dryness, and treating the residue with boiling water, a
pale-yellow chlorinated substance, insoluble in water, is obtained
(Braconnot).
Combinations. Gamboge-yellow is insoluble in water. It combines
with bases, forming Johnston's gambodiates.
Ammonia-salt. Gamboge-yellow absorbs ammonia-gas, and after-
wards dissolves slightly in water, and evolves ammonia when treated
with potash (Unverdorben). It dissolves slowly in warm aqueous
ammonia, with deep hyacinth-red colour, and is precipitated therefrom
by carbonate of ammonia or potash (Büchner). On evaporation there
remains a brittle ammoniacal residue of the colour of gamboge-yellow,
insoluble in water (Johnston).
Potash-compound. - The yellow does not dissolve in strong caustic
potash, even on warming, but easily in potash diluted with 8 parts
of water, forming a dark-red solution. It expels carbonic acid when
boiled with alkaline carbonates. Strong caustic potash, or its car-
bonate throws down a flocculent or gelatinous precipitate, according to
the strength of the solution. The compound freed from admixed car-
bonate of potash by dissolving it in absolute alcohol, is plaster-like
and coherent, neutral, easily soluble in water and in absolute alcohol,
forming dark-brown solutions (Büchner).
Soda-compound. Precipitated from the strong aqueous potash-
compound by a saturated solution of chloride of sodium in the form of
VOL. XVII.
2 E
{
1
418 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
a jelly, or from a more concentrated solution as a coherent mass, which
resembles the potash-compound, but exhibits a brassy metallic lustre,
and is somewhat less easily soluble in water (Büchner).
The gambodiates of the alkaline earths and heavy metals are yellow
powders, insoluble in water and slightly soluble in alcohol. After
drying they are not decomposed at 204°, but emit at that temperature
the odour of the acid (Johnston).
Baryta-salt. The cold aqueous ammonia-salt is precipitated by
chloride of barium, and the precipitate is washed so long as the filtrate
yields a precipitate with nitrate of silver. - Bulky, dark brick-red
flocks, slightly soluble in hot water, and almost as freely in absolute
alcohol: from the latter solution oil of vitriol throws down the com-
pound of gamboge-yellow with baryta, free from sulphuric acid, but
after dilution with water, it precipitates this compound together with
sulphate of baryta. It contains 65.15 p. c. C., 6·48 H., 18.06 O.,
and 10.31 Ba0., corresponding to the formula 4C60H35012,3 Ba0.
(Büchner).
Strontia-salt. Obtained by adding ammonia and the alcoholic solu-
tion of gamboge-yellow to an alcoholic solution of nitrate of strontia.
The yellow precipitate, dried at 100°, contains 9.88 p. c. Sr0.
(3C402408,2Sr09.56 p. c. Sr0) (Johnston).
40
=
The magnesia-salt contains 4.6 p. c. MgO., the brownish-yellow
zinc-salt 11-10 p. c. ZnO (CH208,ZnO 10.95 p. c. ZnO) (John-
ston). The ammonia-salt forms a fine yellow precipitate with proto-
chloride of tin (Büchner); the potash-salt, a brown precipitate with
protosulphate of iron (Pelletier).
Lead-salts. The ammonia-salt precipitates neutral acetate of lead
of a yellowish-red, and the basic acetate of an orange colour (Büchner).
a. Neutral acetate of lead containing ammonia throws down from
the ammoniacal solution, a yellow powder containing 49.23 p. c.
oxide of lead (CH2408,3PbO 49.4 p. c. PbO) (Johnston). b. The
-
precipitate thrown down by neutral acetate of lead from the cold
aqueous ammonia-salt in presence of a slight excess of ammonia, is
reddish and gelatinous. When precipitated boiling, it is flocculent,
easier to wash, and triturable to a light brick-red powder after drying.
It is insoluble in water and weak alcohol, but slightly soluble in abso-
lute alcohol, forming a solution from which oil of vitriol throws down
nothing at first, but after addition of water, a mixture of sulphate of
lead and the lead-compound of gamboge-yellow.-It contains, on the
average, 46.24 p. c. C., 4.62 H., 14.66 O., and 34:48 PbO, corresponding
to
the formula 2060H35012,5Pb0 (Büchner).. C. Alcoholic neutral
acetate of lead throws down from the alcoholic solution of gamboge-
yellow, a yellow powder, containing, at 100° to 188°, 19.47 p. c. PbO
(3CH2408,2Pb0 18.54 p. c. PbŎ) (Johnston). The precipitate is
insoluble in water, sparingly soluble in alcohol, easily in ether, and
contains 14.96 p. c. PbO (Unverdorben). (2C40H240,Pb0 = 14.58
p. c. PbO). —d. On decomposing the precipitate a with acetic acid, a
yellow powder containing 14.78 p. c. PbO remains undissolved. The
same salt with 13 88 p. c. Pb0 is thrown down by ammonia from
the liquid filtered from c, which probably still contains a large quantity
of resin (Johnston).
RESINS (GUM-LAC).
419
Copper-salt. The ammonia-salt forms a green precipitate with
sulphate of copper (Büchner). Unverdorben obtained a brown-red
compound, containing 4.58 p. c. CuO, soluble in ether: Johnston de-
scribes brown yellow precipitates with 18.9, 14.66, and 10-62 p. c. CuO.
Silver-salt. a. Alcoholic nitrate of silver throws down from the
alcoholic solution of gamboge-yellow, on addition of ammonia, a yellow
precipitate, which turns dark-green in the air, and contains, on the
average, 15.66 p. c. AgO (Johnston). -- b. On gradually adding the
aqueous ammonia-salt to aqueous ammoniacal nitrate of silver, and
stirring constantly, a yellow precipitate is produced which dissolves in
more ammonia, is again precipitated by the silver-salt, and unites to
brown flocks on standing. After drying at 121° till it is no longer
soft it contains, 9.71 p. c. AgO (Johnston). c. Büchner, by precipitating
the ammonia-salt containing a slight excess of ammonia with nitrate
of silver, obtained, in the cold, a dirty yellow, somewhat slimy pre-
cipitate, which became flocculent and easier to wash when boiled.
Pale brownish-yellow powder, soluble in ammonia (Büchner).
Büchner.
Johnston.
According to Johnston.
a.
C.
80 C
48 H
480
62.17
60.37
57.94
....
48
6.22
6.03
5.74
16 O
128
16.58
17.72
17.59
AgO....
116
15.03
15.88
18.73
2C40H2408, AgO.... 772
100.00
100.00
100.00
According to Büchner, C6H35O12,AgO.
Gamboge-yellow dissolves easily in alcohol and ether.
17. GUM-LAC. Exudes from the twigs of Aleurites laccifera, Croton
aromaticus, Butea frondosa, Ficus religiosa, and Zizyphus Jujuba in
India, after being punctured by Coccus Lacca. The stick-lac (Lacca in
ramulis) adhering to the twigs, when removed and freed from the
greater part of the colouring matter by boiling with water containing
soda, yields grain-lac (Lacca in granis), from which shellac is obtained
by melting and straining. -Stick-lac boiled with water and precipitated
with alum yields lac dye. Stick-lac is dark-brown; grain-lac and
shellac are yellowish-brown, orange, or black; all the varieties are
translucent, hard, and of a conchoïdal, shining fracture.
Stick-lac contains resin, laccin, and colouring matter (Funke, N. Tr.
18), and according to Hatchett, also wax and gluten. The impurities
mixed with stick-lac contain sulphide of arsenic (Büchner, Ann. Pharm.
59, 96). According to Unverdorben, lac colours water reddish-brown,
whereupon sulphuric acid throws down a red-brown pulverulent pre-
cipitate.
According to John (Chem. Schriften, 5, 1) grain-lac contains two
easily soluble resins and an insoluble resin (laccin), wax, colouring
matter, bitter principle, ash, and impurities. Unverdorben [see his
complete analyses (Pogg. 14, 119)] distinguishes five different resins in
grain-lac. Nees v. Esenbeck & Marquart (Ann. Pharm. 13, 286) found
a substance resembling carmine, which was extracted by water,
besides wax, laccin, and two resins, one of which was soluble in
ether.
2 E 2
420 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
:
Shellac (which, according to Brisson, is of sp. gr. 1·139) contains
two resins and wax, but no laccin; a spurious shellac contained laccin,
three resins, wax, and traces of laccic acid (Nees v. Esenbeck & Mar-
quart). Shellac dissolves easily in aqueous hydrochloric acid, acetic
acid, potash, soda, and borax, but not in ammonia (Hatchett).
Powdered lac, when digested with a little strong ammonia in closed
vessels, swells up to a jelly which dissolves in water, with the excep-
tion of the wax and impurities. Cold aqueous potash dissolves lac
easily the solution is not precipitated by excess of potash. Strong
aqueous carbonate of potash dissolves only a little colouring matter,
and forms a fluid compound of resin and potash, which, after washing
with cold water, dissolves easily in boiling water. The solution
remains clear on cooling, or when too much carbonate is present, soli-
difies to a jelly: it is precipitated in coherent flocks by acids (Berzelius,
Pogg. 10, 255; 12, 426). Lac dissolves with moderate facility in
wood-spirit, and is precipitated from the solution by water. It is
perfectly soluble in fusel-oil and valerianic aldehyde, moderately solu-
ble in valerianic acid, and slightly in valerate of amyl (Trautwein).
dissolves partially in cold creosote (Reichenbach), in more than 100
parts of boiling rock-oil (Saussure), and but slightly in benzene, though
benzene mixes with the saturated solution in wood-spirit or alcohol
(Mansfield). The different kinds of commercial lac behave in various
ways with acetone. Bleached shellac dissolves in 1 parts of acetone,
forming a thick oily varnish; other kinds dissolve only in 3 parts,
and others not at all in acetone (Wiederhold, Polyt. Notizbl. 19, 214).
Shellac does not dissolve completely in melted tallow (Nicholson),
and not perceptibly in castor oil (Stickel).
It
Laccin remains behind as a brittle, transparent, yellowish-brown
mass when grain-lac is treated with alcohol, water, and hot alcohol in
succession: it is purified by levigation (John). According to Büchner,
it is to be regarded as a mixture of resin and wax. When acted
upon by nitric acid, it yields oxalic acid and tallow. It dissolves com-
pletely in caustic potash, and is not precipitated by sal-ammoniac, but
hydrochloric acid throws down from the solution a sticky resin, soluble
in alcohol and ether. Laccin is insoluble in ammonia-water, and in
cold and boiling alcohol, ether, and volatile and fat oils, but dissolves.
in glacial acetic acid and in warm alcohol containing a little sulphuric
or hydrochloric acid (Unverdorben), excepting 5 p. c. of wax (Nees v.
Esenbeck & Marquart). — The laccic acid of Pearson (Phil. Trans. 1794,
383) and John crystallises in needles. It remains in solution when an
alcoholic solution of stick-lac is precipitated by water, and is obtained
by evaporating the filtrate and exhausting the residue with ether. It
forms deliquescent acid crystals, which give white precipitates with
ferric salts and with the salts of lead and mercury, and yield with the
alkalis, lime and baryta, deliquescent salts soluble in alcohol (John).
The bleaching of shellac on the large scale is effected by chlorine or
its compounds, but granulated bone-charcoal answers the purpose
better (Elsner, J. pr. Chem. 35, 374), and especially bone-black puri-
fied by means of hydrochloric acid and not subsequently dried (Kr.).
A perfectly white shellac, having a silky lustre and completely soluble
in alcohol, is obtained by the following process:-25 parts of shellac
are dissolved in 600 parts of water with the help of 10 parts of soda.
The solution is mixed with dilute hypochlorite of soda prepared from
30 parts of chloride of lime, and then with hydrochloric acid so long
RESINS (ICICA-RESIN).
421
as the precipitate dissolves. It is then exposed to the sun for a day or
two, filtered, mixed with sulphite of soda, and precipitated by hydro-
chloric acid (Sauerwein, Hannov. Gewerbebl. 1862, July-Aug.; Chem.
Centr. 1863, 89).
18. ICICA RESIN. From Cayenne. Yellowish-white pieces or
transparent granules having an agreeable odour, which is emitted
when the resin is warmed or powdered. It is friable, crunches between
the teeth, and has a faint taste. When boiled with water it yields no
volatile product and does not dissolve. It requires for complete solu-
tion 55 parts of cold, and 15 parts of boiling alcohol of 36°, and 34
parts of cold oil of turpentine. It consists of three neutral resins,
brean, icican, and colophan, which are all insoluble in alkalis and do not
precipitate lead- or silver-salts.
Preparation of the three resins. Powdered icica-resin is dissolved in
boiling alcohol, and the solution is filtered hot and allowed to cool,
whereupon the brean crystallises. The mother-liquor, when concen-
trated, yields first impure brean and afterwards icican, whilst the colo-
phan, which is much more soluble, remains in solution.
a. Brean.-White, pearly, stellate groups of needles, melting at
about 157° and cooling to a viscid elastic mass, which again becomes
solid at 105°. Tasteless. Neutral.
at 120°
80 C
67 H
480
67
30
24
CS0H64,3HO
571
....
........
Scribe.
mean.
84.06
11.73
83.92
11.82
4.21
4.26
.....
100'00
100.00
-
Brean burns with a smoky flame. When submitted to dry distil-
lation, it melts, turns yellow and brown, gives off volatile oil, and a
yellow amorphous sublimate, leaving charcoal. With hot nitric acid
it evolves red fumes and is converted into a yellow mass, which dis-
solves partially in the acid and is precipitated from the solution by
water. It dissolves in cold oil of vitriol with red colour.
Brean is insoluble in water and in alkalis; it dissolves in 100 parts
of cold alcohol, and in 4.4 parts of ether (Scribe).
b. Icican. Resembles breau in appearance and melting-point, and
in its behaviour on dry distillation and towards acids and alkalis, but
dissolves in 50 parts of cold alcohol.
at 120°
Scribe.
mean.
160 C.........
960
82.12
82.01
137 H
137
11.72
11.64
90
72
6.16
6.35
2C80H64,9H0
1169
100.00
100.00
....
......
c. Colophan. Yellow amorphous mass, melting below 100°, and
having a very slight acid reaction in alcoholic solution. It is insoluble
in alkalis, but very easily soluble in alcohol. It contains 77.93 p. c. C.,
422 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
10.69 H., and 11:47 O. (Scribe, Compt. rend. 19, 129; N. Ann. Chim.
Phys. 13, 166).
19. LABDANUM or LADANUM. A sticky, afterwards drying sub-
stance covering the leaves and branches of Cistus creticus. Black-
brown, soft, of sp. gr. 1.186 (Brisson). Has an agreeable odour and
a bitter taste. According to Guibourt, it contains 86 p. c. of resin and
volatile oil and 7 p. c. of wax, together with substances soluble in
water, ash, and impurities; according to Pelletier (Bull. Pharm. 4, 503)
20 p. c. of resin, 1.9 of wax, 3.6 of gum, 1.9 of volatile oil, malic acid,
malate of lime, and 72 p. c. of sand containing iron.
Labdanum dissolves to the extent of 4th at most when digested
with cold alcohol of sp. gr. 0.83, forming a brown solution. On evapo-
rating the solution, the dissolved portion is left as a dark-brown trans-
parent mass, which gives up bitter substances and colouring matter
to water. When, therefore, labdanum is boiled repeatedly with water,
the residue exhausted with alcohol, and the tincture evaporated in
thin layers at 100°, a purer resin is obtained, which gives up a little
bitter substance to water, without altering in composition. It con-
tains, on the average, 73.20 p. c. C., 10:01 H., and 17.79 O., corres-
ponding to the formula C40H307 (Johnston, Phil. Trans. 1840, 344).
Labdanum does not yield umbelliferone by dry distillation
(Sommer).
20. RESIN OF LAËTIA RESINOSA.-Small, yellowish-white, trans-
parent, brittle granules, having a conchoïdal fracture and smelling
slightly aromatic. When distilled with water, it yields a little volatile
oil, without giving up any thing to the residual water. When heated it
melts, puffs up, and burns with a bright smoky flame, leaving a bitu-
minous charcoal. It dissolves completely in boiling alcohol and is partly
deposited from the solution on cooling (Macaire-Princep, Bibl. univ. 45,
431).
21. MASOPIN. A crystallisable resin forming a constituent of the
sap
of the Dschilte, a Mexican tree. The dried sap, imported in cylin-
drical masses, remains, when powdered and boiled with water, as a
tough elastic mass, from which absolute alcohol extracts the masopin,
leaving caoutchouc. The masopin is precipitated from the alcoholic
solution by water, and may be obtained from ether in white silky
needles, frequently arranged in tufts. The crystals melt at 155° and
solidify, on cooling, to a glassy mass, having a conchoïdal fracture and
melting at 69° to 70°. It is tasteless and inodorous, but has an agree-
able smell when heated.
Genth.
Crystals.
mean.
44 C............
36 H
20
264
83.54
83.46
36
11.39
11.48
16
5.07
5.06
CHH3602
316
100.00
100.00
Masopin yields by dry distillation (1) a brown oil smelling of ginger,
which becomes wine-yellow and limpid when rectified over lime, and
contains 88.02 p. c. C., and 11.49 H.; (2) an acid, which may be ex-
tracted from the crude oil by ammonia, and is precipitated from the
ammoniacal solution in pearly lamina by hydrochloric acid. When
RESINS (MASTIC).
423
combined with lime and precipitated by hydrochloric acid, it forms
delicate dazzling white needles. Its silver-salt is white, smells of cin-
namic acid when burnt, and contains 45-49 p. c. AgO. — Nitric acid
attacks masopin violently at first, and when long boiled with it, dis-
solves it to a clear liquid, which leaves on evaporation a tough amor-
phous mass, soluble in water with wine-yellow colour. The silver-salt
of this acid contains 45-46 p. c. AgO., 30-35 C., and 3.37 H. (Genth,
Ann. Pharm. 46, 124).
22. MASTIC. — From Pistacia Lentiscus. Yellowish translucent tears,
of sp. gr. 1.04 (Pfaff), 1.074 (Brisson), 1.07 (Schrötter). Has a glassy
and transparent fracture, softens between the teeth, melts at 100°
according to Johnston, softens at 80° according to Schrötter, and
begins to froth up and decompose at 105° to 120°. The alcoholic
solution, but not the aqueous decoction, reddens litmus (Bouillon-
Lagrange & Vogel). By dry distillation it yields tar and acetic acid
(Schrötter); no umbelliferone (Sommer): it yields at first, acid water, and
when more strongly heated, a pale-yellow oil, limpid at first and after-
wards thick, whilst a black residue, insoluble in alcohol, remains behind
(Johnston). Mastic dissolves in nitric acid with decomposition, form-
ing camphretic acid (Schwanert): it dissolves also in cold oil of
vitriol, from which it is precipitated by water. It absorbs a little
ammonia-gas and dissolves in aqueous alkalis. See below. It is
soluble in alcohol, with the exception of the beta-resin; easily and
abundantly soluble in acetone according to Wiederhold, and according
to Mansfield freely soluble in benzene. It dissolves in fatty and vola-
tile oils; in cold creosote (Reichenbach); in warm rock-oil, leaving an
opaque white residue; and, according to Stickel, slightly in castor
oil.
Mastic consists of a little volatile oil, a soluble acid resin, and a
non-acid insoluble resin. Picked mastic, analysed as a whole, con-
tained 78.91 p. c. C., 10-42 H., and 10.67 0. (Schrötter, Pogg. 59, 68).
Alpha-resin of Mastic. 1. When a cold alcoholic solution of mastic
is evaporated, and the pale-yellow residue, which is fusible at 100°, is
kept at a temperature of 176° for 18 hours, it has the composition a.
It still contains an admixture of beta-resin, which may be precipi-
tated, in great part, by diluting the solution with a large quantity of
alcohol: the resin thus purified has the composition b, after being
heated to 126° for 18 hours, and the composition c after heating to
176°. — The resin heated to 176°, however, evolves white vapours,
loses its odour, and when treated with alcohol, leaves a large quantity
of the reddish resin d behind, whilst e is dissolved. d is deposited
from a solution in boiling alcohol as a yellow powder: e is a transparent
reddish-yellow mass.
2. Commercial mastic boiled for some hours with water becomes
white, opaque, and less fusible, probably from loss of volatile oil; and
the residue dissolves in alcohol more slowly than before. The alco-
holic solution is evaporated; the residue is boiled for some time with
water to expel adhering alcohol, and afterwards heated to 100° for
48 hours, whereby it becomes soft without quite melting. The opaque,
pale-yellow resin thus obtained, and also the melted fine reddish-
yellow, transparent mass formed by further heating to 115°, exhibit
the composition ƒ, and are almost entirely soluble in alcohol.
424 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
Analyses and formulæ according to Johnston.
a.
b.
C.
d.
e.
f.
C40H3204
C40H3104
C40H3004
C40H3303
C40H3104
C .... 77.32
H.... 10:40
78.35 .......
78.71
77.76
79.42
78.19
10.15
10.22
10.12
10.88
10.33
O.... 12.28
11.50
11.07
12.12
9.70
11.48
100.00
100.00
100·00 ........ 100.00 100.00 ........ 100·00
3. When the alpha-resin is melted in a retort for 24 hours, the tem-
perature being allowed to rise at last to 132°, water and a small quan-
tity of a crystallisable acid pass over. If the operation be suspended
as soon as a pale-yellow liquid makes its appearance in the neck of
the retort, and the red residue be then boiled with alcohol, it is resolved
into a dark-yellow insoluble powder g (which may be removed from
the retort by means of boiling water, and is not fusible at 132°), a
pale-yellow resin h, which is deposited from the alcoholic solution on
cooling, and a reddish-yellow transparent resin i, which remains in
solution. Johnston gives for g the formula CH³005 or C40H³¹05, and
for i the formula C403203; on prolonged heating, therefore, the alpha-
resin C40H³¹¹ breaks up into a resin with 3 atoms and a resin with 5
atoms of oxygen (Johnston).
Analyses by Johnston.
g.
h.
i.
C .......
H
O
76.00
78.14
76.94
9.86
9.74
10.35
14.14
12.12
12.71
100.00
100.00
100.00
Lead-salts of the alpha-resin. a. Semi-acid. When an alcoholic
solution of the alpha- resin is precipitated by alcoholic neutral acetate
of lead, and the solution is filtered from the white precipitate c, and
cautiously mixed with ammonia, a further white precipitate is thrown
down, a portion of which (a) remains undissolved on boiling with
alcohol, whilst the rest (c) is deposited from the alcohol on cooling.
b. Mono-acid. When the above precipitate is boiled with alcohol after
drying (not in a moist state) b remains undissolved. c. Sesqui-salt.
White precipitate, turning yellow at 100°, and melting to a yellow
mass, without decomposition, at 177°.
Analyses and formulæ according to Johnston.
a.
40H3104,2PbO
at 149°.
b.
C¹40H3104,Pbo
C.
3040H3104,2Pbo
45.55
57.64
64.64
H
5.70
7.37
8.45
0
7.39
8.66
8.66
РЬО
41.36
26.33
18.25
100.00
100.00
100.00
—
Silver-salt of the alpha-resin. On mixing the alcoholic resin with
an alcoholic ammoniacal solution of nitrate of silver, a white precipi-
tate is produced, which, when washed with cold alcohol and dried at
149°, has the composition a. If this precipitate be dissolved in boil-
ing alcohol, the slightly coloured solution deposits, on cooling, the pre-
cipitate b, which sticks together in a dark mass at 149° and begins to
RESINS (MYRRH).
425
melt at 177°. — The solution, filtered from a and mixed with more
nitrate of silver, throws down c. These salts are represented by the
formula 2C40H3003,AgO, or 2C40H3104,AgO (Johnston).
Analyses by Johnston (at 121° to 149°).
C
63.00
67.25
65.21
H
8.30
8.64
8.53
O
9.44
7.16
9.76
AgO
19.26
16.95
16.50
100.00
100.00
100.00
Observed
Beta-resin or difficultly soluble resin of mastic. Masticin.
by Neumann (Chymie, 2, 3, 11) and Matthews (Nicholson's Journ. 10,
247): it forms, according to the formerth, according to the latter
th of mastic. It remains behind, when mastic is dissolved in alcohol,
as a white, translucent, tough residue, which may be drawn out into
long threads. On boiling with water, it becomes harder and less
elastic, but recovers its elasticity after drying at 149°. When heated
it swells up and evolves an odour of rock-oil: the resulting porous
mass, after cooling, is brittle and richer in oxygen than before
(Johnston). When burnt it smells like mastic, not like caoutchouc.
It is not perceptibly soluble in boiling alcohol, but more easily soluble in
presence of the alpha-resin and also after being dried, powdered, and
kept. It dissolves in ether and oil of turpentine, but not in caustic
potash (Johnston, Phil. Trans. 1839, 132). — Kunde (Berl. Jahrb. 1795,
142); Funke (A. Tr. 18, 2, 150); Brande (Berl. Jahrb. 1808, 110);
Bonastre (J. Pharm. 8, 575).
Calculation according to Johnston.
Johnston.
40 C............
240
83.63
82.61
31 H
31
10.80
11.01
20
16
5.57
6.38
C40H3102
287
100.00
100.00
23. MYRRH. From Balsamodendron Myrrha. Yellow, brown, or
reddish, with white flocks; translucent, brittle. Has an agreeable
odour and a somewhat acrid, bitter taste. Myrrh rich in oil has a
neutral reaction; that poor in oil is acid (Bley & Diesel). Sp. gr. 1.12
to 1.18 (Ruickholdt). It does not melt when heated, and tåkes fire
with difficulty. When submitted to dry distillation, it does not yield.
umbelliferone (Sommer). When melted with hydrate of potash, it
yields an acid resembling that obtained from guaiacum (Hlasiwetz &
Barth, Zeitschr. Ch. Pharm. 7, 285). When treated with strong nitric
acid, it assumes a black-brown colour, and colours the acid a dirty
violet. Blotting-paper moistened with tincture of myrrh is coloured a
permanent bluish-red by fuming nitric acid (Martiny; Ruickholdt). —
Myrrh distilled with water yields a volatile oil (xiv, 413) and water
having an acid reaction, due to the presence of formic acid (Bley &
Diesel); at the same time a white resinous sublimate condenses in the
upper part of the retort, and the myrrh dissolves almost completely
(Ruickholdt). Water which has been shaken with powdered myrrh
precipitates lead-salts (Bley & Diesel). Myrrh forms with alcohol a
pale golden-yellow tincture, leaving a white residue (Bley & Diesel, N.
Br. Arch. 43, 304).
426 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
Myrrh contains oil, resin (myrrhin), which, according to Brandes, is
decomposible by ether, gum, and 3 p. c. of ash, consisting chiefly of
carbonate of lime and magnesia. The portion soluble in water contains
a gum precipitable by neutral acetate of lead and a second gum pre-
cipitable by the basic acetate (Hekemeijer, Kopp's Jahresber. 1858, 482.
-Pelletier, Bull. Pharm. 4, 54; Brandes, Taschenb. 1819, 51).
The red-brown, brittle, neutral resin, melting at 90-95°, obtained
by evaporating the alcoholic tincture, is Ruickholdt's myrrhin. When
heated it evolves white vapours smelling of myrrh, takes fire, and
burns. It assumes a yellow colour (? Kr.) in strong nitric acid, dis-
solves partially in boiling caustic potash, completely in acetic acid and
in ether, and incompletely in alcohol. Its solution in alcohol is rendered
milky by water. It contains, on the average, 71.82 p. c. C., 8·15 H.,
and 20-03 0., corresponding, according to Ruickholdt, to the formula
C48H32010. When melted and heated to 168° for some time, it froths
up, from evolution of acid water. The transparent red-brown residue,
Ruickholdt's myrrhic acid, is acid, nearly insoluble in caustic potash but
soluble in alcohol and ether, with the exception of a few flocks: it
contains, on the average, 74.79 p. c. C., 8·00 H., and 17.21 O., corres-
ponding to the formula C48H3208 (Ruickholdt, N. Br. Arch. 41, 1). See
also Heldt (Ann. Pharm. 63, 59).
The portion of myrrh insoluble in water, but soluble in strong
alcohol, is nearly insoluble in aqueous carbonate of soda, easily soluble
in ether and chloroform, and to the extent of one-half in bisulphide of
carbon. The portion soluble in bisulphide of carbon assumes a violet
colour when heated with nitric acid (Hager, Pharm. Centralhalle, 1865,
58; Anal. Zeitschr. 3, 483).
Tincture of myrrh kept for three years was found to have deposited
pale-yellow, six-sided prisms, having an acid reaction, fusible, inflam-
mable, soluble in hot alcohol, ether, and oils, also in caustic potash, and
precipitable from the last solution by acids (Landerer, Repert. 68,
362).
Planche (J. Pharm. 26, 500; Ann. Pharm. 37, 121) distinguishes as
myrrhoid a gum-resin of unknown origin, closely resembling myrrh.
It forms irregular warty or striated tears, partly somewhat opaque
and covered with a grey powder, and partly brown-red, transparent,
of conchoïdal fracture, and less wrinkled. After removing the ad-
hering myrrh-powder and washing with alcohol, it is inodorous. Has
a bitter and peppery taste. When triturated with water, it forms an
opaque mud, or with more water a nearly clear, slightly coloured
solution, from which resin is deposited in the form of a yellow oil,
together with light flocks of bassorin. Alcohol throws down gum from
the solution, whilst myrrhoïdin remains in solution. The resin dis-
solves in alcohol, from which it is precipitated in oily drops by water,
but is insoluble in ether. Myrrhoïdin is yellow, turpentine-like,
highly elastic, neutral, and has a persistent bitter and acrid taste; it
produces shining grease-spots on paper. When heated it melts with-
out emitting a resinous cdour, and carbonises without taking fire. It
dissolves easily in cold water and completely in ammonia and caustic
potash the saturated solution turns green with nitric acid. The
alcoholic solution does not precipitate salts of lead, protoxide of tin,
copper, or silver, but yields a slight precipitate with protosulphate of
iron.
Myrrhoïdin dissolves easily in alcohol, ether, and oil of turpen-
tine, but not in olive oil. It produces with tannic acid a white preci-
RESINS (OPOPONAX).
427
pitate, insoluble in excess of alcohol. See also Martiny (Jahrb. pr.
Pharm. 10, 25).
Concerning Myrrha nova, see Bonastre (J. Pharm. 15, 281; N. Tr. 20, 2, 188).
24. OLIBANUM. Frankincense. Thus. The Indian variety is ob-
tained from Boswellia serrata, the Arabian from Amyris Kataf. Yellowish,
translucent, brittle, covered with a mealy powder, and having a dull
splintery fracture. Sp. gr. 1.221. Becomes tough between the teeth;
has a balsamic odour and an acrid, bitter taste. Its alcoholic solution
reddens litmus. When distilled with water it yields an oil. Melts
imperfectly, emitting an agreeable odour. When submitted to dry
distillation, it yields a large quantity of brown empyreumatic oil and a
little acid water [no umbelliferone (Sommer)]: the residue contains
carbon and ash (Braconnot). — Olibanum takes fire when heated in the
air; with nitric acid it forms, according to Hatschett, an artificial
bitter, according to Schwanert, camphiretic acid.
Olibanum contains 5 p. c. or more [4 p. c. (Stenhouse)] of volatile
oil smelling of lemons, 56 p. c. of resin, 30 of gum [agreeing in pro-
perties with gum-arabic (Hekemeijer, Kopp's Jahresber. 1858, 482)]
and 6 of bassorin (Braconnot, Ann. Chim. 68, 60).
The resin of olibanum, obtained by extracting with alcohol and
evaporating the solution, is red-yellow, very brittle, tasteless, softens
at 100°, and melts at a higher temperature. It dissolves in oil of
vitriol, forming a red solution which is precipitated white by water.
When caustic potash is poured upon it and evaporated, it yields a
slightly soluble residue, which forms a thick emulsion with water
(Braconnot).
The olibanum of commerce is a mixture of two resins differing
in appearance: a, consisting of round, opaque, dull and brittle
pieces, which quickly become covered with an opaque layer under
alcohol; and b, of yellow, transparent, long tears, which are softer
and less brittle than a, and remain clear for a longer time in alcohol.
On picking out the two resins, digesting them in cold alcohol for
several days, decanting from gum, evaporating the solution, and
heating the residue to 121° for 16 hours, the residue from a contains
74.15 p. c. C., 9.98 H., and 15.87 O., corresponding to the formula
C40H3206. The residue of b is pale-yellow, brittle, softens at 104°, and
contains 78.04 p. c. C., 10·72 H., and 11·24 O., or 2 at. O. less than a.
In both cases gum remains undissolved (Johnston, Phil. Trans. 1839,
301).
25. OPOPONAX.-From Ferula Opoponax. - Reddish-yellow and
dirty-white; of sp. gr. 1.622 (Brisson). Has a repulsive odour and a
bitter acrid taste; reddens litmus. Contains 42 p. c. of resin, besides
gum, caoutchouc, starch, woody fibre, malic acid, bitter principle, wax,
and volatile oil. -It forms a milk with water. By dry distillation
water, acetic acid, acetate of ammonia, brown empyreumatic oil [um-
belliferone (Sommer)] and charcoal are obtained (Pelletier, Ann. Čhim.
79, 90; Bull. Pharm. 4, 49). — It does not yield styphnic acid with
nitric acid (Böttger & Will).
The resin of opoponax is reddish-yellow and melts at 50°. It is de-
composed by warm nitric acid, with formation of a yellow mass con-
taining artificial bitter and oxalic acid.
- It dissolves in ammonia,
potash, and soda, forming reddish solutions, from which it is precipi-
428 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
tated in reddish flocks by acids. It dissolves in alcohol and ether
(Pelletier).
Opoponax digested with cold alcohol and ether of sp. gr. 0-83 yields.
a pale brown-red solution, leaving on evaporation a transparent brown
resin which has a peculiar odour, melts at 100°, and when kept at that
temperature for some time, is brittle after cooling. After drying for
an hour or two at 100°, it contains, on the average, 63.20 p. c. C., 6·71
H., and 3009 O., corresponding to the formula C40H25014 when it is
more strongly heated, the proportion of carbon is increased about
2 per cent. (Johnston, Phil. Trans. 1840, 352).
Used for cover-
26. VARNISH OF THE PASTO INDIANS (MEXICO).
ing wood and calabashes, for which purpose the varnish is spread out
in thin sheets and laid upon the wood. The coating, which is soft at
first, hardens in the air without cracking: it is not attacked by hot
water, and but slightly by alcohol and caustic potash. The crude
varnish is solid, not friable, of conchoïdal fracture, heavier than water,
inodorous and tasteless. At a little below 100° it becomes elastic like
caoutchouc, but loses its elasticity on cooling. It is combustible, dis-
solves without decomposition in oil of vitriol, from which it is precipi-
tated by water. It is insoluble in alcohol, ether, and volatile and fixed
oils, but swells up very much in ether and softens when heated in
fatty oils.
The varnish purified from a green resin by boiling with alcohol,
forms, so long as it remains moist and warm, a dirty-white, tremulous
jelly, which becomes friable, hard, and brittle on cooling, and is still
soft and elastic at temperatures below 100°. It contains 70·72 p. c. C.,
9.70 H., and 19.58 0.-On boiling the varnish with caustic potash, it
dissolves freely, forming a soap which solidifies on cooling and dis-
solves in more water. Acids added to the soap throw down the
varnish as a shining mass, which may be drawn out in sheets, and
dries up in the air to a brittle mass melting at 130°, losing thereby
the remainder of its water and acetic acid, after which it dissolves in
all proportions in alcohol, ether, and oil of turpentine. It contains, like
the purified varnish, 70.19 p. c. C., 10.30 H., and 19.51 0. (Boussingault,
Ann. Chim. Phys. 52, 216; J. pr. Chem. 3, 325).
27. SAGAPENUM. From Ferula persica? Yellow, brown or reddish
conglomerated granules, having an odour of garlic and an acrid bitter
taste. Softens in the hand, but does not melt at a higher temperature.
Contains, according to Brandes, volatile oil, two resins, bassorin, gum,
malic acid, ash, and impurities. It yields umbelliferone by dry distil-
lation (Sommer), and when treated with nitric acid, forms styphnic or
other acids (Böttger & Will. — Brandes, N. Tr. 2, 2, 97; Pelletier, Bull.
Pharm. 3, 481).
The volatile oil of sagapenum is obtained by distillation with water.
It is lighter than water, yellow, limpid, and has a repulsive odour of
garlic. When exposed to the sun and air, the oil is converted into a
transparent varnish, acquiring at the same time a smell of turpentine.
Strong nitric acid, when heated with it, turns it thick and yellowish-
red, with formation of oxalic acid. It assumes a dark-red colour with
oil of vitriol, and dissolves in alcohol and ether (Brandes).
The alcoholic extract of sagapenum is resolved by ether into two
RESINS (SANDARac).
429
resins. a. The resin insoluble in ether is brown-yellow, brittle, inodo-
rous and tasteless, and fusible when heated. It dissolves easily in
warm caustic potash and in alcohol, but is insoluble in aqueous am-
monia and in volatile and fat oils. b. The resin soluble in alcohol is
red-yellow, transparent, tough at first, and has a slight odour of
sagapenum, and a mild, afterwards bitter taste. It melts when warmed,
and dissolves with dark-red colour in oil of vitriol. It dissolves slightly
in aqueous ammonia, partially only in caustic potash, easily in alcohol
and ether, and very slightly in hot oil of turpentine and oil of almonds
(Brandes).
Sagapenum treated with cold alcohol of sp. gr. 0.83 yields a pale-
yellow solution, a considerable residue soluble in water remaining
behind. The pale-yellow resin which remains on evaporating the
alcoholic solution, has a strong smell of garlic, melts at 100°, and gives
up to water when repeatedly boiled therewith, a substance having a
bitter and onion-like taste: the residue dried at 110°, dissolved in
alcohol, again evaporated, and dried at 66°, is semifluid and contains
69.06 p. c. C., 8·51 H., and 21·43 0: after being melted for some hours
at 100°, it is darker, but still remains sticky, and contains 69.84 p. c. C.,
8.63 H., and 21.53 O. (Johnston, Phil. Trans. 1840, 361).
28. SANDARAC.- From Thuja articulata. Pale-yellow translucent
resin, brittle between the teeth. Sp. gr. 1·05 (Pfaff), 1·092 (Brisson).
Moderately fusible: does not yield umbelliferone by dry distillation
(Sommer). Dissolves in caustic potash. When boiled with water
it yields a bitter, slightly acid liquid: an alcoholic solution of the resin
previously boiled with water reddens litmus strongly, and even on
precipitating the alcoholic solution with water, but little acid is taken
up by the water (Bouillon; Lagrange & Vogel). Sandarac dissolves
easily in alcohol; according to Giese, in cold alcohol, with the excep-
tion of the sandaracin. It dissolves rapidly in cold acetone (Wieder-
hold), and in cold cresote (Reichenbach).
According to Unverdorben (Schw. 60, 82) and Johnston (Phil. Trans,
1839, 293) sandarac appears to contain three different resins: gamma-
resin, precipitable from the alcoholic solution of sandarac by alcoholic
potash, and alpha- and beta-resins, which remain in solution and are
separable by alcohol of 60 p. c., in which the alpha-resin is more parti-
cularly soluble.
Alpha-resin. Its alcoholic solution reddens litmus. It is very solu-
ble in ammonia, and is precipitated, for the most part, unchanged on
boiling. It dissolves in carbonate of soda on prolonged boiling, and easily
in caustic potash, from which it is precipitated as a semi-fluid mass by
excess of potash, and also by salts. It dissolves in alcohol, ether, and
oil of turpentine, but to the extent of one-half only in rock-oil,
although the two portions have the same properties in other respects
(Unverdorben).
Beta-resin.-On extracting the alpha-resin with alcohol, the beta-
resin remains behind as a semi-fluid mass which hardens when boiled
with water. It has an acid reaction. Dissolves easily in ammonia,
and is deposited from the solution only on complete evaporation, not
on simple boiling. It is (partially) precipitable from its potash-solution
by excess of potash: the oily potash-resin dissolves easily in alcohol,
but is insoluble in ether. The beta-resin is easily soluble in absolute
430 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
alcohol, ether, and oil of cummin, but insoluble in rock-oil and oil of
turpentine (Unverdorben).
Gamma-resin. Giese's sandaracin (Scher. J. 9, 536). When the
precipitate produced by alcoholic potash in an alcoholic solution of
sandarac is boiled repeatedly with 84 p. c. alcohol, that liquid takes up
the compound of the beta-resin with potash: the residual compound of
the gamma-resin with potash is then dissolved in 60 p. c. alcohol and
decomposed by hot hydrochloric acid.- White difficultly fusible powder,
having a slightly acid reaction. It takes up ammonia without "becom-
ing soluble in water. Dissolves easily in caustic potash, and is preci-
pitable as a jelly by excess of potash. Soluble in absolute and in 84
p. c. alcohol, but not in that of 60 p. c. Dissolves in ether but not in
volatile oils (Unverdorben). Giese's sandaracin is precipitated from its
ethereal solution in white flocks by alcohol.
This gamma-resin appears to be identical with the first two of
Johnston's resins. a. A concentrated syrupy solution of sandarac in
alcohol, when diluted with a large quantity of alcohol, deposits white
resinous flocks, which after washing with alcohol and boiling with
water, are inodorous and tasteless: they do not undergo alteration at
100°, but cake together at 150°, with coloration. They contain 76.32
p. c. C., 9.91 H., and 13.77 O., corresponding with the formula C¹ºH³¹O¤.
b. Strong solution of caustic potash or lumps of the solid hydrate,
added to the concentrated alcoholic solution of sandarac, produce a
deposit of potash-resin (the gamma-resin of Unverdorben), whilst a
second resin (alpha- and beta-resin of Unverdorben) remains in solu-
tion. The precipitate, washed with hot alcohol, decomposed by hy-
drochloric acid, and purified by repeated boiling with alcohol and with
water, yields a grey friable resin, melting at 260°, and containing 74∙17
p. c. C., 9.41 H., and 16.42 O., corresponding to the formula C40H00
(Johnston).
c. The solution from which the potash-resin has been separated
yields, when precipitated by water and hydrochloric acid, a brittle
resin of a fine yellow colour, which softens at 100°, and is com-
pletely soluble in cold alcohol and cold ether. After drying for 48
hours at 93°, whereby a hydrocarbon seems to be volatilised, it con-
tains 74.13 p. c. C., 9.82 H., and 16·05 0., corresponding with the
formula C40H³¹06 (Johnston).
Concerning Gummi Sicopira, see Peckolt (N. Br. Arch. 109, 37).
29. TACAMAHAC. The West Indian, from Amyris tomentosa, is pale-
brown, opaque, very brittle, of sp. gr. 1·046 (Brisson). It is easily
fusible, and soluble in alkalis and in alcohol. Has an agreeable odour
and aromatic taste, arising from the presence of volatile oil, which
distils with water. The East Indian, from Calophyllum Inophyllum, is
yellowish-green, transparent, soft, of an agreeable odour and bitter
aromatic taste. It melts easily, and dissolves completely in alcohol.
According to Sommer, it does not yield umbelliferone by dry distillation.
C. Fossil Resins containing Oxygen.
1. AMBER. Succinum. Electrum.
Occurs as a fossil in the bed of
the sea, and in alluvial deposits. Concerning its origin and occurrence
FOSSIL RESINS (AMBER).
431
see Göppert (Pogg. 38, 624; N. Br. Arch. 11, 201.- Berl. Acad. Ber.
1853, 449; Pharm. Centr. 1853, 616). Yellow, transparent or trans-
lucent, also white and opaque; sp. gr. 1.065 to 1.070; hard, of smooth,
conchoïdal fracture; strongly negatively electric when rubbed. In hot
oil it becomes so soft that it may be bent, but it is not fusible with-
out decomposition. Inodorous and tasteless.
Pure transparent and slightly coloured pieces of amber contain, on
the average (after deducting 0.19 p. c. of ash), 78.60 p. c. C., 10-19 H.,
10.99 O., and 0.22 N. (Schrötter, Pogg. 59, 64). It contains also sul-
phur in the form of an organic compound, amounting at most to 0.48
p. c., so that, on submitting amber or the portion of it soluble in ether
to dry distillation, hydrosulphuric acid is evolved (Bandrimont, Compt.
rend. 58, 678). It contains a small quantity of fragrant oil, succinic
acid [the white more than the transparent, the former tasting dis-
tinctly acid when chewed (Recluz, J. Chem. méd. 15, 276)], a resin
easily soluble in alcohol (alpha-resin), a second resin less easily soluble
(beta-resin), and an insoluble resin (gamma-resin), amounting to more
than 90 p. c. (Berzelius).
When powdered amber is repeatedly exhausted with warm ether,
which leaves gamma-resin, and the liquid is evaporated, there remains
a mass smelling of turpentine and yielding, by distillation with water,
a volatile oil having an odour of peppermint and rosemary, whilst the
residual water contains succinic acid and deposits a yellow mixture of
two resins. The same resins may be extracted from powdered amber
by warm absolute alcohol, and freed by boiling with water from volatile
oil, succinic acid, and a peculiar body which prevents the crystallisation-
of the succinic acid. A solution of the yellow resinous mixture in
boiling alcohol of sp. gr. 0.84 deposits the beta-resin as a white powder
on cooling and partial evaporation, whilst the alpha- resin is obtained.
by the complete evaporation of the filtrate (Berzelius).
Alpha-resin. — Yellow and transparent; still smelling a little of
volatile oil. It yields with caustic potash a pale-yellow solution preci-
pitable by excess of potash, and from which acids throw down a white
jelly. Dissolves easily in alcohol and ether (Berzelius).
Beta-resin. White inodorous and tasteless powder, melting only
at a high temperature, with incipient decomposition. It forms with
caustic potash a colourless solution from which acids precipitate a jelly
resembling hydrate of alumina, which is white and earthy when dried.
The alkaline solution is precipitated by excess of caustic potash; it
leaves on evaporation a white opaque mass, which when treated with
water, remains for the most part undissolved. The resin dissolves
slightly in cold alcohol of sp. gr. 0·84, and yields with the boiling liquid
a solution from which it is deposited on cooling, in a mass which ad-
heres firmly to the glass; absolute alcohol and ether dissolve it more
easily, and leave it as a fine powder on spontaneous evaporation.
When the mixture of alpha- and beta-resin is dissolved in aqueous
potash, and the solution is evaporated, there remains a residue from
which water and alcohol extract the compound of the alpha-resin, leav-
ing that of the beta-resin undissolved (Berzelius).
Gamma-resin. The gamma-resin, heated in the air, emits fumes.
smelling of heated fat, swells up without melting, and turns black-
brown, and is then soluble in alcohol and in ether. When heated
without access of air, it melts, and on cooling solidifies to a dark-brown
mixture of resins, from which alcohol, ether, and rock-oil, employed in
432 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
succession, extract resins. The gamma-resin yields by dry distillation
colourless water with a trace of succinic acid, and afterwards an empy-
reumatic oil, leaving charcoal. It is insoluble in hot caustic soda, but
when boiled therewith till it melts, it gives off fumes and yields a
colourless empyreumatic oil, leaving a residue from which cold water
takes up the excess of soda containing a little resin and succinic acid,
whereupon the remainder dissolves almost entirely in warm water.
The gamma-resin is insoluble in alcohol, ether, and volatile oils
(Berzelius, Pogg. 12, 419).
When amber is exhausted with ether, the tincture evaporated,
and the residue boiled with water to expel ether and volatile oil, there
remains an opaque, brittle resin of agreeable odour, softening at 90°
and becoming fluid at 170°; after melting it softens only at 100°, and
is transparent and harder than before. When subjected to dry distil-
lation, it yields nearly as much succinic acid as the amber from which
it is obtained. It contains, on the average, 78:49 p. c. C., 10·08 H.,
and 11·43 0.—- The amber-resin insoluble in ether does not yield suc-
cinic acid, even after heating with sulphuric acid (x, 108) (Schrötter,
Pogg. 59, 64).
The portion of amber insoluble in ether and alcohol (Forchhammer's
succinin) contains 79.69 p. c. C., 10-22 H., and 10.19 O., and has there-
fore the same composition as sylvic acid (xvii, 318).— The soluble
portion is a mixture of boloretin (p. 434) and succinin, containing 78.58
p. c. C., 10.07 H., and 11.36 0.: its solution in hot alcohol deposits,
on cooling, flocks resembling boloretin (Forchhammer, Ann. Pharm.
41, 47).
Amber when submitted to dry distillation, melts, turns brown, swells
up, evolves carbonic acid and combustible gas, together with water
containing succinic acid, acetic acid, and empyreumatic oil (Spiritus
succini), and yields a sublimate of succinic acid and a distillate consist-
ing of first a thin, and afterwards a thick empyreumatic oil (xiv, 323);
a residue soluble in alcohol and oils is left behind (Colophonium succini).
The residue when further heated, boils up strongly and yields a
brown-yellow oil: the residue turns solid, carbonises, and gives off
yellow vapours of chrysene (xv, 1) and succisterene (xvi, 248), together
with carbonic acid, hydrocarbons, and a little water. No umbelliferone
is found amongst the products of distillation (Sommer).
Amber is violently attacked by moderately warm nitric acid of sp.
gr. 1.34: the solution obtained by boiling for some days deposits with
water a large quantity of pale-yellow flocks soluble with brown colour
in ammonia, and contains camphretic acid, C20H14014 (Schwanert, Ann.
Pharm. 128, 122). — Oil of vitriol digested with amber at a gentle heat
forms a brown solution from which water throws down yellow flocks
containing sulphur (Unverdorben). Hot oil of vitriol produces a black
resin (Hatchett). On rapidly distilling powdered amber with hydro-
chloric acid, there pass over, besides succinic acid, yellow laminæ,
which, after washing with hot water, may be purified by repeated
crystallisation from absolute alcohol. They form micaceous laminæ,
lighter than water, soft, opaque, inodorous and tasteless, melting
at 85° to 86°, boiling above 300°, containing 85:41 p. c. C. and
13.71 H., or equal numbers of atoms of carbon and hydrogen, and
differing from chrysene (Bley & Diesel, N. Br. Arch. 55, 171). When
amber is boiled with excess of potash, the liquid contains succinic acid
and a small quantity of resin, which dissolves partially in water after the
FOSSIL RESINS (ASPHALT).
433
removal of the alkaline liquid (Berzelius). Alcoholic potash acts in a
similar manner (Unverdorben, Pogg. 8, 407). The mixture of concen-
trated caustic potash and powdered amber evolves when boiled to dry-
ness an odour of camphor, and yields a distillate of amber-camphor
(Reich, N. Br. Arch. 51, 26).
10
The amber-camphor just mentioned is obtained by distilling powdered
amber with 4th its weight of potash and a large quantity of water, and
amounts to ths p. c. It resembles common camphor, has a peculiar
penetrating odour, and is isomeric with borneol (xiv, 332), but acts
less powerfully on polarised light, rotating a ray to the right ([a]j =
4.5°). Like borneol it forms with hydrochloric (xiv, 353) and stearic
acids (xvii, 125) compounds from which potash separates it unaltered;
it is likewise oxidised by nitric acid to a compound isomeric with com-
mon camphor. It appears to exist in amber in the form of a compound
ether (Berthelot & Buignet, Compt. rend. 50, 606; Ann. Pharm. 115, 244).
Boiling water extracts from powdered amber a small quantity of
succinic acid (Gehlen).- Alcohol and ether extract the acid, together
with volatile oil and the soluble resins (Berzelius). It is nearly in-
soluble in acetone (Widerhold), quite insoluble in fusel-oil, valerianic
aldehyde, valerianic acid, and valerate of amyl, but swells up in these
liquids; slightly soluble in carbolic acid (Runge); swells up in creosote,
and dissolves more abundantly than copal (Reichenbach). It dissolves
in 20 parts of cajeput-oil (Draper), is insoluble in rock-oil (Saussure),
not perceptibly soluble in castor-oil (Stickel); other volatile and fat oils
dissolve amber either not at all or very sparingly, if it has not been
altered by fusion.
2. AMBRITE. Occurs in pieces of the size of the head in the lignite
of Drury and Hunu, New Zealand. Amorphous, semi-transparent,
brittle, with a conchoïdal fracture and yellowish-grey colour. Sp. gr.
1.034 at 15°. Combustible. Soluble in bisulphide of carbon, leaving
an amorphous white mass; insoluble in boiling alcohol, ether, oil of
turpentine, benzene, and chloroform. Decomposed by melting with
hydrate of potash or by boiling with nitric acid (v. Hauer). Contains,
according to Maly, 76-53 p. c. C., 10.48 H., and 12-8 O., with 0.19 p. c.
of ash, corresponding to the formula C32H2604 (v. Hauer, Kopp's Jahresber.
1861, 1034).
3. ANTHRACOXENE. From Brandeisel near Schlau in Bohemia.
Occurs between shale in brownish-black brittle layers, 2 lines thick.
Sp. gr. 1-181. Combustible. Melts easily, swelling up. Contains 11
p. c. of ash, the remainder consisting of 75.3 p. c. C., 6.2 H., and 18.5 0.
It dissolves partially in warm ether, leaving a black powder. On
evaporating the ethereal solution, there is deposited, when the ether is
reduced to one-half, a brown powder containing 81-47 p. c. C., 8.71 H.,
and 9.82 0.: in the unaltered state it is insoluble in alcohol, but after
drying at 100°, during which it absorbs oxygen, it is partially soluble
in that liquid. According to Laurentz, it is represented by the
formula C8H107 (Laurentz, Wien. Acad. Ber. 21, 271; J. pr. Chem. 69,
428).
4. ASPHALT. Closely related on the one hand to the fossil-resins,
bitumen, and rock-oil, and on the other hand to coal, but distinguished
from the latter by its fusibility and its solubility in oil of turpentine.
VOL. XVII,
2 F
434
APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
It either occurs in the separate state (Erdpech; Judenpech) or is obtained
from earthy asphalt by boiling it with water (Goudron). Black opaque
lumps, of sp. gr. 1.07 to 1.17, brittle, and frequently with a pitchy
lustre. The asphalt obtained by boiling the earthy substance with
water is often soft, elastic, and sticky, or softens with the warmth of
the hand. It burns with a smoky flame. Dissolves with black colour
in oil of vitriol, generally only partially in ether, but completely in oil
of turpentine, with the exception of earthy impurities. Alcohol takes
up little or nothing. Caustic potash dissolves asphalt (from the Dead
Sea?) according to Thorey, but not that from Dax (Völckel), nor that
from Bentheim (Stromeyer. Thorey, Crell. Chem. J, 6, 56). Asphalt
—
from Bastennes (Meyrac, J. Phys. 94, 128); from Mexico (Regnault,
Ann. des Mines [3] 12, 224; Ebelmen, Ann. des Mines, [3] 15, 523;
Bouissingault Ann. Chim. Phys. 73, 442); Kersten on asphalt from the
island of Brazza, Dalmatia (J. pr. Chem. 35, 271); Stromeyer (Leonh.
u. Bronn, Jahrbuch 1861, 189); Wetherill (Kenngott's Jahrbuch. 1854,
140); Hermann (J. pr. Chem. 73, 230).
Analyses of Asphalt.
Ebelmen.
Boussing- Weth- Strom-
ault.
erill.
eyer.
Cuba. Bentheim.
Regnault.
Pont du
Mexico. Bastennes. Château,
Naples. Coxitambo.
C
80.34
84.54
76.41
80.62
88.67
82.67
86.68
H
9.57
9.58
9.58
8.28
9.68
9.14
9.30
N
1.80
2.37
1.06
0.66
....
O
10.09
4:08
11.64
10.04
1.65
8.19
2.82
...
****
....
100.00
100.00
100.00
100.00 100.00 100.00
99.46
....
and 0.54
p. cash.
The bitumen of Bechelbronn in Alsace occurs mixed with sand, and
is purified by boiling with water, during which the purer bitumen rises
to the surface and is skimmed off. It is tough and dark-brown, and
after being dissolved in ether and evaporated, contains 85.9 p. c. C.,
11.25 H., and 2.85 0. When distilled with water, or when heated to
250° for some days, it yields a distillate of petrolene: the residue is
asphaltene, forming a black shining mass, having a conchoïdal fracture,
softening at 100°, and burning like a resin; it dissolves in ether and
in volatile and fat oils, but not in alcohol. Asphaltene is obtained in a
purer state by heating bitumen to 250° for 40 or 50 hours. It contains
74.23 p. c. C., 9.9 H., and 15 87 O., corresponding to the formula
C0H160³. Petrolene is pale-yellow, of sp. gr. 0.891, and boils at 280°.
It is inflammable. Its vapour-density is 9.415 (calc. for C40H82
9.429). It contains 87.15 p. c. C., and 12.28 H., corresponding to the
formula C4H92 (calc. 88.23 p. c. C., 11.77 H.) (Boussingault, Ann.
Chim. Phys. 64, 145).
32
32
The brownish-yellow asphalt-oil obtained by the dry distillation of
the asphalt-stone of Neuenburg in iron cylinders, when submitted to frac-
tional distillation, passes over for the most part between 120° and 200°,
the smaller portion distilling at 200-250°, and leaves a little dark,
thick residue. Both portions have the same composition (87-46 p. c.
C., 11·61 H., and 0.93 0.) but differ in specific gravity (0·817 and
0-868). They are violently attacked by nitric acid, which converts
FOSSIL RESIN FROM BUCARAMANGA.
435
them into resins, and are dissolved to the extent of one-half by oil of
vitriol, forming red solutions. The undissolved portion, again treated
with oil of vitriol and caustic potash, distils between 120° and 250°,
the distillate varying in specific gravity between 0.784 and 0.867, but
containing, at all the different boiling-points, an amount of carbon and
hydrogen agreeing with the formula CH³ (87.31 to 87.59 p. c. C., 12·30
to 12.69 H.) (Volckel, Ann. Pharm. 87, 139). See also v. Perger (Wien.
Acad. Ber. 35, 489).
5. BERENGELITE.-Occurs in large quantities in the province of St.
Juan de Berengela, 100 miles from Arica. Dark-brown, hard mass,
triturable to a yellow powder. It is insoluble in water, but dissolves
abundantly in cold alcohol, which leaves it on evaporation as a trans-
parent, red, sticky mass, becoming brittle only after some months. It
dissolves easily in ether, and in a boiling dilute solution of caustic
potash, from which it is precipitated by acids, but is insoluble in strong
caustic potash. It is precipitated from its alcoholic solution by neutral
acetate of lead. The crude earth-resin contains 71 01 p. c. C., 9.28 H.,
and 19.71 0. The residue left on evaporating the alcoholic solution
contains, at 100°, 72.81 p. c. C., 9.37 H., and 17.82 0. (Johnston, Phil.
Mag. 14, 89; J. pr. Chem. 17, 110: further Phil. Trans. 1840, 346).
6. BOLORETIN. Occurs in the bark and wood of fossil pines from
Danish peat-bogs, and more abundantly in a grey earth found in hollow
fossil pine-trunks; also in peat from Jylland, and in freshly-dropped
pine-needles. The portion of amber soluble in ether contains boloretin.
It is extracted from these bodies by boiling with alcohol, from which
it is deposited as a grey powder on cooling; and may be purified by
repeatedly dissolving it in boiling alcohol, or by precipitating the alcoholic
solution with neutral acetate of lead, whereby colouring matters are
thrown down. It forms white amorphous flocks, melting at 75°,
decomposible by anhydrous phosphoric acid, with formation of empy-
reumatic oil. Contains
From pine needles...
From Jylland peat: from
to..
73.46 p. c. C., 11:50 H., and 15.04 0.
74.19 p. c. C., 11.84 H., and 13.97 0.
75.50 p. c. C., 11·70 H., and 12·80 0.
According to Forchhammer, it is to be regarded as a hydrate of
turpentine, C4H92 + 5HO (calc. 75.73 p. c. C., 11.7 H.); a part of
the water is expelled when boloretin from fresh pine needles is allowed
to stand for a month covered with alcohol, and afterwards boiled with
water, dried, and melted, the product thus obtained containing 79.6 p. c.
C., 11.01 H., and 9.39 O., and corresponding to the formula CH³² +
3H0 (calc. 80-2 p. c. C., 11.7 H.) (Forchhammer. Ann. Pharm. 41,
44).
32
The lignite of the Westerwald contains a resin soluble in ether,
and a second resin resembling boroletin (Krämer, N. Br. Arch. 27,
73),
7. EARTH-RESIN FROM BUCARAMANGA (New Granada). Occurs in
large pieces, one of which was found to weigh 24 pounds, in an alluvial
deposit yielding gold. - Pale-yellow and translucent, easily fusible,
electric when rubbed, a little heavier than water. Burns with a
slightly smoky flame, leaving no residue. Does not yield succinic acid
2 F 2
436
APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
by dry distillation. Insoluble in alcohol. Swells up in ether, and
becomes opaque. Contains 82.72 p. c. C., 10.85 H., and 6.43 0.
(Boussingault, N. Ann. Chim. Phys. 6, 507; J. pr. Chem. 28, 380).
-
8. COPALIN. Highgate resin or Fossil Copal. From the blue clay of
Highgate-hill, London. - Yellowish-brown or dirty-grey translucent
pieces, having a resinous lustre, softer than copal, harder than pine-
resin. Melts easily without decomposition; smells aromatic and
resinous, especially when broken or warmed. Volatilises, according to
Johnston, at a gentle heat, leaving a little charcoal and ash. Sp. gr.
1.046 (Thomson), 1-05 (Bastick). Very easily inflammable. Dissolves
in oil of vitriol, forming a dark purple solution, from which water pre-
cipitates charcoal (Bastick). According to Bastick, nitric acid converts
it into fosresinic acid; according to Thomson, the acid reddens, and partly
dissolves it, forming a red solution, from which it is precipitated in
white bitter flocks by water. - Copalin dissolves very slightly in alcohol;
the solution is precipitated white by alcoholic neutral acetate of lead
(Johnston, Phil. Mag. Feb. 1839, 87; J. pr. Chem. 17, 107). Insoluble,
or according to Thomson (Thoms. Ann. 2, 9), slightly soluble in boiling
caustic potash; easily soluble in ether (Bastick, Pharm. Journ. 8, 339;
Repert. (3) 10, 169; J. Chim. méd. 25, 383).
.
To this place belongs a fossil resin from the East Indies. Light
honey-yellow, transparent, of waxy lustre, and having a conchoïdal
fracture. Sp. gr. 1·053.
Sp. gr. 1·053. Brittle. Melts easily to a clear liquid, takes
fire, and burns. Dissolves for the most part in oil of vitriol, and slightly
in alcohol (Kenngott, Kenny. Jahresber. 1850 and 1851, 147). Analysed
by Duflos.
Johnston.
Duflos.
80 C
66 H
480
66
........
185.41
11.74
....
84.79
11.79
85.05
85.73
11.48
11.50
20
16
2.85
3.42
3.47
2.77
CS0H6602
562
100.00
100.00
100.00
100.00
.......
Bastick's Fosresinic acid is formed by treating copalin with hot
nitric acid. It is a yellow amorphous powder, very acid and bitter,
slightly soluble in cold, more easily in hot water, soluble also in
alkalis, forming red-brown solutions, precipitable by salts of the
earths and metals. It dissolves in alcohol and ether.
9. EUOSMITE. From the lignite of Thumsenreuth in the Upper
Palatinate. Brown-yellow dusty masses, or hard compact pieces, of
the colour of cherry-tree wax. Brittle, with a conchoïdal fracture.
Has an agreeable odour of camphor and rosemary, even after melting.
Melts at 77°. Burns with a luminous flame, emitting an aromatic odour.
Dissolves slightly in boiling caustic potash, and in boiling ammonia-
water, which it colours yellow. Partially soluble in oil of vitriol, with
separation of carbon; boiling oil of vitriol is coloured yellowish-
brown by it. - Dissolves easily in cold alcohol and ether, and remains
as a glutinous mass on evaporation. Dissolves completely in hot oil
of turpentine (Gümbel, Leonhard u. Bronn, Jahrbuch, 1864, 10). Con-
tains 81.89 p. c. C., 11·73 H., and 6·38 O., corresponding to the formula
C34H2902 (Wittstein).
10. FOSSIL CAOUTCHOUC. The English variety is brown, translu-
cent, of sp. gr. 0·926, soft, less tough and elastic than ordinary caout-
FOSSIL RESINS (HARTIN).
437
chouc, has an even and smooth conchoïdal fracture with somewhat fatty
lustre, and a bituminous smell (Klaproth). The French is black-
brown, opaque, lighter than water, and very tough and elastic
(0. Henry.) Melts easily, and burns with a very smoky flame; after
melting it is very slightly elastic, and soluble in volatile oils (Klaproth).
When submitted to dry distillation, it yields a yellow empyreumatic
oil. The English variety is insoluble in water and alcohol: it swells
up in rock-oil and oil of turpentine without dissolving (Klaproth),
Beitr. 3, 107). — Boiling ether or oil of turpentine extracts from English
caoutchouc a yellowish-brown, sticky, bitter substance, soluble in
aqueous potash; the portion insoluble in ether or oil of turpentine
(about half the caoutchouc) is grey, paper-like, and partially soluble
in potash (O. Henry, J. Chim. méd. 1, 18).
The elastic earth-resin of Derbyshire occurs in three varieties.
1. Brown, sticky, soft, elastic mass, having a strong smell, and giving
off odorous constituents at 100°. Contains 83·88 p. c. C., 13·28 H.,
and 2.84 0. — 2. Dark-brown, caoutchouc-like substance, harder than 1.
When boiled with water, it deposits a soft, white-brown substance,
which is also extracted by boiling alcohol or ether. After boiling with
ether and alcohol, which dissolve 18 p. c., it contains 82.80 p. c. C.,
12.58 H., and 4.62 0.-3. Brittle pieces sometimes occurring in the
soft mass, and containing 84-46 p. c. Č., 12.38 H., and 3.16 0. (Johnston,
J. pr. Chem. 14, 442; Phil. Mag. 13, 22).
11. GUYAQUILLITE. A South American earth-resin from the neigh-
bourhood of Guyaquil. Pale-yellow, opaque, soft, and easily triturable.
Sp. gr. 1.092. Its alcoholic solution tastes very bitter: it yields pale-
yellow prisms on evaporation. The resin melts at 70° to a viscid
liquid, which becomes limpid at 100°, and remains tough and sticky
on cooling. Dissolves very slightly in water. Decomposed by nitric
acid, and dissolved with red-brown colour by oil of vitriol. Soluble
in ammonia-water, and more easily in potash, forming yellow solutions
precipitable by acids: the alcoholic solution is rendered darker and
brown-red by ammonia. Neutral acetate of lead precipitates the
alcoholic solution yellow. Nitrate of silver produces no precipitate at
first: the slight precipitate thrown down after a few hours becomes
more abundant on addition of ammonia, and turns brown or black.
The resin dissolves abundantly in alcohol, forming a pale-yellow
solution. It contains 75.98 p. c. C., 8.18 H., and 15.84 O., correspond-
ing to the formula C40H6O6 (Johnston, Phil. Mag. 13, 329; J. pr. Chem.
16, 102).
SCHRÖTTER. Pogg. 59, 45.
12. Hartin.
Different from Hartite, a fossil-resin not containing oxygen.
From the lignite of Oberhart near Gloggnitz, Austria. Occurs as a
deposit in the transverse fissures of lignite, and is extracted by
ether.
Purification. 1. The hartin obtained by scraping is washed with
ether so long as the liquid is coloured. and the residue, freed from
438
APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBon.
ether, is dissolved in boiling rock-oil, from which crystals are
deposited on cooling. The crystals are pressed, washed with alcohol,
and afterwards with ether, and dried at 200°.-2. If the lignite is
exhausted with ether in a percolator, the ether dissolves hartin
through the medium of the other resins present, and deposits it in
lamine on partial evaporation.
i
Long white needles, of sp. gr. 1-115, without smell or taste,
triturable to a powder between the fingers. Hartin crystallised from
rock-oil softens at 200°, and melts at 2102; that crystallised from
ether melts only at 230°, with decomposition, to a clear yellowish oil,
which afterwards becomes darker, evolving a disagreeable odour, and
solidifies in a waxy mass on cooling. From this mass ether takes up
the changed portion, forming a dark-coloured solution, whilst un-
changed hartin remains behind. Combustible. Distils at 260° as a
yellow empyrumatic oil, which solidifies to a brown-yellow crystalline
mass on cooling. During the distillation, combustible gases are
evolved, and a little acid liquid is also formed. By dissolving the dis-
tillate in ether and evaporating the solution, white crystals are
obtained. Hartin is completely decomposed by hot oil of vitriol, but
scarcely at all by the cold liquid. It dissolves very slightly in abso-
lute alcohol, even at the boiling heat, but is somewhat more soluble in
ether, and still more so in rock-oil.
Schrötter
a.
b. (mean).
40 C
240
78.94
78.26
78.40
32 H
32
10.53
10.92
10.92
.......
4. O
32
10.53
10.82
10.68
C40H320+
304
100.00
100.00
100.00
Schrötter's formulæ is C20H1702.
according to 2.
a was prepared according to 1, 6 from lignite
Amorphous resin from the ethereal extract of Lignite. The ethereal
solution from which hartin has crystallised leaves on evaporation a
black asphalt-like residue, which, when dissolved in a small quantity
of ether, deposits a little more hartin, and may then be separated, by
treating it with absolute alcohol into alpha-resin which dissolves, and
beta-resin which remains behind. The alpha-resin softens at 100°,
and melts at 120°, without becoming limpid: it yields brown precipi-
tates with neutral acetate of lead and nitrate of silver. The beta-
resin softens only at 205°, and puffs up at 210°, from incipient decom-
position.
According to Schrötter.
Schrötter.
Schrötter.
α.
42 C
252
78.51
•
29 H .....
50
29
40
....
9.05
12·44
78.48
9.17
12.35
C40H2905
321
100.00 ... 100.00
32 C
21 H
5 0.
C32H2¹05 253
....... 192
75.9
21
8.3
....
40
15.8
B.
75.66
8.56
15.78
100.0
100.00
....
....
....
....
On Hircin-resin, see Piddington (Chem. Gaz. 1852, 216; Pharm. Centr.
1853, 28.)
13. JAULINGITE. - From Jauling in Lower Austria, occurring in
lignite. Irregular lumps or thin plates of a fine hyacinth-red colour
FOSSIL RESINS (MELANCHYM).
439
and waxy lustre, brittle, triturable to a pale-yellow powder. Sp. gr.
1.098 to 1.111. It is combustible and easily fusible, and yields by
dry distillation a brown empyreumatic oil. - Contains a portion soluble
in bisulphide of carbon, of a brown-yellow colour, brittle, softening at
50°, easily soluble in ether and alcohol, but almost insoluble in caustic
potash, a. The remainder, which may be extracted by ether, is
brown-yellow and brittle, softens at 135°, becomes tough at 160°, and
dissolves in alcohol, ether, and warm caustic potash, b (Ragsky,
Wien. Acad. Ber. 16, 366; Kenng. Jahresber. 1855, 115).
a.
Ragsky.
Ragsky.
b.
mean.
mean.
26 C
78
77.97
18 C
71.05
70.90
20 H
10
10.14
12 H
7.89
7.94
30
12
11.89
C26H 2003
100
100.00
4 O
C18H120+
21.06
21.16
100.00
100.00
....
14. IXOLYTE. - An amorphous hyacinth-red resin, occurring,
together with hartite, in the fossil wood of Oberhart, near Gloggnitz:
it is found more especially in the cracks of the wood, sometimes in
contact with hartite, from which, however, it differs distinctly in colour
and texture. It has a conchoïdal to earthy fracture and a fatty lustre,
and is friable between the fingers. Sp. gr. 1.008. Softens at 76°,
and is still viscid and elastic at 100° (Haidinger, Pogg. 56, 345).
15. KRANTZITE. -Occurs in the lignite of Lattorf, near Bernburg,
in pieces of the size of the fist, containing a light-yellow or greenish
translucent and inodorous resin, covered with an opaque yellowish
coating. The resin has a sp. gr. of 0.968, begins to melt at 225°, but
becomes fluid only at 288°, turning brown, and yields a brown oil and
gases at 300-375°. It dissolves only to a small extent in alcohol
and ether, swells up in volatile and fat oils, and in chloroform and
bisulphide of carbon; is insoluble in alkalis, but dissolves in oil of
vitriol with red-brown colour, and yields by dry distillation a brown oil
free from formic and succinic acids. After being heated till it begins
to melt, a portion is dissolved by alcohol, from which it is precipitated
by neutral acetate of lead: the remainder is taken up by ether, forming
a yellow solution. The ethereal solution leaves on evaporation an acid
amorphous residue, which is friable at 0°, soft at 12°, and contains
79.25 p. c. C., 10:41 H., and 10-34 O., corresponding to the formula
C40H30Ô¹ or C40H3204 (Bergmann, J. pr. Chem. 76, 65; abstr. Chem.
Centr. 1859, 666).
16. MELANCHYM. - Yellowish-brown, bituminous substance, from
the lignite of Zweufelsreuth, near Eger (Haidinger, Kenng. Jahresber.
1853, 134). By dry distillation it yields an empyreumatic oil, ap-
parently free from succinic acid, and leaves charcoal (Rochleder).
Melanchym is resolved by treatment with warm alcohol into a
residual black jelly, and a soluble portion, which is left on evaporating
the solution as a brittle red-brown mass a, triturable to a pale-
brown powder, melting above 100°, and combustible. The black
jelly, after washing with aqueous alcohol, dissolves in caustic potash,
from which hydrochloric acid throws down the brown flocks b
(Rochleder, Ann. Pharm. 78, 248; Wien. Acad. Ber. 6, 53).
440
APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
a.
Rochleder.
b.
Rochleder.
40 C........
28 H
76.80
76.79
80 C
67.22
67.14
8.72
9.06
34 H
4.76
4.79
6 0 ......
14.48
14.15
25 O
28.02
28-07
C40H2806
100.00
100.00
CS0H34025
100.00
100.00
17. MIDDLETONITE. Round masses, occurring in thin layers in
the coal-measures of Leeds. Hard, brittle, transparent, and dark-red
in thin layers; red-brown by reflected light. Sp. gr. about 1·6.
Inodorous and tasteless. Turns black and like coal in the air. It does
not undergo alteration at 205°, melts when submitted to dry distilla-
tion, and burns like a resin on charcoal. Boiling nitric acid softens
and dissolves it with decomposition. Oil of vitriol dissolves it, libe-
rating sulphurous acid, and forming a dark-brown solution. Boiling
alcohol, ether, and oil of turpentine are coloured yellow by it, but
dissolve only traces. It contains 84.59 p. c. C., 8·03 H., and 7.38 0.,
corresponding to the formula C40H22O2 (Johnston, Phil. Mag, 12, 261;
J. pr. Chem. 13, 436).
M
18. PIAUZITE. From the lignite of Piauze (Carniola). Black-
brown, of fatty lustre, and imperfect conchoïdal fracture, friable
between the fingers Sp. gr. 1.22. Melts at 315°, takes fire, and
burns with a brisk flame and much smoke, evolving an aromatic odour.
By dry distillation it yields a yellow, acid oil.
It dissolves com-
pletely in caustic potash and in absolute alcohol, but only partially in
weak alcohol and in ether (Haidinger, Pogg. 62, 275).
19. PYRORETIN. A brown earth-resin from the lignite of Salesl,
near Aussig, in Bohemia. Nodules from the size of a nut to that of
the head, or thick plates, brittle, and easily triturable. Sp. gr. 1·05
to 1.18. Combustible. When boiled with alcohol, it leaves a residue
which is quite insoluble in boiling strong caustic potash (c). The
alcohol, on cooling, deposits the powder a, and when filtered therefrom
and evaporated, leaves a brown resinous mass, which dissolves in
ether, with the exception of some black flocks, and is recovered as a
light brown brittle mass (b) by evaporating the solution (Stanek, Wien.
Acad. Ber. 12, 551; Kenng. Jahresber. 1854, 141).
a.
40 C..........
80.00
Stanek.
80.02
b.
Stanek.
80 C
81.08
81.09
28 H
9.33
4 O..
10.67
9.42
10.56
56 H
9.46
9.47
70
9.46
9.44
C40 H2804 ....
100.00
100.00
C80H5607 ....
100.00
100.00
C.
Stanek.
39 C
22 H
60
76.97
7.24
15.79
76-71
7.31
...
15.98
C38H2206
100.00
100.00
20. RETINASPHALT.- A yellowish-brown body, of earthy appearance,
seldom compact and shining, of sp. gr. 1·07 to 1·35. Fusible. Burns
with white flame, emitting an aromatic odour. Retinasphalt from the
Saalkreise contains 91 p. c. of easily soluble resin, and 9 p. c. of an
FOSSIL RESINS (RESIN OF SETTLING STONES).
441
insoluble resin resembling amber (Buchholz, Schw. 1, 290). That from
Cape Sable contains 42.5 p. c. of easily soluble, 55 p. c. of insoluble
resin, and 1.5 p. c. of oxide of iron and alumina (Troost). That from
Bovey contains, according to Hatchett (A. Gehl. 5, 316), 55 p. c. of
easily soluble, and 42 p. c. of insoluble resin; according to Johnston,
13.23 p. c. of mineral substances, 27-45 of resin soluble, and 59-23 p. c.
of resin insoluble in alcohol, the last of which is Johnston's retinic acid.
It remains, on evaporating the alcoholic solution, as a pale-brown resin,
which emits a resinous odour at 100°, melts with loss of weight at
120°, and gives off bubbles of gas at 205°. It dissolves freely in ether,
from which it is precipitated in great part by alcohol; and is slightly
soluble in alcohol, and precipitable therefrom by water. The alcoholic
solution is slightly precipitated by chloride of calcium, and more abun-
dantly by alcoholic neutral acetate of lead. The acid contains, at 100°,
75.03 p. c. C., 8.77 H., and 16.20 0.; the fused acid 77.08 p. c. C., 8.70
H., and 14·22 O.; the lime-salt 10.26 p. c. CaO.; the silver-salt 41.78
to 43.58 p. c. AgO. Johuston gives the formula C40H27O6 (Johnston,
Phil. Mag. 12, 560; Phil. Trans. 1840, 347; J. pr. Chem. 14, 437; 26,
146). See also Cerutti (N. Br. Arch. 22, 186).
21. RETINITE. Walchovite. Occurs in the coal-mines of Walchow,
in Moravia, in rounded pieces of the size of a bean to that of the head.
Yellow, with conchoïdal fracture and fatty lustre. Brittle. Sp. gr.
1.035 to 1.069. Becomes translucent and elastic at 140°, without
melting, and melts to a clear oil at 250°. When subjected to dry dis-
tillation it yields combustible gas, tar, and aqueous ammonia. Com-
bustible. Alcohol takes up 1.5 p. c., ether 7.5 p. c. of resin: both resins
are transparent, yellow, and tough. Retinite softens in bisulphide of
carbon, but dissolves only to a slight extent: it is likewise very
slightly soluble in boiling rock-oil. Contains 80-40 p. c. C., 10.68 H.,
and 8.74 O., corresponding to the formula C40H3103 (Schrötter, Pogg.
59, 61). See also Cerutti (N. Br. Arch. 22, 286).
Retinite occurs in reddish-yellow brittle layers in the lignite of the
Wilhelmszeche mine in the Westerwald: the branchite or scheererite
found in the same place, likewise passes into a resin, which has the
colour and soft waxy quality of retinite (see above), and does not melt
at 225°, but becomes brittle on cooling, and dissolves completely in
alcohol and ether (Casselmann).
22. SCHLERETINITE. A fossil resin from the coal-mines of Wigan.
Black drops and granules, sometimes as big as nuts, brittle, and of con-
choïdal fracture. Sp. gr. 1.136. Combustible. By dry distillation it yields
water and a large quantity of empyreumatic oil, and leaves a residue
of charcoal. It is insoluble in water, alcohol, ether, and alkalis, and is
slowly decomposed by strong nitric acid. When it is reduced to fine
powder and boiled with water, alcohol, and ether in succession, traces
of oil are dissolved, after which it contains at 120°, on the average,
3·68 p. c. of ash, 76.95 p. c. C., 8.95 H., and 10-42 O., corresponding
to the formula C40II2804 (Mallet, Phil. Mag. (4) 4, 261; Ann. Pharm.
85, 135). This body was erroneously regarded by Dana and Mallet
as identical with Rochleder's pyroretin. See Kenngott (Kenng. Jahrbuch.
1855, 117).
23. RESIN OF SETTLING STONES. From the refuse of a lead-mine in
Northumberland. Partly black and partly amber-yellow, and red or
442 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
brown-red within. Hard, brittle, and of conchoïdal fracture. Sp. gr.
1.16 to 1.54. Does not melt at 105°. Yields by dry distillation a
little transparent rock-oil, and afterwards a red empyreumatic oil,
leaving a large quantity of charcoal. Burns in the air, emitting dense
fumes and an aromatic, slightly burnt odour. Dissolves slowly but
completely in strong nitric acid, and very slightly in alcohol and
ether (Johnston, Ed. N. Journ. of Sc. 4, 122: further J. pr. Chem. 17,
108).
Johnston.
80 C .......
....
66 H....
480
66
85.41
85.29
………....
11.74
11.03
16
....
2.85
100.00
3.68
100.00
2 O......
CS0H6602 ........ 562
The above is the composition after deducting 3.25 p. c. of ash. According to
Johnston, the body is probably free from oxygen, and of the formula CH³.
24. TASMANNITE. From the banks of the Mersey, Tasmania. It is
separated from earthy impurities by digesting it with strong hydro-
chloric acid, the density of which is increased by the addition of chloride
of calcium, and by levigation. It is transparent and brown-red,
has a resinous lustre and a conchoïdal fracture. After deducting ash
it contains 79.34 p. c. C., 10·41 H., 5·32 S., and 4-93 0., corresponding
to the formula C80H62S204. By dry distillation it yields an oil and a
solid product. Burns easily with a smoky flame and a disagreeable
odour. It is slowly attacked by nitric acid, but is not decomposed by
hydrochloric acid. It is not altered by alkalis, and is insoluble in bi-
sulphide of carbon, alcohol, ether, benzene, oil of turpentine, and coal-
oil (Church, Phil. Mag. [4] 28, 465; Zeitschr. Ch. Pharm. 8, 137).
25. RESINS OF PEAT. A. From compact Friesland peat. When peat
which has been exhausted with boiling water is boiled with alcohol, a
brown solution is obtained, whilst delta-resin remains in the peat and
may be extracted by rock-oil. The alcoholic solution deposits on cool-
ing grey flocks of gamma-resin, which may be purified by redissolving
them in boiling alcohol and cooling, and afterwards precipitating the
hot alcoholic solution with alcoholic neutral acetate of lead, filtering
from the precipitate, cooling the filtrate, and dissolving the flocks which
separate in ether. The alcoholic mother-liquor holds in solution alpha-
and beta-resins, the former of which (after evaporating the solution to
dryness, boiling with water, and dissolving in a little alcohol) may be
thrown down as a grey-black precipitate by alcoholic basic acetate of
lead, and the latter precipitated from the filtrate by water in grey-green
flocks free from lead.
- The
The alpha-resin forms a lead-salt containing 56.55 p. c. C., 7·81 H.,
and 21·42 PbO., corresponding to the formula C50H4009, PbO.
beta-resin is gall-green, sticky, melts at 52°, is easily soluble in alcohol
and ether, soluble with red colour in oil of vitriol, insoluble in boiling
caustic potash, and difficultly decomposible by strong nitric acid. It
contains, at 100°, 76-31 p. c. C., 10-98 H., and 12.71 O., corresponding
to the formula C7H709. -- The gamma-resin is white, brownish when
dried, waxy, and melts at 74°. It dissolves in oil of vitriol, forming a
solution precipitable by water, and is soluble in warm caustic potash
from which it is precipitated by acetic acid: it does not dissolve in
cold alcohol. It contains, at 100°, 78·05 p. c. C., 11·94 H., and 10.01 0.,
67
REISINS FROM THE LIGNITE OF WEISSENfels.
443
corresponding to the formula C104H4O9. The delta-resin is deep-
brown, brittle, melts at 68°, and is insoluble in boiling alcohol and hot
caustic potash, but soluble in ether and rock-oil. It contains, at 100°,
79.70 p. c. C., 12·15 H., and 8.15 0., corresponding to the formula
C131H12O (Mulder (J. pr. Chem. 16, 495; 17, 444).
B. The light Friesland peat yields in like manner an alpha-resin
soluble in cold alcohol, and a gamma-resin insoluble therein. The
alpha-resin is black, sticky, fusible at 55°, soluble with red colour in
oil of vitriol, and slightly soluble in caustic potash. It is precipitated
by alcoholic basic acetate of lead, and is soluble in ether. It contains
75.12 p. c. C., 10.21 H., and 14.67 O., corresponding to the formula
C35 H2805.
The gamma-resin is brittle, fusible at 74°, insoluble in caustic
potash, and very easily decomposed by nitric acid. It dissolves in
rock-oil, ether, and in a large quantity of boiling alcohol, from which
it is deposited on cooling. Contains, at 100°, 79-43 p. c. C., 12·54 H.,
and 8.03 0. Water throws down from its solution in oil of vitriol a
precipitate containing sulphuric acid (Mulder, J. pr. Chem. 17, 449).
26. XYLORETIN.In the fossil pine-trunks of Danish peat-hogs.
When these are exhausted with alcohol, the solution evaporated, the
residue again dissolved in ether, and the ether allowed to evaporate
slowly, the xyloretin separates in indistinct crystals, which melt at
165° and are not volatile without decomposition. It evolves hydrogen
with potassium, and forms a potash-salt crystallisable from alcohol.
Contains, on the average, 78.97 p. c. C., 10.87 H., and 10.16 O., cor-
responding to the formula C40H2O (Forchhammer, Ann. Pharm. 41,
42). See also Boloretin (p. 435), retene (p. 8), and Tehoretin (under Fichtelite).
Schrötter (Pogg. 59, 54), by exhausting wood from the peat-beds
of Redwitz in the Fichtelgelbirge with ether, and evaporating the solu-
tion, obtained crystals melting at 145° to 160°, whilst an oil having the
composition C40H0 or C40H32 (88.58 p. c. C., 11.34 H.) remained in solu-
tion. The crystals contain 79.75 p. c. C., 10.03 H., and 9.22 0., and
according to Schrötter, are xyloretin. Retene (p. 8) and fichtelite,
C80H70, have also been found near Redwitz.
27. Resins from the Lignite of Weissenfels.
WACKENRODER.
N. Br. Arch. 60, 23; abstr. Ann. Pharm. 72, 315.
BRÜCKNER. J. pr. Chem. 57, 1.
The lignite-beds of Gerstewitz near Weissenfels (Saxony) contain
layers of opaque, dull, greyish-brown or yellow friable masses, of sp.
gr. 0.493 to 0-522, Kenngott's Pyropissite, from which alcohol extracts
wax-like substances, and which yield by dry distillation as much as 62
p. c. of paraffin (see below) (Kenngott & Marchand, Lieb. Kopp's Jahresber.
1850, 764). This pyropissite was, doubtless, the material employed in
Wackenroder's and Brückner's investigations.
Wackenroder's Cerinin is extracted from pyropissite by ether, and
remains on evaporating the solution, as a soft pasty wax, which be-
comes fluid at 100°, and contains 782 p. c. C., 12.3 H., and 9.5 O., cor-
responding to the formula C4H8O4, but is probably a mixture.
444
APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
1. Leucopetrin. An ethereal extract of the yellow-brown lignite
leaves on evaporation a wax from which boiling 80 p. c. alcohol takes
up 80 p. c., chiefly georetic acid, whilst leucopetrin remains undissolved.
It is purified by crystallisation from boiling absolute alcohol. - Colour-
less tufts of needles which melt at 100°, turning brown and decom-
posing. When treated with warm fuming nitric acid, it evolves a large
quantity of red fumes, without dissolving. It turns brown when
warmed with oil of vitriol and carbonises on boiling. It is insoluble
in caustic potash, soluble in 268 parts of cold absolute alcohol, and
more easily in ether; soluble also in rock-oil and oil of turpentine.
Insoluble in 80 p. c. alcohol.
Calc. according to Brückner.
50 C......
42 H
3 0
C50H4203
Brückner.
at 100°.
300
81.97
81.69
82.00
..
42
11.47
11.41
11.48
24
6.56
6.90
6.52
366
100.00
100:00
100.00
Or perhaps C6H560¹? (by calc. 82·26 C., 11·28 H., 6:46 O.) (Kr.).
2. Georetic acid. The alcoholic solution obtained in 1 solidifies to
a jelly on cooling, from separation of wax, which is completely removed
by concentrating and cooling the solution. From the brown alcoholic
mother-liquor, alcoholic neutral acetate of lead throws down a brown
precipitate of georetic acid, whilst a resin still remains in solution.
The precipitate is washed with alcohol and decomposed by strong
acetic acid, and the georetic acid is allowed to crystallise from alcohol.
It forms small white needles, which dissolve in alcoholic ammonia
and are left free from ammonia on evaporation. Dissolves easily in
boiling alcohol. The alcoholic acid forms with acetate of copper a
dirty-green precipitate containing, at 100°, 12.63 p. c. CuO (calc. for
C24H2¹CuO requires 12.14 CuO.).
Lead-salt at 100°
Brückner.
24 C
21 H
144
43.28
43.36
21
6.31
6.59
70
56
16.84
15.47
Pbo....
111.7
33.57
34.58
C24HaРbos
332.7
100.00
100.00 -
....
2a. The solution filtered from the lead-salt of georetic acid, when
freed from lead by hydrosulphuric acid, still contains a soft, pulveru-
lent resin, which is deposited, on evaporating the solution, in white
light granular masses containing 77.35 p. c. C. and 10-20 H., and ap-
proximately represented by the formula C50H4006.
3. Geomyricin. When the dark-brown lignite is exhausted with
cold alcohol of 80 p. c. to remove georetic acid and other substances, and
afterwards boiled with alcohol of the same strength, the filtrate, before
it is quite cold, throws down geomyricin in the form of a powder,
quickly followed by a gelatinous deposit of geoceraïn. The former
body is obtained more abundantly by boiling the lignite-residue with
absolute alcohol, and may be purified by recrystallisation. Light,
white powder, made up of microscopic capillary crystals. Melts to a
RESINS FROM THE LIGNITE OF WEISSENFELS.
445
yellow, very brittle wax at 80-83°. Burns with a luminous flame. It
is not acted upon by solution of caustic potash, but is attacked by the
fused hydrate.
Brückner.
mean.
68 C........
408
80.31
80.27
68 H......
68
13.38
13.37
4 O....
32
6:31
6.36
C68 H 6804
508
100.00
100.00
4. Geoceric acid. -The solution in boiling alcohol of 80 p. c. ob-
tained in 3, after being freed from geomyricin, still contains geoceric
acid and georceraïn, the former of which may be precipitated from the
boiling solution by alcoholic neutral acetate of lead, whilst the geo-
ceraïn is deposited from the filtrate on cooling. The lead-salt is boiled
with alcohol of 80 p. c., absolute alcohol, and ether, in succession, and
then decomposed by acetic acid, and the geoceric acid thereby sepa-
rated is purified by crystallisation. White lamellar shining mass,
melting at 82°, and very brittle and friable after fusion. - Dissolves
freely in hot alcohol and is deposited almost completely from the
solution on cooling in the form of a non-crystalline jelly.
Brückner.
mean.
56 C ....
336
79.24
78.64
56 H
56
13.21
12.70
4 O
32
7.55
8.66
C56H5604
424
100.00
100.00
Lead-salt.
Brückner.
56 C.......
336
63.79
63.82
55 H......
55
10.63
10.41
3 0....
24
4.38
4.69
РЬО
112
21.20
21.08
C56H55PbO4.... 527
100.00
10000
5. Geocerain. This body is freed from geomyricin by dissolving
it in boiling 60 p. c. alcohol, in which geomyricin is insoluble, and from
adhering lead by means of hydrosulphuric acid. It forms white
lamellar masses fusible to a yellow wax at 80°. Contains 79.11 p. c. C.,
and 13·07 H., and is therefore isomeric with geoceric acid.
6. Geocerinone. Both the yellow and the dark-brown lignite, when
submitted to dry distillation, yield gases and a buttery distillate, from
a solution of which in boiling alcohol of 80 p. c., geocerinone crys-
tallises on cooling. It forms pearly six-sided tables, melting at 50°
and burning with luminous flame. Dissolves in warm oil of vitriol,
and turns brown and carbonises when heated. It is slightly attacked
by fuming nitric acid. A hot saturated solution of bichromate of
potash, with addition of oil of vitriol, produces a copious evolution of
carbonic acid, with a smell of butyric acid, whilst sesquioxide of chro-
mium and an acid precipitable from its alcoholic solution by neutral
acetate of lead are formed. Dissolves slightly in boiling 80 p. c.
alcohol, and easily in absolute alcohol and ether.
446 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
Brückner.
mean.
110 C
660
83.97
83.97
110 H
110
14.00
14.07
20
16
2.03
1.96
C110H11002
786
100.00
100'00
***
According to Brückner, it is the ketone of geoceric acid.
D. Resins extracted from plants.
Soft resin of Althea. - (Trommsdorff, N. Tr. 19, 1, 176).
Resin of Anacahuita-wood. — The wood and bark (previously ex-
hausted with water) are exhausted with very weak caustic potash;
the solution is allowed to stand till clear, and the resin is precipitated
by hydrochloric acid. The precipitate is digested with alcohol, the
extract evaporated, and the residue boiled with water and dried. Con-
tains, on the average, 60.25 p. c. C., 6·99 H., and 32.76 O., correspond-
ing to the formula C4H4O²º (L. Müller, Pharm. Viertelj. 10, 532).
34
Acrid soft resin of the nut-shells of Anacardium occidentale.
Mattos, J. Pharm. 17, 625).
(De
Resin of Angelica-root. — An alcoholic tincture of angelica-root
separates on evaporation into two layers, the lower of which is pale-
yellow and watery, and contains a large quantity of sugar, the upper
brown and resinous. The latter, after washing with water, forms
Buchholz and Brandes' Angelica balsam (N. Tr. 1, 2, 138); it dissolves
in alcohol and ether (Buchner), is quickly turned brown to black by
cold oil of vitriol, but is not coloured by oil of vitriol in alcoholic solu-
tion, and is thereby distinguished from sumbul balsam. When sub-
mitted to dry distillation, it yields colourless and yellow oils, but no blue
vapours, as is the case with sumbul balsam (Reinsch, Repert. 89, 299).
Angelica balsam boiled with caustic potash yields a distillate of
volatile oil, the residue containing angelica wax, angelicin, and the
potash-salt of angelic acid (x, 415) (Büchner).
Angelicin.-From Angelica balsam. The resin-soap formed by
boiling angelica balsam with caustic potash, when evaporated and dis-
solved in water, deposits wax, after the removal of which, on one
occasion, angelicin crystallised from the solution. A more certain
method of preparing it is to dissolve the resin-soap in alcohol, pass
carbonic acid into the solution, evaporate, and treat the residue with
ether, which takes up the angelicin. - Crystallises from alcohol in
delicate colourless needles, inodorous, and at first tasteless, but after-
wards burning and aromatic. Melts easily and creeps up the sides of
a glass vessel without subliming. - Burns with smoky flame. When
boiled with caustic potash, it melts and partially dissolves, the undis-
solved portion crystallising on cooling; from the alkaline solution.
carbonic acid (and a stronger acid more quickly) precipitates white
flocks. Dissolves in alcohol and ether (Buchner, Repert. 76, 167).
-
Angustura-bark contains a hard resin, soluble in potash, alcohol, and
RESINS OF CUBEBS.
447
acetate of ethyl, insoluble in ether, rock-oil, and oil of turpentine; and
a greenish-yellow, soft resin, which assumes a cochineal-red colour
with oil of vitriol, and is soluble in alcohol, ether, and fatty and volatile
oils, but insoluble in caustic potash (Pfaff).
Soft resin of Anthemis Pyrethrum (John. — Gaultier, J. Pharm. 4,
49).
Soft resin of Arnica montana (John, Chem. Schriften).
Soft resin of the buds of Aster glutinosus (John, Chem. Schriften,
2, 79).
Resin of the bark of Atherosperma moschatum. Obtained from the
bark (previously exhausted with dilute sulphuric acid) in the same
manner as the resin of anacahuita-wood. Brown-red; melts at
114°. Dissolves easily in caustic alkalis and their carbonates, from
which it is precipitated by acids, and also in alcohol, but is nearly in-
soluble in ether. Contains at 100°, on the average, 69.38 p. c. C.,
8.85 H., and 21.77 O., corresponding to the formula C2H320¹0 (Zeyer,
Pharm. Viertelj. 10, 517).
Resin of Cannabis indica. When precipitated from the alcoholic
solution by water, it is yellow-brown and narcotic, and acts like mor-
phine, likewise producing contraction of the pupils (T. & H. Smith,
N. J. Pharm. 11, 278). The narcotic resin occurs in greater quantity
in Cannabis indica from Algeria than in that grown in France. It dis-
solves in alcohol, ether, and volatile and fixed oils (Decourtive, N. J
Pharm. 13, 427). When commercial Extractum cannabis is dissolved
in cold alcohol of 83 p. c., filtered, mixed with water till cloudiness is pro-
duced, and digested with animal charcoal, then again filtered, and pre-
cipitated by water, and the precipitate thereby formed is dissolved in
ether and the solution evaporated, a shining pale-brown resin is
obtained, which becomes glutinous when exposed to sunshine, but after
repeated melting, kneading, and cooling, becomes brittle and friable,
and melts at 90°. It has a bitter taste and a narcotic odour. In-
soluble in aqueous ammonia and caustic potash, but easily soluble in
volatile oils. After boiling with acids, it reduces an alkaline solution
of cupric oxide (G. Martius, N. Repert. 4, 534).
Hard resin of Cascarilla (Trommsdorff, N. Tr. 26, 2, 138).
Resin of Centaurea benedicta (Morin, J. Chim. méd. 3, 105).
Resin of the bark of Cornus mascula (Trommsdorff, N. Tr. 17, 1,
37).
Soft resin of Cortex Corova (Trommsdorff, N. Tr. 21, 2, 123).
Resins of Cubebs. - A. Resin insoluble in potash, probably formed by
the oxidation of oil of cubebs (xvi, 272); it is also produced by
digesting oil of cubebs with nitric acid and alcohol. - Coarsely pow-
dered cubebs is freed from volatile oil as much as possible by distilling
it with water, and afterwards exposing it to a current of superheated
steam, and the insoluble residue is collected, dried, and exhausted with
94 p. c. alcohol, which takes up resins, cubebin, cubebic acid, and a
little volatile oil, and leaves them behind on evaporation. This residue
is heated to boiling with strong caustic potash, and diluted with a large
448
APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
quantity of water, and after standing 24 hours, the alkaline liquid,
which contains cubebic acid, is decanted from the resin which has sepa-
rated, and the latter body is washed with hydrochloric acid and water,
and dissolved in hot alcohol, whereupon cubebin (xvi, 273) crystallises
on cooling. From the oily mother-liquor, which consists of a mixture
of oil and resin, the oil is separated by boiling with water, and more
completely by heating to 240°, and the remaining resin is then dissolved
in alcohol, boiled with caustic potash, and with water, again dissolved
in alcohol, decolorised by animal charcoal, and evaporated.
Pale, brownish-yellow, tasteless, soft resin, melting at 60°. It is
violently attacked by fuming nitric acid, and reddened by oil of vitriol,
and therefore probably still contains cubebin. Insoluble in aqueous
alkalis; easily soluble in alcohol, ether, bisulphide of carbon, and chlo-
roform (Bernatzik). See also Trommsdorff (J. Pharm. 21, 69); Dublanc
(J. Chim. méd. 3, 491).
B. Resin soluble in potash. Bernatzik's Cubebic acid. Previously
noticed by Monheim (xvi, 292), and distinguished as a waxy resin.-
The alkaline solution obtained in the preparation of A is nixed with
dilute sulphuric acid, till turbidity is produced, whereupon the still
strongly alkaline solution deposits the cubebic acid on standing and
subsequent concentration. The acid is redissolved in caustic potash,
freed from the soft resin, which separates on diluting the solution, and
precipitated by chloride of barium. The precipitate thus obtained is
dissolved by repeated boiling with water; the solution is concentrated
and decomposed by hydrochloric acid; and the precipitate is washed
with boiling water. - Extractum Cubebarum æther.: on standing, throws
down a crystalline deposit containing cubebic acid. It is thrown upon
a filter to separate the remaining fluid portion, and then treated with
ether or cold alcohol, which leaves cubebin. The tincture is submitted
to distillation, the residue dissolved in caustic potash, and the solution
precipitated with chloride of barium. The precipitate dissolved in
boiling water or boiling alcohol yields crystals of the baryta-salt, from
which the acid may be separated.
Properties. White, amorphous mass, resembling wax, sticky between
the teeth. It softens in the hand, and melts at a somewhat higher
temperature. Tastes like wax.
Decompositions. Turns brown in the air. - Dissolves in oil of vitriol,
forming a fine purple-violet solution, which turns brown at 90° to 100°,
and afterwards blackens; water precipitates from the violet solution
violet-grey flocks, which dissolve in alkalis with green, and in alcohol
with red colour. No sugar is formed thereby, or by boiling with hydro-
chloric acid. Sulphuric acid, added to a solution of the potash-salt
of the acid mixed with bichromate of potash, throws down at first a
resin, which on the addition of more acid and warming, dissolves to a
deep green liquid, and is not precipitated by water. The acid is dis-
solved by nitric acid of 40 p. c., only on warming, and by the fuming
acid in the cold, with yellow colour; excess of alkali colours this solu-
tion (or a solution of the potash-salt mixed with excess of fuming
nitric acid) blood-red, without precipitating the cubebic acid.
The acid is insoluble in cold, and very slightly soluble in boiling.
water. It dissolves very slightly in weak or strong caustic potash and
soda in the cold, but on boiling it with a strong solution and afterwards
diluting, a clear solution is obtained, from which a salt of the acid is
RESINS OF JUNIPER-BERRIES.
449
deposited on concentration. The salts of the alkalis separate from
moderately strong aqueous solutions, or from solution in alcohol, in
crystals which dissolve to a turbid alkaline liquid in water. Mineral
acids throw down cubebic acid from its alkaline salts in the form of
a white resin, long before the solution ceases to be alkaline. -The acid
dissolves in ammonia-water only on warming, and is precipitable by
water or aqueous alkalis.
Baryta-salt. Preparation see above. Obtained from boiling water or
alcohol in white crystalline groups, which form a turbid solution in
water.
Magnesia-salt. The alkaline salts of cubebic acid throw down
from magnesia-salts an amorphous white precipitate, which melts
when warmed. It turns brown in the air, and is insoluble in boiling
water.
The alkali-salts of cubebic acid precipitate metallic salts.
The acid dissolves easily in chloroform, alcohol, and ether (Bernatzik,
N..Repert. 14, 98).
Resin of Fern-root. - Geiger (Mag. Pharm. 17, 78).
Acrid resin of Jatropha Curcas. Soubeiran (J. Pharm. 15, 504;
Br. Arch. 33, 207).
Acrid soft resin of the root of Iris florentina. A. Vogel (J. Pharm. 1,
184).
Resins of Juniper-berries.
Resins of Juniper-berries. - Contained in the old, but not in the
fresh berries, being formed from volatile oil (Rebling, N. Br. Arch.
67, 228). a. The resin obtained by boiling the alcoholic extract
with water is dingy-green, brittle, and triturable to a grey-green
powder. Has a faint odour of juniper-berries, but no taste; softens
and melts when warmed. In boiling potash-ley it becomes harder and
more compact, without dissolving. It dissolves in cold aqueous am-
monia, forming a light green solution, from which it is precipitated by
acids. It dissolves in alcohol, ether, and volatile oils, less easily in
fixed oils (Trommsdorff).
b. Steer's Juniperin. When juniper-berries, after being washed
out with water, are distilled to obtain the volatile oil, the residue, if
strained while hot, deposits in the still, on cooling and evaporation, a
sediment, which must be treated with cold and boiling alcohol in suc-
cession. The resulting extracts, when cooled and distilled, deposit
successively wax and green resin, and finally juniperin as a yellow
powder, which then cakes together to a resin, and as such is separated
and washed. It is converted, by trituration with water, into a yellow
powder, which dissolves completely in 60 pts. of water, and is taken
up by ether when agitated therewith. The juniperin left on evapora-
tion of the ether is light yellow, and burns with flame, emitting the
odour of juniper. It dissolves in oil of vitriol with light yellow colour,
changing to red-brown on standing, and in ammonia with gold-yellow
colour (Fr. Steer, Wien. Acad. Ber. 21, 383).
VOL. XVII.
2 G
450 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
Resin of Laurel. Bonastre (J. Pharm. 10, 30).
Resins of the bark of Lopez-root. The ethereal extract, washed with
water, is resolved by cold alcohol into a sparingly soluble resin,
melting at 170°, and containing 64.25 p. c. C., and 7.99 H., and an
easily soluble resin melting at 48°, containing 69.54 p. c. C., and
7.43 H. Both resins are soluble in caustic potash, and precipitable
therefrom by acids, and are not decomposible by acids with formation
of sugar.
An alcoholic extract of the bark which has been exhausted
with ether leaves on evaporation a third resin, which, after washing
with warm water, is brittle and tasteless, melts at 135°, and contains
62.38 p. c. C., and 3-92 H. It dissolves freely in aqueous alkalis, from
which it is precipitated by acids; does not form sugar, and is nearly
insoluble in ether (Schnitzer, Pharm. Viertelj. 11, 1).
Resin of Lycoperdon cervinum. Biltz (N. Tr. 11, 2, 58).
Acrid resin of Manna. Manna is suspended in an equal weight of
water, and shaken repeatedly with ether, which takes up the resin,
together with a little acid (both in very small quantity). The yellow
ethereal solution leaves on evaporation a yellow resin, which is washed
with water, and dissolved in hot absolute alcohol. The alcoholic solu-
tion, separated from the white powder deposited on cooling, is rendered
milky by water: it is coloured darker, and precipitated by ammoniacal
nitrate of silver, only on standing for some time, and yields with
alcoholic neutral acetate of lead, especially on addition of ammonia, a
brown precipitate, which on one occasion contained 35.75 p. c. C.,
4.46 H., 13-15 O., and 46.64 PbO, and on another occasion, 25.27
p. c. C., 3-12 H., 13-19 O., and 58-42 PbO (Leuchtveiss, Ann. Pharm.
53, 131).
Resin of Medicago. Bernays (Repert. [3] 6, 329).
Acrid resin of Radix Meu. Reinsch (Jahrb. pr. Pharm. 2, 302; 14,
388).
Resin of the Brazilian Clove (Persea caryophyllata). Trommsdorff
(N. Tr. 23, 1, 12).
Resin of Oenanthe crocata.
Resin of Oenanthe fistulosa.
Resins of Grana Paradisi.
cipitable from the alcoholic
lead, and a second resin not
18).
Cormerais (J. Chim. méd. 6, 459).
Gerding (J. pr. Chem. 44, 175).
Grains of Paradise' contain a resin pre-
solution by alcoholic neutral acetate of
precipitable (Sandrock, N. Br. Arch. 73,
Resin of Spanish pepper. Capsicin. - Obtained as a yellowish-red
or red-brown, thick resin, having an extremely burning taste, by
exhausting the alcoholic extract of the pepper with ether, and evapo-
rating the solution. It becomes thicker in sunlight. Dissolves slightly
in water, to which it communicates its harshness. It dissolves easily,
with red-brown colour, in caustic potash, alcohol, ether, and oil of
turpentine: hardens to a solid compound with baryta (Buchholz,
Taschenbuch, 1816, 1; Braconnot, Ann. Chim. Phys. 6, 1, and 122;
Repert. 26, 157). Dilute acids extract from the red-brown resin a
RESINS OF SQUILL (SCILLA MARITIMA).
451
poisonous non-alkaline substance, which inflames the skin: it does not
yield crystals with acids, and is precipitated from its solutions by
alkalis in yellowish-brown flocks (Landerer, Pharm. Viertelj. 3, 34).
Resins of Petasites vulgaris. The alcoholic tincture of the dried
root, when submitted to distillation, leaves a sticky mass, consisting of
petasite balsam. When this is boiled for some hours with moderately
strong caustic soda, a portion of it (the petasitic acid) dissolves, whilst
a volatile oil is driven off, and a pale-yellow resin, Reinsch's petasite,
remains undissolved. The two bodies are separated; the alkaline
solution is precipitated by phosphoric acid; and the yellow-brown flocks
are collected, washed with water, dissolved in alcohol, and the solution
is left to evaporate. Petasitic acid forms brown crystalline flocks,
having an acrid, harsh taste: it gradually turns brown with hydro-
chloric or sulphuric acid, dissolves in dilute caustic soda, and yields a
volatile oil by dry distillation. Petasite smells like the root, is not
acted on by strong caustic soda, and yields by dry distillation, a yellow
oil having an odour of radishes. Its alcoholic solution mixed with a
little hydrochloric or sulphuric acid, assumes a fine emerald-green
colour, which changes to blue, and ultimately to brownish-green, when
hydrochloric acid is employed (Reinsch, N. Jahrb. Pharm. 4, 257).
Resins of Pimpinella Saxifraga. Bley (N. Tr. 12, 2, 80).
The resin of the root of Podophyllum peltatum (Podophyllin) is
obtained by evaporating the alcoholic tincture to a syrup, precipitating
with water, and washing. It is very bitter, and acts as a purgative.
It dissolves in alcohol and ether, and is partially saponified by alkalis.
Ether extracts from the root a black, less active resin (Cadbury,
Pharm. Journ. 18, 179; Chem. Centr. 1859, 46).
Resins of Poplar-buds. From the buds of the black poplar:
Pellerin (J. Pharm. 8, 434); Schrader (A. Gehl. 6, 578); from the buds
of Populus balsamifera: Hegström (Crell. N. Entd. 3, 171); from the
bark: Wittstein, Pharm. Viertelj. 6, 47). Hallwachs obtained from
poplar-buds, the crystals already mentioned (xv, 444); Piccard ob-
tained chrysic acid, C22H806 (Züricher Milth., J. pr. Chem. 93, 369;
Zeitschr. Ch. Pharm. 8, 138).
Acrid soft resin from Semen Ricini. Soubeiran (J. Pharm. 15, 507).
Resins of Squill (Scilla Maritima).
The investigations on Scillitin, the active ingredient of the bulb
of Scilla maritima (Handbuch. viii., [2], 87), have not determined
whether it is to be classed with the resins, the alkaloïds, or the bitter
principles. - Mandel (Compt. rend. 51, 87) distinguishes two peculiar
bodies, the poisonous and irritating sculein, and the non-poisonous.
scillitin, but adds nothing further concerning them. Schroff (N. Repert.
14, 241) also distinguishes a narcotic principle (scillitin) and an acrid
non-volatile principle. Righini (Repert. 63, 87) regards scillitin as
impure veratrin.
a. According to Tilloy (J. Pharm. 12, 635.-N. J. Pharm. 23,
406; Pharm. Centr. 1854, 93) squill contains no volatile acrid principle,
2 G 2
452 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
but crystals of citrate [oxalate (Schroff)] of lime, which irritate and
inflame the skin when rubbed upon it. The active constituents are
an acrid resin and a bitter substance.
Dried squill-powder gives up to ether an agreeably-smelling yellow
fat (or fatty acid?) which may be freed from adhering bitter substance
by means of hot water. When the powder which has been exhausted
with ether is exhausted with alcohol, a very acrid and bitter tincture is
obtained, leaving on evaporation an acrid resin, which is freed from
adhering fat by ether, and from sugar by water. This resin is very
poisonous; it softens in hot water, dissolves in alkalis and alcohol, and
is not altered by acids. The bitter substance is extracted by hot
water from squill previously treated with ether and alcohol; it is pre-
cipitated from the liquid by charcoal, which gives it up again to boiling
alcohol (Tilley).
b. Vogel (Schw. 6, 101) and Lebourdais (N. Ann. Chim. Phys. 24,
62; Ann. Pharm. 67, 252) prepare the bitter substance as follows:-
1. Vogel exhausts the concentrated juice with alcohol, evaporates
the tincture, dissolves the residue in water, precipitates tannic acid with
neutral acetate of lead, removes excess of lead by means of hydro-
sulphuric acid, again filters, and evaporates. There then remains
scillitin, together with sugar and salts, in the form of a colourless,
friable mass, which has a very bitter, afterwards sweetish taste, and
causes vomiting and purging. This mass softens quickly in the air,
and dissolves easily in water and absolute alcohol, and in vinegar.
2. Lebourdais precipitates the highly coloured and very viscid decoction
of squill with neutral acetate of lead, and agitates the cold filtrate with
purified animal charcoal till it loses its colour and bitterness. The
charcoal is then washed and dried, and boiled with alcohol, which takes
up the scillitin, and leaves it behind on evaporation. Amorphous,
neutral, non-hygroscopic mass, which decomposes easily when heated,
dissolves with purple colour in oil of vitriol, afterwards blackening,
and is decomposed by nitric acid. A portion placed upon the tongue
produces the sensation of a caustic. - Bley (N. Br. Arch. 61, 141)
operated in the same way as Lebourdais, avoiding too great heat, and
obtained by spontaneous evaporation, long colourless flexible needles,
having a very bitter taste, becoming amorphous when gently warmed,
and not afterwards susceptible of crystallisation. According to
Wittstein (Repert. [3] 4, 200), the bitter of squill is not precipitable
by basic acetate of lead, nor by hydrated oxide of lead, which latter,
however, precipitates the acrid constituent.
—
c. Marais (N. J. Pharm. 31, 130) and Landerer (Repert. 47, 442)
believed they had obtained an alkaloid, which Tilloy was not able to
isolate.
1. Marais exhausts either the dried squill with 56 p. c. alcohol, or
the fresh bulbs with alcohol of 90 p. c., mixes the tincture with milk
of lime, agitates with ether, separates the supernatant layer of liquid,
and evaporates, whereupon scillitin and fat remain, the latter of which
is removed by again dissolving the residue in alcohol. - Amorphous,
hygroscopic, pale-yellow mass, having a penetrating bitter taste, and
an alkaline reaction. It dissolves in oil of vitriol, forming a violet
solution, from which water precipitates green flocks, and in nitric acid
with red colour, which quickly disappears; it is insoluble in hydro-
RESINS (TURPETH-RESIN).
453
chloric acid, but soluble in ammonia and caustic alkalis, becoming
decomposed and losing its bitter taste. When heated with hydrate of
potash, it evolves ammonia. It does not dissolve in water. Produces
with sesquichloride of iron an orange-yellow, and with bichloride of
platinum a yellow precipitate, and combines with acetic acid. It
dissolves in alcohol and ether. Taken internally, it acts as an emetic
and violent purgative, and afterwards as a narcotic (Marais).
2. Landerer digests the crushed inner portions of squill with very dilute
sulphuric acid, boils down the filtrate to one-half, saturates it with lime.
and sets it aside for three days; then collects and dries the residue,
When this residue is boiled with alcohol, the filtrate deposits on evapo-
ration a very small quantity of extremely bitter needles, which are
insoluble in water, and sparingly soluble in alcohol. The needles have
an alkaline reaction and neutralise acids, forming therewith crystalli-
sable salts, which melt when heated (evolving vapours which excite
coughing), and carbonise, but do not leave a trace of lime. This body
does not appear to be obtained from dried squill.
Sumbul balsam.
Resin of Radix Sumbulus.
When an ethereal
extract of the root is evaporated, and the residue is freed from wax by
dissolving it in 75 p. c. alcohol and again evaporating, there remains
a clear pale-yellow mass of the consistence of Venice turpentine ;
Reinsch's sumbul balsam. A few drops of this body, heated in a warm
glass tube assume an olive-green, afterwards indigo-blue colour.
When submitted to dry distillation, it yields a yellow and a green oil,
and at last a dark-blue oil which, according to Sommer (N. Br. Arch.
98, 1), contains umbelliferone, the retort at the same time being filled
with blue vapours. On dropping the balsam into oil of vitriol, the
liquid assumes a fine purple colour, whereupon water throws down
blue flocks. Oil of vitriol likewise produces a lilac or purple precipitate
in the alcoholic solution. When the balsam is melted with pieces of
caustic potash, and the mass is treated with a little water, angelate
of potash (x, 415) is dissolved, whilst sumbulamate of potash remains
behind. The latter body, when dissolved in water and decomposed by
dilute sulphuric acid, yields sumbulamic acid in the form of a turpentine-
like mass, which crystallises in soft yellow needles on standing for
some weeks. Its potash-salt is crystalline; its solution in absolute
alcohol acquires a violet to blue colour when hydrochloric acid gas
is passed into it, and yields by distillation a colourless oil which
may be freed from acid by carbonate of potash, and is coloured violet
or blue by oil of vitriol: probably the vinic ether of sumbulamic acid
(Reinsch, Jahrb. pr. Pharm. 6, 300; 7, 79; 13, 68).
Resin of Taraxacum officinale. Polex (N. Br. Arch. 19, 51).
Resin of the Tea plant.
Mulder (Pogg. 43, 633).
Meissner (Berl. Jahrb. 29, 2, 69).
Resin of Tormentil root.
Hard resin of blue Grape-skins. Nees v. Esenbeck (Br. Arch. 20,
196).
Acrid Resin of Truffles. Riegel (Jahrb. pr. Pharm. 7, 226).
Turpeth-resin. (Appendix to xvi, 405.)
Turpethum. The root yields 4 p. c. of resin,
From the root of Ipomaɑ
th of which is soluble in
ether.
454 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
The root is exhausted with cold water and dried, afterwards
coarsely comminuted and exhausted with alcohol. After distilling off
the alcohol from the brown tincture, the resin is precipitated by
water, and repeatedly boiled with water and dried, then shaken four
or five times with ether, and precipitated from the alcoholic solution
with ether an equal number of times. The resin thus obtained is
turpethin.
Brown-yellow, inodorous, tasteless at first, afterwards bitter.
Cannot be decolorised. Triturable to a greyish powder, extremely
irritating to the mucous membranes. Melts at 1830.
Spirgatis.
mean (4).
68 C
4:08
56.66
56.60
56 H
56
7.77
7.81
32 O
256
35.57
35.59
C68 H 56032
720
100.00
100.00
Of the same composition, therefore, as jalapin (xvi, 407) and scammonin (xvi.
405) but distinguished therefrom by its insolubility in ether.
Turpethin melted on platinum-foil acquires a brown or black colour,
evolves an acrid odour, takes fire, and burns with a bright smoky flame,
leaving charcoal. It dissolves slowly in oil of vitriol, forming a fine
red solution, which is coloured by water first a deeper red and after-
wards brown and black. It is decomposed by boiling with mineral
acids into turpetholic acid and sugar:
C6956032 + 12 HO = C32H3208+ 3 C12H12012.
Under the influence of strong bases it takes up water and forms salts of
turpethic acid.
Turpethin dissolves easily in alcohol, but not in ether (Spirgatis,
N. Repert. 13, 97; J. pr. Chem. 92, 97.
Turpethic acid. - Obtained from turpethin by dissolving it in baryta-
water, in the same manner as jalapic acid is obtained from jalapin.
-Amorphous, yellow, shining, translucent, very hygroscopic mass.
- Inodorous, and of sourish bitter taste. Has a strongly acid
reaction.
Spirgatis.
mean.
68 O.......
408
53.97
53.88
60 H ....
60
7.94
7.90
36 O
288
38.09
38.22
C68 H60036
756
100.00
100.00
Contains 1 at. HO more than jalapic acid.
Turpethic acid burns on platinum foil with a bright smoky flame. —
When treated with mineral acids, it breaks up into turpetholic acid and
sugar:
CGSH60036 + 8 HO = CH3208 + 3 C¹2¹2012.
The sugar is susceptible of fermentation, tastes sweet, and smells
of caramel when heated. Turpethic acid dissolves in water
(Spirgatis).
Turpethic acid forms a semi-acid and a mono-acid baryta-salt.
RESINS (TURPETH-RESIN).
455
Spirgatis.
Semi-acid.
68 C.......
408
45.78
45.58
58 H
58
6.51
6.63
34 O
272
30.52
30.49
2 BaO
153
17.19
17.30
C69H58 Ba2036
891
100.00
100.00
....
...
Mono-acid.
Spirgatis.
68 C
408
49.54
49.55
59 H
59
7.16
7.22
35 O
280
34.00
34.10
BaO
76.5
9.30
9.13
C6sH59 BaO36
823.5
100.00
100.00
Turpetholic acid. - Obtained, together with sugar, by boiling turpe-
thin or turpethic acid with acids, in the same manner as jalapinolic
acid is obtained from jalapin (xvi, 401). It is purified by washing and
melting it with water, dissolving in weak alcohol, decolorising with
animal charcoal, and crystallising three or four times from dilute
alcohol.
White mass, consisting of microscopic needles and tufts. Melts
at about 88°. Inodorous; tastes harsh. Has an acid reaction.
Spirgatis.
mean.
32 C
192
66.67
66.53
32 H
32
11.11
11.21
8 O..
64
22.22
22.26
C32H3208
288
100.00
100.00
Contains 2 at. water more than jalapinolic acid (xvi, 401).
Decomposes when heated, in the same manner as jalapinolic acid,
emitting an extremely irritating odour, and leaving porous charcoal.
Soda-salt. Dazzling-white, silky mass, appearing under the micro-
scope as rhombic plates with angles of 558 and 125°.
Spirgatis.
32 C........
31 H
192
61.94
61.90
31
10.00
9.99
70
56
18.06
18.03
NaO
31
10.00
10.08
C32H3¹Na08
310
100.00
100.00
Baryta-salt Amorphous.
Spirgatis.
32 C
192
53.99
53.60
31 H
31
8.72
8.75
70
56
15.75
16.02
BaO....
76.5
21.54
21.63
C32H31 BaOS
355.5
100.00
100.00
The acid dissolves easily in alcohol, less easily in ether
(Spirgatis).
Resin of Valerian root (Trommsdorff, Ann. Pharm. x, 10, 222).
456 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
E. Aldehyde-resin.
LIEBIG. Ann. Pharm. 14, 158.
BLEY. N. Tr. 25, 2, 79.
WEIDENBUSCH. Ann. Pharm. 66, 152; Pharm. Centr. 1848, 852; J.
pr. Chem. 46, 252; Chem. Gaz. 1849, 34; Lieb. Kopp's Jahresber.
1847 and 1848, 648.
FR. GÖTZ. N. Repert. 12, 145.
Formation. 1. By heating aldehyde with caustic potash (viii, 278)
(Liebig). The penetrating odour evolved in the reaction is due to the formation
of a thick golden-yellow oil, having an odour of cinnamon and rapidly converted by
oxidation in the air, or with nitric acid, into a resin different from aldehyde-resin
(Weidenbusch).
2. By warming acetal (ix, 40) with alcoholic potash in presence of
air (Liebig).
Döbereiner (Schw. 38, 327; 64, 466) previously noticed the forma-
tion of a resin on burning alcohol containing potash in his vinegar-
lamp (viii, 207): his oxygen-ether (viii, 274) is likewise oxidised by
potash, and more quickly by oil of vitriol, to an indifferent yellow
resin, soluble in alcohol and ether, and bleaching in sunlight.-Wood-
spirit and fusel-oil, in contact with platinum, air, and potash, also form
resins, though more slowly than alcohol (Götz).
The brown colour developed in alcoholic potash on standing, or on
evaporating the solution in air, is due to the aldehyde-resin formed
(Liebig). On boiling an alcoholic solution of soda and saturating it with
an acid, a brown resin is obtained, soluble in alkalis and of varying com-
position. The same solution heated in sealed tubes yields a red resin
insoluble in alkalis. A body having the same composition as the last
is obtained also from wood-spirit: it contains, on the average, 74.88
p. c. C., 8.74 II., and 16.38 O., and may be represented by the formula
CII8O2 (calc. 750 p. c. C., 8:33 H., and 16.67 O.). It is probably
formed from 3 atoms of aldehyde by the elimination of 4 at. water.
Formic acid is also produced in the reaction; but if a little acetate or
formiate of soda is added to the alcoholic soda, the resin produced con-
tains 82.31 p. c. C. and 8.69 H. (Mylius, Chem. News, 1865, 148; Zeit-
schrift Ch. Pharm. 8, 526).
When aldehyde is heated to 160° in a sealed tube for 100 hours, a
resin free from oxygen is formed, together with water, alcohol, and
acetic acid. The resin contains 4 atoms of carbon to 2 atoms of
hydrogen (Berthelot, Compt. rend. 56, 703; Ann. Pharm. 128, 256).
Preparation. 1. Aldehyde (Weidenbusch), or the liquid rich in
aldehyde obtained by distilling alcohol with sulphuric acid and oxide of
manganese (viii, 276, 3) (Liebig) is heated with solution of caustic potash,
and the resin thereby produced is washed with water; the smell of vola-
tile oil, however, is not completely removed even by washing with boil-
ing water (Weidenbusch). On precipitating the resin from its solution
in caustic potash with dilute sulphuric acid, boiling the filtered solution
in warm alcohol, after addition of water, to expel the alcohol, and
drying the precipitated resin at 100° in a vacuum (see analysis b) it is no
longer soluble in water and but incompletely soluble in alcohol (Liebig).
-2. Solution of caustic potash of sp. gr. 1.26 is introduced, together
RESINS (ALDEHYDE-RESIN).
457
with some platinum-black, into a vessel filled with vapour of alcohol,
which is opened from time to time. The potash quickly assumes a
yellow colour, and deposits a dark-brown granular resin, which must be
washed with as little exposure to the air as possible. Thus obtained,
it contains about 9 p. c. of a resin soluble in alcohol, which is probably
a product of oxidation, and may be removed by washing with alcohol
(Götz).
Bley distils a mixture of 1 part of nitric acid of sp. gr. 1.24 and
4 parts of alcohol, and after rectifying the distillate over chloride of
calcium, mixes it with caustic potash, so long as a yellow precipitate is
produced. He then washes the precipitate with water, dissolves it in
ether, and evaporates the solution. This aldehyde-resin is brittle,
pale-brown, and easily fusible: it is decomposed by nitric acid, black-
ened by oil of vitriol, and is soluble in warm hydrochloric and acetic
acids, and precipitable from the latter solution by water. It dissolves
very slightly in warm aqueous ammonia and potash; in cold absolute
alcohol, but in alcohol of 80 p. c. only on warming; and rapidly in ether
and acetate of ethyl, as well as in warm oil of turpentine and oil of
almonds.
Properties. Dark-brown, hard resin, triturable to a pomegranate-
yellow [pale-brown (Liebig)] powder (Weidenbusch). Red, friable
mass, resembling dragon's blood, turning paler and at last fawn-
coloured in the air (Götz). Tasteless.
Liebig.
Weidenbusch.
Götz.
a.
b.
at 100°
a.
b.
over oil of vitrol.
in vacuo.
C ....
65.68
H
7.08
73.34
7.76
O
27.24
18.90
76.40
7.97
15.63
65.62
53.21
7.99
7.53
26.39
39.26
100.00
100.00
100.00
100'00
100.00
Liebig supposes a to contain potash. Götz gives for the resin a, which is in-
soluble in alcohol, the formula ĈHO¹0: b is the portion soluble in alcohol and
precipitable as a lemon-yellow powder by ether and chloroform; Götz assigns to it
the formula C36H30020.
Aldehyde-resin, dried at a moderate heat in the air and afterwards
at 100°, exhales a spirituous odour and sometimes takes fire and burns
like tinder. When strongly heated it burns like a resin, leaving a
shining charcoal (Liebig). The brown alcoholic solution is decolorised
by a little chlorine, whereupon water throws down a white powder
containing chlorine (Weidenbusch). — Neither the resin insoluble in
alcohol nor that soluble therein is decomposed by fused alkalis
(Gotz).
Aldehyde-resin gradually dissolves when washed with water,
forming a dark-brown solution. It is insoluble in bisulphide of carbon
(Götz), partially soluble in oil of vitriol, from which it is precipitated
by water, and nearly insoluble in alkalis (Weidenbusch). See above.
The resin prepared according to 1 dissolves easily in alcohol and
ether (Liebig; Weidenbusch); that prepared according to 2 is insoluble
in alcohol, ether, and chloroform (Götz).
458 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
SECOND APPENDIX TO COMPOUNDS CONTAINING 40 ATOMS OF CARBON.
Humous Substances.
VAUQUELIN. Ann. Chim. 21, 29; Crell. Ann. 1798, 1, 424.
KLAPROTH. A. Gehl. 4, 329.
TH. SAUSSURE.
A. Gehl. 4, 684.
EINHOF. A. Gehl. 6, 381.
PROUST. J. Phys. 63, 320; N. Gehl. 3, 374.
BRACONNOT. Ann. Chim. 61, 187; N. Gehl. 9, 132.
Ann. Chim. 80,
289. - Ann. Chim. Phys. 12, 189; Schw. 27, 344; Gilb. 63, 365.
Ann. Chim. Phys. 31, 40.
BERZELIUS. Thoms. Ann. 2, 314.
Pogg. 29, 3, and 238.
Scher. Ann. 7, 224. — Pogg. 13, 84.
SPRENGEL. Kastn. Arch. 7, 163; 8, 145.
BOULLAY. J. Pharm. 16, 165.
MALAGUTI. Ann. Chim. Phys. 59, 313; J. Pharm. 21, 443.
HERMANN. J. pr. Chem. 12, 277; 22, 65; 23, 375; 25, 189; 27, 165;
34, 156.
PELIGOT. Ann. Chim. Phys. 67, 157; 73, 208; abstr. J. pr. Chem. 18,
188.
MULDER. J. pr. Chem. 16, 246; 21, 203, and 331; 32, 325.
P. THENARD. Compt. rend. 44, 980; 49, 289; 52, 444; Par. Soc. Bull.
1861, 33, and 60.- Compt. rend. 52, 792, 53, 1019.
The uncrystallisable brown or black substances produced by the
decay of many organic compounds, more especially of vegetable tissues,
and resembling the bodies formed by the action of acids or alkalis on
sugar and woody fibre, are distinguished by the general name humus,
humous substance, mould, or peat-substance (Torfmaterie), which terms
include a large number of bodies having a similar external appearance.
They are distinguished from crenic acid by the easy solubility in water
of the latter body, which, however, is converted into insoluble apo-
crenic acid by exposure to the air. The composition of these bodies
being seldom known, and their formulæ not determined with certainty,
they are here treated in succession.
Formation and Sources. I. Humus is formed by the decay of many
organic compounds, more particularly of vegetable tissues, and con-
sequently occurs :
1. In Vegetable Soil. Concerning the formation of humus in the soil
see Soubeiran (N. J. Pharm. 17, 321; J. pr. Chem. 50, 291; Lieb. Kopp's
Jahresber. 1850, 651); Blondeau (Compt. rend. 57, 414; Chem. Centr.
1864, 252). An aqueous extract of the cultivated soil of Versailles
contained a substance allied to sugar or dextrin (Verdeil & Risler,
Compt. rend. 35, 95; Lieb. Kopp's Jahresber. 1852, 786). See also
Risler (N. Arch. ph. nat. 1, 305; Kopp's Jahresber. 1858, 507).
2. In Stable manure: Thénard's fumic acid, Braconnot's azulmic
acid, different from the azulmic acid of this Handbook (xi, 375).
3. In rotten wood (Berzelius; Hermann). The black-brown pulve-
HUMOUS SUBSTANCES.
459
rulent residue of an oak-trunk which had rotted in a marsh, contained
crenic acid, which it gave up to carbonate of ammonia, and an acid
closely allied to apocrenic acid, but more completely precipitable by
hydrochloric acid and insoluble in nitric acid (Berzelius, Pogg. 29, 262).
A deal pump-pipe, which had remained for a long time out of
water, contained in the inner of the wood a large quantity of crenic
acid, and in the outer layers principally apocrenic acid (Winckler,
Jahrb. pr. Pharm. 20, 10; Lieb. Kopp's Jahresber. 1850, 392). See also
A. Vogel (N. Repert. 6, 102).
4. In peat, of which it forms the chief part, together with undecom-
posed woody fibre (Einhof; Proust; Braconnot). In bituminous wood
(Jameson, Scher. J. 7, 419; Braconnot). In lignite.
Concerning crenic acid and humous substances from peat (see
Reinsch (J. pr. Chem. 24, 274); on the humic acid of peat: Wackenroder
(J. pr. Chem. 24, 22); Soubeiran (N. J. Pharm. 18, 16). On humus
from lignite, see Reinsch (J. pr. Chem. 19, 478).
A black humus-like substance, probably rotten peat, found floating
on the water of Loch Dochart, in Scotland, after the occurrence of an
earthquake, contained 76-7 p. c. C., 4-7 H., and 18.6 O., besides traces
of ash and nitrogen (Gregory, Ann. Pharm. 61, 365; Lieb. Kopp's
Jahresber. 1847 and 1848, 808).- Haidinger's dopplerite is an earthy
substance, occurring in a peat-bed at Aussee in Styria. In the fresh
state it is gelatinous and brown-black, but on exposure to the air it
becomes elastic and caoutchouc-like, and contains vegetable fibres,
distinguishable under the microscope. After drying at 100°, whereby
78.5 p. c. of water is expelled, it has a glassy lustre, resembles pitch,
and contains (after deducting ash and 1.03 p. c. of nitrogen) 51.63 p. c. C.,
5.34 H., and 43.03 0., corresponding to the formula C40H25025. Caustic
potash is without action upon it after drying, but with the fresh sub-
stance it evolves ammonia, and dissolves a portion, which is preci-
pitated again by hydrochloric acid (Schrötter, Wien. Akad. Ber. 1849,
285;
Lieb. Kopp's Jahresber. 1849, 781). — Pigotite, a brown mass found
in layers on the granite cliffs on the east and west coasts of Cornwall,
probably formed from the remains of plants, contains Johnston's
mudesous acid in combination with alumina. The acid is dark-brown,
soluble, not deliquescent, and is represented by the formula C2H5O8.
Its silver-salt contains, in addition, 3 at. AgO.; the alumina-salt 4 at.
Al2O³, and 8 at. HO. Chlorine converts it into white gelatinous mudesic
acid C12H5010. Nitric acid forms the same acid as a brown deliquescent
mass (Johnston, Phil. Mag. Nov. 1840; J. pr. Chem. 22, 182).
5. In the bark of many trees, especially in that of Pinus sylvestris
(xv, 487); in cinchona-barks (xvi, 484) (Berzelius); in the bark of Salix
fragilis, and abundantly in the bark of the beech (Braconnot), and in
that of the oak and horse-chesnut (Thomson).
An aqueous decoction of anacahuita-wood yields with neutral
acetate of lead, a precipitate of lead oxide combined with tannic and
humic acids, the latter of which separates on dissolving the precipitate
in acetic acid. When purified by washing, dissolving in aqueous
ammonia, and precipitating with hydrochloric acid, it contains, after
drying at 110°, 45 11 p. c. C., 4.56 H., and 50.33 0., corresponding to
the formula CH10014 (Ludw. Müller, Pharm. Viertelj. 10, 532).
From the alkaline excrescences of unhealthy trees, more especially
of the elm, there exudes a black mass, Klaproth's ulmin, which
460 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
Smithson (J. Phys. 78, 311) recognised as a compound of a humous sub-
stance with potash.
On mould of blighted corn, see Gräger (Ann. Pharm. 8, 67); Lucas
{Ann. Pharm. 37, 90); from Sphæria deusta, Knop (Pharm. Centr. 1851,
648). A brown substance from Mucor septicus also belongs to this
place (Braconnot, Ann. Chim. 80, 289).
II. By imperfect carbonisation or combustion, as well as by the dry
distillation of wood and other organic substances: humus, consequently,
occurs in soot (Braconnot). See xv, 159.- Charcoal prepared at a low
temperature for making gunpowder, contains ulmic acid (Boullay).
III. Many spring waters especially those rising in peat-bogs, as
well as the ochre which is deposited from them, contain soluble humous
substances, which are rendered insoluble by exposure to the air: Ber-
zelius's crenic and apocrenic acids.
The water of the Seine yields with sesquichloride of iron (not in
excess) a precipitate, from which caustic potash extracts an acid
resembling apocrenic acid, and containing 53.1 p. c. C., 2·7 H., 2·4 N.,
and 41.8 Õ. (Peligot, Bull de la Soc. d'Encourag. (1864) 63, 542.
An acid occurring in the mineral water of Ronneburg agrees in
many respects with crenic acid, but its compounds with potash and
soda, when exposed to the air in the moist state, take up oxygen, and
are converted into apocrenates and nitrates (Döbereiner, J. pr. Chem. 1,
113). Concerning Hänle's Brunnensäure, which differs from crenic acid, see Kastn.
Arch. 8, 399; on the crenic acid of the Moldau water, see Pleischl (N. Br. Arch.
17, 81); on crenic acid in rain-water see Salm-Horstmar (Pogg. 54, 254).
IV. Limonite and earthy vivianite, clay iron-stone, pea-ore, also
sand and ferruginous clay contain small quantities of humus (Wiezmann,
Kastn. Arch. 12, 442). On the compound of humus with ferric oxide,
see Nöggerath & Mohr, Ann. Pharm. 25, 93). An oolitic red iron-stone
from Belgium contained 4 per cent. of crenate of ammonia (Phipson,
Compt. rend. 52, 975; Kopp's Jahresber. 1861, 976).
V. Human urine contains a humous substance, which dissolves
easily in aqueous potash, and is precipitable by acids as a curdy black
mass, insoluble in water and alcohol (Proust, Ann. Chim Phys. 14, 264).
Prout's melanic acid (Phil. Ann. 4, 71; Schw. 36, 188), precipitated from
unhealthy dark-coloured human urine by acids, appears to be identical
with the last. A humus-like substance from the excrement of the
nightingale also belongs to this place (Braconnot, Ann. Chim. Phys. 17,
386).
When horses' urine is precipitated by hydrochloric acid, and
caustic potash is added to the filtrate, a precipitate of brown flocks is
thrown down, which, after washing, gives up a large quantity of mag-
nesia to warm hydrochloric acid. After being freed from hydrochloric
acid by washing, and dried, it forms a brown-black powder, which
dissolves very slightly in water and in hydrochloric and nitric acids,
easily in caustic alkalis and their carbonates, also in alcohol, and is
precipitated from the alkaline solutions by magnesia-salts. The urine
of all graminivorous animals, and guano, contain a similar substance
(v. Bibra, Ann. Pharm. 53, 199).
VI. By the action of alkalis on woody fibre, with access of air
(Braconnot); of alkalis on dextro-glucose (or inverted sugar); of acids
on cane-sugar (Malaguti; Boullay). See xv, 318.
HUMOUS SUBSTANCES.
461
Wood-charcoal made at a temperature of 320° is converted by
melted hydrate of potash, with access of air, and more slowly by
aqueous carbonate of potash, into an acid humous substance, which
dissolves in ammonia and aqueous alkalis (Millon, Compt rend. 51, 249;
Kopp's Jahresber. 1860, 68).
VII. The products formed by treating charcoal with nitric acid
very closely resemble crenic and apocrenic acids (Berzelius).
VIII. The brown residue, insoluble in acids and water, which
remains when cast-iron is dissolved in nitric acid, behaves towards
ammonia in the same manner as the ferric salt of apocrenic acid, but
it cannot be obtained in the pure state (Berzelius). See v. 216; xi, 375.
IX. When a mixture of carbonate of soda and phosphorus is
heated to 240° for some hours in a glass tube, a dark-brown mass is
formed, which, when thrown into water, evolves a large quantity of
spontaneously inflammable phosphoretted hydrogen, and yields a brown
solution containing phosphate and carbonate of soda together with
humous substance. The latter body is precipitated from the brown
filtrate by hydrochloric acid, washed with water containing hydro-
chloric acid till it begins to dissolve more freely; again dissolved in
dilute caustic soda, and precipitated by hydrochloric acid. — It is
amorphous and black-brown, and has a conchoïdal fracture, resinous.
lustre, and slightly acid reaction. It contains 44.7 p. c. of ash and
15 p. c. of phosphoric acid, and in 100 parts of the organic substance
forming the remainder, 63.88 C., 4.00 H., and 32·12 O., corresponding
approximately to the formula C40H16016. Its aqueous solution is pre-
cipitated by most salts (Dragendorff, Chem. Centr. 1861, 865).
X. The compound of carbonic oxide and potassium formed in the
preparation of potassium, when dissolved in water and freed as far as
possible from crystallisable salts by evaporating the solution, yields.
with dilute sulphuric acid a brown humus-like precipitate. This body
dissolves with difficulty in cold, more freely in hot water, and in weak
alcohol, but not in absolute alcohol or ether. Its solutions are dark-
brown or black, and opaque, and are completely precipitated by acids,
including acetic acid. It dissolves easily in alkalis, and is precipitated
by metallic salts. The copper-compound, obtained by mixing its solu-
tion in weak alcohol with sulphate of copper, contains at 100°, on the
average, 45-49 p. c. C., 2:45 H., 2.76 N., 19.11 CaO., and 30.19 0.,
corresponding to the formula C38NH12016, 3CuO (W. Mayer. In Gmelin's
Manuscripts).
Certain decomposition-products of gallic acid (xii, 401) and tannic
acid (xv, 458); the carbonaceous mass obtained by treating alcohol
with oil of vitriol (viii, 240); the substances produced by the action
of hydrochloric acid on albumin (see Albumin) are all distinguished
as humous substances.
On the humus-like products formed by heating chloride of carbon with alco-
holic potash, see Berthelot (N. Ann. Chim. Phys. 54, 87; Ann. Pharm. 109, 121) :
on similar substances resulting from the action of sodium on chloroform, in presence
of wood-spirit, alcohol, acetone, &c., see Hardy (Compt. rend. 54, 470; Chem. Centr.
1862, 672. Par. Soc. Bull. 1863, 339).
Contac
462 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
Humous Substances in particular.
A. Boullay's Ulmic Acid.
Boullay (J. Pharm. 16, 165; Schw. 60, 107; Pogg. 20, 63) dis-
tinguishes as ulmic acid the brown substance produced by the action.
of acids on cane-sugar (xv, 256), besides many other bodies evidently
not belonging to this place. Ulmic acid (the source and mode of pre-
paration of which is not given) is said to contain 56.5 p. c. C., 4·81 H.,
and 38.69 0.; the copper-salt, dried at 120° in a vacuum,
the silver-salt
10.5 p. c. CuO.; the lead-salt 26.86 p. c. PbO.;
28.57 AgO.; the two latter salts, however, were partially decom-
posed by washing.
B. Substances produced by the action of Acids on Cane Sugar.
Malaguti's ulmin is obtained by boiling cane-sugar with very dilute
acid (xv, 254); it is freed from ulmic acid, produced at the same time,
by ammonia, or better by caustic potash, after which the insoluble
portion is washed with water, very dilute sulphuric acid, and water, in
succession. It contains, on the average, 56.89 p. c. C., 4·72 H., and
38.39 0., corresponding to the formula C24H12012 (57.14 p. c. C.,
475 H.).
Malaguti's ulmic acid is formed exclusively when the flocks formed
are removed from the further action of the acid. It is obtained,
together with a little ulmin, by boiling 10 parts of sugar, 30 parts of
water, and 1 part of oil of vitriol, and repeatedly removing the scum
which is formed. After drying at 150° it contains 56.98 p. c. C.,
4.76 H., and 37.76 O., and is, therefore, isomeric with ulmin, into
which it is transformed by boiling with water for a few hours. It
dissolves in ammonia and caustic potash. The copper-salt contains.
10·76 p. c. CuO.; the silver-salt 24-32 p. c. of silver (Malaguti, Ann.
Chim. Phys. 59, 413).
According to Mulder, the coloured substances, insoluble in acidu-
lated water, produced by boiling cane-sugar with hydrochloric or sul-
phuric acid, are either brown ulmin-substances containing 2 atoms of
hydrogen more than the number of oxygen-atoms, or black humin-
substances containing equal numbers of atoms of oxygen and hydrogen.
The ulmin of the former and the humin of the latter class are insoluble
in aqueous alkalis, whilst ulmic and humic acids are soluble therein;
ulmin and humin, however, are converted by alkalis into the corre-
sponding acids; and ulmin-substances are transformed by the action
of dilute acids, with access of oxygen, into humin-substances, and
If the sugar has already been
ulmic acid by strong acids into ulmin.
converted by dilute acids into glucic acid, strong acid forms exclusively
humin (Mulder, J. pr. Chem. 21, 203 and 354; 32, 331).
Mulder gives the following formula:--ulmin, C40H16014; ulmic
acid, C40H1412; humin, C40H15015; humic acid, C40H12012. These
formulæ, as well as the entire distinction between ulmin- and humin-
substances, appear to me untenable. Mulder, it is true, refers to many
points of difference between the two classes of bodies, in colour,
HUMOUS SUBSTANCES.
463
behaviour towards acids, acetates, &c.; but to all appearance, it is
not these differences, but trifling variations in the analyses (probably
of substances containing ash) that determine whether a body belongs
to the ulmin or to the humin group. The formulæ of these bodies
appear to be derivable from that of sugar by the abstraction of
water (Kr.).
Calculation for Mulder's Ulmin and Humin substances from sugar.
24 C
145
9
9 H
90
....
C24H9C9
72
64.16
24 C
145
66.82
24 C
3.98
8 H
8
3.69
7 H
145
7
69.71
3.36
....
31.86
80
....
64
29.49
7 0..
56
26.93
226.... 100.00
C24H8O8.... 217
217 .... 100'00
C 6·04, as in Mulder's analyses of these bodies.
C24H707... 208 .... 100.00
1. When 12 parts of sugar, 40 parts of water, and 1 part of hydro-
`chloric acid are heated to 80° for a sufficient length of time, brown
flocks are obtained, which are collected, washed, and dried at 165°.
They contain 65.3 p. c. C., 4.3 H., and 30.4 O., and are, according to
Mulder, a mixture of ulmin and ulmic acid. They are partially soluble
in ammonia.
1 a. The flocks obtained in 1 are rendered insoluble in ammonia by
digestion in hydrochloric acid, the ulmic acid, according to Mulder,
being converted into ulmin. The body, dried at 140°, now contains
65.11 p. c. C., 4·32 H., and 30.57 O., from which numbers Mulder
calculates the formula C40H16014.
2. Ten parts of sugar are boiled with 30 parts of water and 1 part
of oil of vitriol, and the product is dried at 165°. It contains 64.72
p. c. C., 4.50 H., and 30.78 0., and is, according to Mulder, a mixture
of ulmin and ulmic acid not perfectly dry. — It is partially soluble in
ammonia and caustic potash.
2 a. The portion of 2 soluble in caustic potash, when precipitated
by sulphuric acid, dried, triturated, and digested with dilute hydro-
chloric acid to remove potash, is ulmic acid, containing, at 195°, 68.95
p. c. C., 4.23 H., and 26.82 0. According to Mulder C40H140¹².
26. The portion of 2 soluble in aqueous ammonia, when washed
with hydrochloric acid and water, is ulmin. After drying at 140° (at
which temperature the air-dried substance loses 9.2 p. c. of water) it
contains 65.45 p. c. C., 4·47 H., and 30.08 O., and is represented by the
formula C40H16014 (Mulder).
3. Four parts of sugar are boiled with 1 part of strong hydrochloric
acid and 10 parts of water (apparently with excess of air), and the
product is washed and dried at 165°. It contains 65.36 p. c. C., 4·38
H., and 30-26 O., and consists, according to Mulder, of a mixture of
ulmin and humic acid. — It is insoluble, for the most part, in
ammonia.
3 a. The portion of 3 insoluble in ammonia, after washing with
dilute hydrochloric acid and drying at 160° (whereby water containing
acetic acid is expelled), contains 66-71 p. c. C., 4-40 H., and 28.89 0.
= C'40H¹4¹² + 1 HO: Mulder's ulmin.
4. Ten parts of sugar are boiled with 20 parts of water and 2 parts
of oil of vitriol. A portion of the product is black and insoluble in
464 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
caustic potash, and contains, at 140°, 64-67 p. c. C., 4.32 H., and 31.01
O.: Mulder's humin, C40H505. A second portion is soluble in caustic
potash, from which it is precipitated as a brown-black jelly by acids,
and contains, at 140°, 63.25 to 64.01 p. c. C., 4.61 to 4.38 H., and 32·14
to 31.61 0. CH[17015
A portion of the jelly is soluble in ammonia. The reddish insoluble
residue contains, at 140°, 65.66 p. c C., 4·26 H., and 30.08 O., corre-
sponding to the formula C40H16014
The above substances are capable of yielding salts and double
salts.
Ammonia-salt. By treating 2 with aqueous ammonia, evaporating
the filtrate, and drying the product at 140°, the ammonia-salt of ulmic
acid is obtained. It contains 64.84 p. c. C., 3·97 N., 5·06 H., and 26∙13
O., corresponding to the formula C40H14012, NH'O. The ammonia-salt
of humic acid is obtained by treating 3 in a similar manner. It
contains 64.94 p. c. C. and 4.53 H., agreeing with the formula
CH12012_NH 0.
,
Potash-salt. Obtained by dissolving ulmic acid in caustic
potash, evaporating the neutral solution, and drying the residue
at 140°. Contains 12.31 p. c. KO., corresponding to the formula
C'40H14012, KO.
Baryta-salt. Prepared by neutralising the potash-salt with acetic
acid and precipitating with chloride of barium. It cannot be washed.
Dried at 140°, it contains 13.59 p. c. BaO., agreeing with the formula
3CFIIO12,2BaO.
Copper-salt. Obtained from sulphate of copper in the same manner
as the baryta-salt. When dried at 140°, it contains 10.20 p. c. CuO.,
corresponding to the formula C4H10¹², CuO.
Lead-salt. Prepared from neutral acetate of lead in the same
manner as the baryta-salt. At 140° it contains 31.02 p. c. PbO, and is
represented by the formula 3C40H14012, 4PbO.
Ammonio-plumbic salt. Neutral acetate of lead throws down from
the ammonia-salt of ulmic acid, an ammoniacal precipitate containing,
at 140°, 55·03 p. c. C., 3·74 H., and 17·76 Pbo.
Silver-salt. Nitrate of silver throws down from the ammonia-salt
of humic acid, a precipitate free from ammonia, which, after drying at
100°, loses 6·83 p. c. of water at 140°. The salt dried at 100° contains
49.05 p. c. C., 3.23 H., 24-58 O., and 23·14 AgO, and corresponds to the
formula C4H1015, AgO.
Ammonio-argentic salt. - Precipitated by nitrate of silver from an
ammoniacal solution of 1 or 2. Dark-brown and contains ammonia.
Dried at 140° it contains 57·09 to 57.89 p. c. C., 3.61 to 3·90 H., 1·59
N., 23-19 0., and 14-52 to 13:59 AgO., and is, according to Mulder, a
salt of ulmic acid represented by the formula 2C4014012, NH40, AgO.
Decomposition-products of Humin-substances from Sugar. -a. By the
action of Chlorine. Ulmin, ulmic acid, humin, and humic acid, when
subjected to the prolonged action of chlorine in presence of water,
HUMOUS SUBSTANCES.
465
yield one and the same substance, Mulder's chlorohumic acid. This
body is formed rapidly with alkaline ulmic acid, more slowly with humic
acid suspended in water, and only after 20 to 40 hours when humin is
employed. It forms an inodorous pale-red or brick-red jelly, tritu-
rable to an orange-yellow powder. When dried at 120° it has the
composition a, and at 155° the composition b.
a. 50·53 p. c. C., 3·30 H., 35·96 O., 9·87 Cl = C3²CIH13017.
b. 53.41 p. c. C., 3·49 H., 32.36 O., 10·74 Cl = C³²CIH¹2016.
The former acid was prepared from the potash-salt of ulmic acid, the
latter from the ammonia-salt of humic acid.
The acid dissolves when washed with water. It dissolves easily in
ammonia-water and caustic potash, also in alcohol, but not in ether.
-Its baryta-salt, obtained by double decomposition, contains, after
slight washing and drying at 118°, 43.09 p. c. C., 3·04 H., 29.98 O.,
8.64 Cl., and 15.25 BaO., corresponding to the formula CCIH¹³0¹7, BaO
(Mulder).
b. By the action of Nitric acid. When digested with strong nitric
acid, humin and ulmin substances become hot, turn red, and give off a
large quantity of formic acid. When heated with nitric acid diluted
with more than an equal weight of water, they turn red and afterwards
dissolve, and at length yield formic and oxalic acids.
The red substance produced by the action of strong nitric acid con-
tains 53.71 p. c. C., 3·44 H., 5·02 N., and 37.83 0. The body formed
with dilute acid is Mulder's humin-nitric acid, afterwards regarded as
identical with apocrenate of ammonia. After once washing, pressing,
and drying (whereby acid water is expelled) it forms a rust-red powder.
It dissolves in water and in alcohol, but not in ether: it is soluble also
in oil of vitriol, and in aqueous ammonia, potash, and soda, with blood-
red colour, ammonia being evolved by the action of potash. Its me-
tallic salts are brown jellies.
The acid contains, at 120°, 55.43 p. c. C., 2.98 N., 3.49 H., and
38.10 0., corresponding to the formula C4NH18026; the ammonia-salt,
obtained by dissolving the acid in ammonia and evaporating, contains,
at 120°, 51·67 p. c. C. and 4.33 H. — C48NH¹6024,2NHO: the silver-salt,
at 115°, 30.31 p. c. AgO.; the lead-salt precipitated from the potash-
salt by neutral acetate of lead, at 110°, 28.97 p. c. C., 1·80 N., 1·88 H.,
22.67 0., and 44.68 PbO., corresponding to the formula CNH18026,
4PbO (Mulder).
c. By the action of Oil of Vitriol. When ulmin or ulmic acid is
mixed with oil of vitriol and the black pasty mass is diluted, after some
hours, with a large quantity of water, a hard black powder, partially
soluble in ammonia, is obtained. It contains, at 1·55°, 64.35 p. c. C.,
4.17 H., and 31:48 O., corresponding to the formula C4H1015 (Mulder),
or C²4HºOº (Kr.).
d. By the action of Caustic Potash. a. The blood-red solution of
humin and humic acid in very strong caustic potash, when heated to
incipient fusion in a silver vessel, and mixed, after cooling, with
sulphuric acid, yields a black precipitate, which is not decomposed by
chlorine, and is dissolved with difficulty by nitric acid, forming a red
solution. When dried at 145° it contains 70.83 p. c. C., 4.62 II., and
24.55 O., agreeing with the formula C³H¹³0)' (Mulder).
VOL. XVII.
2 II
466 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
B. If the potash-solution is heated for a longer time, till hydrogen
begins to be evolved and carbonic acid formed, nearly the whole of
the dissolved body is thrown down as a black mass, which, after wash-
ing and drying at 140°, contains 77·70 p. c. C., 4·07 H., and 18.23 O.
=C4H100 (Mulder).
7. Lastly, if the fusion is continued so long as the alkali continues
to froth up, and until a faint glowing is perceptible, with empyreumatic
odour, the black insoluble powder contains, at 150°, 86 84 p. c. C.,
3.18 H., and 9.98 O., corresponding to the formula C3H7O3 (Mulder).
C. Products formed by the Action of Potash on Vegetable Fibre.
Peligot's Ulmic Acid.
Braconnot heats sawdust, paper, or linen with an equal quantity of
hydrate of potash and a little water in a silver crucible, till the mass
becomes soft and the sawdust dissolves with frothing; then cools the
product, dilutes with water, and precipitates the filtrate with sulphuric
acid. The brown flocks still contain about 4 per cent. of ash. They
dissolve in ammonia and in alcohol.
When woody fibre purified as much as possible is heated with half
its weight of hydrate of potash and a little water, with constant
stirring, till the mass becomes soft, but not until the fibres are com-
pletely dissolved, acids throw down from the filtrate a yellow precipi-
tate, which melts in boiling water, and contains, at 100°, 64.57 to
66.3 p. c. C., and 6·2 to 6·3 H. (Peligot).
When the mixture is heated more strongly and for a longer time,
with a larger proportion of potash, a black precipitate, Peligot's ulmic
acid, is obtained. It contains at 120°, on the average, 70-7 p. c. C.,
6·1 H., and 23.2 O., corresponding to the formula CH¼0° (Peligot).
Probably C4H106 (70·59 C., 5·88 H) (Kr.).
The potash-salt, prepared from hydrate of potash and excess of
ulmic acid, contains, after evaporation in a vacuum and drying at 120°,
16·8 p. c. KO.—The silver-salt, precipitated from the ammonia-salt by
nitrate of silver, contains 31.4 p. c. of silver (Peligot).
D. Crenic Acid.
BERZELIUS. Pogg. 29, 3, and 238; Lehrbuch. 3, Aufl. 8, 393.
Quellsäure. Humusquellsäure. Krensäure.
Source. In many springs, especially abundant in the Porla spring
in Oerebro Län (Sweden), and in the ochre deposited therefrom. In
ochre from the soil of Lisma; in a bog-ore from Smaland; in a white
mealy earth, consisting chiefly of silica, from Degernä.
On the occurrence of crenic acid in rotten wood, see below.
Preparation. From the ochrey deposit of the Porla Spring. The finely
powdered deposit is boiled with caustic potash, till it assumes the
flocculent appearance of precipitated sesquioxide of iron; it is then
HUMOUS SUBSTANCES (CRENIC ACID).
467
filtered and washed, and the filtrate is supersaturated with so much
acetic acid, that on adding acetate of copper, a brown (not a green) pre-
cipitate is produced; and the apocrenic acid is thrown down by the
addition of acetate of copper. After neutralising the filtrate with
carbonate of ammonia and heating it to 50° till the supernatant liquid
appears of a pure blue colour, the crenic acid is precipitated as copper-
salt, which is washed and decomposed under water by hydrosulphuric
acid. The liquid can be filtered from sulphide of copper only after
standing 24 hours in a stoppered vessel, after which the pale-yellow
filtrate is evaporated in a vacuum. There remains a dark-yellow
fissured mass, containing, besides crenic acid, the compounds of the
acid with lime, magnesia, and manganese. This mass is treated with
absolute alcohol, which dissolves crenic acid and a little crenate of
magnesia; the alcoholic solution is rapidly evaporated in a vacuum;
the yellowish-brown residue is dissolved in water, and mixed with small
portions of neutral acetate of lead, so long as brown apocrenate of
lead is produced, and until the precipitate produced by a drop of the
acetate either re-dissolves, or appears of a greyish-yellow colour only;
and the liquid is filtered and precipitated by basic acetate of lead. The
precipitate thus obtained is well washed and decomposed by hydro-
sulphuric acid, and the filtrate is evaporated in a vacuum.
Properties. Pale-yellow transparent mass, becoming yellow and
opaque on prolonged drying. Tastes sharply and distinctly acid; a
strong solution is styptic, a dilute solution tasteless. Reddens litmus.
Decompositions. The aqueous, and still more the alcoholic solution
turns dark in the air, and leaves a brownish residue. When submitted
to dry distillation, the acid softens, swells up, emits fumes, and yields.
a yellow acid distillate, containing ammonia and a thick yellowish-
brown oil, leaving charcoal. When heated with nitric acid, it evolves
a little nitric oxide, and on evaporating the liquid, there remains a
yellowish mass, which still behaves towards alkalis and acetate of
copper like crenic acid. - The acid in combination with alkalis under-
goes alteration in the air like gallic acid, becoming brown and passing
into apocrenic acid.
The acid dissolves in all proportions in water. Its concentrated
solution is syrupy. It dissolves without alteration in cold nitric acid.
The salts of crenic acid are amorphous. The acid expels acetic acid
from the acetates. The crenates of the alkalis are easily alterable in
the air. Their concentrated aqueous solutions resemble vegetable
extracts. The salts of the alkaline earths are less easily soluble; those
of the metals are, for the most part, sparingly soluble precipitates,
dissolving more or less on washing. - The acid forms neutral and acid
salts.
Ammonia-salt.—Becomes acid on evaporation, and leaves a brown,
extract-like mass, still containing a large quantity of ammonia.
Potash-salt. Prepared by dropping a solution of the acid in abso-
lute alcohol into acetate of potash, also dissolved in absolute alcohol.
-Nearly white precipitate, yellow and horny after drying. Neutral.
Dissolves in alcohol of sp. gr. 0·86.
The soda-salt behaves like the potash-salt; the baryta-salt like the
lime-salt.
2H 2
468 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
Lime-salt. - Neutral. Pale-yellow flocks, obtained by precipita-
ting chloride of calcium with excess of the potash-salt. It dissolves
in a larger quantity of water, and remains on evaporation as a yellow
transparent varnish, which is often white and earthy within. With
excess of crenic acid, it forms an acid salt insoluble in alcohol, and with
lime-water pale-yellow flocks of a basic salt. On neutralising crenic
acid as completely as possible with hydrate of lime, evaporating the
solution in a vacuum, boiling the yellow transparent residue a few times
with alcohol, and drying at 100°, there remains a lime-salt containing
20.59 p. c. of lime.
The magnesia-salt is easily soluble in water; the acid salt slightly
soluble in absolute alcohol.
Alumina-salt. Aqueous crenic acid and moist hydrate of alumina
yield a yellow insoluble compound, or with a larger proportion of acid
a soluble compound. The latter body is not precipitated by am-
monia, and even after evaporation therewith is perfectly soluble in
water.
Silicic acid precipitated from a liquid containing crenic acid takes
up a portion of the acid, which is only partially extracted from it by
potash.
Lead-salts.
·Basic acetate of lead throws down from crenates of
the alkalis a yellowish white basic salt. The precipitate produced by
neutral acetate of lead in aqueous crenic acid redissolves at first: on
continuing to add the neutral acetate so long as (owing to the presence
of apocrenic acid) a brown or dark-yellow precipitate is produced, then
filtering, dropping the filtrate into neutral acetate of lead, washing the
precipitate thereby formed with alcohol, and drying it in a vacuum and
afterwards at 100°, a neutral salt is obtained, containing 51.2 p. c.
of oxide of lead.
Ferrous salt. The aqueous acid dissolves iron, forming a soluble
acid salt, which oxidises in the air.
Ferric salt. Aqueous crenic acid produces in ferric salts free from
acid, dark streaks, which quickly disappear, after which a pale reddish-
grey, almost white precipitate is produced. After drying, the precipi-
tate is earthy, and of a dirty white colour. It dissolves completely in
ammonia, and remains on evaporation as a reddish-yellow residue, from
which water dissolves a neutral double salt, leaving a basic salt behind.
-It is decomposed, without being dissolved, by caustic alkalis and
their carbonates.
Copper-salt. Crenic acid precipitates acetate of copper completely
at 50° only; the crenates of the alkalis also precipitate sulphate of copper.
The precipitate is dirty-white when first thrown down, but soon turns
greenish-grey. It dissolves slightly in water and easily in acetic and
crenic acids. The solution in acetic acid leaves on evaporation a red
residue containing suboxide of copper.
The mercurous salt is insoluble, the mercuric salt soluble.
Silver-salt. Crenic acid scarcely renders nitrate of silver turbid at
first, but after a time it produces a whitish-grey precipitate, which
gradually assumes a dark-purple colour. The precipitate forms a
HUMOUS SUBSTANCES (APOCRENIC ACID).
469
colourless solution with nitric acid and a pale-yellow solution with
ammonia. A crenate of an alkali with a small quantity of nitrate
of silver remains clear, on account of the formation of a double salt,
but with a larger quantity of the nitrate, crenate of silver is thrown
down.
Crenic acid dissolves in all proportions in absolute alcohol. If it
contains salts of crenic acid, it becomes opaque before the alcohol
extracts the acid,
E. Apocrenic Acid.
BERZELIUS. Pogg. 29, 3, and 238.
Quellsatzsäure.
Occurs in the water of the Porla spring and in other waters, being
produced by the action of the air on crenic acid.
Preparation. The precipitate of apocrenate of copper obtained in
the preparation of crenic acid (p. 466) is washed a few times with
water, which it still colours yellow, since the precipitate is more soluble
in pure water than in saline solutions. It is then decomposed under
water by hydrosulphuric acid; the sulphide of copper is allowed to
subside; the dark-brown liquid is evaporated; and the residue is ex-
hausted with absolute alcohol, whereby salts are left behind and two
different modifications of apocrenic acid are dissolved, according to the
quantity of alcohol employed. An additional quantity of the acid may
be obtained from the sulphide of copper.
a. A small quantity of alcohol takes up from the above residue,
apocrenic acid, which is black-brown and fissured after drying, and
triturable to a dark-red powder. It reddens litmus, has a styptic taste,
dissolves with brown colour in water, and is partially precipitated in
flocks by acids and by sal-ammoniac.
b. The undissolved portion of the residue, when warmed with more
alcohol, gradually dissolves with brown colour, and remains on evapo-
ration similar in appearance to a. It reddens litmus, has less taste
than a, and becomes paler and soft in water, without dissolving.
c. A modification of apocrenic acid, likewise sparingly soluble in
water, is extracted from the sulphide of copper by aqueous acetate of
potash. On evaporating the solution, it is obtained as apocrenate of
potash and is freed from admixed acetate by means of alcohol of sp. gr.
0.86. Hydrochloric acid precipitates the acid, though incompletely,
from a solution of the potash-salt.
The acid prepared according to a, and that prepared according to b
and c, are distinguished by the following behaviour. When precipi-
tated from their solutions by hydrochloric acid, re-dissolved in caustic
potash, and mixed with freshly precipitated hydrate of alumina, the
Ïatter body acquires a dark colour, and precipitates b and c completely,
but in the case of a, a salt of crenic acid remains in solution, and may
be precipitated by acetate of copper. According to Berzelius, this
crenic acid was not merely an admixture, but formed, in combination
with a second body, the apocrenic acid a.
Apocrenic acid dissolves in cold nitric acid of sp. gr. 1.25, forming
470
APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
a solution which loses its colour when heated, with evolution of a little
nitric oxide, and leaves on evaporation an acid pale-yellow mass
behaving like crenic acid.
It expels acetic acid from its salts, forming apocrenates. Its salts
are amorphous, black-brown, and generally less easily soluble in water
than the crenates. The soluble salts are precipitated by acids, with
the exception of acetic acid.
Ammonia-salt. On dissolving 100 parts of the acid dried at 100°
in aqueous ammonia, and evaporating the solution, there remain 113.22
parts of ammonia-salt dried at 100°. This salt has an acid reaction,
and is soluble in water. When dried at 100° in a current of air, it gives
off ammonia and becomes partly insoluble in water.
Potash-salt. A solution of the acid in acetate of potash gives off
acetic acid when evaporated, and leaves a neutral residue from which
alcohol takes up the remaining acetate of potash. The apocrenate
forms a black, fissured, easily pulverisable mass, soluble in water with
brown colour, and completely precipitable from the solution by alcohol.
The soda-salt resembles the potash-salt. The baryta- and lime-salts
are black-brown precipitates, which gradually dissolve on washing with
water. The basic salts are quite insoluble.
Alumina-salt. A small quantity of hydrate of alumina dissolves in
aqueous apocrenic acid: a larger quantity throws down the acid from
its solution in water or alkalis, in the form of a black-brown precipitate,
which when obtained from alkaline solution, leaves potash and alumina
on ignition, and is insoluble in ammonia.
The lead-salt contains, at 100°, 45°25 p. c. of oxide of lead.
Ferrous salt. The neutral salt is soluble in water. By exposure
to the air, it is converted into basic ferric salt. The basic ferrous salt,
precipitated from the potash-salt mixed with a little ammonia by proto-
salts of iron, is a black precipitate, turning brown in the air, like the
ochre of the Porla spring.
Ferric salt. The acid and its potash-salt throw down from ferric
sulphate, black flocks which dissolve with black colour in ammonia. On
evaporating the solution, there remains a black extract, from which
water takes up a neutral double salt, whilst a basic ferric salt remains
undissolved. The salt dissolves in caustic potash and then deposits
a basic salt, whilst apocrenate of potash remains in solution, together
with a little sesquioxide of iron, which may be removed by hydrosul-
phuric acid.
Cupric salt. Acetate of copper mixed with acetic acid, throws
down from aqueous apocrenic acid, an acid salt, in the form of a brown,
gummy precipitate, which dissolves slightly, with dark colour, in
water. From this solution a little alkali precipitates the neutral salt.
Apocrenic acid does not precipitate solutions of gelatin, even on
addition of hydrochloric acid.
HUMOUS SUBSTANCES.
47]
Analyses of Crenic and Apocrenic acids of unknown origin, by Hermann
(J. pr. Chem. 12, 284).
Crenic acid.
Apocrenic acid.
OREO
39.49
61.4
N
7.50
15.0
H
7.69
4.8
....
45.32
18.8
100.00
100'0
Hermann's nitrogen determinations seem to be all wrong (Kr.).
F. Substances derived from Peat, Rotten Wood, and Vegetable Mould.
From Peat. Sprengel's Humic Acid.-Pulverised peat is treated with
hydrochloric acid to remove salifiable bases, and the residue is digested
with aqueous ammonia for some days in a stoppered vessel. The
ammoniacal solution thus obtained is diluted, filtered, and precipitated
by hydrochloric acid, and left at rest, in order that the hydro-
chloric acid may dissolve as much as possible of the bases from the
precipitated humic acid. The precipitate is then washed and dissolved
in aqueous carbonate of soda, and the solution is filtered (whereby
sesquioxide of iron and alumina are removed), and precipitated with
excess of hydrochloric acid. After standing for 24 hours, the liquid
is decanted, and the precipitate washed with hot and cold water in
succession, the wash-waters acquiring a deeper colour the more com-
pletely the hydrochloric acid is removed (Sprengel).
Shining, black, jet-like mass, breaking up into irregular fragments,
which exhibit a conchoïdal fracture. Very hygroscopic. Tastes sour
and styptic in the moist state. Reddens litmus (Sprengel), according to
Berzelius and Einhof, on account of adhering acid.
When submitted to dry distillation, it yields gases, acetic acid, and
empyreumatic oil, leaving a hard, dense charcoal. Burns with flame.
Chlorine decolorises the water in which humic acid is suspended,
throwing down a white resin. Nitric acid forms artificial tannin; oil
of vitriol carbonises it on heating. In the moist state it absorbs
oxygen.
Freshly precipitated humic acid dissolves slightly in cold, and more
freely in hot water. When the solution is frozen, the dissolved portion
is thrown down. The acid is likewise rendered insoluble by perfect
drying. The brown solution in oil of vitriol is precipitated by
water.
Humic acid forms salts with bases. It expels carbonic acid from
alkaline carbonates, and forms precipitates of acid humaies with
solutions of earthy and metallic salts. The humates of the alkali-
metals yield by double decomposition with metallic salts, sometimes
neutral, sometimes basic compounds. The insoluble salts, when freshly
precipitated, form brown or black slippery masses, which contract very
much on drying, and break up into black shining particles. The salts
insoluble in water dissolve for the most part in aqueous alkalis,
especially in ammonia, and partly also in aqueous alkaline carbonates
which, however, decompose some of the other salts. See particulars
about the salts in the original memoirs (p. 458.).
472 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
Humic acid dissolves in hot acetic acid, and in alcohol before drying,
but not afterwards (Sprengel).
From Peat, Rotten Wood, Vegetable Mould (Mulder, J. pr. Chem. 21,
321).
a. From Peat. When peat is washed with water and alcohol to
remove soluble matters and resins, and the residue is boiled with car-
bonate of soda, a dark solution is obtained, from which acids throw
down a brown or black jelly, the liquid still remaining of a dark colour.
The jelly dissolves in washing, as soon as the wash-water becomes
free from acid. By this treatment, black peat from the Haarlem lake
yielded humic acid, whilst light brown Friesland peat yielded ulmic
acid.
The humic acid contains 7.5 p. c. of ash, and likewise ammonia,
which cannot be completely separated, but is partly expelled at 140°.
When dried at 140°, it contains 60.13 p. c. C., 4·74 H., 3.61 N., and
31.52 O., and according to Mulder, is represented by the formula
C4H12O,NH3 + 4HO.
The ulmic acid contains 1.4 p. c. of ash, but is free from ammonia.
Its ammonia-salt is obtained by dissolving it in ammonia, evaporating
the solution, and drying the residue at 140°. The acid, dried at 140°,
contains 62.02 p. c. C., 4.65 H., and 33.33 0., corresponding to the
formula C40H18016. The ammonia-salt contains, at 140°, 61.20 p. c. C.,
and 4·91 H., corresponding to the formula C4H¹0¹²,NH³ + 3HÔ.
b. From the rotten wood of Salix alba. Obtained in the same
manner as a. Contains ammonia, and 1.9 p. c. of ash. Dried at 140°,
it contains 59.09 p. c. C., 4.97 H., 2.80 N., and 33.18 0., agreeing with
the formula of the ammonia-salt of humic acid, C40H12012, NH3 + 5Hо
(Mulder). By again dissolving the substance in caustic potash and
precipitating with sulphuric acid, a precipitate is obtained, containing,
at 140°, 62.50 p. c. C., 4.88 H., and also ammonia.
c. From Vegetable Mould. Obtained by washing the mould with
boiling water, boiling it with carbonate of soda, precipitating the
solution with hydrochloric acid, washing the gelatinous precipitate
with water, drying, and boiling with alcohol, to remove crenic and
apocrenic acids. The jellies thus obtained still contain ammonia and
varying proportions of ash, amounting in some cases to 27 per cent.
According to Mulder, they are in most cases to be regarded as humic
acid, C40H12012, with ammonia and water.
Humous substances from Vegetable Mould.
1.
OKHO
C ....
57.45
2.
61.90
Co
N
3.25
....
....
4.52
34.90
99.12
4.65
3.
4.
5.
57.54
60.04
56.91
Suoraa
3.31
6.11
4.71
4.66
5.31
31.99
31.67
100.00
100.00
AN
6.
7.
8.
9.
10.
OREO
C
58.44
59.09
57.87
55.18
60.94
N
3.63
3.52
2.35
H
5.27
5.12
4.98
5:00
4.85
32.16
33.63
37.47
100.00
100.00
100.00
HUMOUS SUBSTANCES.
473
2 was obtained by dissolving 1 in caustic potash and precipitating with acids.
4 was prepared from 3 by digesting it in hydrochloric acid, boiling with alcohol,
and collecting the undissolved portion. 5 and 6 are the same substance, 5 being
dried at 140°, and 6 at 195°. Boiling water took up a large proportion of 9, and
left 10 undissolved.
J
Mulder's crenic and apocrenic acids are obtained from tilled soil, and
according to Hermann, are identical with his humocrenic and torfo-
crenic acids; the former is, according to Mulder himself, identical with.
humin-nitric acid, and also with Stas's phloretin (xvi, 8). To obtain
these bodies the soil is boiled with water, and with carbonate of soda
in succession; the latter solution is precipitated with dilute sulphuric
acid, and filtered from the humin thereby thrown down; and the filtrate
is mixed, first with caustic potash, then with acetic acid to slightly
acid reaction, and lastly with acetate of copper, which throws down
apocrenic acid. The filtrate, neutralised with carbonate of ammonia,
yields a precipitate of crenic acid in combination with oxide of copper,
which is purified by dissolving it in acetic acid, and precipitating with
alcohol.
The apocrenate of copper contains ammonia, on which account
Mulder regards it as a double salt, and assigns to the acid the formula
C48H12O24. Dried at 140°, it contains 42.8 to 47·1 p. c. CaO., the organic
part containing 51.39 p. c. C., 3.91 H., 3.73 N., and 40.97 0. When
decomposed by hydrosulphuric acid, it yields apocrenic acid.
The crenate of copper contains phosphate of copper, and generally
also ammonia. On one occasion, after having been purified by repeatedly
dissolving it in acetic acid, and precipitating with alcohol, it was
obtained almost free from nitrogen, and contained 60.17 p. c. of oxide
of copper. The organic part contained, in 100 parts, 46.87 C., 4.97 H.,
and 48.16 0., corresponding to the formula CH¹²Q¹6 + 3HO (Mulder,
J. pr. Chem. 32, 321).
16
Humous acids of Russian black earth (Tschornosem) (Hermann, J. pr.
Chem. 12, 277).
a. From the solution obtained with carbonate of soda, sulphuric
acid throws down a in brown flocks.
b. On exhausting untilled black earth with hydrochloric acid, and
afterwards with carbonate of soda, and precipitating the latter solution
with hydrochloric acid, the substance b is obtained. Similar treatment
of earth cultivated for many years, yields the body c.
All three acids may be resolved into crenic, apocrenic, and humic
acids, in different proportions.
a..
b.
c.
OKEO
56.73
59.68
60.83
14
N
13.69
8.02
11.05
H
5.34
4.12
4:31
24.24
28.18
23.81
100.00
100.00
100.00
L
Hermann (J. pr. Chem. 22, 65; 23, 375; 25, 189; 27, 165; 34, 156)
distinguishes eleven different humous substances, most of which he
regards as nitrogenous, even when they are obtained from substances
free from nitrogen, as in the case of bodies prepared from cane-sugar,
according to xv, 255, the nitrogen being absorbed from the air. (See
also xv, 157.) They are as follows:-
474 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
I. Substances insoluble in acetate of soda, soluble in alkalis, and
precipitable from the solutions by mineral acids. Humic acids in the
more restricted sense.
1. Anitrohumic acid. The substance formed, according to Mala-
guti (xv. 275), by the action of sulphuric acid on sugar in the absence
of air; Malaguti's ulmic acid.
2. Saccharo-humic acid. The acid produced in a similar manner to
the last, but with access of air. It contains 6.88 p. c. of nitrogen, and
in the copper-salt 10.8 p. c. CuO.
3. Ligno-humic acid.- Obtained from pale-brown rotten wood by
boiling it with aqueous carbonate of potash, which dissolves humous
extract and ligno-humic acid, and leaves nitrolin undissolved. From
the solution the ligno-humic acid alone is precipitated by hydrochloric
acid in the form of a brown jelly. Dried at 100° it contains 57.23
p. c. C., 6·47 N., and 5.22 H.; and in the copper-salt, 5-1 p. c. CuO.
4. Metaligno-humic acid. Formed by boiling freshly precipitated
ligno-humic acid with water, by which it loses its sliminess, becoming
pulverulent, and altering its capacity of saturation. The acid con-
tains at 100°, 56.94 p. c. C., 6.77 N., and 5.00 H.: the copper-salt
7.04 p. c. CuO.
II. Substances soluble in alkalis and acetate of soda, and pre-
cipitable by mineral acids. Hermann's apocrenic acids. Berzelius's
apocrenic acid belongs to this place, but is found to differ from the
substances 5 and 6.
5. Torfic acid. Obtained from Russian peat by boiling it with
carbonate of soda, supersaturating the solution with acetic acid, pre-
cipitating with acetate of copper, dissolving the precipitate in caustic
potash, and precipitating with hydrochloric acid. This precipitate,
dissolved in a strong solution of acetate of soda, and evaporated
nearly to dryness, deposits a little humic acid, whilst torfic acid
remains in solution, and may be precipitated by acetate of copper and
separated as above. In alkaline solution it absorbs oxygen. The
salts of the alkalis are soluble and dark-brown: the remaining salts
are basic, neutral, or acid, generally insoluble, but soluble in caustic
alkalis and their carbonates, if the base consists of lime, alumina, oxide
of iron, or oxide of copper. The acid dried at 100° contains 61.92
p. c. C., 7·73 N., and 4:31 H.: the neutral potash-salt contains 14·7
p. c. KO.; the acid soda-salt 5.27 NaO; the lime-salts 8.5 to 13·55
CaO.; the copper-salt 9.58 to 13 p. c. CuO.
6. Tula and Siberian Arvic acid (Tula-und Siberische Ackersäure).
Obtained from tilled soil in the same way as 5. Differs from 5 only
in the percentage of nitrogen, which varies from 4.89 to 15.00 per
cent.
III. Substances soluble in water. This class includes Berzelius's
crenic acid.
7. Humus-extract. -Occurs in tilled soil, peat, and rotten wood;
also in soot, wood-tar, and pyroligneous acid. (See xv, 151.)--When
rotten wood is boiled with carbonate of soda, and the filtrate is super-
saturated with nitric acid, a precipitate of ligno-humic acid is thrown
down, whilst humus-extract remains in solution. The latter body is
precipitated by the addition of nitrate of lead and ammonia, and the
HUMOUS SUBSTANCES.
475
precipitate is washed, agitated with dilute sulphuric acid not in excess,
and exhausted with alcohol. On evaporating the alcoholic solution,
the humus is left as a brown transparent varnish, containing, at 100°,
according to the analysis of the lead-compound, 56.68 p. c. C.,
4.56 H., and 4·50 N. Ït yields by dry distillation an empyreumatic
liquid holding humus-extract in solution. Dissolves easily in water,
with the exception of an insoluble portion produced during evaporation.
From the concentrated, but not from dilute solutions, various acids
and salts throw down the extract as a brown resinous precipitate.
The compounds with baryta and lime are sparingly soluble: the latter
compound is formed by boiling rotten wood or garden mould with.
lime, and separates in the form of brown pellicles on the surface of the
liquid on evaporation. The extract prevents the precipitation of
sesquioxide of iron and other metallic salts by ammonia: it is not
precipitated from its solutions by neutral metallic salts, or by ammo-
niacal acetate of copper, and is thereby distinguished from crenic
acid. The precipitate produced by basic acetate of lead is of a light
colour in the moist state, but brown after drying: it contains
40 p. c. PbO. The precipitate thrown down by ammoniacal sulphate
of copper contains at 110°, 35.00 p. c. CuO., 15.77 HO., and 49.23 of
humus extract. The extract dissolves easily in alcohol.
8. Humocrenic acid. Occurs in Black earth. The solution of
lignocrenic acid in excess of alkali absorbs oxygen and nitrogen,
according to Hermann, and forms with nitric acid a precipitate of
"Torfsatzsäure," together with humo-crenic acid, which is thrown
down from the filtrate by ammonia and basic acetate of lead. The
lead-salt forms yellowish flocks, containing, at 100°, 76-62 p. c. PbO.,
the remainder containing 52.01 p. c. C., 4:47 H., and 6.60 N. The
copper-salt is grey-green, and contains, at 100°, 50 p. c. CuO., the
organic portion containing 46.71 p. c. C., 5.01 H., and 6-11 N.
9. Torfocrenic acid. Occurs in peat, in black earth, and in the
mineral water of Moskau. It is slowly produced by the action of the
air on alkaline "Torfsatzsäure," and is separated from the solution in
the same way as 8. It forms lead-salts containing 62.0 to 82·5 p. c.
of lead-oxide, the organic part containing 42.05 p. c. C., 5·30˚H.,
and 6.25 N. The copper-salt contains 58.0 p. c. CuO., the remainder
containing 33.91 p. c. U., 6-34 H., and 5-12 N.
10. Torfoxycrenic acid. Occurs, together with 8, in the Moskau
mineral water. The water is evaporated toth of its volume and filtered,
and the filtrate is acidified with acetic acid and precipitated, at 60°,
with acetate of copper, which throws down torfoxycrenate of copper,
whilst torfocrenic acid, precipitable by ammonia, remains dissolved in
the filtrate. The lead-salt contains 73.5 p. c. PbO., and in the residue
60.54 p. c. C., 243 H., and 11.6 N.; the copper-salt contains 60 p. c.
CuO., the organic portion containing 41.21 p. c. C., 4.63 H., and
8.28 N.
IV. Substances insoluble in acids and alkalis.
11. Nitrolin. The principal constituent of rotten wood, remaining
behind when the wood is washed and boiled with water and carbonate
of soda. It is brown, and still shows the structure of the wood, and
becomes horny on drying. Contains, at 100°, 56.13 p. c. C., 6·32 H.,
and 13.20 N., or more frequently only 4 p. c. N.
476 APPENDIX TO COMPOUNDS CONTAINING 40 AT. CARBON.
G. Substances obtained from Lignite. Herz's Carbo-ulmic and Carbo-
humic acids.
When powdered lignite (from the coal of the Hohenpeissenberg in
Southern Bavaria) is boiled with alcohol to remove resin, and after-
wards subjected to prolonged boiling with strong caustic soda, and
the deep-brown liquid thereby formed is filtered and precipitated with
hydrochloric acid, dark-brown flocks are obtained, from which alcohol
takes up carbo-ulmic acid, leaving carbo-humic acid undissolved.
Carbo-ulmic acid contains, on the average, 62.36 p. c. C., 4·77 H.,
and 32.87 0., corresponding with the formula CH18016: the silver-salt
contains 50.79 p. c. Ag0.
Carbo-humic acid contains, at 130-140°, 64.59 p. c. C., 5.15 H.,
and 30.26 0.; the silver-salt 25.21 p. c. Ag0. (Herz, N. Repert. 10,
496).
H. Substances obtained from Dung.
Braconnot's Azulmic acid. When decomposed stable manure is ex-
hausted with water, a residue containing ulmic acid is left, whilst the
aqueous solution contains azulmic acid precipitable by acids. The
latter acid is also obtained by evaporating the aqueous extract to a
syrup, mixing it with alcohol of 32° B., decanting the slightly coloured
alcohol, and decomposing the precipitated black mass with acids.
forms a black, brittle mass, having a jet-like lustre, and leaving a
yellowish-brown ash when burnt, and carbon free from nitrogen when
carbonised. It dissolves in ammonia and alkalis, but not in alcohol
(Braconnot, N. Ann. Chim. Phys. 12, 212).
It
P. Thénard's Fumic acid (acide fumique, Düngersäure) is also pre-
cipitated by acids from the aqueous solution of fermented dung;
Thénard, however, purifies it by boiling the precipitate with the liquid,
which causes it to cohere, washing, dissolving it ten times in ammonia-
water, and precipitating with acids, so that at last the wash-waters
remain colourless. It forms an amorphous black mass, having a
shining fracture, and containingth per cent. of ash, and 60.5 p. c. C.,
5.1 H., 5.5 N., and 28.9 O., besides sulphur. According to Thénard,
it is represented by the formula C30NH15011. It forms decomposition-
products with chlorine and nitric acid, and is rendered soluble by
exposing its ammonia-salt to the air, especially together with clay, or
by the action of ozone, whereby nitric acid is formed, or when its lime-
salt is boiled for 14 days with carbonate of lime, sesquioxide of iron,
and water, whereby the oxide of iron is reduced if air is excluded, or
alternately reduced and oxidised if air is admitted. The acid forms
soluble salts with ammonia and the alkalis, and insoluble salts with the
other bases: its ammonia-salt, however, precipitates salts of alumina
only after addition of chloride of sodium, and does not precipitate
phosphate of alumina even in presence of excess of ammonia. Thénard
regarded as identical with this fumic acid, a brown nitrogenous product
which he obtained by heating dextro-glucose with ammonia (xv, 318)
or with nitrate of baryta (xv, 319), or by heating cellulose, milk-sugar,
and cane-sugar with phosphate of ammonia (Thénard).
IDRYL.
477
COMPOUNDS CONTAINING 42 ATOMS OF CARBON.
Primary Nucleus C42H14.
Idryl.
C4H1%.
C. BÖDEKER. Ann. Pharm. 52, 100; J. pr. Chem. 33, 249.
Occurs in Stupp, a black mass mixed with globules of mercury, ob-
tained in an experimental distillation of mercury in closed vessels
from a mercurial mineral found in Idria (Idrialite).
Stupp is boiled repeatedly with alcohol, and the solution, after cool-
ing, is separated from the yellow laminae of a hydrocarbon different
from idryl, which is deposited, and freed from the greater part of the
alcohol by distillation, whereupon a brownish-black oil collects at the
bottom of the vessel. This oil is boiled repeatedly with acetic acid so
long as it continues to take up idryl and deposit it from the golden-
yellow solution in needles on cooling. The needles are washed with
acetic acid and with water, and recrystallised from alcohol, the
lamine which are first deposited from the strong solution on cool-
ing, and consist of the hydrocarbon differing from idryl, being
removed.
Properties. Loose crystalline mass of needles, collecting in
nodules when slowly evaporated. Under the microscope rhombic
laminæ are discernible. The crystals are nearly colourless, with a
tinge of yellowish-green, and form a colourless powder when tritu-
rated. Melts at 86° to a clear pale-yellow oil, which solidifies to a
radiated crystallised mass. Sublimes easily in very delicate laminæ.
Has a faint, somewhat smoky odour, and no particular taste, but pro-
duces a slight burning sensation on the tongue.
42 C........ 252 ........ 94.73
14 H
C2H1
14
266
Bödeker.
mean.
94.57
5.27
5'46
100'00
100.03
Isomeric or polymeric with chrysene (xv, 1).
Idryl assumes a golden-yellow colour in cold oil of vitriol, and dis-
solves freely therein at 100°, forming a deep greenish-yellow liquid
not precipitable by water; sulphurous acid is not given off till the
liquid is strongly heated.
478
PRIMARY NUCLEUS C42H14.
Idryl dissolves slightly in acetic acid, alcohol, ether, and oil of turpen-
tine in the cold, and very freely when warmed, the last three solutions
when saturated at the boiling heat, becoming solid on cooling. A very
small quantity of idryl dissolved in these liquids produces a fine
bluish iridescence, similar to that of a solution of sulphate of
quinine.
The hydrocarbon obtained in the preparation of idryl forms delicate
lamine, which melt above 100° only, and sublime in fine colourless
laminæ before melting completely. It contains 93.65 p. c. C., and
5.67 H. It dissolves in oil of vitriol, with brown-red colour, when
warmed, and is somewhat less easily soluble than idryl in acetic acid
and alcohol.
Appendix to Idryl.
Idrialin.
DUMAS. Ann. Chim. Phys. 50, 193; Ann. Pharm. 5, 16; Schw. 66, 83;
N. Tr. 26, 1, 212.
SCHRÖTTER. Baumgärtner's Zeitschr. für Phys. &c., 3, 245.
LAURENT. Ann. Chim. Phys. 59, 385; 66, 143.
BÖDEKER. Ann. Pharm. 52, 100.
!
Occurs in idrialite from Idria, which consists almost entirely of this
substance. See Schrötter (Baumgärtner's Zeitschr. 4, 5). First noticed by
Hacquet in 1778.
Preparation. 1. The pulverised mineral is slowly sublimed in a
current of carbonic acid, the temperature being ultimately allowed to
rise till the glass softens. The melted mass yields successively mercury
and idrialin, which are collected and separated by treatment with boil-
ing oil of turpentine (Dumas). 2. The finely powdered idrialite is
boiled with 20 or 30 parts of oil of turpentine, which, after cooling and
filtering from the deposited idrialin, is again poured upon the idrialite
until the mineral is exhausted (Laurent). Bödeker decolorises the pro-
duct with animal charcoal, recrystallises from acetone or from a
mixture of alcohol and oil of turpentine, and washes the crystals with
alcohol.
Properties. Very light colourless laminæ, having a pearly lustre.
Laurent.
Bödeker.
42 C
14 H
0
252
91.97
91.85
91.64
92.11
14
5.11
5.30
5.27
5.29
8
2.92
2.85
3.09
2.60
CHO
274
100.00
100.00
100.00
100.00
...
Dumas and Laurent considered idrialin to be free from oxygen.
(Traité 4, 305) doubles the formula.
Gerhardt
Idrialin does not melt without decomposition, and distils undecom-
posed in very small quantity only (Dumas). It dissolves in warm
oil of vitriol with indigo-blue colour, forming a conjugated sulphuric
STRYCHNINE.
479
acid, the potash-salt of which forms fine silvery crystals (Schrötter).
The baryta- and lead-salts of the acid are likewise soluble (Bödeker).
Idrialin forms with chlorine a solid compound, soluble with purple
colour in oil of vitriol (Schrötter). Fuming nitric acid forms a dark-
brown solution precipitable by water (Schrötter).
When idrialin is boiled with strong nitric acid, a red powder,
Laurent's nitrite d'idrialase, is obtained, which is insoluble in water,
ether, and boiling alcohol, but dissolves partially, with brown colour,
in caustic potash, and explodes on charcoal or when heated.
It con-
tains 62.67 p. c. C., 3.10 H., and 10.50 N., from which numbers
Laurent calculates the formula C30X2H8, and Gerhardt (Traité, 4,
306) the less probable formula CX³H²³O² (65.2 p. c. C., 2.9 H.,
9.0 N.).
Idrialin is insoluble in boiling water, and very slightly soluble in
boiling alcohol and ether, but freely soluble in boiling oil of turpentine,
from which it is deposited almost entirely on cooling (Dumas). Boiling
bisulphide of carbon, rock-oil, and oil of turpentine dissolve idrialin very
freely, but take up very little of it from the mineral containing it, except
when heated above their boiling-points in closed vessels. Linseed-oil,
olive oil, and crosote dissolve the mineral almost entirely when heated
therewith (Schrötter).
Primary Nucleus C42H28; Oxyazo-nucleus C42N2H2004.
Strychnine.
C40N2H22O = C42N2H2004, H2.
PELLETIER & CAVENTOU. Ann. Chim. Phys. 10, 142; J. Pharm. 5, 145;
N. Tr. 3, 2, 224; Repert. 7, 169; Berl. Jahrb. 1820, 206; abstr.
Gilb. 63, 287. Ann. Chim. Phys. 26, 44; Schw. 42, 65; Repert.
18, 69.
PELLETIER & DUMAS. Ann. Chim. Phys. 24, 176.
MERCK. N. Tr. 20, 1, 134.
LIEBIG. Pogg. 21, 21 and 487. — Ann. Pharm. 26, 56.
DUFLOS. Schw. 62, 68.
REGNAULT. Ann. Pharm. 26, 17; J. pr. Chem. 16, 763. — Ann. Pharm.
29, 58.
PELLETIER. Ann. Chim. Phys. 63, 165; Ann. Pharm. 22, 114. — J.
Pharm. 24, 154; Ann. Pharm. 29, 49; J. pr. Chem. 14, 180.
GERHARDT. Ann. Pharm. 42, 312. Compt. chim. 1845, 116; Rev.
scient. 10, 192. - N. Ann. Chim. Phys. 7, 251.
DITR. BRANDIS. Ann. Pharm. 66, 257; Instit. 1848, 194; Pharm. Centr.
1847, 952; Lieb. Kopp's Jahresber. 1847 and 1848, 627.
NICHOLSON & ABEL. Chem. Soc. Qu. J. 2, 241; Ann. Pharm. 71, 79;
Pharm. Centr. 1849, 785; N. Ann. Chim. Phys. 27, 401; N. J. Pharm.
16, 305; Lieb. Kopp's Jahresber. 1849, 380.
HORSLEY. Pharm. Journ. 16, 177; J. pr. Chem. 72, 312; Instit. 1856,
463; Lieb. Kopp's Jahresber. 1856, 758.
SCHÜTZENBERGER. Compt. rend. 47, 79 and 235; Instit. 1858, 239; J.
pr. Chem. 75, 122; Ann. Pharm. 108, 349; Chem. Centr. 1858, 677;
Kopp's Jahresber. 1858, 373.
480 PRIMARY NUCLEUS C2H26; OXYAZO-NUCLEUS CN2H200+.
Discovered by Pelletier & Caventou in 1818. Occurs [combined with
igasuric acid (x, 229) ? See also Marsson (N. Br. Arch. 55, 295)] in the Nux
vomica of Strychnos Nux vomica (Handbuch viii. [2], 57), together with
brucine and igasurine; in the Faba St. Ignatii of Strychnos Ignatii, to-
gether with a very small quantity of brucine; in very small quantity
in Lignum colubrinum from Strychnos colubrina (Handbuch, viii [2], 56).
In the root-bark of Strychnos Tieuté and in Upas Tieuté, the Japanese
arrow poison, together with traces of brucine (Pelletier & Caventou),
whereas the North American arrow-poison contains curarin. Java
arrow-poison, found in a bamboo, contained 62 p. c. of strychnine
Frerichs, Pharm. Viertelj. 12, 542).
Concerning the quantities of brucine and strychnine present in pharma-
ceutical preparations of the above plants, see F. Mayer (N. Jahrb. Pharm.
23, 38; Chem. Centr. 1865, 320).
The base known as strychnine is, according to Schützenberger, a mixture of
three different bases, having the formulæ C4ºN2H22O4, C42N2H22O4, and C44N2H22O4.
The base with 42 atoms of carbon is said to be immediately deposited from dilute
hydrochlorate of strychnine in long slender needles on addition of ammonia, whilst
that with 40 atoms of carbon crystallises from the filtrate in octahedra after a
quarter of an hour. These statements stand much in need of confirmation (Kr.).
Preparation. I. From Nux vomica. The nuts are either rasped or bruised :
to render them fit for the latter operation, Milarch roasts them in an oven.
Or they
may be subjected to an atmosphere of steam for half an hour in a close vessel, and
afterwards dried.
1. Nux vomica is boiled with water till it becomes soft: it is then
bruised, returned to the boiling water, boiled for two hours, pressed,
and again boiled twice. The liquid thus obtained is evaporated to a
syrup and mixed with alcohol so long as gum is precipitated, the
strychnine, brucine, colouring matter, and a little fat remaining in
solution. The precipitate is washed with alcohol, and the alcoholic
liquids are evaporated to an extract and diluted with cold water,
whereby fat is thrown down. The filtrate is heated and decomposed
with excess of milk of lime, which precipitates strychnine and brucine.
The precipitate is pressed, dried, and boiled two or three times with
85 p. c. alcohol, which takes up strychnine, brucine, and colouring
matter. The alcohol is distilled off and the residue digested with cold
alcohol of 54 p. c., whereby brucine and colouring are dissolved, whilst
strychnine remains behind, and is purified by crystallisation from
boiling 85 p. c. alcohol [Corriol's process (J. Pharm. 11, 492; N. Tr.
12, 1, 173; abstr. Mag. Pharm. 13, 148) modified by Soubeiran, N. J.
Pharm. 45, 230)].
2. Nux vomica is boiled with alcohol; the tincture is evaporated;
and the extract is dissolved in water; the fat thereby separated is
removed; the filtrate is boiled for a few minutes with a quantity of
magnesia amounting tond of the nux vomica employed; and the
greenish-yellow precipitate is collected. It contains chiefly strychnine,
which is obtained by boiling it with alcohol of 38° B., evaporating the
solution, and washing the resulting crystals with very cold alcohol of
22° B. The brucine is deposited from the filtrate from the magnesia
precipitate after the lapse of a few days only (Pelletier & Caventou).
3. Rasped nux vomica is digested with five times its weight of 40
p. c. alcohol for a day, at a gentle heat. The liquid is strained through
STRYCHNINE.
481
0
50
linen, and the residue is pressed and treated twice again in the same
way. The whole of the tinctures are submitted to distillation and
further evaporated down to the weight of the nux vomica employed.
About th of neutral acetate of lead is added; the liquid is filtered
from the precipitate, evaporated to one-half, mixed with th of cal-
cined magnesia, and allowed to stand for a week, with frequent stirring.
The precipitate is then collected, washed, dried, and exhausted thrice
with hot 80 p. c. alcohol, which takes up strychnine, brucine, and
colouring matter. After distilling off the alcohol, the strychnine and
brucine are separated by means of 40 p. c. alcohol, as in 1 (Wittstein,
Darstell. u. Prüfung, 215). The processes of Wittstock (Berzel. Lehrb. 3 ed. 6,
296) and Winckler (Mag. Pharm. 19, 261) are similar to the foregoing. Pelletier &
Caventou had previously employed basic acetate of lead, for which Neuhaus (N. Tr.
11, 2, 198) substituted the neutral acetate.
See the methods of Duflos (Berl. Jahrb. 28, 2, 208. - Schw. 62, 69) and
O. Henry (J. Pharm. 16, 752; Repert. 37, 123), who extract with alcohol or water
containing sulphuric acid; also the similar method of Ferrari (Brugn. Giorn.
16, 457; abstr. Schw. 40, 492). N. E. Henry (J. Pharm. 8, 401; N. Tr. 7, 1,
336) and Robiquet extract with boiling water. O. Henry (J. Pharm. 21, 222)
precipitates the bases with infusion of galls (rii, 177): Lebourdais and Tilloy
(N. J. Pharm. 23, 406) precipitate them with animal charcoal. See p. 266.
According to Wittstein, 213 parts, according to Pelletier & Caven-
tou, 354 parts of nux vomica yield 1 part of strychnine.
II. From Ignatius' beans. —1. The rasped beans are first exhausted
with warm ether to remove fat, and then boiled repeatedly with alcohol.
The alcoholic liquid thus obtained is evaporated; the residue is boiled
with magnesia and water; and the precipitate thereby formed is washed
with cold water and boiled with alcohol, which, after filtering and eva-
porating, deposits the strychnine (Pelletier & Caventou). Or the beans
may at once be boiled with alcohol, and the fat separated by cooling the
liquid for some days (Steinmann. Schw. 25, 410).2. One part of the
beans is digested for a few days with 2 parts of 75 p. c. alcohol and
4 parts of water, the tincture is poured off, and the softened beans are
dried over a water-bath, pulverised (now an easy process), and exhausted
with a warm mixture of sulphuric acid, 2 parts of alcohol, and 4 parts
of water. The mixed tinctures are then precipitated with basic acetate
of lead, filtered, and freed from excess of lead by means of sulphuric
acid; the perfectly clear filtrate is evaporated down to the weight of
the beans employed; and the now brown and gelatinous liquid is
exhausted with warm alcohol. The tincture, mixed with water and
freed from alcohol by distillation, is precipitated with ammonia, and the
precipitate is purified by dissolving it in water containing sulphuric
acid, and, lastly, by crystallising it from hot alcohol (Geiseler, Ñ. Br.
Arch. 2, 73).
III. From Upas Tieuté. This substance is dissolved in water; the
filtrate is digested with magnesia; the reddish-yellow precipitate, after
washing and drying, is boiled three times with alcohol; and the reddish
tincture is evaporated. The strychnine thus obtained is coloured green
by nitric acid, on account of an admixture of strychnochromin (p. 505).
It is purified by dissolving it in dilute sulphuric acid, digesting with
animal charcoal, precipitating with magnesia, exhausting the precipi-
tate with alcohol, and evaporating (Pelletier & Caventou).
VOL. XVII.
21
!
482 PRIMARY NUCLEUS C42H26; OXYAZO-NUCLEUS CN H200+.
Strychnine containing brucine is purified by treating it with cold
weak alcohol, which dissolves almost exclusively brucine, and re-
crystallising from hot strong alcohol (Pelletier & Caventou). Cold
absolute alcohol takes up the brucine, leaving strychnine undissolved.
The two alkaloïds may also be separated by dissolving them in very
weak nitric acid, not in excess, and evaporating the solution, whereupon
the nitrate of strychnine first separates in white feathery crystals, the
brucine-salt afterwards forming hard solid crystals. The greater part
of the latter salt remains in the mother-liquor as a gummy mass, which
is to be again treated with magnesia and alcohol (Wittstock; Pelletier
& Dumas). When a strongly acid solution of the two bases in acetic
acid is mixed with chromate of potash, the strychnine alone is preci-
pitated, and may be recovered from the precipitate by means of
ammonia (Horsley). Strychnine containing brucine is reddened by
moderately strong nitric acid: the pure alkaloïd behaves as described
below.
Detection of Strychnine in cases of poisoning. --The substance to be
examined is digested with very weak hydrochloric acid for an hour or
two, at a temperature of 60° to 80°; the liquid is strained; and the
residue is again exhausted with hot water containing hydrochloric acid.
The extracts are then mixed with a slight excess of ammonia and evapo-
rated to dryness, together with sand. The dry residue is exhausted
three or four times with hot fusel-oil, and the extracts are filtered through
paper moistened with fusel-oil. The filtrate contains, besides strych-
nine, fat and colouring matter, which are got rid of by shaking the
filtrate with 10 or 12 times its volume of hot water containing hydro-
chloric acid, the greater part of these bodies then remaining in solution
in the fusel-oil, whilst the strychnine is taken up by the acidulated water.
The hot acid liquid is shaken with fresh portions of fusel-oil, so long
as it gives up colouring matter, and is then evaporated, mixed with a
slight excess of ammonia, and again shaken with fusel-oil, which now
takes up the free strychnine, and leaves it behind on evaporation. If
necessary, the residue is purified by again dissolving it in hydrochloric
acid, shaking with fusel-oil, &c.; it may then be recognised by the
reactions given below (v. Uslar & J. Erdmann, Ann. Pharm. 120, 121 ;
J. pr. Chem. 86, 59; Pharm. Viertelj. 11, 255; Kopp's Jahresber. 1861,
866; J. Erdmann, Ann. Pharm. 122, 360; Anal. Zeitschr. 1, 400; Kopp's
Jahresber. 1862, 613). For other methods, some of which differ from
the above only in chloroform or ether being employed instead of fusel-
oil, see the following memoirs. These methods are applicable for the
detection of other poisonous alkaloïds.
STAS. Bull. de l'Académie de Méd. de Belgique, 9, 304; N. J. Pharm. 22,
281; J. pr. Chem. 55, 232; Jahrb. pr. Pharm. 24, 313; Kopp's
Jahresber. 1851, 640.
FLANDIN. Compt. rend. 86, 517; J. pr. Chem. 59, 185; Chem. Gaz. 1853,
215; Kopp's Jahresber. 1853, 687.
OTTO. Ann. Pharm. 100, 39; abstr. J. pr. Chem. 70, 117; Kopp's
Jahresber. 1856, 755.
STEVENSON MACADAM.
Jahresber. 1856, 759.
Pharm. Trans. 16, 120, and 160; Kopp's
DE VRIJ & VAN DER BURG. Pharm. Journ. 16, 448; Pharm. Viertelj.
6, 543; N. J. Pharm. 31, 542; Kopp's Jahresber. 1857, 602.
STRYCHNINE.
483
E. PROLLIUS. N. Br. Arch. 89, 168; Chem. Centr. 1857, 231; Kopp's
Jahresber. 1857, 604.
H. SCHRÖDER. N. Br. Arch. 93, 190; Kopp's Jahresber. 1857, 604.
JORDAN. N. Repert. 10, 156; Anal. Zeitschr. 1, 131; Kopp's Jahresber
1861, 870.
To detect strychnine in beer, Graham & Hofmann (Pharm. Journ.
11, 504; Ann. Pharm. 83, 39) shake the beer with animal charcoal in
the proportion of 4 four ounces of charcoal to a gallon, let it stand
over night, collect and wash the charcoal once or twice with cold water,
and boil it for half an hour with 8 ounces of alcohol, which takes up
the strychnine. The residue which remains on evaporating the alcohol,
is shaken with a few drops of caustic potash and ether, the latter of
which takes up strychnine, recognisable, after evaporating the solution,
by means of oil of vitriol and chromate of potash.
On the means of distinguishing morphine from strychnine, see Hünefeld (Schw.
60, 454); santonine from strychnine, Wittstein (Pharm. Viertelj. 6, 273): on the
volumetric estimation of strychnine by means of iodomercurate of potassium, see
F. F. Mayer (Pharm. Viertelj. 13, 43; N. J. Pharm. 46, 124; Kopp's Jahresber.
1863, 703); by means of biniodide of potassium, Wagner (Dingl. 151, 40; Anal.
Zeitschr. 1, 102; Kopp's Jahresber. 1861, 867).
Properties. Small, white, four-sided prisms, terminated by low, four-
sided pyramids (Pelletier & Caventou). Crystals of the right prismatic
(rhombic) system, with the faces y, i, and u (Fig. 53). Angle y: y =
91° 12' and 88° 48'; i: i 93° 4' and 86° 56'; u: u = 94° 16' and
85° 44'. Besides these there are faces of the octahedron, the edges of
which are truncated by the faces y, i, and u. Cleavable parallel to y.
Lustre vitreous, pearly on the cleavage-faces. Hardness between 2
and 2 (Kengott, Pogg. 95, 614). Schabus (Krystallgestalten, 79)
observed the faces y, i, and u. Angle y: y = 90° 50′ 75", and 89° 9′ 25″;
y: u = 118° 28′ 5'' ; i : i = 93° 30′ (calc. 93° 35'); u : u = 94° 28'.
Strychnine contaminated with a trace of lime crystallises in long, silky,
flexible needles (Robiquet, J. Pharm. 17, 101). Strychnine is per-
manent in the air, and unaltered by light. It rotates a ray of polarised
light to the left: in alcoholic solution [a]r 132.08° to 136.78'. The
rotation is much less in acid solutions, but the addition of ammonia
seems to restore it to the original amount (Bouchardat, N. Ann. Chim.
Phys. 9, 213).-Strychnine does not lose weight when heated (Liebig),
and does not melt without decomposition (Pelletier & Caventou;
Fresenius). According to Robiquet, Merck, and Wittstein, it is fusible
without decomposition. It is inodorous, but has an intolerably bitter,
afterwards somewhat metallic taste. It is the most poisonous of the
vegetable bases, 1th of a grain being sufficient to kill a large dog, with
tetanic convulsions. It turns reddened litmus blue (Pelletier & Caven-
tou). Resists putrefaction (Robin, Compt. rend. 32, 773).
When very small portions of powdered strychnine are carefully
heated on a piece of platinum-foil having a hemispherical depression
covered with a slip of glass, the glass receives an opaque white deposit
of sublimed strychnine, appearing under a magnifying power of 80
diameters, to consist of round, sharply defined granules. On the addi-
tion of a drop of water, the sublimate crystallises in four-sided prisms,
arranged in crosses and stars. On adding ammonia-water, it deliquesces
to oil-drops, in which isolated quadratic octahedrons with truncated
212
484 PRÍMARY NUCLEUS CH; OXYAZO-NUCLEUS C42NIT²ºO¹.
summits, and groups of short, broad, four-sided prisms are formed.
Addition of hydrochloric acid also causes crystallisation, partly in crossed
tufts of needles, partly in broad, four-sided prisms. Very dilute chromic
acid does not alter the granular deposit at first, but soon produces
fine yellow crystalline stars, and ultimately double pyramids, very
different from those formed with brucine under similar conditions
(Helwig, Anal. Zeitschr. 3, 46).
Liebig.
Pelletier
and Dumas.
mean.
42 C.......
2 N
252
75.44
77.24
75.35
28
8.38
8.92
5.81
22 H
22
6.58
6.54
6.70
40
32
9.60
7.30
12.14
C42N2H2204
334
100.00
100.00
100.00
ONHO
Nicholson.
Regnault.
Gerhardt.
and Abel.
mean.
mean.
74-76
75.66
75.38
8.45
8.05
8.66
6.81
6.90
6.71
9.98
9.39
9.25
100.00
100.00
100.00
Earlier formula: C30NH1603 and C44N2H23O5 (Liebig); C43N2H23O4 (Regnault);
C40N2H22O4 and CN²H²*O* (Gerhardt). The above formula, proposed by Regnault
(Ann. Pharm. 29, 58), was shown by Nicholson and Abel to be correct.
Decompositions. 1. Strychnine, when cautiously heated, gives off
colourless vapours, probably of undecomposed strychnine, and after-
wards melts to a brownish liquid, which gives off a large quantity of
brown vapours and leaves a carbonaceous residue (Duflos). It car-
bonises at 312° to 315°, and when submitted to dry distillation, puffs
up, turns black, evolves carbonic acid and combustible gas, and yields
an empyreumatic oil, a little water, and acetic acid, leaving charcoal
(Pelletier & Caventou).2. Melts on platinum-foil like wax, and takes
fire when more strongly heated, leaving a bulky charcoal (Merck).
3. When subjected to electrolysis, it behaves like morphine (xvi, 425)
(Hlasiwetz & Rochleder).-4. When heated with sulphur to the melt-
ing-point of that body, it is decomposed, with formation of a large
quantity of sulphuretted hydrogen (Pelletier & Caventou). — 5. Strych-
nine assumes a yellow colour with iodine, or in the vapour of iodine
(Donné), and forms with it a peculiar compound (q. v.).
6. Bromine produces a resinous precipitate in strong solutions of
hydrochlorate of strychnine; the solution contains bromostrychnine,
which is thrown down by ammonia as a white precipitate, crystallising
from alcohol in needles, and forming with hydrochloric acid a salt
having a silky lustre. It contains 1 atom of bromine to 1 atom of
strychnine (Laurent, N. Ann. Chim. Phys. 24, 312; Ann. Pharm. 69,
14). Bromine-water produces in aqueous solutions of strychnine a
white turbidity, which disappears on agitation; the liquid, which is
yellow at first, becomes colourless in 24 hours. Dilute solutions of
STRYCHNINE.
485
300
5 0 0
strychnine salts (containing th to th of strychnine) give a
curdy yellowish-white precipitate with bromine-water (Duflos;
Merck).
7. Dry chlorine does not act upon strychnine or its salts (Marchand),
but when the gas is passed into water in which strychnine is sus-
pended, an evolution of heat takes place, and chorostrychnine is formed
as a white scum; hydrochlorate of strychnine is also produced at first,
but by the further action of chlorine it is entirely converted into
chorostrychnine, so that the nearly colourless liquid contains in solu-
tion only hydrochloric acid, with the exception of a few flocks precipi-
table by ammonia. Salts of strychnine immediately yield the white
scum with chlorine (Pelletier). A turbidity and precipitate are pro-
duced even in a solution of 1 part of acetate of strychnine in 5,000 or
8,000 parts of water (Marchand, J. pr. Chem. 14, 191). The precipitate
is formed gradually, and only in presence of excess of chlorine (De Vrij
& Van der Burg). The turbidity produced by chlorine-water in water
containingth of acetate of strychnine is increased by heat (Merck).
An aqueous solution of strychnine is not affected by chlorine-water
(Duflos). The precipitate is not coloured by nitric or sulphuric acid
(Lepage, J. Pharm. 26, 140; N. Br. Arch. 25, 300); it forms a colour-
less solution in ammonia (Fresenius), and dissolves easily in ether
and alcohol (Pelletier; Riegel, N. Br. Arch. 58, 274). — Chlorine passed
into a hot aqueous solution of hydrochlorate of strychnine forms
Laurent's chlorostrychnine (p. 515).
Solution of chloride of lime throws down from dilute solutions of
acetate of strychnine, a white precipitate insoluble in dilute sulphuric
and acetic acids, but easily soluble in alcohol, also in glacial acetic
acid and alkaline liquids (Horsley).
8. Aqueous hydrochlorate of strychnine boiled with nitrite of potas-
sium evolves nitrogen and forms oxystrychnine and bioxystrychnine
(Schützenberger). By taking up 6 atoms of water and 2 or 4 atoms of oxygen.
9. Strychnine dissolves very rapidly in fuming nitric acid, forming
a greenish-yellow solution, which turns lemon-yellow when diluted
with water (Duflos). Nitric acid of sp. gr. 1.2 forms a white salt
(Duflos). Even the strong acid does not colour strychnine in the cold
(Robiquet), but when heated, turns it brownish-yellow, without evolv-
ing red vapours: after cooling, water throws down from the non-
unctuous mass a yellow precipitate which melts in boiling water to a
yellow resin, afterwards dissolves, and is deposited from the solution
on cooling in yellow shining crystalline nodules. The precipitate
dissolves very easily in alcohol, and explodes when heated (Gerhardt,
Compt. chim. 1845, 136). This body is probably nitrate of nitro-
strychnine, and the same product which Pelletier & Caventou regarded
as acid nitrate of strychnine (Nicholson & Abel). To this place belong
also the orange-coloured tufts of needles which Ménétriès obtained by
warming strychnine with strong nitric acid and evaporating the solu
tion rapidly; they explode when heated, evolving nitric oxide. The
further action of nitric acid produces oxalic acid (Pelletier & Caventou).
On treating the products formed by nitric acid with caustic potash,
volatile bases are set free (Anderson). Strychnine containing brucine
(Robiquet), and consequently commercial strychnine (Lefort), turns red
with nitric acid.
486
PRIMARY NUCLEUS C4211; OXYAZO-NUCLEUS CN2H2º04.
10. Cold oil of vitriol does not colour strychnine: fuming sulphuric
acid colours it slightly brown, and when heated with it forms a
greenish-yellow solution (Duflos). Oxidising agents produce with solu-
tions of sulphate of strychnine containing a large excess of sulphuric
acid, characteristic colours, which serve for the detection of very small
quantities of strychnine (Marchand; Lefort).
a. When the solution in oil of vitriol is made in a platinum basin,
and the platinum is connected with the positive pole, and a platinum
wire dipping into the acid with the negative pole of one cell of a gal-
vanic battery, a purple-red coloration is produced (Letheby, Pharm.
Journ. 16, 10; Kopp's Jahresber. 1856, 758).
b. On dissolving strychnine in oil of vitriol containing 1 p. c. of
nitric acid, and adding a trace of peroxide of lead, a blue coloration is
produced, passing to violet, red, and in a few hours to yellow (E. Mar-
chand, J. Chim. méd. 20, 15). Or the strychnine may be triturated with
peroxide of lead and the oil of vitriol containing nitric acid dropped
upon the mixture (E. Marchand, N. J. Pharm. 4, 200). The violet
colour appears also in the absence of nitric acid, and is then more per-
manent, but it is produced only with concentrated sulphuric acid, since
water destroys it (Lefort, Rev. scient. 16, 355; also N. J. Pharm. 21,
172). Marchand (J. Chim. méd. 24, 197; J. pr. Chem. 44, 185), on the
contrary, considers the addition of nitric acid advantageous. Riegel
(Jahrb. pr. Pharm. 8, 290) and Wittstein employ sulphuric acid of sp.
gr. 14. Solutions of strychnine-salts give the blue colour only after
evaporation to dryness (Riegel).
c. On adding bichromate of potash to a solution of strychnine in oil of
vitriol spread out upon porcelain, violet streaks make their appearance
in the liquid, starting from the bichromate, after which the whole liquid
acquires a fine violet colour, or with a larger quantity of strychnine a
pure blue (Otto, J. pr. Chem. 38, 511; also Ann. Pharm. 100, 50; L.
Thomson, Pharm. Journ. 9, 24; N. J. Pharm. 17, 276; Lieb. Kopp's
Jahresber. 1850, 617). It is better to employ the bichromate in lumps
than in powder or solution (Otto).
d. Ferrocyanide of potassium produces with strychnine a dark-violet
coloration, more permanent than that produced with bichromate of
potash the colour may be obtained also in presence of other organic
substances (Davy, N. J. Pharm. 24, 204). This colour also passes
through red into yellow, though more slowly than that obtained in c
Ann. Pharm 88, 402). Nitroprusside of sodium proposed by Horsley
(Chem. News, 1862, 341) as a reagent, acts only when it contains ferro-
cyanide of potassium (Rodgers; Neubauer; Werther).
e. On adding small portions of black oxide of manganese to a solution
of strychnine in pure oil of vitriol, or in sulphuric acid containing nitric
acid (prepared according to xvi, 141), a violet-purple coloration is im-
mediately produced, passing into dark-red in the course of an hour.
The colour remains unchanged when the liquid is slowly diluted with
four to six times its volume of water, and on nearly neutralising the
solution with ammonia, the violet-purple colour reappears. When super-
saturated with ammonia, the liquid becomes yellowish-green to yellow,
but on acidifying it with dilute sulphuric acid, the violet-purple colour
again makes its appearance (J. Erdmann, Ann. Pharm. 120, 188).
Mack had previously employed manganese and sulphuric acid for the
recognition of strychnine (N. Br. Arch. 46, 314).
f. Chloric acid and chlorates, chlorous acid, iodic acid and iodates,
STRYCHNINE.
487
also sulphate of manganese and permanganate of potash produce in the
sulphuric acid solution of strychnine, similar colorations, or a red colour
which in some cases quickly disappears (Lefort). The violet colour
produced by iodic acid passes gradually into red-brown, which colour
remains permanent for many days (Landerer, Pharm. Zeitschr. 1,
86). Concerning this reaction, see also Copney (Pharm. J. Trans. 16, 23 ; Pharm.
Viertelj. 6, 80: Guy, Pharm. J. Trans. [2], 2, 558 and 602; 3, 11 and 12; Anal.
Zeitschr. 1, 90 and 92): De Vrij and Van der Burg (loc. cit.).
Strychnine dissolved in a large quantity of milk may also be de-
tected by means of peroxide of lead and oil of vitriol containing nitric
acid (Erdmann & Marchand, J. pr. Chem. 31, 374). The presence of
santonin or starch does not prevent the recognition of strychnine by
bichromate of potash and oil of vitriol: sugar, quinine, or morphine
renders this reaction indistinct, but not that with peroxide of manganese
(Brieger, Jahrb. pr. Pharm. 20, 87). Strychnine may be detected by
chromate of potash even in presence of quinine, cinchonine, starch, or
dextrin, provided the oil of vitriol be added first (Vogel, N. Repert.
Pharm. 2, 560). The presence of morphine is prejudicial to the
strychnine-reactions (Reese, Chem. News, 1862, 316; Chem. Centr.
1862, 557: Horsley). Thomas (Amer. Journ. Pharm. 1862, 227), on
the contrary, finds that strychnine is recognisable even when mixed
with 3 parts of morphine. The two bases may be separated by means
of caustic potash, which does not dissolve strychnine; or by chloro-
form, which dissolves only strychnine (Thomas, Chem. News, 5, 352);
or by benzene, which dissolves strychnine very easily, but not morphine
(Rodgers, Chem. News, 6, 15); neutral chromate of potash also throws
down from a strong solution of the two bases, after brisk stirring, a
golden-yellow crystalline precipitate of chromate of strychnine, whilst
the morphine-salt crystallises only after a longer time (Horsley). Fer-
rocyanide of potassium may be advantageously substituted for the
neutral chromate (Neubauer).
Tartar-emetic, tartaric acid, and bitartrate of potash prevent the
detection of strychnine by chromate of potash and oil of vitriol when
the alkaloïd is present in the form of nitrate, but not when pure.
Strychnine as nitrate may be detected by peroxide of lead and oil of
vitriol, even in presence of tartrates (Gorup-Besanez, Handwörterb. [2]
1, 468; Kopp's Jahresber. 1856, 757). Pure strychnine, or the hydro-
chlorate or acetate, may be distinctly recognised by means of chromate
of potash and sulphuric acid when mixed with 20 or 30 parts, but not
distinctly when mixed with 60 parts of tartar-emetic. The presence
of a large quantity of sugar or tartaric acid does not interfere with the
reaction in the case of hydrochlorate and acetate of strychnine, but a
mixture of 1 part of nitrate of strychnine with 20 parts or more of
tartar-emetic immediately assumes a green colour. The strychnine
reaction is obtained, however, with peroxide of lead and oil of vitriol,
even when a mixture of 1 part of nitrate of strychnine and 60 parts of
tartar-emetic is employed (Hagen, Ann. Pharm. 103, 159). Accord-
ing to Bingley (Chem. Gaz. 1856, 229; Kopp's Jahresber. 1856, 757),
terchloride of antimony interferes with the bichromate of potash
reaction.
Dilute sulphuric acid, added to a mixture of chlorate of potash and
strychnine, produces Rousseau's strychnic acid, or when the action
proceeds further, a red resinous colouring matter, soluble in water and
alcohol, but insoluble in ether (Rousseau).
488
PRIMARY NUCLEUS C2H26; OXYAZO-NUCLEUS C42N HO¹.
}
To prepare strychnic acid, Rousseau triturates 3 parts of strychnine with 1 part
of chlorate of potash and a little water, and drops oil of vitriol upon the mixture,
whereupon it becomes hot and acquires a transient red colour; after which he
dilutes and boils. If the reaction is incomplete, pure strychnine (!), or the sulphate
crystallises from the liquid as it cools, and on evaporating the mother-liquor
colourless acid needles of strychnic acid are deposited. The crystals do not taste
bitter; they decompose when heated, leaving charcoal, and are soluble in water and
slightly in alcohol, and form crystallisable salts with potash and oxide of copper
(Rousseau, J. Chim. méd. 20, 415).
When strychnine is treated with peroxide of lead and dilute sulphuric
acid (in the same manner as cinchonine, p. 202), a straw-yellow powder
is obtained, which dissolves very slightly in cold, and somewhat more
freely in boiling water, and is deposited from a solution in hot water
containing sulphuric acid on cooling. It dissolves in alcohol, and very
easily in caustic potash, which it seems to neutralise (C. Marchand,
N. J. Pharm. 4, 28; J. Chim. méd. 20, 366).
11. Hot solutions of iodic acid colour strychnine and its salts violet-
red, and produce a black precipitate on standing (Riegel).—12. Chromic
acid colours it violet-blue (Eboli).
13. Strychnine cautiously heated with lumps of solid hydrate of
potash, forms a red-brown mass, from a solution of which in boiling
water, acids evolve a disagreeable odour, and throw down an abun-
dance of yellow flocks, which are deposited from their solution in
boiling alcohol on cooling, and are insoluble in water, ether, and cold
alcohol. On melting strychnine with hydrate of potash, the mass
turns brown and black, evolves hydrogen with slight intumescence,
gives off water and a little chinoline (xiii, 244), whilst carbonate of
potash remains in the residue (Gerhardt).
14. Iodide of methyl (Stahlschmidt), iodide of ethyl, chloride of amyl
(How), bibromide of ethylene (Ménétriès), form derivative compounds
(pp. 506-514).
15. With chloride of benzoyl, strychnine forms hydrochlorate of
strychnine and benzostrychnide, C42N2H21(CH502)04, a white bitter
product, which melts above 100°, solidifies in a crystalline mass, and
is very slightly soluble in water and insoluble in acids, but easily
soluble in alcohol and ether (Schützenberger).
16. Strychnine is not decomposed in contact with a fermenting
mixture of sugar and yeast (Larocque & Thibierge, J. Chim. méd. 18,
689).— 17. It is not decomposed in the animal organism, nor by putre-
faction after death; it has been detected three years after death in the
bodies of animals poisoned with it (Macadam, loc. cit.: Rodgers &
Girdwood, Pharm. Journ. 16, 497; Pharm. Viertelj. 6, 549; Kopp's
Jahresber. 1857, 603). See also J. Erdmann (Ann. Pharm. 122, 360);
De Vrij & Van der Burg (loc. cit.).
Combinations. A. With Water. Strychnine dissolves in 6,667
parts of cold, and in 2,500 parts of boiling water (Pelletier & Caventou).
According to Duflos, it dissolves in about 6,000; according to Abl, in
7,200 parts of water. The cold solution diluted with 100 times its
bulk of water, still tastes distinctly bitter (Pelletier & Caventou).
STRYCHNINE.
489
Strychnine does not dissolve in aqueous ammonia (Merck); neither
does caustic potash increase its solubility in water (Duflos).
B. With Iodine.-Tincture of iodine or biniodide of potassium pro-
duces in solutions of strychnine-salts, a dense kermes-brown precipi-
tate; a cold aqueous solution of strychnine, however, is not affected by
iodine-water (Duflos). A solution of 1 part of strychnine in 1 part of
alcohol and 3 parts of water, when warmed with a little tincture of
iodine and left to cool spontaneously, deposits crystals of an
iodine-compound, probably CN2H22O,I2. The crystals are six-sided
prisms, exhibiting in a very high degree the property of double absorp-
tion of light (Herapath, Chem. Gaz. 1855, 320; 1856, 394; Kopp's
Jahresber. 1855, 568; 1856, 758). On precipitating with tincture of
iodine, a solution of strychnine in weak alcohol acidified with hydro-
chloric or hydriodic acid, and dissolving the brown precipitate in
boiling alcohol, highly lustrous red-brown prisms are obtained, which
do not lose weight at 140°, and are represented by the formula
C42N2H22O4, HI,21 (Tilden, Chem. Soc. J. [2] 3, 99).
When 2 parts of strychnine are triturated with 1 part of iodine, a
brown mass is obtained, which gives up to cold water traces only,
and to boiling water a small quantity of hydriodate of strychnine.
Boiling alcohol dissolves the mass, and when cooled and concentrated,
deposits laminæ of iodostrychnine of the colour of mosaic gold, and
afterwards crystals of hydriodate of strychnine. The lamina are
nearly tasteless at first, but afterwards taste bitter and harsh; they
evolve iodine when heated, and carbonise without melting. They are
decomposed by oil of vitriol and by strong nitric acid, with separation
of iodine, and by hydrochloric acid when heated therewith. They set
free strychnine when heated with caustic potash (not with ammonia),
and are decomposed by nitrate of silver, even in the cold, iodide of
silver and nitrate of strychnine being formed. They are easily soluble
in boiling alcohol, very slightly soluble in boiling water, and insoluble
in ether (Pelletier).
84 0
4 N
44 H
80
3 I
....
Pelletier.
504
48.04
49.53
Regnault.
47.75
56
5.34
44
4.19
4.54
61
6.10
381
36.33
39.50
100.00
2 C¤N²H²0¹,31.... 1049
C. With Acids. Strychnine dissolves easily in acids, even when
very dilute, neutralising them completely. It also precipitates the
oxides from most of the salts of the heavy metals, though often only
partially, double salts being formed. The salts of strychnine are for
the most part crystallisable, extremely bitter, and on account of their
solubility, more highly poisonous than pure strychnine. Alkalis and
their carbonates (and magnesia) precipitate strychnine from its salts,
in the form of a pulverulent precipitate, which does not dissolve to
any great extent in excess of the precipitant, and crystallises after a
time in delicate closely grouped needles. The precipitate thrown down
by ammonia from a solution of strychnine in dilute hydrochloric acid,
dissolves in excess of the precipitant, but in a short time the strych-
nine crystallises from the ammoniacal liquid in distinct needles
490
PRIMARY NUCLEUS C4H26; OXYAZO-NUCLEUS C2N²H²ºO¹.
(Fresenius). See also Anderson (N. J. Pharm. 13, 443). Bicarbonate
of soda throws down strychnine from neutral, moderately strong solu
tions of its salts; on dropping an acid into the liquid, in quantity not suf-
ficient to decompose the whole of the alkaline carbonate, the carbonic
acid set free dissolves the precipitate. Bicarbonate of soda does not
throw down a precipitate in acid solutions of strychnine, but crystals
are formed in the liquid on standing, or a precipitate is formed on boiling
(Fresenius). Very dilute solutions of strychnine, mixed with tartaric
acid, are not (or at least not immediately) precipitated by alkaline
bicarbonates; less dilute solutions deposit needles in a quarter of an
hour, the whole of the strychnine crystallising out (Oppermann, Compt.
rend. 21, 810; J. pr. Chem. 36, 445). The salts of strychnine (and
the alkaloïd itself) are recognised by their behaviour with chlorine-
water, nitric acid, chromate of potash and oil of vitriol, sulphocyanide
cf potassium, and mercuric chloride. (See above.) On the delicacy of
the particular reactions, see Wormley (Sill. Amer. J. [2] 28, 216; J. pr.
Chem. 80, 382).
Carbonate of Strychnine. The precipitate thrown down from
strychnine-salts by alkaline carbonates is free from carbonic acid
(How; Langlois) (contrary to Pelletier & Caventou); but an unstable
carbonate of strychnine may be obtained by decomposing hydrochlorate
of strychnine with carbonate of silver (How). Freshly precipitated
strychnine dissolves easily in an aqueous solution of carbonic acid.
(Pelletier & Caventou); after standing some time at 0°, the solution
deposits crystals, which do not evolve carbonic acid, either with acids,
or at a temperature of 300° (Langlois, N. Ann. Chim. Phys. 48, 502;
Ann. Pharm. 100, 374).
Strychnine combines with metaphosphoric acid (Nicholson & Abel).
Phosphate of Strychnine. - Ordinary bisodic phosphate throws down
from strychnine-salts a granular crystalline precipitate (v. Planta).
A. Bibasic. An aqueous solution of B is digested for some time with
finely powdered strychnine, and the crystals which separate are purified
by two or three crystallisations. The mother-liquor contains a large
quantity of the salt B. Large rectangular tables, often so thin as to
exhibit a splendid green colour. The salt does not redden litmus. It
is much less soluble in water than B. The crystals lose 17.6 p. c.
of water at 100° (18 at. 17.45 p. c. HO) (Anderson), and are
also rendered anhydrous by drying over oil of vitriol in a vacuum
(Nicholson & Abel).
84 C
4 N
47 H
11 0
РО5
2 (C42N2H2204,HO),HO,PO³
at 121°.
Anderson.
504
65.79
66.51
56
7.31
47
6.13
6.54
88
11.49
71
9.28
766
100.00
B. Neutral. Prepared by digesting strychnine with moderately
strong phosphoric acid, the solution, on cooling, crystallising in radiated
groups of long needles, which redden litmus and have a very bitter taste.
The salt dissolves in 5 or 6 parts of cold, and in a much smaller
quantity of hot water. At 127° [or over oil of vitriol in a vacuum
STRYCHNINE.
491
7.69 p. c. HO)
(Nicholson & Abel)] it loses 7.95 p. c. of water (4 at.
(Anderson, Ann. Pharm. 66, 55; Quart. J. Chem. Soc. 1, 55.)
58.33
Regnault.
at 140°
Anderson.
****
59.85 58.72 59.05
42 C
2 N
25 H
70.....
PO5
5.78.... 5.85.... 5.96 .... 5·97
Dried.
252
28
6.48
....
25
56
12.97
...
71
16:44
100.00
C42N2H2204,HO,PO5 + 2aq..... 432
Regnault's salt probably contained an admixture of A (Anderson).
Monosodic phosphate does not form with strychnine a double salt of
phosphate of soda and phosphate of strychnine (Anderson).
Hydrosulphate of Strychnine. -Strychnine suspended in water is
dissolved by a current of hydrosulphuric acid, forming a colourless,
very bitter solution, which leaves pure strychnine when evaporated.
(Pelletier & Caventou).
Hyposulphite of Strychnine. Formed in a mixture of strychnine,
alcohol, and hydrosulphate of ammonia on standing in the air. - Large
rhombic plates. Neutral. Loses 3.91 to 4.3 p. c. of water at 200°
(2 at. = 4·3 p. c. HO). Dissolves in 114 parts of cold, and in a smaller
quantity of hot water (H. How, Pharm. Centr. 1855, 95).
How.
at 100°
mean.
42 C
2 N
252
63
63.07
28
7
24 H
24
6
5.93
80
64
16
2 S......
32
8
8.29
C42N³H2204,HO,S2O2 + aq.
4.00
100
....
Sulphate of Strychnine.-A. Neutral. Obtained by saturating
dilute sulphuric acid with finely powdered strychnine (Nicholson &
Abel). Small transparent cubes (Pelletier & Caventou); large four-
sided prisms (Nicholson & Abel). The cubes turn dull in the air,
without losing weight, and melt in their water of crystallisation at a
gentle heat (Pelletier & Caventou). The salt loses 13.08 p. c. of water
at 135° (7 at. 14.1 p. c. HO) (Regnault). Neutral (Nicholson &
Abel). Rotates a ray of polarised light to the left; [a]r = 25·58° for
the salt dried at 40° (Bouchardat). Dissolves in less than 10 parts
of water (Pelletier & Caventou), in 48 parts (Abl), in about 50 parts
(Bouchardat).
The anhydrous salt forms crystals belonging to the square prismatic
or quadratic system. Octahedrons with basal face (fig. 24). Angle
p: e = 102° 3'; e : e' = 92° 30′; e:e" 155° 54'. The edge formed
by p and e is truncated by the face of a second octahedron, forming
with p an angle of 125° 26', and with e an angle of 156° 37". Cleavable
parallel to p (Descloizeaux, Compt. rend. 44, 909; Pogg. 102, 474). Ram-
melsberg (Krystall. Chemie, 380) observed the following angles: p:e
= 101° 40'; e : e' =
e: e' — 92° 20′; e : e" = 156° 40'; and between p and e the
truncation-face of a more obtuse octahedron, forming with p an angle
432
PRIMARY NUCLEUS CH2; OXYAZO-NUCLEUS C2N2H2004.
of about 160°. The salt with 7 atoms of water belongs to the right
prismatic or rhombic system: the simplest form as in fig. 65. Angle
u: t = 107° 14′
107° 14'; u: u' = 145° 30'; t: i = 137° 48'; i: i above 84° 24' :
between u and t there is a truncation-face, forming with t an angle of
125° 45'. The angle ii is sometimes replaced by two horizontal
prisms, one of which forms with t an angle of 118° 40', the other an
angle of 99° 50'. The parallel u-faces often disappear, in which case
the crystals assume the form of monoclinic prisms. The t-faces are
prominently developed, so that the crystals have the form of square
tables with bevelled edges. The crystals have a glassy lustre; pearly
on the face t (Schabus, Krystallgestalt. 80).
Dried.
252
42 C.........
....
2 N
28
65.80
7.31
....
23 H
23
6.01
50
40
10.44
SO3
40
10.44
C42N2H2204,HO,SO3
383
100.00
....
Liebig.
Regnault.
at 100° at 130°-205°
64-76
5.99
...
65.35
....
6.10
Nicholson
& Abel.
in vacuo.
65.68
6.17
10.44
B. Acid. Obtained from A by the addition of sulphuric acid.
Long, thin, very acid needles (Nicholson & Abel).
Nicholson & Abel.
42 C
2 N
...... 252
28
58.33
58-73
****
6.48
24 H
24
5.56
5.83
60
2 SO3
4.8
11.12
80
18.51
18.33
C42N2H22O1,2 (HO,SO³)
432
100.00
Sulphate of Iodostrychnine. When the brown-red precipitate thrown
down by biniodide of potassium in solutions of strychnine, is dis-
solved in alcohol containing sulphuric acid, the solution yields crystals
of sulphate of iodostrychnine, which polarise light (De Vrij and Van
der Burg). Stellate groups of prisms, of a fine green colour by
reflected, deep blood-red by transmitted light, thick crystals being
quite opaque (Herapath).
On
Iodate of Strychnine. - Iodic acid produces neither colour nor pre-
cipitate in aqueous solutions of strychnine (v. Planta). See above.
gently heating strychnine in aqueous iodic acid, the solution, in the
absence of brucine, assumes a wine-red colour, and yields when con-
centrated, long tufts of needles, which are coloured red on the surface,
and may be decolorised by washing with cold water. The crystals
dissolve very easily in water (Serullas, Ann. Chim. Phys. 45, 275;
Pogg. 20, 595). When strychnine suspended in warm water is exactly
neutralised with iodic acid, or when iodate of baryta is decomposed by
sulphate of strychnine, long flat pearly needles are obtained, containing
45.92 p. c. of carbon and 42.80 of iodic acid (Pelletier).
Periodate of Strychnine. On dissolving strychnine in warm aque-
ous periodic acid, colourless, highly lustrous, rectangular prisms [6-sided
prisms, terminated by 4-sided pyramids (Langlois)] are obtained,
which effloresce over oil of vitriol, explode violently when heated, and
STRYCHNINE.
493
dissolve with moderate facility in hot water and alcohol. The aqueous
solution turns brown when evaporated in the air (Bödeker, Ann.
Pharm. 71, 64; Langlois, N. Ann. Chim. Phys. 34, 278; Ann. Pharm.
83, 174).
Hydriodate of Strychnine. - Iodide of potassium throws down from
strychnine-salts a dense crystalline precipitate (v. Planta). On wash-
ing the precipitate with water, dissolving it in alcohol, and evapora-
ting the solution, glassy four-sided needles are obtained (Merck). The
salt may also be prepared by dissolving strychnine in aqueous hydri-
odic acid (Pelletier), but the excess of acid must be quickly removed by
washing, as otherwise decomposition-products are formed (Nicholson
& Abel). Small white laminae or needles, which do not lose weight in
a vacuum. Neutral and very bitter. Dissolves slightly in cold water
and much more freely in alcohol (Pelletier).
Nicholson & Abel.
42 C.......
2 N
23 H
40
I
Crystals.
252
Pelletier.
mean.
54.62
55.08
54.60
28
6.07
23
4.98
5.02
32
6.95
127
27.38
26.12
27.12
...
462
100.00
C42N2H2204,HI
Hydrobromate of Strychnine. Formed by dissolving strychnine in
aqueous hydrobromic acid, and leaving the solution to crystallise
(Nicholson & Abel).
In a vacuum.
Nicholson & Abel.
42 C
252
60.72
60.83
2 N
23 H
28
6.74
23
5.54
5.60
40
32
7.71
Br
80
19.29
18.69
C42N2H2204, HBr
415
100.00
Chlorate of Strychnine.
The rose-red solution of strychnine in
aqueous chloric acid deposits thin short prisms, or solidifies completely
when concentrated. Iodic acid throws down from a solution of the
salt a precipitate of iodate of strychnine (Serullas, Ann. Chim. Phys. 45,
280).
Perchlorate of Strychnine. Obtained from perchlorate of baryta
and sulphate of strychnine. Small colourless or pale-yellow, glassy
rhombic prisms, which after drying at 30° become opaque at 170°,
losing 3.8 p. c. of water, and explode when more strongly heated.
Dissolves slightly in cold water, and much more freely in alcohol
(Bödeker, Ann. Pharm. 71, 62).
Crystals.
Bödeker.
C42N2H22O4, HO
343
75.80
76.99
C107
91.5
20.22
19.21
2 HO
18
3.98
3.80
C42N²H²²0+,HO,C107 + 2aq.
452.5
100.00
100.00
Hydrochlorate of Strychnine. 100 parts of strychnine take up 14.6
to 15.02 of hydrochloric acid gas (Liebig). When exposed to a current
494
PRIMARY NUCLEUS C2H26; OXYAZO-NUCLEUS CNH2004.
of hydrochloric acid gas, and afterwards heated to 150, 100 parts of
strychnine retain 10.67 parts of hydrochloric acid (Regnault) (1 at. =
10.93 parts HCl.). A solution of strychnine in warm aqueous hydro-
chloric acid solidifies to a silky mass of needles (Regnault). The salt
is neutral towards vegetable colours (Nicholson & Abel). It exerts a
left-handed rotatory action on polarised light; [a]r=28·18°. Dis-
solves in about 50 parts of water at 22° (Bouchardat). — The needles
lose the whole of their water of crystallisation, amounting to 7·17
p. c., at 120°, or in a vacuum (3 at. = 6.79 p. c. HO) (Nicholson &
Abel). According to Gerhardt, on the contrary, the salt dried at 100°
loses 4.81 p. c. (= 2 at.) of water, at 130° only.
Regnault.
at 130°
Gerhardt.
at 160°
65.08
Dried.
42 C
2 N
252
68.01
....
28
7.56
68.01
7:40
....
23 H...
23
6.20
6.77
6.94
....
....
40
32
8.65
Cl.......
35.5
9.58
9.33
C¹²N2H22O¹,HCl .... 370·5
100.00
....
....
Nicholson.
& Abel.
mean.
67.82
6.43
9.55
Hydrofluate of Strychnine. Strychnine dissolves in hydrofluosilicic
acid, with separation of silica. - The easily formed solution of strych-
nine in warm aqueous hydrofluoric acid yields crystals, which give off
hydrofluoric acid over hydrate of lime.-Colourless right rhombic
prisms, having an acid reaction, slightly soluble in cold, easily in hot
water, and sparingly soluble in alcohol. The salt loses 5.9 p. c. of
water (3 at. 6 p. c. HO) over oil of vitriol, becoming opaque, soft,
and sticky. At 100° it gives off 7:43 p. c. of water (4 at. 8 p. c.),
and not more at 150°; at a higher temperature it reddens and is decom-
posed (Elderhorst, Ann. Pharm. 74, 77).
Elderhorst.
42 C
2 N
27 H
5 O
4 F
C+2N2H2204,4HF + aq.
Over oil of vitriol.
mean.
252
28
59.61
6.61
59.33
•
...
27
6.33
6.15
40
9.50
75.2
17.95
422.2
100.00
Elderhorst likewise found the per-centage of strychnine in the salt, and the
increase in weight on evaporating strychnine with excess of hydrofluoric acid, to
agree with the above formula.
Nitrate of Strychnine. When strychnine is dissolved in nitric acid
diluted till it tastes faintly acid, fine colourless needles of the nitrate
are obtained on cooling. Strong uitric acid forms decomposition-
products, but no acid salt (Nicholson and Abel). - Silky tufts of long,
flexible needles, very bitter, and even more poisonous than pure strych-
nine. Neutral. When heated to a little over 100°, it turns yellow,
swells up, and decomposes violently, without development of light
(Pelletier & Caventou). Rotates a ray of polarised light to the left;
for the salt dried at 40°, [a]r = 29.25° (Bouchardat).
= 29.25° (Bouchardat). Soluble in 50
parts of cold water (Cap & Garot); in 80 parts of water at 18.75°
(Abl); in 2 parts of boiling water (Wittstein). Soluble in 60 parts of
STRYCHNINE.
495
cold, and 2 parts of boiling alcohol of 80 p. c. (Wittstein); in 26 parts
of glycerin, and in 400 parts of fat oil (Cap & Garot). Insoluble in
ether (Pelletier & Caventou).
Regnault.
Ettling Nicholson
at 130° mean. & Will. & Abel.
42 C
3 N
23 H
10 O
252
63.47
63.24
42
10.58
10.35
23
5.79
5.89
a
...
80
20.16
20.52
1
397
100.00
63.55
****
63.40
....
5.85
C42N2H2204,HO,NO5
100.00
Phosphantimonic acid (xiv, 227) produces in solutions of strychnine-
salts a copious, yellowish-white curdy precipitate, or in more dilute
solutions a cloudiness only (Schultze). Phosphomolybdic acid (xiii, 164)
precipitates strychnine yellowish-white (Sonnenschein); metatungstic
acid precipitates it from more dilute solutions (Scheibler, J. pr. Chem.
80, 204).
Chromate of Strychnine. A. Neutral. Neutral chromate of
potash throws down from solutions of strychnine-salts an amorphous
precipitate (Horsley), consisting, according to André, of a mixture of
acid salt with free strychnine. The yellowish-brown precipitate,
separated from the mother-liquor and dissolved in hot water, deposits
on cooling, orange-yellow needles, which are neutral and sparingly
soluble in water and alcohol (Nicholson & Abel).
C42N2H2204
HO,CrO3
at 100°.
334
Nicholson and Abel.
84.53
61.2
15:47
15.34
....
395.2
100.00
C42N2H2204,HO,CrO³
B. Acid. Acetate of strychnine is completely precipitated by free
chromic acid, and also by a mixture of 1 part of bichromate of potash
with 14 volumes of water and 2 volumes of oil of vitriol, dilute solu-
tions of chromic acid, producing groups of small crystals and cubes,
and stronger solutions at once throwing down, even from very weak
solutions of strychnine, a gold-coloured precipitate, which turns darker
on exposure to light (Horsley, Pharm. J. Trans. 16, 177; J. pr. Chem. 72,
312; Inst. 1856, 463; Kopp's Jahresber. 1856, 758). Long, orange-red
needles, but little soluble in water (André, N. J. Pharm. 41, 341).
Assumes a purple-red colour in oil of vitriol (De Vrij & Van der
Burg).
Arsenite of Strychnine. - CN2H2204,HO, AsO³. Formed by heating
12.38 parts of arsenious acid with 800 parts of water and 10 parts of
hydrochloric acid of sp. gr. 1·18, till it dissolves, adding to the solution
41.95 parts of strychnine, and crystallising (Chiappero, N. Br. Arch.
115, 94). As the crystals thus obtained contain hydrochloric acid,
(Ceresoli, N. J. Pharm. [4], 1, 343) dissolves 3.3 parts of arsenious acid
in 3.12 parts of caustic potash and 40 parts of water; mixes the solu-
tion with a solution of 12 parts of strychnine in 20 parts of water and
2.65 parts of oil of vitriol; boils; filters the liquid hot, sulphate of
potash being left behind; evaporates the filtrate; and exhausts the
residue with absolute alcohol. Dull white cubes, efflorescing in the
air, having a bitter metallic taste, and without action on light. Soluble
496
PRIMARY NUCLEUS CH; OXYAZO-NUCLEUS CNH⁰O¹.
in 35 parts of cold, and in 10 parts of boiling water, in alcohol, and
less freely in ether (Ceresoli).
Arseniate of Strychnine.-C42N2H2204,3HO, As05+ IIO. An aqueous
solution of the acid mixed with strychnine yields monoclinic prisms,
soluble in 15 parts of cold, and in 5 parts of hot water, and with
difficulty in alcohol and ether. Forms with morphine a crystallisable
double-salt, containing 1 atom of arsenious acid to each atom of base
(Chiappero).
-
Chlorozincate of Strychnine.-A. Anhydrous. A hot alcoholic solu-
tion of strychnine throws down hydrated oxide of zinc from an alco-
holic solution of chloride of zinc, forming at the same time a double
salt, which crystallises from the liquid after boiling for some time,
filtering hot, and cooling. On adding hydrochloric acid to the boiling
liquid, rendered cloudy by hydrated oxide of zinc and by strych-
nine thrown down at the same time, till it becomes clear, the whole
solidifies, on cooling, to a crystalline mass of the same salt, which is to
be washed with alcohol. Pearly laminæ, composed of regular quad-
ratic tables (Gräfinghoff).
Gräfinghoff.
Dried in the air or at 100°.
mean.
42 C.......
252
57.47
57.37
2 N
28
6.39
6.21
23 H
23
5.25
5.27
40
32
7.30
7.57
Zn
2 Cl...
32.5
7.42
7.43
71
16.17
16.15
438.5
100.00
100.00
C4N2H22O¹,HCl + ZnCl
B. Hydrated. Obtained from the mother-liquor of A by spon-
taneous evaporation, or by mixing alcoholic hydrochlorate of strychnine
with chloride of zinc, and leaving the solution to evaporate. Transpa-
rent glassy prisms, which become cloudy at 130°, and lose 3.90 p. c. of
water at 150° (2 at. 3.94 p. c. HO) (Gräfinghoff, J. pr. Chem. 95,
229).
42 C
2 N
25 H
Gräfinghoff.
mean.
252
55.21
55.20
28
6.14
6.10
25
5.47
60
48
10.52
Zn
32.5
7.12
7.10
2 Cl
71
15.54
15.48
C42N2H22O+ HCl + ZnCl,2HO
456.5
100.00
........
Chlorocadmiate of Strychnine.-C42N2H22O4, HCl, CdCl. White glitter-
ing scales, long needles, or large transparent prisms. Does not lose.
water at 130°. Dissolves slightly in cold and hot water (Galletly,
Edin. New. Phil. J. 4, 94; Chem. Centr. 1856, 607).
Sulphate of Copper and Strychnine? - By boiling an aqueous solu-
tion of sulphate of copper with strychnine, a pale-green liquid is
obtained, yielding very long needles on evaporation (Pelletier & Ĉaven-
tou).
Strychnine decolorises ammoniacal sulphate of copper on boiling,
STRYCHNINE.
497
and forms crystals of a compound of strychnine and cupric oxide con-
taining a little ammonia (Horsley).
Iodomercurate of Strychnine. -Iodomercurate of potassium throws
down from strychnine-salts a dense white precipitate insoluble in hy-
drochloric acid (v. Planta; De Vrij). The precipitate is yellowish-
white and remains amorphous (Delffs). By mixing solutions of 1 at.
hydrochlorate of strychnine, 3 at. iodide of potassium, and 1 at. chloride
of mercury, shining microscopic crystals are obtained, having the
composition CN2H22O¹‚HI + 2HgI. The crystals are insoluble in cold
and in hot water, and but little soluble in boiling alcohol (Groves,
Chem. Soc. Qu. J. 11, 97; Chem. Centr. 1858, 890).
Bromomercurate of Strychnine is obtained in the same way as the
iodine-compound, by substituting bromide for iodide of potassium
(Groves).
Strychnine with Mercuric chloride. Mercuric chloride throws down
from a solution of strychnine in weak alcohol, a white crystalline
precipitate, insoluble in water, alcohol, and ether (Nicholson &
Nicholson & Abel.
42 C
2 N
252
41.64
41.52
28
4.63
22 H
22
3.63
3.77
4 O
32
5.29
2 Cl
71
11.73
11.74
2 Hg.
200
33.08
33.12
C42N2H2204,2HgCl
605
100.00
Sulphate of Strychnine with Mercuric Chloride. - Obtained in the form
of a crystalline mass by dissolving the foregoing compound in sul-
phuric acid (Nicholson & Abel).
C42N2H2204
HO,SO3
2HgCl...
C40N2H2204,HO,SO³ + 2HgCl
Nicholson & Abel.
334
51.09
49
7.49
7.27
271
41.42
654
100.00
Mercuric chloride throws down a precipitate from hydriodate of
strychnine (Caillot).
Chloromercurate of Strychnine. Mercuric chloride throws down
from hydrochlorate of strychnine (and from the sulphate and nitrate
after addition of chloride of sodium) a dense pulverulent precipitate,
which soon turns gelatinous, and on addition of hydrochloric acid or
sal-ammoniac, is converted (without dissolving) into a mass of needles.
(v. Planta). The salt is also formed by dissolving the compound of
mercuric chloride and strychnine in hydrochloric acid. It dissolves
with difficulty in water, but easily in alcohol, from which it crystallises
(Nicholson & Abel).
I
2 K
VOL. XVII.
498
PRIMARY NUCLEUS C42H26; OXYAZO-NUCLEUS Oª²N²H²º04.
Nicholson & Abel.
42 C
2 N
23 H
4 0
3 Cl
2 Hg....
252
39.27
39.28
******
28
4.36
23
3.58
3.88
***
32
4.98
106.5
16.61
16.59
200
31.20
31.38
641.5
100.00
C42N2H2204,HCl + 2HgCl
Strychnine forms a sparingly soluble compound with mercurous
nitrate (Nicholson & Abel).
Alcoholic nitrate of silver throws down from alcoholic strychnine a
crystalline compound containing equal numbers of atoms of nitric acid,
oxide of silver, and strychnine (Regnault).
Strychnine forms a sparingly soluble compound with protochloride
of platinum (Nicholson & Abel).
Chloroplatinate of Strychnine. - Bichloride of platinum throws down
from hydrochlorate of strychnine, a yellowish-white precipitate
(Robinet), nearly insoluble in water and ether, and soluble with
difficulty in boiling alcohol, from which it crystallises in scales re-
sembling mosaic gold. Dissolves with decomposition in strong nitric
acid (Nicholson & Abel), but not perceptibly in hydrochloric acid (v.
Planta).
Nicholson
Liebig. Gerhardt. & Abel.
42 C.....
2 N
252
....
28
46'65 ....
5.18
23 H
23
40.....
Pt
3 Cl
32
...
98.7
106.5
4.26 ....
5.92
18.27
....
....
....
mean.
47.39 .... 46.69
4.53
4.44
C42N2H2204,HCl,PtCl²
19.72 17.82 17.85 .. 18.16
540.2 100.00
....
Chloriridiate of Sodium throws down from strychnine-salts a
red-brown precipitate, not perceptibly soluble in hydrochloric acid
(v. Planta).
Chloropalladite of Strychnine. - Protochloride of palladium throws
down from hydrochlorate of strychnine, brown flocks, which dissolve
in water and alcohol, and crystallise in dark-brown needles on cooling
the solution (Nicholson & Abel).
C42N2H2204,HC1,C1
Pd
C42N2H2204,HCl,PdCl
Nicholson & Abel,
mean.
406
53.3
459.3
88.41
11.59
......
11.50
100.00
Chloroaurate of Strychnine. Thrown down by terchloride of gold
from strychnine-salts as a lemon-yellow precipitate, which is very
slightly soluble in water [insoluble in hydrochloric acid (v. Planta)],
easily soluble in alcohol, but insoluble in ether (Larocque & Thibierge).
The precipitate deposits gold in boiling water, and crystallises from
alcohol in pale orange-coloured crystals (Nicholson & Abel).
STRYCHNINE.
499
42 C
2 N
22 H
at 100°.
252
40
Au.....
4 Cl
C42N2H22O+, HCl,AuCl³
Nicholson & Abel.
mean.
37.41
37.33
+49
28
4.15
22
3.42
3.55
32
4.75
196.7
29.19
29.15
1442
21.08
672.7
100.00
Hydrocyanate of Strychnine. The easily formed solution of strych-
nine in aqueous hydrocyanic acid leaves strychnine free from the acid
when evaporated (Pelletier & Caventou).
Hydroferrocyanate of Strychnine. A. With 1 at. Ferrous Cyanide.
This salt is deposited in nearly colourless needles on mixing cold
saturated solutions of ferrocyanide of potassium and neutral salts of
strychnine. More dilute solutions yield pale-yellow, rectangular, four-
sided prisms, the ends of which are formed by two faces inclined to
the edges of the prism. Hygroscopic. The salt dissolves slightly
in cold water and alcohol, and more freely in the hot liquids. The
aqueous solution, on boiling, deposits strychnine, turns yellow, and
yields crystals of hydroferrocyanate of strychnine. Loses 6-12 p. c. of
water at 100° (6 at. = 6.37 p. c.), and afterwards also hydrocyanic acid
(Brandis).
Brandis.
90 C
7 N
Over chloride of calcium.
mean.
540
63.68
64.38
98
11.56
54
6.37
6.51
128
15.09
28
3:30
3.36
848
100.00
54 H
16 O
Fe.....
2 (C42N2H2204,HCy),FeCy + 8aq.
B. With 1 at. Strychnine and 2 at. Ferrous Cyanide. The precipi-
tate produced by alcoholic hydroferrocyanic acid in alcoholic solutions
of strychnine-salts, dissolves at first on agitation, forming a clear solu-
tion which deposits the salt A; but when the hydroferrocyanic acid is
added to acid reaction, the salt B is thrown down as an amorphous
acid precipitate, which is to be washed with alcohol and water, and dried
over oil of vitriol. This compound is also obtained by mixing hydro-
ferrocyanic acid with hydroferricyanate of strychnine. After drying
it is permanent in the air, but in the moist state is easily decomposed,
especially on warming, with formation of free hydrocyanic acid, a blue
precipitate, and hydroferricyanate of strychnine. It is slowly decom-
posed by acids, with separation of Prussian blue, and by caustic potash,
with formation of amorphous white flocks. It is insoluble in water
and alcohol. Loses 3.08 p. c. of water at 100° (2 at. = 3.5 p. c.) and
then decomposes (Brandis).
Brandis.
Over oil of vitriol.
mean.
48 C
5 N
28 H
288
56.02
56.27
70
13.62
28
5.44
5.86
1
90
72
14.03
2 Fe
56
10.89
9.98
C42N2H22O¹,HCy,2FeCy + 5aq.
514
100.00
**AS
2 к 2
500
PRIMARY NUCLEUS CH2; OXYAZO-NUCLEUS CNHºO±.
Brandis supposes the salt to contain 1 at. more of hydrocyanic acid. According
to the above formula, it corresponds to ferrocyanide of iron and potassium (vii, 474).
Hydroferricyanate of Strychnine. Obtained from the foregoing
salt; also by boiling strychnine with water and Prussian blue, or by
mixing hot saturated solutions of strychnine-salts and ferricy-
anide of potassium. The free strychnine is removed by means of
alcohol, and the salt is afterwards washed with cold water. Small,
very brilliant, golden-yellow prisms. - Extremely hygroscopic. Dis-
solves very slightly in water and is decomposed by long boiling there-
with, setting free hydrocyanic acid and throwing down oxide of iron
and strychnine. Potash and ammonia, added to the salt, precipitate
strychnine; ferrous salts throw down Prussian blue. Ferric salts
form a clear blue solution, from which flocks of Prussian blue are
gradually deposited. The crystals lose in a vacuum over oil of
vitriol, 182 p. c. water (3 at. = 2.04 p. c.), at 100°, altogether, 3.86
p. c. (6 at. = 4·06 p. c.), at 136°, 4.78 p. c. (8 at. 5.43 p. c.) after-
wards turning green and, at 200°, black (Brandis).
Crystals.
138 C
12 N
81 H
24 O
....
828
62.48
Brandis.
63.23
168
12.68
81
6.11
6.38
192
14.48
2 Fe....
56
4.25
4.11
3 (C42N2H2204,HCy) + Fe²Cy³ + 12aq.
1325
100.00
...
at 136°.
Brandis.
138 C
12 N
73 H
16 O
2 Fe
828
66.08
168
13.41
12.94
73
5.83
128
10.21
56
4:47
4.44
......
1253
3 (C42N2H2204,HCy) + Fe²Cy³ + 4aq.
100.00
Strychnine with Mercuric Cyanide. — Precipitated from an alcoholic
solution of strychnine by excess of mercuric cyanide. Small prisms,
slightly soluble in water and alcohol, insoluble in ether (Nicholson &
Abel).
46 C
4 N
22 H
40
2 Hg
C42N2H22O+,2HgCy
at 100°.
Nicholson & Abel.
276
47.08
46.96
56
9.59
22
3.75
3.78
32
5.46
200
34.12
34.16
586
100.00
....
Hydriodate of strychnine is precipitated by cyanide of mercury
(Caillot).
Hydrochlorate of Strychnine with Mercuric Cyanide. A. With 1 at.
Mercuric Cyanide. On mixing hot very dilute aqueous solutions of
hydrochlorate of strychnine and cyanide of mercury, a large quan-
tity of needles is deposited after standing for a short time.
needles are to be washed with water and alcohol in succession.-
The
STRYCHNINE.
501
Colourless well-formed crystals, soluble in hot water and alcohol (Kohl
& Swoboda, Wien. Acad. Ber. 9, 252; Ann. Pharm. 83, 339).
Kohl &
Swoboda.
44 C
3 N
23 H
Cl
Hg
40
C42N2H22O¹,HCl + HgCy
Crystals.
Nicholson
& Abel.
264
53.18
52.53
53.87
4.2
8.46
23
4.63
4.72
35.5
7.13
100
20.14
20.20
19.72
32
6.46
496'5
100.00
B. With 4 at. Mercuric Cyanide.
Obtained by Brandis in the same
manner as Nicholson & Abel afterwards obtained A. White, pearly,
rectangular tables and prisms (Brandis).
50 C
6 N
23 H
Cl
4 Hg
4 O
Crystals.
Brandis.
300
34.32
34.76
84
9.60
23
2.63
35.5
4.05
4.00
45.74
45.25
32
3.66
100.00
C42N2H2204,HCl + 4HgCy 874.5
Hydroplatinocyanate of Strychnine. Platinocyanide of potassium
throws down from an aqueous solution of nitrate of strychnine a
copious white precipitate, which is quickly transformed into lamina.
It crystallises from alcohol in short tufts of needles and four-sided
prisms. Dissolves easily in boiling alcohol. Gives off its water of
crystallisation at 120° (Schwarzenbach, Pharm. Viertelj. 8, 518).
C42N2H2204,HCy²
Crystals.
387
Schwarzenbach.
76.84
Pt
2 HO
98.7
19.59
19.41
18
3.57
3.5
C¹²N²H³-04,HCy,PtCy + 2aq.
503.7
100.00
Hydrosulphocyanate of Strychnine. Sulphocyanide of potassium,
added to aqueous strychnine salts, throws down a dense crystalline
precipitate, which disappears on heating, and again makes its appear-
ance in long silky needles as the solution cools (Artus; v. Planta).
The precipitate thrown down from dilute solutions of the hydrochlorate
appears under a magnifying power of 250 diameters, as flat needles,
truncated at one end, or terminated by an acute angle, sometimes
isolated, sometimes united in irrregular groups (Anderson, N. J. Pharm.
13, 443). Permanent in the air; neutral; of bitter and burning taste.
Melts when gently warmed, solidifying on cooling, and leaves a
porous charcoal when more strongly heated. The salt dissolves very
slightly in cold water, but more easily in water at 70° (Artus); accord-
ing to Lepage, it dissolves in cold water, but not in water containing
sulphocyanide of potassium. It is very easily soluble in alcohol, and
precipitable from the solution by water (Artus); insoluble in ether
(Artus, J. pr. Chem. 3, 320; 8, 253. Henry, J. Pharm. 24, 194,
Lepage, J. Pharm. 26, 140. Winckler, Repert. 53, 397).
502
PRIMARY NUCLEUS C42H26; OXYAZO-NUCLEUS C42N2H2004.
Alcoholic strychnine and not too dilute hydrosulphocyanic acid.
yield transparent needles, which melt at 110° to 120° without losing
weight (Dollfus, Ann. Pharm. 65, 215).
Crystals.
Dollfus.
44, C
3 N
264
67.17
67.70
Nicholson
& Abel.
66.93
42
10.69
23 H
23
5.85
6.39
5.92
...
2 S
32
8.14
40
32
8.15
...
C42N2H2204,U³NHS2
393
....
100.00
C42N2H2204
Or:
334
Dollfus.
Nicholson
& Abel.
84.98
84.86
****
C2NHS2
59
15.02
14:45
14.96
C42N2H22O4, C²NHS2
393
100.00
99.82
Nitroprusside of Sodium throws down crystalline precipitates from
strychnine-salts (Neubauer, Anal. Zeitschr. 1, 515). It does not form
precipitates, but colours the salts on evaporation (Werther, J. pr. Chem.
89, 498). See p. 486.
Acetate of Strychnine. The neutral salt crystallises with difficulty,
the acid salt easily (Pelletier & Caventou). According to Abl, the
salt dissolves in 96 parts of water, and according to Schlimpert (N.
Jahrb. Pharm. 13, 248) in 15·1 parts of chloroform.
Oxalate of Strychnine. - A. Neutral.-Obtained by neutralising
oxalic acid with strychnine (Nicholson & Abel). Formed also by
boiling strychnine with aqueous parabanic acid, and cooling the filtrate,
no oxalurate crystallising out (Elderhorst). — Long flat needles, neutral
towards vegetable colours. Turns white at 100°, and loses 9·88 p. c.
of water (9 at. = 9.65 p. c.) (Elderhorst, Ann. Pharm. 74, 83).
at 100°.
Elderhorst.
88 C
4 N
528
69.66
69.20
56
7.39
46 H
46
6.07
6.56
16 O
128
16.88
2042N2H2204,C4H²08.... 758
100.00
Or:
Nicholson & Abel.
2C42N2H22O¹ ....
668
88.13
87.98
C4H208
90
11.87
11.86
....
100.00
99.84
2C N2H22O4, C4H2O8.... 758
B. Acid. Obtained from A and free oxalic acid. Has an acid
reaction (Nicholson & Abel).
C42N2H2204
C+H2OS
C42N2H22O1,CH³O®
Nicholson & Abel.
334
78.77
78.69
90
21.23
20.82
424
100.00
99.51
04.0
Mellitate of Strychnine. Obtained by mixing an alcoholic solution
STRYCHNINE.
503
of strychnine with alcoholic mellitic acid, as a crystalline precipitate,
which is dazzling-white and glittering when dry. - Crystallises from
water in silky tufts of prisms. Gives off 1-2 p. c. of water at 100°, and
17 p. c. at 120°, and contains (dried?) 20-39 p. c. of hypothetical
anhydrous mellitic acid. Soluble in 1,500 parts of cold, and in 650
parts of boiling water, but perfectly insoluble in alcohol (Karmrodt, Ann.
Pharm. 81, 170).
Tartrate of Strychnine. See p. 217. The strychnine-salts of tartaric
and of antitartaric acid contain different proportions of water, and
behave differently when heated; they have also different degrees of
solubility (Pasteur).
A. Dextrotartrate. a. Neutral. The solution of 2 atoms of
strychnine in 1 atom of bitartrate of potash yields fine crystals, which
give off 14.3 p. c. of water at 100°, and no more below 170º. At 190°
they become slightly coloured (Pasteur). On neutralising tartaric acid,
or aqueous bitartrate of potash with strychnine, neutral shining
needles an inch long are obtained. The needles effloresce in the air,
become anhydrous at 130°, and dissolve easily in water and alcohol
(Arppe, J. pr. Chem. 53, 331).
2C42N2H2204,C8H6O¹2
8 HO.....
2C42N2H2204,C8H6O12 + 8aq.
Crystals.
818
Arppe.
91.91
72
8:09
7.59
7.76
890
100.00
7 at. water 719 per cent. Pasteur's determination would correspond with 15
atoms of water (calc. 14:43 p. c.). The dried salt contains 81:40 p. c. strych-
nine (calc. 81.66 p. c.) (Nicholson and Abel).
b. Acid. Formed by dissolving strychnine in excess of tartaric
acid. Slender shining needles, soluble in water. Permanent in the
air: of acid reaction. According to Arppe, it loses the whole of its
water of crystallisation at 125° [at 100° (Pasteur)], and nothing more
below 170°, at which temperature, however, it becomes coloured.
It remains transparent in absolute alcohol, without dissolving (Pasteur).
This salt is formed, according to Nicholson & Abel, by boiling strych-
nine with solution of bitartrate of potash.
Arppe. Pasteur.
Needles.
C42N2H22O4
334
62.08
C8H6O12
150
27.88
6HO
54
10.04
10.1
10.3
C42N2H22O4, C8H6O12 + 6 aq.
538
100.00
The anhydrous salt contains 68 74 p. c. of strychnine (calc. 69.00 p. c.)
(Nicholson and Abel).
B. Antitartrate of Strychnine. The neutral salt loses 7·8 per cent.
of water at 100°, and nothing more at 200°, but becomes coloured at
the latter temperature, though more slowly and to a less extent than
the dextrotartrate. The acid gives off salt the whole of its water of
crystallisation, amounting to 10-3 p. c., at 100° more quickly than the
corresponding dextrotartrate. It becomes coloured more slowly than the
latter salt at 170°, and turns opaque in absolute alcohol (Pasteur, N.
Ann. Chim. Phys. 38, 437).
504
PRIMARY NUCLEUS C42H26; OXYAZO-NUCLEUS CNH2004.
Tartrate of Antimony and Strychnine. Obtained in the same way as
the corresponding quinidine-salt (p. 302). Lamellar tables or very
brittle needles. Dissolves with difficulty in water (Stenhouse, Ann.
Pharm. 129, 25).
50 C
2 N
27 H
18 O
Sb
at 100°
Stenhouse.
300
48.44
48.70
28
4.52
27
4.36
4.39
144
23.26
120.3
19.42
19.62
100.00
C¹²N³H2O¹,HO,SbO³‚C³H¹Ò¹º .... 619-3
Croconate of Strychnine crystallises from alcohol in small yellow
needles, soluble in water and alcohol. Rhodizonate of strychnine is
hyacinth-red, and soluble with reddish-yellow colour in water and
alcohol (Heller).
Picrate of Strychnine. - Alcoholic picric acid throws down from
alcoholic solutions of strychnine, a yellow precipitate, which crystallises
from hot solutions, on cooling, in fine yellow crystals (Kemp, Repert.
71, 164).
Picrotoxin unites with strychnine (See under BRUCINE) (Pelletier &
Couerbe).
Hippurate of Strychnine. When excess of strychnine is boiled
with a hot saturated solution of aqueous hippuric acid, the filtrate does
not yield crystals on cooling; but when evaporated, it becomes syrupy,
and afterwards forms a transparent amorphous mass, which in a few
months turns hard and white, and then consists of microscopic needles
collected in nodules (Elderhorst, Ann. Pharm. 74, 77).]
Gallic acid does not precipitate acetate of strychnine (Pfaff). —
Tannic acid and tincture or infusion of galls throw down from salts
of strychnine dense precipitates (Pfaff; Henry), which become denser
on the addition of a little hydrochloric acid, and do not dissolve in a
large quantity of the acid (v. Planta). Strychnine behaves like
quinine towards oleic and margaric acids (p. 294) (Attfield; Tripier). -
It does not act upon sugar, gum, or starch (Pelletier & Caventou).
Betuloretinate of Strychnine. - Nitrate of strychnine throws down
from the soda-salt of betuloretinic acid a precipitate, which turns crystal-
line during washing. The salt dissolves in alcohol, and remains as a
yellow resin on evaporating the solution (Kösmann, N. J. Pharm. 26,
204).
Strychnine dissolves in 240 parts of alcohol of 20° B., but not in
absolute alcohol (Merck). It is soluble in 120 parts of cold, and in
10 parts of boiling 80 p. c. alcohol (Wittstein). It is insoluble in ether
(Pelletier & Caventou). Soluble in 300 parts of glycerin (Cap & Garot).
-According to M. Pettenkofer, it dissolves in 5 parts, according to
Schlimpert, in 7 parts of chloroform. It dissolves in benzene (Mans-
field), in cold picamar and cold creosote (Reichenbach); easily in volatile
oils, partly crystallising from a hot saturated solution on cooling
(Pelletier & Caventou). According to M. Pettenkofer, it dissolves
in 100 parts, according to Cap & Garot, in 200 parts of olive oil. Fal
oils, according to Pelletier & Caventou, dissolve only traces of it.
M
OXYSTRYCHNINE.
505
Appendix to Strychnine.
Strychnochromin. A resinous yellow colouring matter, from the
lichens of false Angustura, also from those found on the bark of Strychnos
Pseudochina, as well as from Upas Tieuté. — The lichens are exhausted
with ether, and then with alcohol; the alcoholic tincture is evaporated;
and the residue is boiled repeatedly with water, which dissolves
extractive matters, and leaves the yellow. - Reddish-yellow, tasteless,
non-poisonous powder. It dissolves in strong nitric acid with fine
green colour, which disappears on diluting the solution with water,
but appears again when the liquid is concentrated, and is turned
yellow by hydrosulphuric acid, protochloride of tin, and ferrous sul-
phate. Strong nitric acid also throws down from alcoholic strychno-
chromin, a green precipitate which loses its colour when washed. Oil
of vitriol turns strychnochromin green; strong caustic potash decom-
poses it.
-It is nearly insoluble in boiling water and dilute alkalis;
soluble in acetic acid, from which it is precipitated by alkalis; easily
soluble, with reddish-yellow colour in alcohol; and very slightly soluble
in ether and volatile oils (Pelletier, J. Pharm. 5, 546; N. Tr. 4, 2, 221.
Pelletier & Caventou, Ann. Chim. Phys. 26, 54).
The stychnine prepared from Nux vomica, Faba St. Ignatiï, and
Upas Tieuté obstinately retains a yellow colouring matter, which remains.
in solution when an aqueous extract of the Upas is precipitated with
magnesia, and is obtained as a yellow extract on evaporation. This
body is coloured bright red by strong nitric acid: it dissolves easily
in water and alcohol, and is not precipitated by neutral acetate of lead
(Pelletier & Caventou).
Conjugated Compounds and Derivatives of Strychnine.
Oxystrychnine.
C42N2H28012.
Chem.
SCHÜTZENBERGER. Compt. rend. 47, 79; Instit. 1858, 239; J. pr.
75, 122; Chem. Centr. 1858, 677; Ann. Pharm. 108, 349; Kopp's
Jahresber. 1858, 373.
An aqueous solution of sulphate of strychnine is boiled with nitrite
of potash so long as nitrogen is evolved, and the pale-yellow liquid is
precipitated with ammonia. A boiling alcoholic solution of the pale
yellow flocks thus obtained deposits first yellow crystals of oxystrych-
nine and afterwards red crystals of bioxystrychnine.
Large orange-yellow, transparent, apparently rectangular prisms,
truncated at the edges. Less bitter than strychnine. - Decomposes at
300°, without previous loss of water: melts when heated on platinum
foil, and burns with a bright flame. Soluble in alcohol, but not in
water. The platinum double-salt contains 16.1 p. c. of platinum (calc.
for C42N2H28O¹²,HCl,PtCl2 requires 16-2 p. c. Pt).
506
PRIMARY NUCLEUS C42H26; OXYAZO-NUCLEUS CªN²H²ºO¹.
at 250°.
Schützenberger.
42 C......
252
62.37
62.50
2 N
28
6.93
7.05
28 H
12 O........
28
6.93
7.05
96
23.77
23.40
C42N2H28012
404
100.00
100.00
....
Bioxystrychnine.
C42N2H28014.
SCHÜTZENBERGER. Literature and Preparation (p. 505).
Bitter orange-red prisms, which decompose at 300°, without pre-
vious loss of water. Insoluble in water: soluble in alcohol more
freely than oxystrychnine, and in ether. The platinum double-salt
contains 15.65 p. c. of platinum, corresponding to the formula CN2H28O¹4,
HCl,PtCl² (by calc. 15.8 p. c. Pt).
Schützenberger.
42 C................
252
60.00
59.76
2 N
28
6.66
6.52
28 H
28
6.66
6.85
14 0......
112
26.68
26.87
C42N2H28014
420
100.00
********
100.00
Methyl-strychnine.
C44N2H2404 C4N2H2(CH)04.
—
C. STAHLSCHMIDT. Pogg. 108, 513; abstr. Chem. Centr. 1860, 196;
Répert. Chim. pure 2, 135; Kopp's Jahresber. 1859, 395.
Formestrychnin. Known only in combination with water and acids.
Finely powdered strychnine is treated with a slight excess of
iodide of methyl, the combination of the two bodies, which proceeds
spontaneously at first, with evolution of heat, being completed by
gently warming the mixture for some hours. The excess of methylic
iodide is distilled off, and the residue dissolved in water, a little uncom-
bined strychnine only remaining undissolved. The solution, on cool-
ing, yields crystals of hydriodate of methyl-strychnine, from which the
base may be separated by either of the following methods.
a. The hydriodate is agitated with 3 or 4 parts of cold water and
with oxide of silver; the liquid is filtered from the iodide of silver thereby
formed, and evaporated to a syrup, which deposits crystals of hydrate
of methyl-strychnine. The dark mother-liquor, however, is no longer
susceptible of crystallisation: it is better, therefore, to proceed as fol-
lows. b. The hydriodate is decomposed with the proper quantity of
sulphate of silver, and the solution is separated from iodide of silver,
mixed with baryta-water, and evaporated to dryness. A solution of
the residue yields on evaporation, crystals of hydrate of methyl-strych-
METHYL-STRYCHNINE.
507
:
nine containing excess of water (see below), from which the normal
hydrate of methyl-strychnine may be obtained by drying at 130° to
240°.
44 C
2 N
at 130° to 140°
264
72.13
28
7.65
26 H
26
7.10
60
4.8
13.12
C42N2H2¹ (C²H³) 04 + 2HO.... 366
100.00
Stahlschmidt.
71.79 to 73.07
7.01 7.61
""
7.41 7.67
""
Stahlschmidt considers the salt to contain 1 at. water less.
C44N2H2505, requires 73.96 p. c. C., 7·84 N., 7·00 H., and 11.20 0.
His formula,
Decompositions. 1. Methyl-strychnine, when heated, evolves white
vapours, melts, turns darker, and burns with smoky flame, leaving
charcoal. 2. It turns yellow and brown when heated with oil of
vitriol. 3. A solution of methyl-strychnine mixed with bichromate
of potash throws down a brown-red precipitate on addition of one drop
of dilute sulphuric acid, or acquires a blood-red to violet colour when
more dilute.-4. Methyl-strychnine is not perceptibly acted on by
chlorine. 5. It is not affected by chlorate of potash and oil of vitriol:
water added to the mixture immediately colours it blood-red.
6. The yellowish-red solution of methyl-strychnine in nitric acid
becomes decolorised when heated, with liberation of nitric oxide and
probably also of methylic nitrite: it throws down a large quantity of
white flocks on addition of water, and assumes a dark red colour with
protochloride of tin.
Aqueous methyl-strychnine (especially that obtained by decom-
posing the hydriodate with oxide of silver) acquires a dark wine-red
to olive-green colour when evaporated, and deposits a black resin,
which dissolves in acids with evolution of carbonic acid, forming an
inky solution precipitable by caustic potash. When heated with strong
nitric acid, it evolves nitric oxide and carbonic acid: the liquid deposits,
on cooling, a brown mass, a solution of which in boiling water throws
down a yellow powder as it cools. The same yellow powder is preci-
pitated by water from the nitric acid mother-liquor: it dissolves in
boiling water and alcohol, puffs up slightly when heated, turns brown
and dissolves partially in caustic potash or ammonia, and is restored to
its original colour by acids. Its solution in hydrochloric acid yields
with bichloride of platinum a yellow precipitate containing, at 110°,
13.74 p. c. of platinum.
-
Combinations. With Water. - Hydrate of Methyl-strychnine. -Yel-
lowish, highly lustrous crystals, perfectly formed, and attaining a
length of half an inch. Prismatic. Combination of y, a, and u (fig. 53);
but with hemihedral development of the face a. Angle y: y before =
108° 50'; at the side = 71° 10′ (observed 71° 15'); u: u above
94° 26'; at the side = 85° 34′ (observed = 85° 25'); y : u = 113° 17′
(observed
113° 20′); a: y = 147° 50′ (observed); a : u = 136° 30′
(Rammelsberg, Pogg. 109, 378). Loses a part of its water of crystal-
lisation at 100° and the rest at 135°. Does not taste bitter, and does
not poison rabbits, when given to the extent of 11 grains in the
course of a day. It dissolves easily in water.
Hydrated methyl-strychnine forms with acids easily soluble salts,
which generally crystallise well. Aqueous methyl-strychnine throws
508
PRIMARY NUCLEUS C42H26; OXYAZO-NUCLEUS C¹NºHO¹.
down the oxides from salts of nickel, cobalt, iron, and copper; it like-
wise precipitates salts of alumina, and does not redissolve the preci-
pitate when added in excess.
Phosphate of Methyl-strychnine.
Obtained by neutralising the
aqueous base with phosphoric acid.
White crystalline mass, having
a slightly acid reaction. Dissolves easily in water and alcohol.
Loses
7.66 p. c. of water at 130° (4 at.
7.43 p. c. HQ).
at 130°.
Stahlschmidt.
C44N³H404,3HO
375
84.08
PO5
71
15.92
17.10
100.00
....
CNH (C²H³)04,3HO,PO5 446
Sulphate of Methyl-strychnine. - A. Neutral. Obtained by neutralis-
ing the aqueous base with dilute sulphuric acid, or by decomposing hy-
driodate of methyl-strychnine with sulphate of silver. It is deposited
from the solution evaporated to a syrup in thin pearly laminæ. Dis-
solves easily in water. The crystals effloresce in the air, and lose
10.26 p. c. of water at 100° (5 at. = 10∙18 p. c.).
Stahlschmidt.
44 C
2 N
25 H
50
SO3
C42N2H21 (C2H³)04,HO,SO³
at 100°.
264
66.49
66.10
28
7.07
25
6.29
6.51
40
10.08
40
10.07
9.95
397
100.00
....
B. Acid. Crystallises more easily than A, after addition of free
acid, in strongly acid laminæ. - Loses 3.61 p. c. of water at 100°
(2 at. 3.66 p. c.).
C44N2H2404,2HO
2 SO³.....
CN?H2(C*H3)O*,2(HO,SO3)
Hydriodate of Methyl-strychnine.
at 100°
Stahlschmidt.
366
82.06
80
17.94
18.62
446
100.00
Fine
212 parts of cold, and easily in hot water.
pearly lamina, soluble in
Dissolves with difficulty in
alcohol.
44 C
2 N
Crystals.
Stahlschmidt.
264
55.46
55.10
28
5.88
25 H
25
5.25
5.81
40
I
32
6.74
127
26.67
26.62
C¹²N²H²¹ (C²H³)0¹‚HI .... 476
100.00
Hydrobromate of Methyl-strychnine. - Bromide of potassium imme-
diately throws down from a strong solution of the hydrochlorate, slender
needles of this salt, sparingly soluble in cold, easily soluble in hot
water and in alcohol.
Crystals.
Stahlschmidt.
C44N2H2404,H
Br
349
81.35
80
18.65
18.5
C42N2H21 (C2H3) O',HBr
429
100.00
METHYL-STRYCHNINE.
509
Hydrochlorate of Methyl-strychnine. - Formed by neutralising the
aqueous base with hydrochloric acid, or by decomposing the sulphate
with chloride of barium. Fine prisms, half an inch long, soluble in
water and alcohol. Effloresces over oil of vitriol, and loses 8.22 p. c.
of water at 100° (4 at. = 8·56 p. c.).
44 C
2 N
25 H
*
at 100°.
Stahlschmidt.
264
68.66
68.44
28
7.29
25
6.50
6.87
40
CI
32
8.32
....
35.5
9.23
9.10
C42N2H21 (C2H3) 04,HCI
384.5
100.00
....
Nitrite of Methyl-strychnine. On decomposing the hydriodate with
nitrite of silver and evaporating the solution, a radiated crystalline
mass is obtained, which dissolves easily in water and alcohol, and
evolves nitrous acid with acids. When heated, the compound melts,
puffs up, evolves acid vapours, and leaves a brown-black residue, in-
soluble in water, the easily formed alcoholic solution of which dries up
to an asphalt-like mass, even after addition of hydrochloric acid.
Nitrate of Methyl-strychnine. - Slender needles, sparingly soluble
in cold water, easily soluble in hot water and alcohol, insoluble in ether.
When heated, the salt turns yellow, melts, puffs up, and burns with
luminous flame, leaving charcoal.
44 C.......
at 100°.
Stahlschmidt.
264
64.23
63.71
3 N
25 H
42
10.22
10.81
25
6.08
6.22
4
10 O......
80
19.47
19.26
C42N2H21 (C2H³) O¹,HO,NO5
411
100.00
100.00
....
Chromate of Methyl-strychnine. Neutral chromate of potash throws
down from the hydrochlorate, a red-brown precipitate, which is
deposited from its solution in boiling water, as it cools, in the form of a
powder.
Chloromercurate of Methyl-strychnine. - The white precipitate thrown
down by mercuric chloride from hydrochlorate of methyl-strychnine, dis-
solves slightly in cold water and alcohol, and crystallises from a hot
solution in tufts of needles on cooling.
CN2H2O4,HC1, C1
5 Hg
at 100°.
Stahlschmidt.
566
500
53.09
46.91
46.65
100.00
…….....
C42N2H2¹ (C2H³)04,HCl + 5HgCl.... 1066
Chloroplatinate of Methyl-strychnine.—Pale-yellow precipitate, soluble
with difficulty in water and alcohol, insoluble in ether. Contains, at
100°, 17·57 p. c. of platinum (calc. 17·81 p. c.).
Chloroaurate of Methyl-strychnine. - Pale-yellow precipitate, crystal-
lising from solution in hot water or alcohol in orange-coloured tufts of
needles. Decomposes on long boiling, with separation of gold. Con-
510
PRIMARY NUCLEUS C42H26; OXYAZO-NUCLEUS C42N2H2º04.
tains, at 100°, 28.68 p. c. of gold (calc. for C42N2H²(C²H³)Oª,HCl,AuCl³,
28.59 p. c. Au).
Hydroferrocyanate of Methyl-strychnine.- Ferrocyanide of potassium
throws down from a solution of hydrochlorate of methyl-strychnine
mixed with a little hydrochloric acid, a yellow precipitate which crys-
tallises from a solution in boiling water. On long boiling or by pro-
longed contact with hydrochloric acid, the precipitate is decomposed,
with separation of Prussian blue. After drying at 100°, it contains 6.2
p. c. of iron, corresponding to the formula CN2H2(CH3)04,2HCy +
FeCy (calc. 6.14 p. c. Fe).
Ferricyanide of potassium throws down from hydrochlorate of methyl-
strychnine, a white precipitate, which crystallises from hot water in small
shining prisms, and is insoluble in alcohol.
Acetate and Oxalate of Methyl-strychnine are easily soluble and crys-
tallise with difficulty.
Methyl-strychnine dissolves easily in alcohol, but very slightly in
ether.
Ethylstrychnine.
C46N2H2604C40N2(C4H5)H1904, H2.
H. How. Trans. Roy. Soc. Edin. 21, 1, 27; Chem. Gaz. 1854, 321, 341
and 365; Ann. Pharm. 92, 326; J. pr. Chem. 63, 300; Pharm. Centr.
1855, 26; Kopp's Jahresber. 1854, 514.
Vinestrychnin. Known only as hydrate and in combination with acids. The
hydrate may be regarded as analogous to hydrated oxide of ammonium.
When strychnine is heated to 100° with iodide of ethyl and alcohol
for 20 minutes in a sealed tube, and the hydriodate of ethylstrychnine
thereby formed is decomposed by moist oxide of silver, a purple-red
solution containing ethylstrychnine is obtained. The solution is allowed.
to evaporate spontaneously without exposure to carbonic acid; the red
crystalline residue is dissolved in a little water and filtered from the
flocks which separate; and after again evaporating in a vacuum, the
residue is dissolved in hot anhydrous alcohol, from which small colour-
less prisms of hydrate of ethylstrychnine crystallise as it cools. Or
the base may be precipitated from the alcoholic solution by ether, in the
form of a jelly, which soon becomes crystalline. It is bitter, and has
an alkaline reaction.
46 C
2 N
31 H
In vacuo.
How.
276
67.81
68.13
28
6.88
31
7.61
8.19
90
72
17.70
C42N2H21 (C4H5)04,HO + 4aq.
407
100.00
....
The crystals do not lose water at 100°, but decompose at a higher
temperature. When heated with iodide of ethyl, they form hydriodate of
ethylstrychnine, and, if alcohol is present, also a basic product. The
aqueous solution of the crystals is purple-red: it evolves an odour of
ETHYL-STRYCHNINE.
511
volatile bases when boiled.
The crystals give the strychnine reaction
with oil of vitriol and bichromate of potash.
Aqueous ethylstrychnine combines with acids, generally even
when in combination with bases, precipitating the oxides. It pre-
cipitates the chlorides of calcium and barium only when heated, but
decomposes the salts of the heavy metals, sulphate of magnesia, and
sulphate of alumina, even in the cold.
Carbonate of Ethylstrychnine.
absorbs carbonic acid from the air.
The aqueous solution of the base
A. Neutral. When moist carbonate of silver is agitated with
hydriodate of ethylstrychnine and water, a colourless solution, free
from iodine, is obtained. The solution acquires a yellow colour if
allowed to stand over the precipitate. When evaporated in a vacuum
or at 100°, it leaves a crystalline residue, from which water takes up
carbonate of ethylstrychnine, leaving white flocks of a new base
undissolved.
B. Acid. Formed by passing carbonic acid into the solution
obtained according to A, and evaporating the filtrate in a vacuum or
at 100°. White crystalline mass, not deliquescent, and having an
alkaline reaction. Dissolves easily in water and in absolute alcohol,
and is precipitated from the latter solution in colourless prisms by
ether.
How.
mean.
C46N2H2604,2HO
2002
C42N9H2¹ (C4H5)04,2(HO,CO2)
380
89.62
44
10.38
AAA
10.53
4,24
100.00
A solution of ethylstrychnine saturated with hydrosulphuric acid
and exposed to the air, becomes converted into hyposulphite, which may
be obtained in crystals.
Sulphate of Ethylstrychnine. The neutral salt in water dissolves
less easily than the hydrochlorate; the solution, supersaturated with
sulphuric acid, yields pearly needles and flocks, probably of an acid
salt.
Hydriodate of Ethylstrychnine. -Shining, white, four-sided prisms
or needles, which do not lose weight at 100°, and at a higher tem-
perature melt, carbonise, and give off repulsive alkaline vapours, con-
densing to a yellow oil. The salt dissolves in 170 parts of water at
15° in 50 or 60 parts of boiling water, and less freely in ammonia-
water and caustic potash, so that these liquids throw down the salt
from its aqueous solution. Soluble in alcohol. When distilled with
carbonate of soda, it yields a heavy oil, only partially soluble in
acids.
46 C
2 N
27 H
Crystals.
276
How.
56.31
56.27
28
5.71
27
5.50
5.60
I
127
25.93
25.98
4 O
32
6.55
C¹²N° (C¹H³) H²¹Q¹HT........ 490
100.00
512 PRIMARY NUCLEUS C42H26; OXYAZO-NUCLEUS C42N²H²º04.
Hydrochlorate of Ethylstrychnine forms easily soluble needles.
Nitrate of Ethylstrychnine. - Formed from the hydriodate and nitrate
of silver. Colourless, highly refractive prisms, very slightly soluble
in cold, easily soluble in boiling, water.
46 C
3 N
27 H
10 O
Crystals.
How.
276
64.94
64.60
42
9.88
27
6.35
6.53
80
18.83
425
100.00
C42N2H2¹ (C+H5) O¹,HO,NO5
Chromate of Ethylstrychnine.
position, forms short yellow prisms.
parent tables, or tufts of needles, obtained by double decomposition.-
Dissolves slightly in cold, easily in boiling water. - Loses 3.60 p. c.
(= 2 at.) of water at 100°.
The neutral salt, obtained by double decom.
• Acid salt. Golden-yellow, trans-
How.
46 C
2 N
28 H
60
2 CrO3
C42N2H21(C*H5)O4,2(HO,CrO3)
Dried.
mean.
276
57.33
57.15
28
5.81
28
5.81
5.91
48
9.99
101.4
21.06
20.87
481.4
100'00
Mercuric chloride throws down from hydrochlorate of ethylstrych-
nine, a white precipitate which crystallises from hot water in needles.
-Chloroaurate of ethylstrychnine forms colourless shining prisms.
Chloroplatinate of Ethylstrychnine. Yellow precipitate, becoming
crystalline after a few hours. Dilute solutions yield stellate groups of
crystals.
C46N2H2604,HC13
Pt..
C42N2H21 (C4H5)04,HCl,PtCl
Crystals.
How.
469.5
82.63
98.7
17.37
17.46
568.2
100.00
Acetate of Ethylstrychnine remains behind in the form of a gum on
evaporating its aqueous solution.
Compounds obtained from Strychnine and Bibromide of
Ethylene.
MÉNÉTRIES. N. Petersb. Acad. Bull. 4, 570; J. pr. Chem. 85, 230;
Chem. Centr. 1862, 145; Kopp's Jahresber. 1861, 542.
When strychnine is heated to 100° for a quarter of an hour with
alcohol and excess of bibromide of ethylene in a sealed tube, white
crystals are formed, which may be freed from excess of the bibromide
and from alcohol by heat, and allowed to crystallise from water.
The crystals are bihydrobromate of ethylene-strychnine or, according to
Ménétries, bromide of strychnine-bromethyl. They dissolve slightly in
COMPOUNDS FROM STRYCHNINE AND ETHYLENIC BROMIDE. 513
cold, and easily in hot water and alcohol, are not precipitated by
ammonia or aqueous alkalis, and exhibit the reactions of strychnine
with oil of vitriol and bichromate of potash.
Ménétriès.
46 C
2 N
26 H
40
Br
Br
C42N2H20 (C4H4) O¹,2HBr
Crystals.
mean.
276
52.87
52.68
28
5.36
26
4.98
5.05
32
6.13
80
15.33
15.48
80
15.33
522
100.00
In contact with silver-salts, the crystals give up half their bromine,
and in contact with moist oxide of silver, the whole of the bromine, as
bromide of silver, thus forming two distinct series of compounds.
A. Compounds containing Bromine.
When the crystals are decomposed by sulphate of silver, and the
filtrate is freed from excess of silver and of sulphuric acid by baryta-
water, and afterwards treated with carbonic acid and filtered, an
alkaline liquid is obtained, which leaves on evaporation a resin re-
presented by the formula CN²H²¹(C¹H¹Br)O¹, 2HO., the hydrated oxide
of strychnine-bromethylammonium of Ménétriès.
Sulphate. C42N2H21 (C'H Br)04,2(HO,SO³).
Obtained from sul-
phate of silver and bihydrobromate of ethylene-strychnine.
Nitrate. Delicate white needles, sparingly soluble in cold, easily
soluble in hot water, not decomposible by ammonia or caustic potash.
– By evaporation with an excess of nitric acid, it is converted into a
pale-yellow crystalline nitro-compound.
46 C
3 N
26 H
10 O
Br
C¹²N2H2¹ (C+H¹Br) O¹‚HO,NO³
Ménétriès.
276
54.76
54.62
4.2
8.34
26
5.16
5.27
....
80
15.87
80
15.87
504
100'00
Platinum-salt. — Chloride of platinum throws down from the hydro-
chlorate (which crystallises with difficulty) a pale orange-yellow
precipitate.
Ménétriès.
C42N2H2¹ (C+H4Br) O¹,HCl, Cl²
548.5
84.75
Pt
98.7
15.25
15.24
647.2
100.00
C42N2H2C+H+Br04,HCl,PtCl²
B. Compounds free from Bromine.
A solution of bihydrobromate of ethylene-strychnine assumes a
wine-red colour when digested with excess of moist oxide of silver,
and leaves, on evaporation of the filtrate, white alkaline hydrate of
VOL. XVII,
2 L
514 PRIMARY NUCLEUS C2H26; OXYAZO-NUCLEUS CN2H2004.
ethylene-strychnine, C42N2H20(CH)04, 2HO, which dissolves easily in
water. Chlorine passed into the aqueous solution of this substance
forms (1) trichlor-ethylene-strychnine, C42N2HCl(CH)04, a white frothy
body which dissolves in alcohol and ether, and carbonises at
160°, with liberation of hydrochloric acid; and (2) a base precipitable
from the concentrated solution by chloride of platinum, probably
C42N2H¹ºCl(CH)0. When an aqueous solution of hydrate of ethy-
lene-strychnine is mixed with nitric acid, the liquid deposits first a
white crystalline powder, insoluble in water, but soluble in strong
acids, and afterwards, on evaporating with nitric acid, an orange-red
body, which explodes when heated, probably nitrate of nitro-ethylene-
strychnine CN2H19X(CH)04,HO,NOS.
19
Hydrate of ethylene-strychnine is not precipitable by ammonia or
caustic potash. It produces with iodide of potassium a white precipi-
tate; with protochloride of tin a white precipitate, insoluble in excess
of the tin-salt; with mercuric chloride a white crystalline compound.
The acid sulphate, C42N2H20(C4H4)O¹,2(HO,SO), is crystallisable.
The easily soluble hydrochlorate contains 9.1 p. c. chlorine, corre-
sponding to the formula CNH20(CH)04, HCl (calc. 8.99 p. c. Cl):
it produces a pale orange-yellow precipitate with bichloride of pla-
tinum.
Chromate. Bichromate of potash throws down a yellow precipitate
from aqueous hydrate of ethylene-strychnine.
46 C
2 N
26 H
60
2CrO3
#
Ménétriès.
276
57.57
57.74
28
5.85
26
5.42
5.90
48
10.01
101.4
21.15
20.96
20
C4²N²H²º (C4H¹)04,2(HO,CrO³)
479.4
100.00
....
Amylstrychnine.
C52N2H3204 = C42N2(C'¹ºH¹¹) H²¹04.
H. How. Trans. Roy. Soc. Edin. 21, 1, 27; Ann. Pharm. 92, 326.
Mylestrychnin.
When finely powdered strychnine is heated to 100° with absolute
alcohol and chloride of amyl for 100 hours in a sealed tube, an oily
body is formed, which solidifies to a crystalline mass when the alcohol
and excess of amylic chloride are evaporated. An aqueous solution
of the hydrochlorate of amylstrychnine thus obtained, when decom-
posed by moist oxide of silver, yields an alkaline purple-coloured
solution of amylstrychnine, which behaves like the corresponding
ethyl-compound.
Hydrochlorate of Amylstrychnine. Colourless oblique rhombic
prisms. Precipitated unaltered from the aqueous solution after some
time by ammonia, and immediately by caustic potash. Prolonged
heating to 100° with ammonia in a sealed tube decomposes it, strych-
nine and other products being apparently formed. It loses 12.54 p. c.
of water at 100³ (7 at. = 12·29 p. c.), still retaining 1 atom.
CHLOROSTRYCHNINE.
515
52 C
2 N
34 H
50
Cl
at 100°.
How.
312
69.41
69.37
28
6.24
34
7.56
7.84
*****
40
8.90
35.5
7.89
8.03
449.5
100.00
...
....
C42N2 (C¹ºH¹¹) H²¹04,HCl + aq.
Nitrate of Amylstrychnine.
Radiated groups of colourless needles,
which give off 15.90 p. c. of water at 100° (10 at. = 15.9 p. c.), still
retaining 1 atom.
52 C
3 N
34 H
11 0
at 100°.
How.
312
65.54
65.32
......
42
8.82
34
7.14
7.26
88
18.50
100.00
C2N2H2(C10H1)O,HO,NO + aq... 476
Chromate of Amylstrychnine.
water.
Yellow crystals, soluble in boiling
C52N2H3204,2HO
2 CrO3
C42N2H2¹ (C¹0H¹¹)04,2 (HO,CrO³)
water.
at 100°
How.
422.0
80.63
101.4
19.37
19.63
523.4
100.00
Hydrochlorate of amylstrychnine forms with mercuric chloride a
white sparingly soluble double-salt, which crystallises from boiling
It produces with terchloride of gold a yellow amorphous pre-
cipitate; and with bichloride of platinum a pale-yellow crystalline com-
pound of varying composition.
Oxychlorazo-nucleus C42N2CIH1904.
Chlorostrychnine.
19
C4²N²CIH²¹0¹ = C²²N²CIH¹⁹04,H².
LAURENT. Compt. rend. 24, 220; N. Ann. Chim. Phys. 24, 313; Ann.
Pharm. 69, 14; J. pr. Chem. 46, 52.
A hot solution of hydrochlorate of strychnine assumes a rose-red
colour when a current of chlorine gas is passed into it [on account of the
presence of brucine (Pelletier)], and after some time deposits a resin, whilst
the solution contains hydrochlorate of chlorostrychnine. On adding
ammonia to the solution, drop by drop, till a slight permanent precipi-
tate is produced, and filtering the liquid, the chlorostrychnine is thrown
down from the filtrate as a white precipitate, which must be washed
on the filter.
Chlorostrychnine, neutralised with dilute sulphuric acid and evapo·
rated, yields crystals of sulphate.
2 L 2
516 PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS CH20³.
CN2H2O*,HO ...
Cl
SO³..
7 HO.....
Crystals.
342
Laurent.
71·20
35.5
7.39
7.30
40
8.31
8.58
63
13.10
13.00
480.5
100.00
C42N2H¹C104,HO,SO³ + 7HO
Pelletier's chlorostrychnin (see p. 485) differs from the above. It is obtained by
completely decomposing a solution of strychnine in 100 parts of water with chlorine,
washing the white mass thereby thrown down with cold and boiling water, and dissolving
it in ether, which leaves shining white lamine on evaporation. The body tastes
bitter, though less bitter than strychnine; it evolves hydrochloric acid and car-
bonises at 150°; is nearly insoluble in water, only slightly soluble in acidulated
water, and does not combine with acids. It crystallises from its easily formed
solution in alcohol in microscopic needles. Contains 47.76 p. c. C., 5·19 N., 4:37 H.,
24-57 Cl., and 18·11 O (Pelletier). See also Regnault (Ann. Pharm. 29, 62), who
doubts the purity of this product, having found in chlorostrychnine the same
quantity of carbon and hydrogen as Pelletier, but a larger proportion of chlorine.
Primary Nucleus C42H30; Oxygen-nucleus C42H22O8.
Scoparin.
C42H22O10 C42H2208,02.
=
STENHOUSE. Ann. Pharm. 78, 15; Phil. Trans. 1851, 422; abstr.
Chem. Soc. Qu. J. 4, 216; Pharm. Centr. 1851, 437: Lieb. Kopp's
Jahresber. 1851, 570.
Source. In Spartium Scoparium, together with sparteïne (xiii, 152,
and xvi, 282). Reinsch obtained from the same plant a bitter sub-
stance (Jahrb. pr. Pharm. 12, 141).
10
Preparation. The decoction obtained by boiling the plant for six or
eight hours with water, when evaporated to th of its bulk, and left
at rest for 24 hours, solidifies to a jelly containing scoparin, together
with chlorophyll and a little sparteïne. The jelly is washed with a
little cold water, dissolved in boiling water containing a few drops of
hydrochloric acid, filtered, and set aside till it solidifies; and the jelly
again formed is purified by washing, pressing, drying in a water-bath,
and dissolving in boiling water, which now leaves most of the chloro-
phyll undissolved. The chlorophyll may also be precipitated from the
aqueous solution by long continued boiling; it is deposited from a
moderately concentrated solution before the scoparin, and may be
separated by filtration at the proper point.
Scoparin thus obtained forms, after drying in a vacuum, a pale-
yellow, brittle, amorphous mass, which is tasteless, inodorous, and
neutral. By precipitating its cold ammoniacal solution with hydro-
chloric acid, dissolving the somewhat more solid jelly in boiling water,
and cooling slowly, a small quantity of pale-yellow crystalline stars is
obtained, together with gelatinous scoparin. The solution in hot
alcohol likewise yields a jelly on partial evaporation, and also crystals
in the cold. When an attempt is made to recrystallise the latter from
hot alcohol, there remains a residue which dissolves with difficulty in
CARDOL.
517
water and alcohol, and is obtained as a jelly having the original
degree of solubility only by dissolving it in ammonia-water, and pre-
cipitating with hydrochloric acid.
The crystals and the jelly have the same composition after
drying.
In a vacuum or at 100°.
Stenhouse.
mean.
42 C
252
58.06
57.67
22 H
22
5.06
5.35
20 O..
160
36.88
36.98
C42H22O20
434
100.00
100.00
Stenhouse's formula is half the above.
J
-
Scoparin puffs up when heated, carbonises without subliming, and
burns with bright flame. A solution in potash or in acids is decomposed
by boiling, with formation of a greenish-brown resin. - Scoparin
assumes a blue-green colour with bromine, and a dark-green with solu-
tion of chloride of lime. With nitric acid it forms picric acid.
Scoparin is sparingly soluble in cold, more freely soluble in hot
water, forming pale-yellow solutions. It dissolves slightly in strong
acids, very easily, with deep yellowish-green colour, in caustic am-
monia, the fixed alkalis and alkaline carbonates, less easily in lime-
and baryta-water. The ammoniacal solution leaves, on spontaneous
evaporation, a green jelly nearly free from ammonia.
Scoparin throws down greenish-yellow flocks from neutral and basic
acetate of lead. It does not precipitate corrosive sublimate or nitrate of
silver.
Soluble in cold, and more freely in hot alcohol.
Primary Nucleus C42H32; Oxygen-nucleus CHO².
Cardol.
C42H8004 = C4H30O*,O.
STÄDELER. Ann. Pharm. 63, 137; abstr. J. pr. Chem. 43, 250; Pharm.
Centr. 1848, 65; Chem. Gaz. 1848, 29 and 58; N. J. Pharm. 13,
457; Kopp's Jahresber. 1847 and 1848, 574.
Kardöl. The acrid oily principle occurring, together with anacardic acid, in
the pericarp of the fruit of Anacardium occidentale (Handbuch, viii; [2], 8).
Preparation. The pericarp of the nut, freed from the mild oily
kernel, is bruised and exhausted with ether; the ether is distilled off;
and the residue is freed from tannic acid by washing with water.
The remaining mixture of about 90 p. c. anacardic acid, 10 p. c.
cardol, and a little ammonia-salt, is dissolved in 15 or 20 parts of
alcohol, and the solution is digested with freshly precipitated hydrated
oxide of lead, so long as it remains acid, and until the whole of the
anarcardic acid is precipitated. The liquid is then filtered, boiled with
small quantities of hydrated oxide of lead (whereby ammonia is evolved
and a violet lead-compound precipitated), again filtered, and freed
518
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS C42H³°³.
from alcohol by distillation. 'There then remains dark wine-red cardol,
a moderately strong alcoholic solution of which is to be mixed first
with water till cloudiness is produced, then with aqueous neutral
acetate of lead, and afterwards boiled and decolorised by dropping into
it basic acetate of lead, which throws down a brown glutinous precipi-
tate. The decolorised solution is freed from lead by sulphuric acid,
and after distilling off the alcohol, the remaining cardol is washed
with water.
Properties. Yellow oil, exhibiting a reddish tinge when in con-
siderable quantity. Sp. gr. 0.978 at 23°. Inodorous in the cold, but
has a slight agreeable odour when warmed. Neutral. It inflames and
blisters the skin, producing wounds which heal very slowly.
42 C
at 100°.
252
80.25
79.91
30 H
30
9.55
9.86
40
32
10·20
10.23
C42H3004
314
100.00
100.00
....
Städeler.
79.98
9.80
10.22
100.00
Städeler's formula contains 1 atom of hydrogen more, making the number of
hydrogen-atoms uneven.
Decompositions. 1. Cardol is not volatile without decomposition;
it yields by dry distillation a moderately limpid oil.-2. When pure
it alters but slowly in the air, acquiring a darker colour. - It
burns with a bright, very smoky flame.3. Moderately dilute.
nitric acid converts it into a thick cochineal-red liquid, insoluble in
ammonia and potash, but soluble therein on addition of alcohol, forming
a solution from which neutral acetate of lead throws down violet
flocks. On dropping cardol into cooled nitric acid of sp. gr. 1·3, a
brick-red mass is produced, with evolution of gas, the ultimate product
being a vermilion-red powder, which dissolves with difficulty in water
and alcohol, and colours the water yellow, even on repeated washing,
without giving up the whole of the nitric acid. Hot nitric acid acts
violently on cardol, producing an abundant evolution of nitric oxide,
and converting it into an orange-red resin, which dissolves with yellow
colour on boiling, and is precipitated by water or neutral acetate of
lead. On evaporating the nitric acid solution to dryness, fatty acids were volatilised,
and the residue, when more strongly heated, seemed to yield a sublimate of suberic
acid: the cardol employed, however, was not quite pure. 4. The deep-red
solution of cardol in oil of vitriol, on absorbing moisture, deposits
brown-yellow crusts, which are insoluble in water; water added to the
solution throws down a little coloured gum, soluble in water. No
conjugated compound of sulphuric acid is formed thereby. - 5. Under a layer
of moderately strong caustic potash, cardol is converted into a tough
The solution assumes a
yellow mass, which afterwards dissolves.
blood-red colour in the air, and forms red or violet precipitates with
salts of the earths and heavy metals.
pure
When the red alkaline solution is saturated with carbonic acid and
evaporated, and the residue is digested with alcohol and filtered from
carbonate of potash, a filtrate of a fine red colour is obtained, from
which neutral acetate of lead throws down a little carbonate of lead.
After removing this last, the addition of a little ammonia throws down
a violet precipitate, soluble in pure alcohol, and precipitable again by
ANACARDIC ACID.
519
ammonia. The precipitate contains 68.2 p. c. oxide of lead, 27.5
p. c. C., 3.2 H., and 6.5 0. When the alkaline solution is exposed to
the air for some time at a temperature of 60° to 80°, whereby it
acquires a brown-red colour, and is then saturated with carbonic acid,
a solid brown resin is deposited, which may be freed from adhering
carbonate of potash by washing with water. This resin dissolves in
ether, also in alcohol, with the exception of a black-brown potash-
compound; the solution appears red-brown by transmitted, and of a
fine green colour by reflected light, and is rendered dark-yellow by
acids. From the alcoholic solution neutral acetate of lead throws
down a red-brown precipitate, soluble in ether and re-precipitable by
alcohol. The precipitate contains, at 80°, 32-08 p. c. PbO., 50·96 C.,
6·05 H., and 11.47 O., corresponding approximately with the formula
C84H600 14,3PbO.
6. A mixture of cardol and hydrated oxide of lead, moistened with
alcohol, and exposed to the air, assumes a violet colour, whereupon.
boiling alcohol extracts from it a red lead-compound, leaving the
greater part of a brownish colour behind. - 7. Cardol throws down
from nitrate of silver, on addition of ammonia, pale-yellow flocks, which
decompose rapidly, with separation of silver.
Cardol is insoluble in water.
Compound of Cardol with Oxide and Acetate of Lead. A solution
of cardol in weak spirit free from air, does not precipitate neutral
acetate of lead, but produces with the basic acetate, a white precipi-
tate, which rapidly assumes a flesh-red to brown-red colour in the air,
and must be washed and dried in a vacuum. Oil of vitriol decomposes
it, evolving acetic acid.
46 C.........
33 H
70.....
4 РЬО
at 60°.
Städeler.
276
33.94
34.25
33
4.05
4.20
56
6.89
6.74
448
55.12
54.81
100.00
100.00
C4H³PbO4, C2H3004,3PbО........ 813
Cardol dissolves easily in alcohol and ether.
Appendix to Cardol.
Anacardic Acid.
STÄDELER. Ann. Pharm. 63, 137.
Occurs, together with cardol (p. 517), in the pericarp of the nut of Anacardium
occidentale.
In the preparation of cardol described at p. 517, anacardic acid is
thrown down as lead-salt, together with decomposition-products of
cardol. The pure lead-salt may be obtained by filtering the alcoholic
solution at the proper point from the brown resin which is first thrown
down, and treating the filtrate with freshly precipitated oxide of lead.
But inasmuch as a large quantity of anacardic acid is carried down in
the first precipitate, it is better to precipitate the alcoholic solution
completely with hydrated oxide of lead, wash the precipitate with
520
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS CHO³.
alcohol so long as the wash-liquids are rendered cloudy by water, and
decompose the lead-salt under water by hydrosulphate of ammonia.
From the solution of the ammonia-salt, dilute sulphuric acid throws
down the anacardic acid as a soft mass, which afterwards solidifies,
and after washing with water, dissolves in alcohol, leaving sulphur
and sulphide of lead. The alcoholic solution is still coloured: it must
therefore be mixed with water till cloudiness is produced, then heated,
and basic acetate of lead dropped into the liquid so long as colouring
matter (together with a little anacardic acid) is thrown down in the
form of dark oily drops. The anacardic acid may be recovered from
the precipitate by dissolving it in alcohol, adding water till turbidity is
produced, dropping basic acetate of lead into the liquid, and removing
the coloured precipitate. The solutions thus obtained are boiled
with moist carbonate of baryta; the brown pellicle which forms is
removed after 12 hours; the now colourless solution, after addition of
alcohol, is precipitated at the boiling heat with alcoholic neutral acetate
of lead; and the precipitate is decomposed by alcoholic sulphuric acid.
After filtering from sulphate of lead, distilling off the alcohol, and
adding water, the anacardic acid separates in the form of an oil, which
afterwards solidifies.
Properties. White crystalline mass, melting at 26°, and crystal-
lising slowly on cooling. It is inodorous in the cold, but exhales an
odour at 100°, without losing weight, and does not yield condensable
products at 150°. It tastes slightly aromatic, afterwards burning,
but does not produce blisters. It leaves a greasy stain on paper, and
when dissolved in alcohol reddens litmus strongly.
Calculation according to Städeler.
Städeler.
44 C............
264
32 H
32
7 0.......
56
C44H3207
352
....
mean.
75.04
75.05
9.07
9.18
15.89
15:77
100.00
100'00
Städeler's formula is not admissible, but no other formula is consistent with the
analysis. Limpricht (Lehrb. 1103) doubles the formula: the acid, may, however,
with greater probability be regarded as a mixture, perhaps containing fatty
acids (Kr.).
Decompositions. 1. Anacardic acid, heated above 200°, yields a
distillate of colourless limpid oil. - 2. On long exposure to the air, it
deliquesces and turns rancid. Burns with bright smoky flame.
3. Oil of vitriol dissolves the acid freely, with light blood-red colour,
and the solution on absorbing water deposits a tough resin, which
dissolves in ammonia, and is re-reprecipitated by acids. The acid
colours cold nitric acid of sp. gr. 1.3 yellow, and is converted thereby
into a pale-yellow elastic mass. Hot nitric acid evolves a large quan-
tity of nitric oxide, and produces a yellow scum, which afterwards dis-
solves, and appears to form suberic and butyric acids.
Combinations. Anacardic acid forms with bases, partly crystalline
partly amorphous salts, which emit a fatty odour at 100°, without
losing weight. According to Städeler, the salts are mono- or semi-
acid,
ANACARDIC ACID.
521
Ammonia-salt. When the syrupy solution of anacardic acid in
aqueous ammonia is evaporated in a vacuum, there remains a soap,
which dissolves in water only after addition of ammonia, and is pre-
cipitated from the solution by sal-ammoniac.
Potash-salt. Anacardic acid, added to a moderately dilute solution.
of caustic potash so long as it dissolves, forms a solution which is not
precipitated by water, but which deposits white flocks on passing into
it a current of carbonic acid. When the solution, together with the
precipitate, is evaporated to dryness in a vacuum, and the residue is
exhausted with ether, the ethereal solution leaves on evaporation a
white amorphous mass, easily soluble in alcohol and water, and pre-
cipitable by saline solutions. It contains 12·06 p. c. potash, and is,
therefore, the mono-acid salt, C4H8¹KO (calc. 14.22 p. c. KO.).
Baryta-salt. The precipitate thrown down from the ammonia-salt
by chloride of barium turns brown on drying, and contains, at 80°,
31.30 p. c. of baryta (calc. for C4H3ºBa207 requires 31.41 p. c. BaO.).
Lime-salt. Alcoholic chloride of calcium throws down from an
alcoholic solution of anacardic acid, on addition of ammonia only, a
granular or gelatinous precipitate, which dries up to brown particles.
It contains, at 60°, 13.76 p. c., and at 100°, 13.97 p. c. lime
(C44H30 Ca²07 requires 14.33 p. c. Ca0.).
Lead-salt. Alcoholic neutral acetate of lead throws down from the
boiling alcoholic acid, a heavy, granular, micro-crystalline precipitate,
which turns yellow and rancid when kept.
Städeler.
mean.
44 C
30 H......
264
47.43
47.23
30
5.37
5'43
5 0.....
40
7.18
6.92
2 PbO
224
40.02
40.42
C44H30Pb207
558
100.00
100.00
....
Compound of the Lead-salt with Acetate of Lead. This body was
obtained on one occasion, in winter, as follows: The ethereal solution of
anacardic acid and cardol obtained by exhausting the pericarp, was eva-
porated; the residue dissolved in alcohol; and the solution was mixed
with water till cloudiness was produced, and precipitated with alcoholic
neutral acetate of lead, so that the greater part of the anacardic acid
was thrown down, together with colouring matter, in the form of a
brown resin. This precipitate, washed with alcohol and dissolved in
warm alcohol containing acetic acid, yielded a brown turbid liquid, from
which, after the separation of the deposit, the double salt crystallised
in the cold. It forms white, pearly lamine, resembling cholesterin,
permanent in the air, and feeling like talc. With oil of vitriol it
evolves acetic acid. When heated, it puffs up to a white froth, evolving
a large quantity of acetic acid, and afterwards melts to a colourless
oil, turns brown, and decomposes. - In warm water it becomes viscid
without dissolving. It is insoluble in cold alcohol, and decomposes
when boiled therewith, with separation of the lead-salt of anacardic
acid. Ether extracts from the compound the lead-salt of anacardic
acid, leaving the acetate undissolved.
522 PRIMARY NUCLEUS CH32; OXYGEN-NUCLEUS C¹²H²Oª.
48 C........
34 H
9 O......
2 PbO
C44H31Pb07 + C4H³PbO4
at 50°.
288
46.71
Städeler.
47.07
34
5.50
5.55
72
11.66
10.94
224
36.13
36.44
618
100.00
100'00
The ammonia-salt precipitates cobalt salts violet, nickel salts white,
and ferrous sulphate white.
Ferric salt. A mixture of alcoholic anacardic acid and alcoholic
sesquichloride of iron, throws down, on addition of ammonia (not suffi-
cient to neutralise the acid), a dark-brown resinous precipitate, con-
taining, at 60°, 18 p. c. sesquioxide of iron.
Silver-salt. Alcoholic nitrate of silver throws down from strong
alcoholic solutions of anacardic acid, a white precipitate, which blackens
slowly and slightly in the air, excepting when an excess of ammonia is
also added. The salt decomposes at 130°, melting to a fine steel-blue
mass. It dissolves in alcohol, especially when acidulated.
44 C.......
31 H
at 80°.
264
Städeler.
57.56
57.56
31
6.74
6.82
6 O......
AgO
48
10.45
10.25
116
25.25
25.37
C44H³¹ Ag07
459
100.00
100.00
....
Anacardic acid dissolves easily in alcohol and ether. It is not con-
verted into an ether by passing hydrochloric acid gas into its alcoholic
solution.
GEOFFROY.
Oxygen-nucleus C42H2804.
Helenin.
C42H2806 = C42H2804,0²?
Traité de la matière medicale, 6, 247.
NEUMANN. Chemie, Dresden, 1755, 1, 746.
DEHNE. Crell. Chem. J. 3, 12.
IlOFFMANN. Taschenbuch, 1787, 150.
KRÜGER & CORVINUS. Scher. J. 7, 575.
FUNKE. A. Tr. 18, 1, 74; Ann. Chim. 76, 102.
JOHN. Chem. Schriften. 4, 64.
FR. NEES V. ESENBECK. Br. Arch. 28, 3.
GERHARDT. Ann. Chim. Phys. 72, 163; Ann. Pharm. 34, 192; abstr.
J. pr. Chem. 20, 47. — N. Ann. Chim. Phys. 12, 188; Rev. scient.
19, 15; J. pr. Chem. 35, 66; abstr. Berz. Jahresber. 25, 659.
Alantcampher.
Noticed by Lefébure and by Geoffroy & Spiess; described more
exactly by Hoffmann and by Krüger & Corvinus; and completely
investigated by Gerhardt.
HELENIN.
523
Source. In the root of Inula Helenium. Crystallises, contaminated.
with resin, from Tinctura Helenii (Krüger & Corvinus); crystallises or
sublimes frequently from the alcoholic extract. See Rump (N. Br. Arch.
32, 215), H. Müller (N. Br. Arch. 32, 216), Groneweg (N. Br. Arch. 37, 266).
Röttscher (N. Br. Arch. 30, 169) regarded such crystals as benzoic acid. Elecam-
pane-root 5 or 6 years old, when dried in an oven, yielded a sublimate of helenin,
which was not obtained from the fresh root (Rich, N. J. Pharm. 5, 74).
Fine white needles, melting at 75°, which crystallised, after long standing, from Ex-
tractum Inula spirituosum prepared from old root, contained 64-01 p. c. Č., 9.27 H.,
and 26.72 O., corresponding with the formula C16H1405, and not agreeing with
Gerhardt's analysis of helenin (Hoyer, Pharm. Viertelj. 13, 554).
Preparation. 1. The fresh root, sliced, is boiled with alcohol of 80
p. c.; and the hot filtrate is mixed with 3 or 4 times its volume of cold
water, whereupon it becomes slightly turbid, and in the course of 24
hours deposits the helenin in white needles (Delffs, Pogg. 80, 440).
Gerhardt exhausts the fresh root with alcohol of 36°, distils off the
greater part of the alcohol, and cools the liquid, whereupon the helenin
crystallises. It is purified by several times repeated crystallisation
from alcohol. The tincture of the dried root yields on evaporation.
a brown oily layer, which is difficult to purify, and solidifies on cooling
(Gerhardt). 2. When the root is distilled with 5 parts of water, the
helenin passes over as an oil, partly solidifying at the bottom of the
distillate, and partly crystallising from the liquid in needles (Funke;
John). The distillate deposits brown flocks, which yield helenin
when dissolved in alcohol and evaporated, whilst an oil remains in solu-
tion (Nesenbeck). In this way helenin is obtained pure, but in too
small quantity (Gerhardt).
Properties. White, four-sided, brittle prisms (Gerhardt). Accord-
ing to Gerhardt, it is lighter, according to others, heavier than water.
It has a very faint odour and taste (Gerhardt); according to older
statements it has the odour of elecampane, and has a peculiar aromatic
taste. Its vapour produces stupefaction (John). It melts to an oil at
72°, and solidifies to a crystalline mass on cooling, but not after being
kept in the melted state for a few minutes (Gerhardt). It sublimes
undecomposed in talc-like lamina, and distils with vapour of water.
According to Gerhardt, it boils at 275° to 280°, evolving a very faint
odour, and undergoing partial decomposition. Neutral.
Gerhardt.
Dumas.
mean.
(J. pr. Chem. 4, 434) Earlier.
Later.
42 C
28 H
60
252
76.83
76.9
77.15
76.46
28
8.53
8.8
8.54
8.66
48
14.64
14.3
14.31
....
14.88
C42H2S06
328
100.00
100.0
100.00
100.00
Gerhardt's earlier formula was C30H2004. According to Dumas, C¹4H9O2.
Decompositions. 1. Helenin dissolves in moderately dilute nitric
acid, and is precipitated from the solution by water in its original state.
Fuming or hot dilute nitric acid evolves a large quantity of nitric oxide
and converts it into a red resin, nitrohelenin. On one occasion fine
crystals, differing from oxalic acid, were obtained. 2. Helenin dissolves in
524
PRIMARY NUCLEUS CH2; OXYGEN-NUCLEUS CH2804.
¦
i
oil of vitriol, forming a red solution, from which it is precipitated
by water, unchanged at first: on standing, or when warmed, the
solution blackens, and evolves sulphurous acid, and on addition of
water throws down dirty-brown flocks. A solution of helenin in fuming
sulphuric acid deposits yellow resinous flocks on addition of water,
whilst free sulphuric acid and helenin-sulphuric acid remain in solu-
tion. The easily soluble bitter baryta-salt of the latter acid decomposes
when the solution is evaporated at a gentle heat. Helenin does not yield
an oil when distilled with oil of vitriol. 3. By distillation with anhydrous
phosphoric acid it yields helenene (p. 13).-4. Helenin is not acted.
upon by dry chlorine at ordinary temperatures, even in sunshine; but
on passing chlorine over fused helenin, chlorhelenin and hydrochloric
acid are formed. — 5. Helenin absorbs hydrochloric acid gas, assuming
a yellow colour. It is coloured dark-red by stannic chloride and ter-
chloride of antimony.-6. It is not decomposed by heating with aqueous
or alcoholic potash: when heated with the fused hydrate, the greater
part is volatilised, and a portion is carbonised. On heating it to 250°
with potash-lime, it evolves hydrogen abundantly; the residue dissolved
in water, deposits, on addition of hydrochloric acid, a large quantity of
sticky resinous flocks. Helenin distilled with caustic lime, yields a yellow
oil having an odour of acetone (Gerhardt).
Helenin is insoluble in water (Nesenbeck; Gerhardt). It is nearly
insoluble in cold, and very slightly soluble in boiling water (Krüger &
Corvinus). It absorbs hydrochloric acid gas, and dissolves in oil of vitriol and in
nitric acid (see above). It absorbs sulphurous acid, forming a liquid which
under diminished pressure gives off the gas and again becomes crys-
talline (Bineau, N. Ann. Chim. Phys. 24, 335).
Helenin dissolves in hot strong caustic potash and is precipitated
undecomposed by acids (Gerhardt). — It dissolves in strong acetic acid,
forming a colourless solution, which when evaporated or mixed with
water, deposits crystals of helenin (Gerhardt). It dissolves with diffi-
culty in cold, and easily in hot alcohol, from which it crystallises on
evaporation, and is precipitated in flocks by water (Krüger & Corvinus).
It is easily soluble in ether, oil of turpentine (John), volatile and fatty
oils, and creosote (Gerhardt; Nesenbeck).
Nitrohelenin.
GERHARDT. Ann. Chim. Phys. 72, 172.
Helenin is warmed with an excess of moderately strong nitric acid.
till the product formed is soluble in ammonia; the ammoniacal solution
is dropped into water; and the yellow precipitate is purified by dis-
solving it in alcohol and precipitating with water.
Yellow friable mass containing nitrogen and, on the average, 55.38
p. c. C., 5.98 H., besides oxygen. Gerhardt formerly proposed the
formula C30X2H1804.
Nitrohelenin is not volatile without decomposition. It is converted
into oxalic acid by an excess of nitric acid. —With melted hydrate of
potash it evolves ammonia.
Slightly soluble in water; easily soluble in nitric acid. Dissolves
very easily in aqueous ammonia with red colour, and is precipitated from
PHILYGENIN.
525
the solution as a rust-brown powder by acids, also by salts of lead and
silver. Dissolves easily in alcohol.
Chlorhelenin.
? C42C14H2406 C42C14H2404,02.
=
GERHARDT. Ann. Chim. Phys. 72, 175. — N. Ann. Chim. Phys. 12,
189.
Chlorhydrate de Chlorhellenine.
Formation. See p. 524.
Preparation. Dry chlorine is passed over helenin fused in a water-
bath so long as the mass continues to give off vapours of hydrochloric
acid, and the residue is boiled with alcohol. The yellow flocks depo-
sited from the yellow tincture on cooling, are washed and dried in a
vacuum at 100°.
Yellow powder, lighter than water.
Gerhardt.
mean.
a.
b.
C.
42 C
252
54.08
47.39
52.3
52.5
24 H
24
5.15
5.51
5.7
5.7
4 Cl
142
30.47
37.10
30.6
30.2
60
48
10.30
10.00
11.4
11.6
C42H24C1406
466
100.00
100.00
100.0
100.0
a, b, and c were different, preparations. Gerhardt himself considers the formula
doubtful (Traité 4, 297).
Chlorhelenin heated below its melting-point gives off a large quan-
tity of hydrochloric acid gas, leaving a chlorinated resin, which car-
bonises when more strongly heated. It burns with difficulty, with a
green-edged flame. - Produces with oil of vitriol a fine carmine-red
coloration, which disappears on addition of water. - Dissolves easily
in hot caustic potash, with formation of chloride of potassium and a
yellowish-red solution, from which hydrochloric acid throws down red
chlorinated flocks. Chlorhelenin passed over red-hot quick-lime yields.
naphthalin, leaving a large quantity of carbon.
Chlorhelenin is insoluble in water. It dissolves slightly in cold, and
more easily in hot alcohol, forming a yellow solution from which it is
precipitated in light flocks by water. It dissolves very easily in
ether.
Oxygen-nucleus C42H22O19.
Philygenin.
C42H24012 = C42H22O10,H²O².
BERTAGNINI. Ann. Pharm. 92, 109.
BERTAGNINI & LUCA. Compt. rend. 51, 368.
526 PRIMARY NUCLEUS C42H32; OXYGEN-NUCLEUS C42H22O10.
Formed, together with grape-sugar, by boiling philyrin with dilute
hydrochloric acid, and deposited from the liquid in resinous drops.
White pearly crystalline mass, fusible without decomposition or loss
of weight.
Bertagnini.
& Luca.
Crystals.
42 C ....
24 H
252
67.74
Bertagnini.
67.71
67.67
24
6.45
12 O
96
25.81
6.67
25.62
6.46
25.87
C42H24012
372
100.00
100.00
100.00
...
....
Polymeric with saligenin (xii. 233).
Philygenin is violently attacked by nitric acid, and is coloured
amaranth-red by oil of vitriol. It is not acted upon by dilute acids or
by an alkaline solution of cupric oxide. With chlorine, bromine, and
nitric acid, it forms the following products:-
Bibromophilygenin CBr HO¹;
Nitrophilygenin
-
Bichlorophilygenin C2C12H22O12;
C42XH23012; Binitrophilygenin C42X2H22O12;
Bromonitrophilygenin C+BrXH22O12; Chloronitrophilygenin CCLXH 20¹².
Philygenin is nearly insoluble in cold, and but slightly soluble in
boiling water. It dissolves in potash and ammonia; less freely than
philyrin in alcohol; easily in ether, from which it crystallises.
Glucoside of Philygenin.
Philyrin.
C54H34022 - C42H24012, C¹¹²H¹0010.
CAREONCINI. Gaz. eclettica di chimica. November 1836. Repert. 58,
323; Ann. Pharm. 24, 242; Berz. Jahresber. 17, 306.
C. BERTAGNINI. Ann. Pharm. 92, 109; Pharm. Centr. 1855, 124; Pharm.
Viertelj. 4, 436; N. Phil. Mag. 9, 78; N. Ann. Chim. Phys. 43,
351.
BERTAGNINI & LUCA. Compt. rend. 51, 368; abstr. Ch. Pharm. Zeitschr.
3, 779; Chem. Centr. 1861, 29.
Phillyrin, more properly philyrin, from píλvpa (Wittstein, Pharm. Viertelj. 4,
436).
Source. In the stone-linden tree, Philyrea latifolia and media, most
abundant in the bark, in smaller quantity in the leaves.
Preparation. A decoction of the coarsely powdered bark is evapo-
rated down to four times the weight of the bark employed; it is then
clarified by means of albumin, and, after cooling, mixed with milk of
lime to slightly alkaline reaction, and left at rest for 20 or 30 days.
The deposit formed is collected, dried, powdered, and exhausted with
boiling alcohol of 55°; and the tincture thus obtained is digested with
animal charcoal, filtered, freed from alcohol by distillation, mixed with
water, and set aside to crystallise (Carboncini). Bertagnini treats the
PHILYRIN.
527
decoction of the bark with oxide of lead or lime, and evaporates the
filtrate, from which the philyrin crystallises.
J
The crystals lose their water (see below) over oil of vitriol, or when
warmed, and the anhydrous philyrin afterwards melts at 160° to a
colourless liquid, which solidifies to a fissured mass on cooling.-
Inodorous; very slightly bitter (Bertagnini). According to Carboncini
it is tasteless in itself at first, but afterwards, or when dissolved, very
bitter and acrid.
Bertagnini & de Luca.
Anhydrous.
mean.
54 C...........
34 H
324
60.67
60.53
34
6.37
6.37
22 O
176
32.96
33.10
C54H34022
534
100.00
100.00
Decompositions. 1. Fused philyrin, heated to 200°, assumes a faint
red colour, afterwards turning darker; at 250° it evolves empyreumatic
vapours and combustible gas, and at 280° leaves charcoal. 2. It
dissolves in oil of vitriol with reddish-violet colour, undergoing decom-
position. —3. When boiled with dilute hydrochloric acid, it is broken up
into philygenin and grape-sugar :
C5+H3+022 + 2HO = CH²012 + C¹²H¹2012.
This decomposition is not effected by emulsin or by wine-yeast, but
when submitted to the lactic fermentation, philyrin likewise yields
philygenin and the decomposition-products of sugar.-4. Bromine,
chlorine, and nitric acid form derivatives corresponding to those of
philygenin (p. 526). Bromophilyrin and chlorophilyrin crystallise in
needles, and are resolved by dilute acids into bromophilygenin or
chlorophilygenin and sugar. Dilute nitric acid forms yellow silky
crystals; stronger acid produces crystalline granules; the boiling con-
centrated acid forms oxalic acid and shining laminæ, with evolution of
carbonic and nitrous acids.-5. Philyrin is not acted on by an alkaline
solution of cupric oxide (Bertagnini).
-
Combinations. Hydrated Philyrin. - Philyrin crystallises from its
solutions in white, very light, silvery scales, containing varying pro-
portions of water of crystallisation, which it gives up over oil of
vitriol, or when heated to 50° or 60° (Bertagnini & de Luca). Bertag-
nini formerly stated the proportion of water at 47 p. c. (3 at. =
4.8 p. c.).
Bertagnini.
54 C......
37 H
25 O
Crystals.
324
mean.
57.75
57:77
37
6.60
6.73
200
35.65
35.50
C54H34022 + 3aq.
561
100.00
100.00
Philyrin dissolves in 1,300 parts of water at 9°, and freely in boiling
water (Bertagnini & de Luca). It is insoluble in cold dilute acids, but
soluble in warm acetic acid, from which it crystallises unchanged on
cooling (Carboncini). It is not acted on by aqueous ammonia or by-
alkalis, and is not precipitated by metallic salts (Bertagnini).
It dissolves in 40 parts of alcohol at 9°, and more easily in the
528
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS CH2013.
hot liquid; insoluble in ether (Bertagnini), and in volatile and fat oils
(Carboncini).
Primary Nucleus C42H34; Oxygen-nucleus C2H22O12.
Columbin.
C42H22O14 C42H22O12,0².
WITTSTOCK. Pogg. 19, 298; Berz. Jahresber. 11, 288.
BUCHNER. Repert. 37, 418.
LEBOURDAIS. N. Ann. Chim. Phys. 24, 63; Ann. Pharm. 67, 251; J. pr.
Chem. 45, 363.
BÖDEKER. Ann. Pharm. 69, 47; abstr. Pharm. Centr. 1849,
Gaz. 1849, 149; Kopp's Jahresber. 1849, 477.
145;
Chem.
The bitter constituent of columbo-root from Menispermum palmatum.
Discovered by Wittstock, Planche (Bull. Pharm. 3, 289) having pre-
viously described a bitter extract under the name of columbo bitter.
It occurs in crystals in the cells of the root (Bödeker).
Preparation. The root is exhausted with alcohol of 75 p. c.; the
alcohol is distilled off; and the residue evaporated to dryness over a
water-bath. The dry residue is again taken up by water, and the
thick turbid solution thereby formed is shaken with ether so long as
that liquid takes up columbin. The ethereal layer, when decanted and
freed from most of the ether by distillation, deposits the greater part
of the columbin in crystals as it cools; the remainder crystallises from
the oily mother-liquor on standing. The crystals are purified by
washing them with cold ether, pressing, and recrystallising from boil-
ing absolute ether, till the whole of the fat is removed, which is known
by the complete solubility of the columbin in boiling acetic acid
(Bödeker). Wittstock either exhausts the root with ether, leaves the
solution to evaporate in the air, and purifies the crystals by dissolving
them in acetic acid; or he evaporates to one-third an extract of the
root with alcohol of sp. gr. 0.835, whereupon the columbin crystallises,
but in a less pure state. 16 ounces of the root yield 1 dram of
columbin (Wittstock).
Lebourdais exhausts the powdered root with cold water, and allows-
the infusion to percolate through purified animal charcoal, which takes
up columbin and colouring matter. The charcoal, after washing with
cold water and drying, is exhausted with hot alcohol, which takes
up the columbin and leaves it in coloured crystals on evaporation.
Prolonged washing of the charcoal with water removes most of the
bitter, the rest remaining in the charcoal together with nearly the
whole of the colouring matter. When the aqueous solution is strained
through fresh charcoal, it again gives up the whole of the columbin,
which may be extracted from the charcoal, after drying, by hot alcohol,
and obtained in a pure state by evaporating the solution.
Properties. White or translucent prisms, and slender needles, belong-
ing to the right prismatic system. The crystals are similar to fig. 55,
but with the addition of the face m of fig. 53. Between m and u there
are faces of a second prism, too narrow to be measured. Angle u: u
COLUMBIC ACÍD.
529
- 125° 30'; u: i = 152° 45′ ; u : m = 117° 15'; i: i' = 167° 19';
i : l = 123° 391' ; i : u = 119° 31'. The faces of the crystals are smooth
and shining. There seems to be no cleavage-plane (G. Rose, Pogg. 19,
441). Inodorous. Tastes very bitter.
Neutral. Melts like wax
when warmed (Wittstock).
at. 115°
42 C......
252
65.28
22 H
22
14 O
112
5.69
29.03
C42H22014
386 100.00
....
Liebig.
(Pogg. 21, 30).
65.45
6.17
28.38
100.00
Bödeker.
mean.
65.20
5.98
28.82
100.00
Decompositions. Columbin decomposes when heated, and burns with
a smoky flame. Oil of vitriol colours it orange, afterwards dark-red ;
water throws down from the solution a rust-coloured precipitate.
Columbin is dissolved by nitric acid of sp. gr. 1·25 only when warmed,
with evolution of red vapours, and is partially precipitated from the
solution by water (Wittstock). — By fusion with caustic potash it yields
a compound from which acids throw down brown flocks. — It is not
decomposed by emulsin (Bödeker).
Columbin dissolves in aqueous alkalis, and is precipitable from the
solution by acids. It is not precipitated from its solution in alcohol
or acetic acid by neutral acetate of lead, nitrate of silver, or other
metallic salts (Wittstock).
It
Columbin dissolves in acetic acid of sp. gr. 1.04 as easily as in
boiling alcohol, and crystallises from the solution in regular forms.
dissolves in 30 or 40 parts of boiling alcohol of sp. gr. 0.835, and very
slightly in cold alcohol and ether, though the solutions taste very bitter.
It is soluble to a slight extent in volatile oils. —It is not precipitated
from the solution in alcohol or acetic acid by tincture of galls
(Wittstock).
Appendix to Columbin.
Columbic Acid.
BÖDEKER. Ann. Pharm. 69, 47.
Occurs, together with berberine (p. 185) and columbin, in columbo root.
The alcoholic extract of the root is dried and exhausted with hot
lime-water, and the filtrate is mixed with hydrochloric acid, not in
excess, whereby a yellow amorphous precipitate is produced. Or the
turbid aqueous solution of the alcoholic extract is mixed with a little
hydrochloric acid, and the amorphous precipitate thereby thrown down
is removed by filtration, before it becomes mixed with berberine-salt.
The precipitate is freed from admixed berberine by washing with water,
and from columbin by boiling with ether, which dissolves also a little
columbic acid, and the remainder is dissolved in caustic potash and
treated with a current of carbonic acid, which throws down a small
quantity of brown flocks. The filtrate, supersaturated with hydro-
chloric acid, deposits the columbic acid in white flocks which condense
to a pale straw-yellow powder when washed with water.
VOL. XVII.
2 M
530 PRIMARY NUCLEUS C42H36; OXYGEN-NUCLEUS C4H1018.
Amorphous powder, remaining in the form of a varnish on evapo-
rating its solutions. Reddens litmus strongly. Less bitter than
columbin.
The acid dried at 40° loses 2.52 p. c. of water at 100°, and as much
more at 115°, corresponding altogether to 2 atoms (calc. 4.53 p. c.
HO).
at 115°
Bödeker.
42 C.......
23 H
252
23
66.49
66.64
6.07
6.29
13 O.........
104
27.44
27.07
...
C42H22O12 + aq.?
379
100.00
100.00
****
Bödeker supposes the acid still to contain water.
Columbic acid burns with flame on platinum foil. — It is not decom-
posed by cold nitric acid. It dissolves in warm oil of vitriol, and is
precipitated from the solution by water.
The acid is nearly insoluble in water, but dissolves in dilute caustic
potash with pale brownish-yellow colour. Alcoholic neutral acetate of
lead throws down from the alcoholic solution a yellow lead-salt, which
contains 30.19 p. c. of oxide of lead at 100°, but loses 4·29 p. c. of
water more at 130°.
Columbic acid dissolves in alcohol with pale-yellow colour, very
slightly in cold ether, and more freely in acetic acid.
36
Primary Nucleus C42H6; Oxygen-nucleus C¹²H¹80¹8.
Euxanthic Acid.
C42H18022C42H18018, 04.
J. STENHOUSE (1844). Phil. Mag. 25, 322; Ann. Pharm. 51, 423.
0. L. ERDMANN. J. pr. Chem. 33, 190; 37, 386; abstr. N. J. Pharm.
10, 154. — J. pr. Chem. 71, 195.
LAURENT. Compt. chim. 1849, 377; abstr. Compt. rend. 26, 33; Kopp's
Jahresber. 1849, 456.
Purreesäure. Purreic acid. Acide euxanthique ou purreïque.
Discovered simultaneously by Stenhouse and by Erdmann, and
nore fully examined by the latter chemist.
Source. In purree (Indian yellow, Camel's urine), a colouring matter
of doubtful origin, imported from India and China, in which it occurs
as magnesia-salt, amounting to about 50 per cent. of the purree
(Stenhouse). On the origin of purree, see Guibourt (Rev. scient. 14, 18, and 23),
Batka (J. pr. Chem. 33, 248), and Stenhouse and Erdmann (loc. cit.). It occurs
in commerce in two varieties, crude purree and Jaune Indien purifié,
the latter of which appears to be obtained by boiling the crude
purree with water, and mixing the residue with carbonate of magnesia
(Erdmann).
Preparation. Purree is boiled with water so long as it gives up
EUXANTHIC ACID.
531
colouring matter, and the residue is decomposed by heating it with
dilute hydrochloric acid, whereby a clear solution is obtained, which
deposits euxanthic acid on cooling. The aqueous decoction contains chloride
of potassium and a black pitchy substance having an excrementitious odour (on
one occasion this last body was replaced by benzoate of potash), together with small
quantities of euxanthate of magnesia. The mother-liquor, filtered from the
acid which is deposited, yields, when evaporated, a little euxanthic
acid, but contaminated with euxanthone. The acid is washed with
cold water and recrystallised from alcohol, to remove magnesia and
adhering organic substances, and is then converted into pure crystal-
lised ammonia-salt, the boiling solution of which is decomposed by
hydrochloric acid, whereupon the euxanthic acid is deposited on
cooling, and must be recrystallised from alcohol (Erdmann). Sten-
house boils purree, cut in small pieces, with water containing a large
quantity of acetic acid; filters from dark brown flocks and other
impurities; adds to the filtrate neutral acetate of lead so long as a
brownish-yellow bulky precipitate is thrown down; washes the preci-
pitate with cold water; and decomposes it with hydrosulphuric acid;
then boils the mass with alcohol, and filters from sulphide of lead. On
cooling the alcoholic solution, euxanthic acid crystallises, but as it
still contains a large quantity of magnesia, it is dissolved in a hot
solution of carbonate of soda; the solution is filtered; the filtrate is
decomposed by hydrochloric acid; the euxanthic acid thereby thrown
down is washed with cold water, pressed, dissolved in hot water,
and again precipitated with neutral acetate of lead; and the precipitate
decomposed by hydrosulphuric acid, and boiled out with alcohol. The
acid which crystallises from the alcoholic solution is, lastly, purified
by recrystallising it five or six times from alcohol.
Euxanthic acid thus obtained contains 2 atoms of water, which
may be expelled by heating to 130°.
Properties. See Hydrated Euxanthic acid (p. 532).
Stenhouse.
mean at 130°.
Erdmann.
Laurent
42 C
18 H
252
56.50
55'08
mean at 130°.
56.35
56.37
18
22 O........
176
4.04
39.46
4.43
4.03
4.07
...
40.49
39.62
39.56
C42H18022
446
100.00
100.00
100.00
100.00
Erdmann proposed the formula C40H16021; Stenhouse, C20H9011; Gerhardt,
(N. J. Pharm. 10, 157) the one above given, which was confirmed by Lau-
rent's experiments (Compt. Chim. 1849, 377), and was afterwards adopted by
Erdmann himself (J. pr. Chem. 71, 195). The formation of hamathionic acid,
together with euxanthone, by the action of oil of vitriol on euxanthic acid, and like-
wise the formation of terchloreuxanthone, CC13H9O12, on dissolving bichloreuxanthic
acid in oil of vitriol, throw doubt, if not upon the empirical correctness of this
formula, at least upon the relation between euxanthone (p. 181) and euxanthic acid
which it seems to express (Kr.).
Decompositions. 1. Euxanthic acid burns with bright flame on plati-
num foil (Erdmann).-2. It melts when heated to 160° or 180°,
evolving carbonic acid and water, and is converted into euxanthone,
which sublimes at a stronger heat (Erdmann; Stenhouse). In this
reaction no other product than carbonic acid and water is evolved :
C42H180 = C4012012 + 2002+ 6HO (Laurent).
2 M 2
532
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS C42HiŌis.
In a sublimation apparatus the acid partially carbonises, and yields an
abundant sublimate of euxanthone (Stenhouse).—3. It dissolves freely
in oil of vitriol, becoming hot, and forming a yellow or reddish-yellow
solution, without evolution of gas; after some time the solution solidi-
fies to a pulpy mass of euxanthone, whilst hamathionic acid remains in
solution (Erdmann). The filtrate reduces alkaline solutions of cupric
oxide (W. Schmid, Ann. Pharm. 93, 88).
On diluting the solution in sulphuric acid with water, separating the precipitated
euxanthone, and saturating the filtrate with carbonate of baryta, a yellow liquid con-
taining baryta is obtained, which when evaporated deposits brown flocks and turns
acid. When evaporated in a vacuum, it leaves Erdmann's hamathionate of baryta in
the form of a brown gum containing 3143 p. c. of baryta, from a solution of which
basic acetate of lead throws down a yellow amorphous lead-salt containing 13.89
p. c. C., 1·16 H., 15·75 O., 6·82 SO³, and 62:38 PbO. The aqueous hamathionic
acid, separated from the lead-salt by hydrosulphuric acid, forms a very acid syrup
(Erdmann).
4. Euxanthic acid is converted by bromine into bromeuxanthic acid,
and by aqueous chlorine into chloreuxanthic acid. Excess of chlorine
converts it into a yellow powder, the brown solution of which in
caustic ammonia or its carbonate, does not yield crystals (Erdmann).—
5. Alcoholic euxanthic acid is converted into euxanthone on passing
hydrochloric acid gas into it (Erdmann).
6. Cold nitric acid of sp. gr. 1.31 converts euxanthic acid, on stand-
ing for 24 hours, into nitroeuxanthic acid without dissolving it.
Traces of oxalic acid are also formed. When euxanthic acid is heated
with nitric acid, a violent evolution of gas takes place, and a dark red-
dish-yellow solution is formed, which deposits coccinonic acid on
cooling, and contains also oxalic acid. By prolonged boiling, styphnic
acid is produced, but ultimately the liquid contains only oxalic acid
Erdmann). See xi, 230. Purree heated with pure nitric acid yields stychnic acid,
and with nitric acid containing hydrochloric acid a large quantity of oxalic acid
(E. Kopp, Compt. chim. 1849, 153),
Erdmann's coccinonic acid forms yellow crystalline granules, containing 38.6 to
44.5 p. c. C., and 109 to 2:07 H.; its scarlet potash-salt contains 19-42 p. c. of
potash. Probably a mixture of various nitro-acids.
7. Euxanthic acid is decomposed by boiling with oxide of manganese
and sulphuric acid, with formation of formic acid (Stenhouse).-8. It
dissolves in melted hydrate of potash, with scarlet colour, and is pre-
cipitated by acids in the form of a resin (Stenhouse).-9. The acid
does not reduce alkaline solutions of cupric oxide (W. Schmid, Ann.
Pharm. 93, 88).
Combinations.
With Water. — A. Hydrated Euxanthic acid.
a. With 2 at. Water. Crystallises from alcohol in pale straw-
yellow, shining needles, which give off 4.35 p. c. of water at 130°
(Erdmann). Tastes sweetish at first, and afterwards slightly bitter.
Erdmann.
Crystals.
C42H18022
2 HO
446
18
96.13
3.87
4.35
C42H18022 + 2aq.
461
100.00
EUXANTHIC ACID.
533
b. With 6 at. Water.
The euxanthic acid precipitated from the
ammonia-salt by hydrochloric acid loses 10.98 p. c. of water on
drying (Erdmann).
C42H18022
6 HO
Erdmann.
446
54
89.2
D
10.8
10.98
100.0
C42H18022 + 6aq. 500
B. Aqueous solution. Euxanthic acid is nearly insoluble in cold
water and rather more soluble [easily soluble (Stenhouse)] in boiling
water (Erdmann).
C. With Salifiable Bases. Euxanthic acid forms with bases salts
represented by the formula C42HMO22: they frequently contain
water of crystallisation, even after drying at 100°. Laurent's formulæ
(Compt chim. 1849, 377) here adopted differ from those of Gerhardt (Traité, 3, 768),
in which the potash and ammonia-salts dried at 100° are supposed to be anhydrous.
The acid dissolves easily in caustic alkalis and their carbonates,
eliminating carbonic acid from the latter. The euxanthates of the
fixed alkalis and of ammonia dissolve very easily in pure water,
but are nearly insoluble in strong solutions of alkaline carbonates
(Erdmann). The aqueous acid does not precipitate salts of lime,
baryta, strontia, magnesia, or silver (Stenhouse). The soluble salts
of euxanthic acid form with most metallic salts yellow precipitates
which are soluble in pure water but insoluble in the liquids in which
they are formed. They precipitate chloride of barium and calcium
yellowish white and gelatinous; the sulphates of manganese, nickel, and
zinc, lemon-yellow; and throw down from ferrous sulphate a white
precipitate quickly turning greenish brown, almost black, and from
ferric sulphate a black-green precipitate. They precipitate corrosive
sublimate yellowish, after some time only, and nitrate of silver
yellowish and gelatinous, the latter precipitate turning brown on
exposure to light, and dissolving when washed with cold water
(Erdmann). The salts of euxanthic acid are decomposed by mineral
acids, and less completely by acetic acid, with separation of crystalline
euxanthic acid. The solution of euxanthate of potash, mixed with
a large excess of potash and heated to boiling, yields, on addition of
hydrochloric acid, an amorphous semi-fluid precipitate, which partly
floats on the liquid in oily drops, and is gradually transformed into
crystalline euxanthic acid. When heated in an open vessel, the salts
give off yellow vapours of euxanthone (Erdmann).
Euxanthate of Ammonia. Crude euxanthic acid is treated with
excess of strong aqueous carbonate of ammonia at a gentle heat,
whereupon the acid dissolves, with evolution of carbonic acid. The
solution on slightly cooling deposits an abundance of the crystalline
ammonia-salt, which is nearly insoluble in excess of carbonate of
ammonia; it must be collected, washed with aqueous carbonate of
ammonia, pressed, and dried over oil of vitrol. Small, flat, yellow
shining needles. At 120° it loses weight slowly and continuously
(Erdmann).
534
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS C42H18018.
Erdmann.
Over oil of vitriol.
mean.
42 C
N
23 H
240
252
52.39
52.3
***
14
2.91
23
4.78
4.7
192
39.92
CH17021,NH¹O+2aq..... 481
100.00
Euxanthate of Potash. Obtained by dissolving euxanthic acid,
with the aid of a gentle heat, in aqueous bicarbonate of potash,
washing the pale crystalline scales deposited on cooling with aqueous
carbonate of ammonia, to remove adhering carbonate of potash,
pressing, and drying over oil of vitrol (Erdmann).
Erdmann.
42 C .....
19 H
at 120°.
252
50.22
49.81
19
3.78
3.72
23 O
184
36.61
36.84
ко
47.2
9.39
9.63
C42KH¹7022 + 2aq.
502.2
100.00
100.00
1.44
BALENCIA
Euxanthate of Magnesia. Forms the principal constituent of purree.
The aqueous acid and its ammonia-salt do not precipitate magnesia-
salts, but a solution of sulphate of magnesia mixed with sal-ammoniac
and ammonia produces in moderately dilute aqueous euxanthate of
ammonia, a pale yellow slimy turbidity, and after a few minutes the
mixture solidifies to a reddish-yellow transparent jelly, which after-
wards becomes crystalline. Shining yellow crystalline powder, losing
13.95 p. c. of water at 130° (8 at. = 12.9; 10 at. 15.6 p. c.).·
the crystalline state it is nearly insoluble in boiling water (Erdmann).
Erdmann.
In
42 C.......
18 H
22 O
2 MgO
at 130°.
252
51.85
51.83
18
3.70
3.49
176
36.21
35.80
40
8.24
8.88
100.00
100.00
CHMgO,MgO,HO 4.86
....
Erdmann found 9.2 and 9.57 p. c. MgO in another preparation.
Euxanthate of Lead. a. Basic. Obtained by precipitating
alcoholic euxanthic acid with an alcoholic solution of neutral (or
basic) acetate of lead, washing the orange-yellow, somewhat gelatin-
ous precipitate repeatedly with boiling alcohol, and drying it at 100°.
The salt melts when strongly heated, and yields a sublimate of
euxanthone (Stenhouse).
Stenhouse.
at 100º.
42 C'......
18 H
252
37.61
35.99
18
2.69
3:01
22 O.....
176
26.26
26.84
2 PbO
224
33.44
34.16
C42H¹7PbO22, PьO,но
670
100.00
100.00
...
b. Neutral. Obtained in yellow spongy flocks by precipitating
euxanthate of ammonia with nitrate of lead at the boiling heat
(Erdmann).
BROMEUXANTHIC ACID.
535
Erdmann.
at 120°.
42 C
252
45.90
44.78
17 H
17
3.09
3.07
21 O
168
30.60
31.43
РЬО
112
20.41
20.72
....
C'42H¹7PbO22
549
100.00
100.00
....
Euxanthate of Copper. Sulphate of copper throws down from
aqueous euxanthate of ammonia, at medium temperatures, a yellow
gelatinous precipitate, which converts stronger solutions into a pasty
mass, and settles in a pulverulent form when the liquid is heated.
After drying it is brown and triturable to a yellow powder. — In the
moist state it dissolves freely in pure water, but not in presence of
cupric sulphate (Erdmann).
Euxanthic acid dissolves very freely in boiling alcohol and ether. It
is precipitated from its alcoholic solution in the crystalline form by
water (Stenhouse).
Oxy-bromine-nucleus C42Br2H16018.
Bromeuxanthic Acid.
C42Br²H¹6022 = C42Br2H16018,04.
ERDMANN. J. pr. Chem. 37, 394.
Acide euxanthique bibromé (Laurent).
Formation and Preparation. Euxanthic acid suspended in water is
agitated with excess of bromine, and the yellow pulverulent product is
collected on a filter, washed with water and cold alcohol, and dissolved
in boiling alcohol. On cooling the solution, the greater part is de-
posited, but a portion remains in solution, and is obtained as an amor-
phous acid on evaporation.
Properties. Yellow crystalline powder, giving off 3.1 to 4 p. c. of
water at 130°. On evaporating the alcoholic solution, and sometimes
also on precipitating the salts with hydrochloric acid, amorphous
microscopic globules are obtained, which likewise occur mixed with
the needles of the crystallised acid.
Erdmann.
Crystallised. Amorphous.
(mean.)
at 130°.
42 C
2 Br
252
41.72
40.56
40.82
160
26.49
28.29
27.48
16 H.....
16
2.65
2.57
2.66
22 O .....
176
29.14
28.58
29.04
C42Br2H16022
604
100.00
100.00
100.00
Bromeuxanthic acid forms with oil of vitriol a solution from which
water throws down bromeuxanthone in the form of a yellow powder.
With bases it forms salts, which are for the most part gelatinous.
536
OXY-CHLORINE-NUCLEUS C42CPH1601.
The ammonia-salt is formed by dissolving the acid in aqueous ammonia.
From this solution hydrochloric acid generally throws down the acid in
the crystalline form; but on one occasion Erdmann obtained a precipi-
tate which deliquesced to a viscid syrup at 50°, and dried up to glassy
amorphous particles, only slowly soluble in ammonia, and afterwards
yielding the amorphous acid by precipitation with hydrochloric acid.
The solution of bromeuxanthate of ammonia immediately yields with
carbonate of ammonia, a gelatinous precipitate, in which needles form
after some time, till the entire precipitate becomes distinctly crystal-
line. The crystals, collected on a filter, dried over oil of vitriol, and
dissolved in water, exhibit the following reactions. Bicarbonate of
potash produces a yellow curdy precipitate, made up of tough threads;
carbonate of soda immediately forms a stiff jelly, which dissolves when
heated, and re-appears in the non-crystalline state on cooling; chloride
of barium produces a yellow jelly in which microscopic globules are
formed after some weeks; chloride of magnesium mixed with sal-am-
moniac and ammonia forms a yellow jelly; acetate of lead an orange-
yellow, and sulphate of copper a yellow jelly.
Amorphous bromeuxanthic acid dissolves in alcohol much more
freely than the crystalline variety.
Oxy-chlorine-nucleus C2C12H16018.
Chloreuxanthic Acid.
C¹¹²Cl²H¹60²² = C¹²Cl²H¹6019,04.
ERDMANN. J. pr. Chem. 37, 392.
Acide euxanthique bichloré.
Euxanthic acid is suspended in water, and chlorine is passed
through the liquid, till the acid no longer appears crystalline, and
becomes flocculent. When the current of chlorine is continued too long,
another product is formed (p. 532). When the flocks are collected on a
filter and crystallised repeatedly from alcohol, unchanged euxanthic
acid remains in the mother-liquors.
Golden-yellow, shining crystalline scales, which give off their water
of crystallisation at 130°.
42 C.......
at 130°.
Erdmann.
252
48.93
48.64
2 Cl
71
13.79
14.41
16 H
16
3.11
3:08
22 O......
176
34.17
33.87
C42C12H16022
515
100'00
100.00
Erdmann's earlier formula was C40C12H14021. The above formula was proposed
by Gerhardt (N. J. Pharm. 10, 158).
Decompositions.
Chloreuxanthic acid forms with oil of vitriol a
solution from which water throws down chloreuxanthone (p. 184) in
the form of a yellow powder. The supernatant liquid is free from hydro-
NITROEUXANTHIC ACID.
537
chloric acid, but holds in solution, besides sulphuric acid, an acid con-
taining chlorine and sulphur, and forming a soluble salt with baryta.
Combinations. Chloreuxanthic acid is insoluble in water.
It forms with bases the chloreuxanthates, which are gelatinous preci-
pitates, or are thrown down as such when their aqueous solutions are
mixed with excess of alkaline carbonates. The yellow solution of the
acid in caustic ammonia is converted by caustic ammonia, the fixed
alkalis, and their carbonates, into a transparent jelly, which afterwards
becomes crystalline when carbonate of ammonia or potash has been
employed. The ammoniacal solution yields orange-yellow gela-
tinous precipitates with chloride of barium, acetate of lead, nitrate of
nickel, and sulphate of copper; yellow gelatinous precipitates with
sulphate of zinc and nitrate of silver; a brown jelly with ferric sulphate.
None of these precipitates afterwards become crystalline. They
dissolve in a large quantity of water, and cannot, therefore, be
washed.
Chloreuxanthic acid dissolves with difficulty in cold, freely in
boiling alcohol.
Oxy-nitro-nucleus C42XH17018.
Nitroeuxanthic Acid,
C42NH17026 C42XH17018,04.
ERDMANN. J. pr. Chem. 37, 400.
Acide euxanthique nitré.
=
Dry euxanthic acid dropped into cold nitric acid of sp. gr. 1.31
becomes converted in 24 hours into a pale-yellow granulo-crystalline
deposit, surmounted by a yellowish-red liquid. The deposit is collected
and dissolved in boiling alcohol, from which the greater part of the
acid separates on cooling.
Microscopic, foliated crystals, of a pale straw-yellow colour.
at 120°.
Erdmann.
42 C........
252
51.32
50.75
N......
14
2.85
3.23
•
17 H
17
3.46
3.36
26 O......
208
42.37
42.66
CXH170 … 491
100.00
100'00
Nitro-euxanthic acid, when heated with nitric acid, is converted
into coccinonic acid, with simultaneous formation of oxalic acid
(p. 532). It dissolves very slightly in water.
The acid
The salts of nitroeuxanthic acid explode when heated.
dissolves in aqueous carbonate of ammonia and carbonate of potash with
yellow colour: strong solutions solidify, on cooling, to a clear jelly,
which gradually contracts and afterwards becomes crystalline. The
jelly produced by caustic ammonia is transparent and quite amorphous.
The neutral ammonia-salt forms with the chlorides of barium aud
538
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS C42H4016.
calcium, yellow precipitates, soluble in a large quantity of water; with
acetate of lead, lemon-yellow; with ferrous sulphate, reddish-brown;
with ferric sulphate, pale-brown; with nitrate of nickel and sulphate of
copper, yellow; with nitrate of silver, orange-yellow. All these pre-
cipitates are gelatinous.
Nitroeuxanthate of Lead. The precipitate thrown down by acetate
of lead from the ammonia-salt of nitroeuxanthic acid is washed with
boiling water. It forms when dried a reddish-yellow glassy mass,
having a conchoïdal fracture.
42 C
N
17 H
26 O
2 РЬО
at 120°.
Erdmann.
252
35.24
34.84
15
14
1.95
17
2.37
2:08
208
29.09
224
31.35
32.13
100.00
C42XH¹6PbO22,PbO,HO. 715
Nitroeuxanthic acid dissolves very slightly in alcohol, even at the
boiling heat.
Primary Nucleus C42H40; Oxygen-nucleus C42H24016.
Beta-erythrin.
C42H24020 C42H24016,04.
(Appendix to xiii, 150.).
MENSCHUTKIN. Par. Soc. Bull. 1864, 424; Zeitschr. f. Chem. 8, 112.
LAMPARTER. Ann. Pharm. 134, 243.
Occurs in a dwarf variety of Roccella fuciformis, the ordinary varieties of which
contain erythric acid (xii, 381).
Preparation. The lichen is digested in thin milk of lime for an
hour at the ordinary temperature, the liquid is filtered, and the residue
is pressed and again treated with milk of lime. The solutions are
precipitated with dilute sulphuric acid, and the precipitate (which is
heavier and less gelatinous than when thrown down by hydrochloric or
carbonic acid, owing to admixed sulphate of lime) is washed, pressed,
and exhausted with alcohol, from which beta-erythrin crystallises on
careful evaporation (Lamparter). The alcoholic solution must not be
heated above 40° or 50° (Menschutkin).
Air-dried beta-erythrin loses water of crystallisation at 100°.
Properties. White crystalline powder, or indistinctly crystalline
globules. Scarcely reddens litmus. When dry it is permanent in the
air. Melts at 115° to 116°, evolving carbonic acid copiously (Lam-
parter). Ordinary erythrin melts at 137°, and evolves carbonic acid
only at temperatures above 200°.
BETA-PICROERYTHRIN.
539
Menschutkin.
Lamparter.
at 100°.
mean.
mean.
42 C
252
57.8
57.21
57.02
24 H
24.
5.5
5.71
5.72
20 O
160
36.7
37.08
37.26
C42H24020
436
100.0
100'00
100.00
1.
Lamparter supposes beta-erythrin dried at 100° still to contain 1 at. water.
Homologous with erythric acid (xii, 381) ?
Decompositions. 1. By fusion (see above).
1. By fusion (see above).
Beta-erythrin melts on
platinum foil, and burns with bright flame when more strongly heated.
2. Moist and impure beta-erythrin turns red in the air. 3. When
boiled with water it is resolved into orsellinic acid and beta-picro-
erythrin :
C42H24020 = C16H808 + C26H16012.
By boiling with strong alcohol, orsellinate of ethyl (xii, 373) is obtained
instead of orsellinic acid. 4. Solutions of beta-erythrin in aqueous.
alkalis leave on evaporation, amorphous products and carbonates, the
beta-picroerythrin first formed being, doubtless, resolved into carbonic
acid, erythroglucin, and beta-orcin. 5. Beta-erythrin acquires a
transient deep-red colour by contact with solution of chloride of lime.
It reduces nitrate of silver.
Combinations.
With Water. Crystallised beta-erythrin loses 4.60
p. c. (Lamparter), 4.51 p. c. of water at 100° (Menschutkin) (2 at. =
3.96 p. c. HO.).
It is nearly insoluble in water, but easily soluble in aqueous alkalis
and alkaline earths.
Basic acetate of lead throws down from the (ammoniacal?) solution
a white jelly which cannot be obtained pure, even by prolonged wash-
ing (Menschutkin).
Menschutkin.
42 C ........
252
29.72
27.54
20 H......
20
2.35
2.62
4 Pb
416
49.05
49.40
20 O ......
160
18.88
20.44
C42H20Pb4020
848
100.00
100.00
Beta-erythrin dissolves easily in alcohol and ether.
Appendix to xiii, 150.
Beta-picroerythrin.
C26H16012.
A solution of beta-erythrin in alcohol boiled for four or five hours,
is no longer precipitable by water; and on distilling off the alcohol
and dissolving the residue in water, orsellinate of ethyl crystallises
out, whilst beta-picroerythrin remains in solution. The latter body is
freed from traces of beta-orcin by treating it with ether, and may
540
PRIMARY NUCLEUS C42H42.
be crystallised from solution in a very small quantity of boiling
water.
Concentrically arranged needles, triturable to a very light powder.
Has a slightly acid reaction.
Dried at 100° or over oil of vitriol.
26 C ......
156
16 H
16
12 0.....
96
C26H16012
268
....
Menschutkin.
mean.
58.20
58.29
5.97
6.34
35.83
35.37
100.00
100'00
ess.
Differs from picroerythrin (xii, 380) in containing C2H2 more and 2HO
Beta-picroerythrin is resolved by boiling with a large quantity of
baryta-water into carbonic acid, erythroglucin (xii, 385), and beta-orcin
(xiii, 150). When a large excess of baryta is employed, these products are dark-
coloured, but when the baryta is not in excess they are obtained nearly colourless.
Beta-picroerythrin produces with bromine-water a yellow precipitate,
soluble in ether; it is not affected by boiling tincture of iodine.
assumes a transient red colour with chloride of lime. Nitrate of silver
throws down from ammoniacal beta-picroerythrin a reddish precipitate,
from which the metal is reduced on warming.
It
Beta-picroerythrin dissolves very easily in water, aqueous alkalis,
and baryta-water. The ammoniacal solution yields a white precipitate
with basic acetate of lead. It dissolves very easily in alcohol, very
slightly in ether (Lamparter; Menschutkin).
Primary Nucleus C42H42.
Medullic Acid.
C42H4204 = C2H42,04.
K. EYLERTS. Pharm. Viertelj. 9, 330; N. Br. Arch. 104, 129.
A fatty acid, which, according to Eylerts, occurs, together with
palmitic and oleic acid, combined with glycerin, in beef-marrow. It
is obtained by saponifying the fat, decomposing the soap, and treating
the fatty acids according to Heintz's method (xvi, 210), going down
in the first portions of the magnesian precipitates. Its melting-point
is 72.5°, and is not raised by recrystallisation.
at 50°.
Eylerts.
42 C
252
42 H
42
77.30
12.88
N
40
32
9.82
77.04
12.98
9.98
77.21
12.89
9.90
C2H2O4
326
100.00
100.00
100.00
BRYONIN.
541
Primary Nucleus C42H4; Oxygen-nucleus C2H32012.
Bryoretin.
C42H34014 = C42H32012, H2O2.
WALZ. N. Jahrb. Pharm. 9, 223.
Aqueous bryonin is resolved by boiling with dilute sulphuric acid
into sugar and a yellow resin, which is separated by digestion with
ether into a soluble portion, bryoretin, and an insoluble portion, hydro-
bryoretin. Both bodies are amorphous.
Walz.
Walz.
Bryoretin.
mean.
Hydrobryoretin.
mean.
42 C
35 H
14 O
63.16
8.77
28.07
....
....
63.23
8.80
27.97
42 C
60.43
...
59.97
37 H
8.87
....
16 O
30.70
9.36
30.67
C42H35014
100.00
100.00
+ 2HO
100.00
100.00
***
Glucoside of Bryoretin.
Bryonin.
G. F. WALZ. N. Jahrb. Pharm. 2, 65, and 217; N. Br. Arch. 96,
150; Chem. Centr. 1859, 5; Pharm. Viertelj. 7, 550. — N. Jahrb.
Pharm. 16, 8.
The bitter principle of Bryonia alba (Handbuch, viii [2], 37). - The substance
formerly described as Bryonitin is, according to Walz's later statements, a mixture
containing fat.
Vitalis, Frémy, and Chevallier (J. Chim. méd. 1, 345) described as
bryonin, a bitter, indistinctly crystalline body soluble in water, obtained
by precipitating the sap of the root of Bryonia alba with ammonia, and
evaporating the filtrate. Vauquelin (Ann. du Mus. 8, 80; Berl. Jahrb.
1807, 14) and Dulong (J. Pharm. 12, 158) described under the same
name the portion of the inspissated sap soluble in alcohol and water.
Brandes & Firnhaber (Br. Arch. 3, 356) precipitated the aqueous solu-
tion of the alcoholic extract with basic acetate of lead, evaporated the
filtrate freed from lead, and described as bryonin the portion of the
residue soluble in alcohol, but obtained no substance exhibiting cha-
racteristic reactions. They found also in bryony root a resin soluble,
and another resin insoluble in ether.
Schwerdtfeger (Jahrb. pr. Pharm. 7, 228) obtained from the fresh
root of Bryonia dioica (by exhausting it with water and alcohol, pre-
cipitating with basic acetate of lead, and decomposing the precipitate
with hydrosulphuric acid) tufts of pearly needles containing nitrogen,
and having a bitter and acrid taste. The body dissolves in water and
dilute acids, from which it is precipitated by ammonia, and is soluble
also in alcohol, but not in ether.
542 PRIMARY NUCLEUS C44H32; OXYGEN-NUCLEUS C4H2012.
Preparation. An alcoholic extract of the dried root is exhausted
with cold water; the solution is precipitated with basic acetate of lead
and filtered; and the filtrate, freed from lead by hydrosulphuric acid,
is neutralised with carbonate of soda and precipitated by tannic acid.
The precipitate thus obtained is dissolved in alcohol and decomposed by
digesting it for some hours with quick-lime suspended in alcohol;
after which the solution containing bryonin is filtered, decolorised
with animal charcoal, and evaporated. The residue is purified by
washing with ether, and by again dissolving it in alcohol, precipitating
with tannic acid, and decomposing the precipitate with quick-lime.
Colourless, very bitter mass, triturable to a white powder.
Calculation according to Walz.
96 C
576
80 H
80
38 O
304
C96HSUO38 .... 960
Walz.
60.00
59.72 to
60.11
8.33
8.28
8.51
""
31.67
32.00
31.38
وو
100.00
100.00
100.00
Bryonin is resolved by boiling with dilute acids into sugar, bryo-
retin, and hydrobryoretin. According to Walz thus:
C96H80038 + 4H0 · C42H35014+ C42H37016+ C12H12012.
100 parts of bryonin yielded 17.8 parts of grape-sugar, as calculated
from the amount of cuprous oxide thrown down. It is coloured
red-brown by oil of vitriol, whereupon water produces a white pre-
cipitate. Fuming nitric acid produces a substance insoluble in water.
Bryonin does not reduce alkaline solutions of cupric oxide.
Bryonin dissolves easily in water and in 2 or 3 parts of alcohol,
but not in ether. The aqueous solution precipitates bichloride of platinum
and tannic acid (Walz).
COMPOUNDS CONTAINING 44 ATOMS OF CARBON.
Primary Nucleus C44H32; Oxygen-nucleus C4H20012.
Brasilin or Sapan-red.
C44H20014C44H20012,02.
BOLLEY. Züricher Mitth. 1865, 2; J. pr. Chem. 93, 351; Zeitschr. f.
Chem. 8, 192.
The colouring matter of sapan-wood (from Casalpinia Sapan) and
of Brazil-wood (from Casalpinia Crista, C. brasiliensis, and other
species). Discovered by Chevreul, and erroneously regarded at p. 287,
vol. xvi, as hæmatoxylin.
Preparation. From the crystalline deposit which had formed in a
vessel filled with extract of sapan-wood. It is not obtained pure, or
HYDRASTINE.
543
only with difficulty, from Brazil-wood. The deposit is dissolved in
absolute alcohol and the filtrate is left to crystallise without exposure
to air or light.
Properties.
Amber-yellow to brownish rhombohedrons, or short
oblique rhombic prisms.
Bolley.
mean.
44 C
264
66.66
66.61
20 H
20
5.06
5:00
14 O
112
28.28
28.39
C44H20014
396
100.00
100.00
....
Differs from hæmatoxylin by containing the elements of carbolic acid more than
that body.
With nitric acid it yields picric acid.
Combinations.
Hydrated Brasilin. — A solution of brasilin in weak
spirit or aldehyde, yields small straw-yellow or golden-yellow needles,
belonging to the oblique prismatic or monoclinic system; they turn
brown and give off 6·61 p. c. of water at 90°, and no more at 120°
(3 at. = 6.39 p. c. HO).
44 C.........
23 H
Needles.
264
Bolley.
62.41
62.78
23
5.43
5:45
136
32.16
31.77
C44H20014 + 3aq.
423
100.00
100.00
....
17 O......
Brasilin is soluble in water. The reddish solution is coloured deep
carmine-red by traces of ammonia, fixed alkalis, or baryta-water. By
slow evaporation of the alcoholic solution in air containing ammonia,
spangles having the lustre of cantharides are obtained, which evolve
ammonia when treated with caustic potash. A solution of brasilin in
aqueous bisulphite of soda yields colourless crystals containing sul-
phur.
Brasilin is soluble in alcohol and ether.
Primary Nucleus C4H34; Oxyazo-nucleus C4NH2¹012.
Hydrastine.
C44NH29012 = C4NH2¹012, H2.
DURAND. Amer. Pharm. Journ. 23, 112; N. Jahrb. Pharm. 18, 143.
J. D. PERRINS. Pharm. Journ. [2] 3, 546; N. Repert. 11, 304; abstr.
N. Jahrb. Pharm. 18, 143; Chem. Centr. 1862, 552; Kopp's Jahres-
ber. 1862, 381.
MAHLA. Sill. Amer. J. 86, 57; J. pr. Chem. 91, 248; Zeitschr. f. Chem.
7,287.
Observed by Durand in 1851, but first investigated and shown to be an indepen-
dent body by Perrins.-Occurs, together with berberine, in the root of Hydrastis
canadensis, a North American plant of the ranunculaceous order.
544
PRIMARY NUCLEUS CHH; OXYAZO-NUCLEUS CNH21012.
The mother-liquor obtained in the preparation of berberine (p. 187)
is diluted with a large quantity of water and freed from alcohol, and
ammonia is cautiously added to it till the precipitate produced remains
constant, whereby resins are thrown down. The filtrate, mixed with
a slight excess of ammonia, deposits hydrastine as a fawn-coloured
precipitate, which is washed and purified by crystallisation from
alcohol, with the aid of a little animal charcoal (Perrins). — Durand
treats the aqueous extract of the root with magnesia, and boils the
precipitate with alcohol, from which the hydrastine crystallises on
spontaneous evaporation. Hydrastine may also be obtained by ex-
hausting the root with chloroform, ether, or benzene (Perrins). The
yield is about 14 p. c. of the dried root (Perrins).
Properties. White, highly lustrous four-sided prisms, belonging to
the monoclinic system (Mahla), becoming opaque on drying. Melts a
little above 100° (Perrins), at 135° (Mahla) to a colourless resin. Has
an alkaline reaction (Durand). Tasteless (Mahla); tastes bitter and
narcotic, especially in its soluble compounds. It produces no particu-
lar effect on rabbits in doses of 5 grains (Perrins).
Mahla.
at 100°
mean.
44 C
N
264
66.49
66.54
14
3.53
3.80
23 H
23
5.76
5.85
12 O
96
24.22
23.81
100.00
100.00
C44NH23012 ........ 397
Mahla's formula contains 1 at. hydrogen more.
Decompositions. Hydrastine when strongly heated evolves yel-
lowish vapours and an odour of carbolic acid (Mahla). When heated
on platinum-foil it burns with smoky flame (Mahla). - When mois-
tened with nitric acid, it turns yellowish-brown (Perrins), and dissolves
with red colour (Mahla). It dissolves in oil of vitriol, forming a yellow
solution, which turns red when warmed; the latter solution is turned
brown by chromate of potash (Mahla). Oil of vitriol together with
chromate of potash or peroxide of lead, colours hydrastine a brick-
red, different from the purple-red of strychnine (Perrins). Chlorine-
water produces a blue iridescence in the aqueous salts (Perrins).
Boiling potash-ley does not act upon hydrastine (Mahla).
Hydrastine is insoluble or nearly so in water. - It forms with acids
easily soluble, very bitter non-crystalline salts. The phosphate and
iodate are less easily soluble. Double salts are obtained with gold,
mercury, and platinum (Perrins). The salts are precipitated white by
alkalis. The granular precipitate thrown down by ammonia is quickly
transformed into crystals (Perrins). The salts are precipitated white
by iodide of potassium and ferrocyanide of potassium, yellow by
chromate of potash, brown by biniodide of potassium (Mahla).
Hydrochlorate of Hydrastine. The easily formed solution of hy-
drastine in dilute hydrochloric acid leaves on evaporation, an amorphous
gum, the aqueous solution of which exhibits a blue fluorescence
(Mahla).
GURGUNIC ACID.
545
at 100°.
C44NH23012
HCI
397.0
36.5
C44NH23012, HCI
433.5
****
Mahla.
91.58
8.42
8.48
100'00
Terchloride of gold throws down from hydrochlorate of hydrastine
a reddish-yellow precipitate, which melts to a resin when heated, and
afterwards dissolves (Mahla).
Chloroplatinate of Hydrastine. - Yellowish-red precipitate contain-
ing 16.17 p. c. of platinum (calc. for C4NH230¹HCI,PtCl requires
16:36 p. c. Pt) (Mahla).
Picrate of Hydrastine dissolves with difficulty in strong alcohol, and
crystallises from the solution in needles having the aspect of wavellite
(Perrins).
Hydrastine dissolves easily in alcohol, ether, chloroform, and benzene.
Primary Nucleus C4H36; Oxygen-nucleus C4H4O².
Gurgunic acid.
C44H3408 — C44H³40²,06.
C. WERNER. Zeitschr. Ch. Pharm. 1862, 588; Chem. Centr. 1863, 202;
Kopp's Jahresber. 1862, 461.
A constituent of wood-oil or gurguna balsam, a product imported
from Calcutta, and obtained from various species of Dipterocarpus.
32
When the reddish-brown balsam is distilled with water, a volatile
oil, C¹ºH2, passes over, whilst the acid remains behind, together with
other constituents. The residue is dissolved in boiling potash-ley;
the red-brown solution is mixed with excess of sal-ammoniac and
filtered; and the filtrate is precipitated with hydrochloric acid. The
acid, which is thrown down in dense yellow flocks, is dissolved by
shaking the liquid with ether, and is obtained, on evaporating the
ethereal layer, in the form of a crust, which is purified by repeated
crystallisation from alcohol.
Properties. Colourless, crumbly, opaque crystalline crusts. Melts
at 220° and solidifies in a crystalline mass at 180°. Colours litmus
wine-red.
Werner.
at 100-120°.
mean.
44 C.....
264
72.91
72.62
34 H
34
9.40
9.65
8 0......
64
17.69
17.73
C44H3408
362
100.00
100.00
Decompositions. The acid boils at 260°, and yields as distillate an
amorphous mass, the alcoholic solution of which turns yellow in the
air. It is decomposed by nitric acid, and carbonised by oil of vitriol.
It remains unchanged in boiling water.
The acid is bibasic, but only its neutral salts, C4H92M208, are known.
VOL. XVII.
2 N
546 PRIMARY NUCLEUS CHHS; OXYGEN-NUCLEUS C44H26012.
It dissolves easily in aqueous ammonia, and forms soaps with the
alkalis. The remaining salts are insoluble.
Potash-salt. Obtained from its alcoholic solution in deliquescent
laminæ. Contains 18.16 p. c. of potassium, or rather more than cor-
responds to the formula C4H32K208 (17-88 p. c. K), on account of the
admixture of carbonate.
Baryta-salt. Obtained by pouring a hot ammoniacal solution of
the acid into excess of dilute chloride of barium, and drying the
product in the air, and afterwards at 100°-120°.-White amorphous
precipitate, slightly soluble in water.
Werner.
88 C
67 H
3 Ba
18 0
2CH3O,3(BaO,HO)....
mean.
528
55.90
55.26
67
7.09
6.72
205.5
21.77
22.05
144
15.24
15.97
...... 944-5
100.00
100.00
4
Lime-salt.-Resembles the baryta-salt.
CHH320S......... 360
Werner.
90
2 Ca............
40
10
10.04
C4H32 Ca208
400
100
The ammonia-salt forms with cupric salts, a fine blue precipitate,
which quickly assumes a chrome-green colour. It throws down a
flocculent precipitate from bichloride of platinum.
Silver-salt. White flocks, turning slightly red-brown in the light.
Dissolves slightly in water.
Werner.
mean.
44 C ......
264
45.83
45.60
32 H
32
5.55
5.59
2 Ag
80
216
37.52
37.48
64
11.10
11.33
CHH³ Ag2Os
576
100.00
100.00
The acid dissolves easily in strong alcohol, but not in alcohol of
75 p. c. It dissolves easily in ether, slowly in benzene, and with diffi-
culty in bisulphide of carbon.
Primary Nucleus C44H38; Oxygen-nucleus C44H26O¹².
Limonin.
? C44H2014 = C44 H26012, 02.
BERNAYS. Repert. 71, 306.
K. SCIIMIDT. Ann. Pharm. 51, 338; J. pr. Chem. 33, 51.
Limone. Occurs in the pips of lemons and apples.
HESPERIDIN.
547
Preparation. The pips, beaten to a pulp with water, are exhausted
with cold alcohol. The tincture thus obtained deposits the limonin on
standing, in the form of a white powder and crystalline laminæ
(Bernays).
Properties. White powder, made up of microscopic rhombic crystals.
It does not alter at 200°, but melts at 240° to a yellow transparent
resin, which solidifies to an amorphous mass on cooling, and crystallises
again from acetic acid. Neutral. It has a strong pure bitter taste,
and is without action on the organism in doses of 60 milligrammes
(Schmidt).
Schmidt.
at 120°.
mean.
44 C .....
26 H
264
65.67
65.98
26
6.48
6.53
14 0.......
112
27.85
27.49
C44H26014
402
100.00
100.00
The above is the formula given by Weltzien. (System. Zusammenst. 666);
according to Schmidt it is C2H25013.
Limonin dissolves very slightly in water. It dissolves in oil of
vitriol, forming a blood-red solution, from which it is precipitated
unaltered by water, without forming a conjugated acid. The yellow
solution in warm strong nitric acid, even after standing for some time,
deposits the limonin unchanged, on addition of water. Limonin is not
affected by boiling with chromate of potash and sulphuric acid. — It is
insoluble in aqueous ammonia, but easily soluble in potash-ley, from
which it is precipitated by acids (Schmidt).
Limonin dissolves easily in alcohol and in acetic acid, but very
slightly in ether (Schmidt). The alcoholic solution is precipitated by
tannic and picric acids (Bernays).
Appendix to Limonin.
Hesperidin.
LEBRETON. J. Pharm. 14, 377; Repert. 31, 261.
JONAS. N. Br. Arch. 27, 186.
LEPAGE. J. Chim. méd. 17, 583.
LANDERER. Repert. 52, 215.
Occurs in sweet and bitter
Discovered by Lebreton in 1828.
oranges and lemons, both ripe and unripe, more especially in the white
spongy portion of oranges, the juice which exudes on cutting through
the fruit being rendered milky by hesperidin. It occurs abundantly in
the germs of orange-blossom, but not in the petals or filaments.
Plisson (J. Pharm. 15, 156) found hesperidin in a resinous mass, which was
deposited from oil of lemons; he may, however, have confounded it with bergaptene
(xiii, 345). Crystals from oil of bergamot, described by Ricker (Jahrb. pr. Pharm.
14, 326), are probably bergaptene.
2 N 2
548
PRIMARY NUCLEUS CHH39; OXYGEN-NUCLEUS C4H60¹².
Widnmann's hesperidin (see below) appears to differ from that of Lebreton.
Preparation. The white part of unripe oranges, freed from the
outer green peel and the inner portion, is exhausted with water, at a
temperature of 25° to 30°; and the filtrate is concentrated, separated
from the albumin which is deposited, neutralised with lime-water, and
evaporated to a syrup, which is repeatedly treated with alcohol of 40°B.,
whereby gum, albumin, salts, and other matters are left behind. The
alcoholic tincture yields on evaporation a very bitter granular extract,
which on standing for a week with 20 times its weight of water or
distilled vinegar, gradually deposits crystalline hesperidin. Purifica-
tion is effected by recrystallisation from hot alcohol (Lebreton). —
When unripe oranges are preserved in vinegar or alcohol of 22° B.,
hesperidin crystallises at the bottom of the vessel (Lebreton; Landerer).
Hesperidin is also deposited in white nodules from a very strong
tincture of curassao-shells on standing for six weeks (Lepage).
The mother-liquor of hesperidin contains in solution the bitter prin-
ciple of oranges, which is obtained on evaporation as a brown extract,
the aqueous solution of which is coloured bright-yellow by ammonia,
brown-red by ferric sulphate, and is not precipitated by gelatin. It
dissolves in alcohol, but not in ether (Lebreton).
Properties of Hesperidin. - Very delicate, silky tufts of needles,
grouped in nodules; inodorous; tasteless at first, afterwards bitter,
probably owing to adhering bitter substance. Neutral (Lebreton).
According to Lepage, it is tasteless; according to Landerer, bitter and
acid. It is phosphorescent when gently warmed (Bonastre).
Decompositions. 1. Hesperidin melts above 109°, and solidifies on
cooling to a brownish-yellow transparent mass, which tastes bitter and
sweet, and does not again crystallise from alcohol. When submitted
to dry distillation, it does not yield ammonia, but leaves a porous char-
coal. - 2. It burns on red-hot charcoal, giving off fumes and a slightly
aromatic odour. 3. In cold nitric acid it assumes a yellowish-red,
afterwards a permanent orange yellow colour, and dissolves when heated,
forming a brown-red solution, changing to pale-yellow, with formation
of oxalic acid and a little yellow artificial bitter. -4. Oil of vitriol turns
hesperidin first orange-yellow, afterwards bright red, changing in 12
hours to a rusty colour; the red solution is rendered pale-yellow by
water (Lebreton). Hesperidin is precipitated unchanged from its orange-
yellow solution in oil of vitriol by water (Jonas). 5. In strong
hydrochloric acid, hesperidin acquires a greenish-yellow colour, which
is destroyed by water (Lebretou). Hydrochloric acid does not affect
solid hesperidin, but on boiling the alkaline solution with excess of
hydrochloric or sulphuric acid, a deep orange-red resin is deposited,
which is soluble in water, insoluble in alcohol, soluble in oil of vitriol
with rose colour, in ammonia with greenish-yellow, and in caustic alkali
with deep-red colour (Jonas).
Combinations. Hesperidin is nearly insoluble in cold, soluble in 60
parts of boiling water, which deposits ths of the amount dissolved on
cooling. It is insoluble in dilute sulphuric or hydrochloric acid, but easily
soluble in aqucous fixed alkalis (Lebreton); also in aqueous ammonia,
ERUCIC ACID.
549
remaining free from ammonia on evaporating the solution (Jonas); it
is precipitated from the alkaline solutions by acids (Lepage). It forms
with lime a soluble compound, precipitable by alcohol (Jonas).
The aqueous solution of hesperidin does not precipitate neutral or
basic acetate of lead. According to Lebreton, it precipitates ferric
sulphate brown-red; but according to Plisson, it does not.
Hesperidin dissolves slightly in cold, and freely in hot glacial acetic
acid. The solution is not rendered turbid by water (Lebreton), but is
precipitated by alcohol (Jonas); it leaves hesperidin free from acetic
acid on evaporation (Lebreton).
It dissolves very sparingly in cold, very easily in hot alcohol; the
solution is rendered only slightly turbid by water. - It is insoluble in
cold and hot ether, and in volatile and fat oils (Lebreton).
Widumann's Hesperidin is likewise obtained from unripe oranges. —
The sliced peel of the green fruit is digested in alcohol of sp. gr. 0.900,
whereupon, after standing for six weeks, the liquid is found to contain
lamine floating in it. These laminæ, when recrystallised form four-
sided glassy transparent prisms, bevelled with two faces. The
crystals crunch between the teeth, and have a faint sweetish taste.
They are inodorous, and have an acid reaction, and when heated melt
and decompose, leaving charcoal. -Decomposed by strong nitric acid,
with formation of oxalic acid. Dissolves in cold oil of vitriol, car-
bonising when heated.
Dissolves in 40 parts of cold, and in 10 parts of boiling water,
forming a solution, which is slowly precipitated by basic acetate, but.
not by neutral acetate of lead. Nearly insoluble in alcohol, either cold
or boiling, which precipitates it in laminæ from the aqueous solution.
Insoluble in ether, and in oils both fat and volatile (Widnmann,
Repert. 32, 207).
Primary Nucleus C4H42.
Erucic Acid.
C44H4204 C44H42,0*.
=
ST. DARBY. Ann. Pharm. 69, 1; Pharm. Centr. 1849, 177; Chem. Gaz.
1849, 163; Kopp's Jahresber. 1849, 347.
F. WEBSKY. J. pr. Chem. 58, 449; Pharm. Centr. 1853, 808; Kopp's
Jahresber. 1853, 443.
J. pr.
STÄDELER. Ann. Pharm. 87, 133; Pharm. Centr. 1853, 811; J.
Chem. 61, 374; Kopp's Jahresber. 1853, 445.
R. OTTO. Ann. Pharm. 127, 183; abstr. J. pr. Chem. 99, 316; Chem.
Centr. 1864, 111; Répert. Chimie pure, 6, 148; N. J. Pharm. 45,
103; Kopp's Jahresber. 1863, 335. — Zeitschr. Ch. Pharm. 8, 276;
Ann. Pharm. 135, 226.
Brassic acid. - Occurs in the fat oil of black and white mustard-
seed (Darby). In rape oil (Websky).
Preparation. A. From fatty oil of mustard. The fatty acids,
obtained by saponifying the oil, salting out, and decomposing the
550
PRIMARY NUCLEUS C44H42.
soap, are digested over the water-bath with finely triturated oxide of
lead; the plaster thereby formed is exhausted with ether, which takes
up oleate of lead; and the insoluble residue is decomposed with alco-
holic hydrochloric acid. On distilling off the alcohol, erucic acid remains.
behind, and may be purified by repeated crystallisation from alcohol
(Darby). Otto saponifies the fat oil of white mustard-seed with oxide
of lead, and treats the plaster with ether, which, according to him,
but contrary to Darby's statement, dissolves the lead-salt of erucic
acid. He then mixes the ethereal solution with hydrochloric acid,
removes the chloride of lead thereby formed, evaporates the solution
over the water-bath, and purifies the residue, which solidifies in the
cold, by washing with water and recrystallisation from alcohol.
B. From Rape-oil. The fatty acids obtained by decomposing the
soap with hydrochloric acid, and afterwards completely freed from the
acid, are dissolved in an equal bulk of alcohol of sp. gr. 0·835; the
solution is cooled to 5°, and left to crystallise; and the crystals are
separated and pressed. The crystals are again crystallised three times
from their own weight of alcohol, at last at a temperature of 10°, and
pressed, and are finally melted with water to remove alcohol (Websky).
Properties. White, shining, very thin needles, often an inch long,
melting at 34° [33° to 34° (Otto)], and solidifying at 33° (Darby).
Long white, tasteless, and inodorous needles, arranged in masses re-
sembling wavellite, melting at 32° to 33°, and solidifying at a somewhat
lower temperature. The melted mass has a glassy lustre, and a
lamellar fracture, with large cavities. Has an acid reaction.
manent in the air (Websky).
Per-
Otto.
Darby.
Websky.
mean.
mean.
mean.
44 C
264
78.11
77.53
78.25
77.90
42 H
42
12.43
12.60
12.56
12.55
40
32
9.46
9.87
9.19
9.55
CHH404
338
100.00
100.00
....
100·00
100.00
.......
(
Websky proposed the formula CH3O4, which Städeler, who recognised the
identity of the two acids, altered to the above. The melting-point of the acid
is not altered by repeated crystallisation, and is the same in the portions of the acid
which solidify first and in those which crystallise afterwards. Partial precipitation
with neutral acetate of lead also fails to yield any portion having a different melting-
point (Darby; Websky).
Decompositions. 1. The acid when exposed to the air gradually
becomes coloured, and turns rancid (Otto). When heated to 100° for
several days it assumes a yellow to brown colour, afterwards melts at
a lower temperature, and solidifies to a tallowy mass after melting.
During this change it acquires an aromatic odour, and at first becomes a
little heavier, but afterwards (especially at 130°) loses weight (Websky).
-2. With bromine it forms bromerucic acid, without elimination of hydro-
bromic acid (Otto).-3. It is converted by nitrous acid (not by sulphurous
acid) into an isomeric crystalline acid (the erucadic acid of this Handbook)
(Websky). Otto did not observe any change in the acid, which exhi-
bited the same melting-point after treatment with nitrous acid as before.
4. It is decomposed by fused hydrate of potash, with evolution of
bydrogen; the products of decomposition include neither acetic nor
ERUCIC ACID.
551
arachidic acid (p. 370) (Otto).-5. On passing hydrochloric acid gas
into alcoholic erucic acid, an oil is produced, which crystallises below 0°,
and contains 77·05 p. c. C., and 12.00 H. (Otto).
Soda-salt. Obtained in the same way as laurate of soda (xv, 47).
- Slightly yellow crusts, unalterable at 110°. The solution in absolute
alcohol forms a jelly on cooling (Websky).
Websky.
44 C
264
73.33
73.77
41 H.
41
11.39
11.39
3 0.....
24
6.67
6.36
NaO
31
8.61
8.48
C44H¹¹NaO4
360 ....... 100·00
100.00
Baryta-salt. An alcoholic solution of the soda-salt throws down
from alcoholic acetate of baryta white flocks (Darby), which crys-
tallise from alcohol in small nodules (Otto). It softens at 75°, and
turns yellow at 100°, giving off an odour and increasing in weight
(Websky).
Dried over oil of vitriol or in vacuo.
Darby.
Otto.
44 C
264
65.09
64.36
65.00
41 H
41
10.11
10.40
10.10
30
24
5.92
6.34
6.12
BaO
76.6
18.88
18.90
18.78
C*H*BaO*
405'6
100.00
100.00
100.00
Lead-salt. Precipitated from a solution of the soda-salt by alco-
holic neutral acetate of lead (Darby). The (moist? Kr.) lead-salt
softens at 60°, and liquefies at 80° (Websky). It is insoluble in ether.
See p. 550.
Dried in vacuo.
Darby.
44 C......
264
59.87
59.7
41 H
41
9.29
9.3
30
24
5.44
5.6
РЬО
112
25.40
25.4
C44H¹¹PbO4
441
100.00
100.00
Websky found varying amounts of oxide of lead in the salt washed with hot
water.
Silver-salt. Thrown down from the alcoholic ammonia-salt by
nitrate of silver, as a curdy precipitate, which soon turus dark and
must be dried in a vacuum (Darby). The precipitate thrown down
from the soda-salt immediately turns brown-red (Websky).
Darby.
C44H4103
AgO
329
74
116
26
25-7 to 26
445
100
...
C44H¹¹AgO4
Erucic acid dissolves very easily in alcohol and in ether (Websky).
552
PRIMARY NUCLEUS C4H.
Erucadic Acid.
C44H42O4 = C44H42,04.
WEBSKY. J. pr. Chem. 58, 459.
Erucic acid absorbs nitrous acid gas, becoming yellow and odorous,
and when recrystallised from cooled alcohol, yields erucadic acid, whilst
a brown oil remains in solution (p. 550).
White, inodorous and tasteless mass, melting at 59 to 60°, and
solidifying at 58 to 59° to a shining mass of fine needles.
Websky.
mean.
44 C ......
264
78.11
77.89
42 H....
42
12.43
12.58
4 0......
32
9.46
9.53
CH*O*
•
338
100.00
100.00
Isomeric with erucic acid, to which it bears the same relation that elaïdic acid
bears to oleic acid (p. 74).
The acid becomes coloured and odorous at 120°. Its soda-salt is
obtained in the same way as that of erucic acid, and becomes coloured
at 110°.
1. SINAPOLEIC ACID.
tard.
Appendix to Erucic Acid.
Occurs in the seeds of black and white mus-
It is separated from an ethereal solution of the lead-salt by
hydrochloric acid and alcohol, and is converted into a baryta-salt by
Gottlieb's method (p. 63) (Darby, Ann. Pharm. 69, 6).
According to Darby.
38 C............ 228
36 H........
4 O.....
BaQ
According to Städeler.
61-2 40 C
240
....
36
9.6 39 H .....
39
....
32
8.8 50
40
60.71
9.87
10.06
76.6
20.4
BaO
76.6
....
…..
....
Darby.
60.57 to 61.20
9.81,, 9.76
19.36 19.90 20.4
C38H36BaO5 372.6 100 0 C40H37 Ba04,2HO 395.6 100-00
....
....
""
The percentage of baryta is not altered by repeated crystallisation. Städeler
(Ann. Pharm. 87, 135) supposes the salt to contain either (in Darby's formula)
1 atom or (in his own formula) 2 atoms of water. The liquid acid of rape-oil may,
according to Städeler, be sinapoleic acid.
2. CRYSTALLINE FAT FROM OIL OF MUSTARD.-The expressed oil of
mustard (apparently of the white seed) is shaken up with cold alcohol of
36° B.; and the alcohol is decanted and evaporated to one-third,
whereupon the fat crystallises on cooling. It forms white, pearly,
transparent lamina and needles, melting at 120°, solidifying in a
crystalline mass on cooling, and volatilising partially undecomposed.
It is slowly converted by nitric acid (without formation of oxalic acid)
into a yellow resin, which assumes a scarlet colour with potash. It is
FATTY OILS OF WHITE MUSTARD.
553
not saponifiable by potash. Dissolves in cold alcohol and ether, and
more freely in the hot liquids (Henry & Garot, J. Chim. méd. 1, 469;
Berz. Jahresber. 6, 242 and 243). This fat appears to be cholesterin
(Kr.). Darby found the soaps of the fatty oils of white mustard quite
soluble in water, which is contrary to the statements of Henry &
Garot. The latter chemists, by exhausting with ether the sulpho-
cyanate of sinapine (xiv, 528) which crystallises from the above
extract on further evaporation, obtained a red fat of mustard, the
vapour of which reddened paper held over it. The oil dissolves in
alcohol, forms a cochineal-red solution with ether, and does not redden
ferric salts.
3. SIMON'S SINAPISINE. Different from the sinapisine of Boutron
and Frémy (xiv, 524). — Obtained only from black mustard. - Flour
of mustard is repeatedly exhausted with alcohol of 94 p. c. until the re-
sidue is quite free from harshness; the residue is pressed; and the
liquid is filtered and distilled to remove the greater part of the alcohol.
The residual liquid is then shaken with four times its bulk of ether:
the ether is poured off; and this operation is repeated at least five
times. The extract remaining on distilling off the ether is again
treated with small quantities of ether, which leaves sugar, fat oil (?),
and soft resin undissolved; the ethereal solution is evaporated, and
the residue taken up afresh with a small quantity of ether. This last
proceeding is repeated until the residue is completely soluble in ether,
whereupon the residue is dissolved in alcohol of 90 p. c., which leaves
fatty oil undissolved; the solution is decolorised with animal charcoal;
and the filtrate is evaporated. A portion of the sinapisine now crys-
tallises out, while another portion crystallises only after the sponta-
neously evaporated mother-liquor is treated afresh with alcohol, and
the fatty oil still present is removed. The product is purified by re-
crystallisation from ether and alcohol. Fifty-five pounds of mustard
yield 80 grains of sinapisine. — Dazzling-white crystals, having the
appearance of fish-scales. Less easily fusible than the fat and sus-
ceptible of sublimation. Free from sulphur.—Insoluble in acids and
in alkalis, and does not colour them yellow. Dissolves with moderate
facility in alcohol, very easily in ether, and in oils both fat and volatile
(Simon, Pogg. 43, 651; 50, 379).
4. FATTY OIL OF BLACK MUSTARD. - From Sinapis nigra. Golden-
yellow or brown-yellow oil of sp. gr. 0·902 (Fontenelle), 0·917 at 15°
(Schübler); thicker than olive-oil (Fontenelle), thinner than olive-oil
and rape-oils, becoming thick at 12° to 15°, and solidifying to a
brownish-yellow mass at 17.5° (Schübler, Br. Arch. 14, 99). The
cold-pressed oil has a faint odour of mustard, and a mild taste; when
hot-pressed it is acrid. It does not easily turn rancid. With mer-
curous nitrate it assumes an orange-yellow colour, without solidifying.
It forms a yellow, very hard soda-soap. Dissolves in 1000 parts
(Fontenelle, J. Chim. méd. 1, 131; Berz. Jahresber. 6, 263), 1200 parts
Thibierge, N. Tr. 4, 2, 259) of alcohol of sp. gr. 0·833, and in 4 parts
of ether.Contains the glycerides of erucic acid, of a peculiar oleic
acid, and of stearic acid (Darby).
5. FATTY OIL OF WHITE MUSTARD. From Sinapis alba. Limpid,
amber-yellow, inodorous oil, of sp. gr. 0-9142 at 15° (Schübler), 0·9153
(van Kerckhoff). Tastes mild (Darby); somewhat acrid (Schübler). Does
554
PRIMARY NUCLEUS C4H42.
not solidify in the cold of winter, but becomes thick and turbid
(Darby). It thickens at 11° to 15°, and solidifies at 16° to a
yellowish-white butter (Schübler). Contains sulphocyanate of sinapine
(xiv, 528), which it gives up to strong alcohol (Henry & Garot).
Contains the glycerides of erucic acid, and of a peculiar oleic acid.
(Darby, Ann. Pharm. 69, 1).
6. BRASSICA-OILS. - From the seeds of various species of Brassica
(Handbuch, viii [2], 38. The following have been distinguished :-
a. Oil of Winter Rape. (Winterrepsöl. Winterrübsenöl.)- From
Brassica Napus oleifera, Dec. Brownish-yellow; of sp. gr. 0.902
(Brandis), 0915 at 15° (Lefebvre), 0-9182 at 11° (Scharling), 0-9193
(Brisson), 0·9128 at 15°; of the commercial hot-pressed oil 0.917
(Schübler). Deposits tallow at 1°, and solidifies completely to a
yellowish-white butter at 4° (Schübler). The freshly expressed
oil deposits mucus on standing, becoming clear, and appearing greenish-
yellow in the upper, golden-yellow in the lower layers. When heated
to 200° it acquires a greenish-yellow colour and a stronger odour, and
at 350° undergoes decomposition, giving off vapours which condense to
an acid, limpid, yellowish-green oil, having a strong odour. At 0° it
solidifies in 6 or 8 hours to a butter, which melts slowly at 5° to 6°.
It contains the glycerides of erucic acid and a peculiar fluid oleic acid,
which does not yield sebacic acid on distillation. It dissolves slightly
in alcohol, easily in ether (Websky).
b. Colza-cil. (Kohlrepsöl. Kohlsaatöl. Huile de Colza.)- From
Brassica compestris oleifera, Dec. Brownish-yellow, nearly inodorous
and tasteless oil, having, when expressed hot or when long kept, a
disagreeable after-taste (Schübler). Sp. gr. 0.9136 (Schübler), 0.9143
(van Kerckhoff), 0.915 at 15° (Lefebvre). It is the least límpid of
the brassica-oils. It deposits a little tallow at 4°, and solidifies to
a yellow butter at 6° (Schübler). The yellow cold-pressed oil
contains, on the average, 70.32 p. c. C., 10.58 H., and 19.10 O.; it
forms with chlorine a yellow, very viscid compound of sp. gr. 1·060
at 10°, containing 17.68 p. c. of chlorine, and with bromine a similar
compound of sp. gr. 1.253 at 21.5°, containing 32.5 p. c. of bromine.
These bodies are represented by the formulæ C²°CIH¹04 and C²ºBrH¹704
(Lefort, N. J. Pharm. 23, 284). With alcoholic ammonia it yields a
small quantity of amide, solidifying at 82° (Carlet).
c. Oil of Summer Rape. (Sommerrepsöl. Sommerrübsenöl.) - From
Brassica præcox, Dec. Brownish-yellow, viscid oil, of sp. gr. 0-9139
(Schübler), 0.9171 (van Kerckhoff), 0.9157 at 15° (Lefebvre), 0.9223 at
11° (Scharling). It deposits tallow at 8° only, and solidifies to a
yellow-white butter at 10° (Schübler).
d. Oil of Turnip-stemmed Cabbage (Kohlrübenöl. Huile de navette.)
From Brassica Napobrassica, Mill. Resembles winter rape-oil. Sp. gr.
0.9141 at 15° (Schübler), 0-9179 at 11° (Scharling). Viscid: deposits
tallow below 0°, and solidifies to a yellowish-white butter at · 4°
(Schübler).
e. Turnip oil. (Wasserrepsöl. Wasserrübenöl.)—From Brassica Rapa.
Brownish-yellow oil, the thinnest of the brassica-oils; has a sp. gr. of
0.9167 at 15°. Deposits tallow at 4° to -6°, and solidifies to a
1
OIL OF CHINESE RADISH.
555
whitish-yellow butter at 7.5°. Remains greasy when exposed to
the air (Schübler). Braconnot resolved this oil (or a ?) by pressure, at
4°, into 54 parts of yellow oil, not solidifiable in the cold, and 46 parts
of tallow melting at 7.5°, and yielding, when treated with sulphuric or
nitric acid, a tough elastic mass, but no stearic or oleic acid. —It yields
soaps inferior to those made with olive-oil or animal fats (Pelletier).
On the adulteration of rape-oil, see Laurol (N. J. Pharm. 2, 397; J. pr. Chem.
28, 251); Gobley (N. J. Pharm. 4, 285). Rape-oil yields by distillation with
water an acid distillate, having an odour of radishes, upon which floats
an oily layer having a burning taste. The same products are obtained
by distillation with aqueous potash (Glaser, Repert. 22, 102). — By the
dry distillation of rape-oil, a mixture of acrolein [sebacic acid (Schar-
ling, J. pr. Chem. 43, 264)], fatty acids, and hydrocarbons is obtained,
the latter of which, when passed over heated soda-lime, yield butyric
and valerianic acids, and when oxidised with nitric acid, a brown-red,
oily nitro-compound, and a mixture of fatty acids, including acetic,
propionic, butyric, valerianic, caproic, and oenanthylic acids (Schneider,
Ann. Pharm. 70, 107). See also Reichenbach (J. pr. Chem. 1, 377) on the dry
distillation of rape-oil. Fresh rape-oil, boiled with oxide of lead and
water, yields lead-plaster and neutral glycerin; but oil which has become
thick from exposure to the air, yields, besides lead-plaster, a liquid
which, after removing the lead by means of hydrosulphuric acid, has
an acid reaction, and reduces nitrate of silver, probably owing to the
presence of acrylic acid (Ludwig, Apoth. Ver. Zeit. 1, 181).
Rape-oil distilled with excess of alkali emits an odour of amylic
butyrate (Al. Müller, Handwörterb. 6, 874). — It takes fire with chlorate
of potash and oil of vitriol (A. Vogel). In contact with mercurous
nitrate it is converted into a dark brown thick honey in the course of
two or three days (Davidson). Rape-oil assumes a green colour with
oil of vitriol (Heidenreich; van Kerckhoff, Kopp's Jahresber. 1859,
701). 15 grammes of the oil mixed with 5 grammes of oil of vitriol
becomes heated by 55°, and with 7 grammes of sulphuric acid con-
taining 90 p. c. of oil of vitriol, by 37.5° (Fehling). - Pale rape-oil (a?)
agitated with 4th of its volume of sulphuric acid of sp. gr. 1.475 re-
mains uncoloured after 15 minutes, but with acid of sp. gr. 1.53 it
acquires a faint red, and with acid of sp. gr. 1·635 a brown colour. It
is not coloured by similar treatment with syrupy phosphoric acid, or
with nitric acid of sp. gr. 1.33 or weaker. A mixture of nitric and
sulphuric acids colours it dark-brown in two minutes. When heated to
boiling with 4th of its volume of caustic soda of sp. gr. 1:34, it yields
a solid dirty-white mass (Calvert, J. pr. Chem. 61, 354). All the
brassica oils blacken silver vessels in which they are boiled with excess
of alkali, even when mixed with linseed or nut-oil, owing to the pre-
sence of sulphur (Mailho, Compt. rend. 40, 1218; Kopp's Jahresber.
1855, 822).
f. Oil of Chinese radish. From the seeds of Raphanus Chinensis,
Miller. Brownish-yellow oil, having a mild odour and taste, of sp. gr.
0.9187 at 15°. Thickens at 10°, and soldifies to a white mass at
- 16° (Schübler).
556
PRIMARY NUCLEUS CH; OXYGEN-NUCLEUS CHH2010
Oxygen-nucleus C4H32010.
Colocyntheïn.
? C44H32012 = C44H32010,0².
The colocynthin of Walz breaks up, when boiled with dilute sul-
phuric acid, into sugar and colocyntheïn, the latter of which separates
in the form of a resin, and may be purified by dissolving it in absolute
ether. It contains at 100°, on the average, 65.99 p. c. C., 8.62 H.,
and 25.99 O., from which numbers Walz calculates the formula
C44H32013 (66 p. c. C., 8 H.). If colocyntheïn is to be regarded as an
independent body, the formula C4H33013 C4H32012, HO may perhaps
be substituted for that just given (Kr.).
=
Glucoside of Colocyntheïn.
Colocynthin.
HERBERGER. Repert. 34, 368.
LEBOURDAIS. N. Ann. Chim. Phys. 24, 58; Pharm. Centr. 1848, 763.
BASTICK. Pharm. J. Trans. 10, 239; N. J. Pharm. 19, 346; abstr.
Kopp's Jahresber. 1850, 550.
WALZ.
N. Jahrb. Pharm. 9, 16, and 225; Pharm. Viertelj. 7, 558; N.
Br. Arch. 96, 141. N. Jahrb. Pharm. 16, 10.
Braconnot (J. Phys. 84, 338) and Meissner (N. Tr. 2, 1, 27), previously attempted
to prepare the bitter principle of colocynth. Occurs principally in the pulp, and
to a less extent in the pips of bitter apple (Walz).
Preparation. 1. Extract of colocynth, prepared with alcohol of
sp. gr. 0.84 and thoroughly dried, is treated with cold water, and the
liquid is filtered, colocynthitin then remaining in the residue. The
aqueous liquid is precipitated with neutral acetate of lead, the preci-
pitate is removed, and the filtrate is precipitated with the basic acetate.
After separating the last precipitate, the liquid is freed from lead by
hydrosulphuric acid, and precipitated with aqueous tannic acid not in
excess; the liquid is warmed, together with the precipitate, till the
latter melts to a resin, which is then washed, dissolved in alcohol, and
decomposed by agitating the solution with basic acetate of lead, or by
digesting it with hydrated oxide of lead. The liquid, filtered from
tannate of lead, freed from lead by hydrosulphuric acid, and decolorised
with animal charcoal, leaves, on spontaneous evaporation, golden-
yellow colocynthin, which is to be triturated and digested with anhy-
drous ether, whereupon pure colocynthin remains behind (Walz).
In this process a loss of colocynthin is incurred; (a) in the colocynth
exhausted with alcohol, from which it may be obtained by exhausting
the colocynth with water, precipitating the extract with alcohol,
evaporating the filtrate, and treating the residue in the same way as
the alcoholic extract; (b) in the precipitates thrown down by the
neutral and basic acetates of lead, which precipitate it together with
COLOCYNTHIN.
557
colocynthitin, resin, and colouring matter (for the method of recovering it
from these precipitates see N. Jahrb. Pharm. 9, 226); (c) in the liquid precipi-
tated by tannic acid. The liquid is evaporated to one-half, neutralised
with soda, and precipitated with tannic acid (!), and the precipitate is
treated as above. The filtrate now obtained still contains colocynthin,
which may be recovered by precipitating it with basic acetate of lead,
neutralising the filtrate with caustic soda, precipitating with tannic
acid, and decomposing the precipitate as above. Four and a-half
pounds of colocynth yield 10 drachms of colocynthin (Walz).
2. Colocynth is macerated in water for two days and pressed; the
press-cake is treated with a little cold alcohol of 20° B.; and the
residue is exhausted with a large quantity of warm, not boiling, alcohol
of 38° B. The latter tincture is evaporated to an extract, which is
freed from fat by ether, and dissolved in a large quantity of water;
the solution is filtered and precipitated with neutral acetate of lead;
and the filtrate is freed from lead by hydrosulphuric acid, evaporated
to a syrup, and mixed with a slight excess of ammonia. The yellow
flocks thereby precipitated are dissolved in alcohol and decolorised with
animal charcoal, and the filtrate is evaporated to dryness (Herberger).
In this way the greater part of the colocynth is left in solution
(Walz). Bastick precipitates with neutral acetate of lead the extract
prepared with cold water and heated to boiling; filters after cooling;
frees the filtrate from lead by sulphuric acid, and from acetic acid by
boiling; and evaporates to dryness. From the residue strong alcohol
takes up colocynthin, which remains, on evaporation, as a neutral
reddish-brown resin. Colocynthin thus prepared is not completely
soluble in water (Walz). Lebourdais precipitates a concentrated
infusion of colocynth with neutral acetate of lead, and allows the
filtrate to run slowly through a funnel containing animal charcoal;
then washes the charcoal, which has taken up colocynthin, with water,
dries it, and boils it with alcohol, which leaves small nodules when
evaporated. The whole of the colocynthin is precipitated by char-
coal only after long standing (Walz).
Properties. Amorphous yellow mass, which is said to crystallise in
whitish-yellow tufts when the alcoholic solution is slowly evaporated
(Walz).
Calculation according to Walz.
56 C.......
42 H
23 O.....
C56 H42023
Walz.
mean at 100°.
336
59.78
59.41
42
7.47
7.64
A
184
32.75
32.95
562
100.00
100.00
Decompositions. 1. Colocynthin, when heated, burns without leaving
a residue. 2. It forms with oil of vitriol a deep red solution, which
afterwards turns brown, and is rendered turbid by water (Walz). Bastick's
3. It dissolves in nitric acid of
colocynthin is carbonised by oil of vitriol.
sp. gr. 1·45, with abundant evolution of red fumes, and forms a yellow
amorphous acid, precipitable by water (Bastick). According to Walz
it dissolves in nitric acid of sp. gr. 1.52, apparently unaltered.
4. By mixing its aqueous solution with dilute sulphuric or hydrochloric
acid, and more completely by long boiling therewith, it is resolved into
558
PRIMARY NUCLEUS CH4.
colocyntheïn and sugar, 13 parts of colocynthin yielding a quantity of
sugar, which reduces an amount of alkaline solution of cupric oxide
corresponding to 1 part of grape-sugar:
C56H12O23 + 2HО
C44H32013+ CH2O (Walz).
5. Bromine-water precipitates aqueous colocynthin and decolorises
it. Colocynthin reduces terchloride of gold in 24 hours (Walz).
Colocynthin dissolves in 8 parts of water at 12°, and in 6 parts
of boiling water, aud is deposited from the solution in the form of an
oil on cooling. The aqueous solution does not precipitate metallic
salts, and renders ferrous sulphate only slightly cloudy.-It dissolves
in 6 parts of weak, and in 10 parts of absolute alcohol, and is pre-
cipitated from the solution by ether, in which it is not soluble.
It is precipitated from its aqueous solution by tannic acid (Walz).
Resin of Colocynth. When an alcoholic extract of colocynth is
freed from fat by ether, and from bitter substance by water, the resin
remains as a yellowish-brown, brittle, inodorous, very bitter mass,
which melts when heated, dissolves with yellow colour in hot nitric
acid, and colours oil of vitriol dark brown. It dissolves in warm
aqueous ammonia and potash to a yellowish-brown liquid, precipitable
in yellow flocks by acids; and is easily soluble in alcohol, but insoluble
in ether and in fatty and volatile oils (Meissner). The resin dissolves
for the most part in aqueous carbonate of soda, throwing down yellowish-
grey flocks, and is soluble to a great extent in warm aqueous oxalic
acid, forming a solution, from which it is thrown down as a yellow-
white precipitate by tannic acid.
Colocynthitin. To prepare this substance, the portion of alcoholic
extract of colocynth which is insoluble in water is exhausted with
ether; the brown solution is decolorised with animal charcoal; the
filtrate is evaporated; and the dry residue is washed with absolute
alcohol. The undissolved portion, dissolved in boiling alcohol, and
decolorised with animal charcoal, yields crystals of colocynthitin on
cooling, whilst the remainder of the solution solidifies to a jelly, which
is slowly transformed into a crystalline powder of colocynthitin. -
Tasteless crystalline powder, consisting of microscopic oblique rhombic
prisms. Contains at 100°, on the average, 69.8 p. c. C., 9.4 H., and
20.8 0. It is soluble in boiling, but insoluble in cold absolute alcohol
(Walz).
Primary Nucleus C4H4.
Benic Acid.
C4H40404H4,04.
MULDER & A. VÖLCKER. Scheik. Onderz. 3 Th. 5 St. 545; J. pr. Chem.
39, 351: abstr. Ann. Pharm. 64, 342.
Respecting Walter's benic acid, see xvi, 365.
Source. In oil of ben (xvi. 386) from Moringa oleifera.
BENIC ACID.
559
Preparation. The fatty acids obtained by saponifying the oil and
decomposing the soap, are separated by pressure into a fluid and a
solid portion, the latter of which is crystallised from alcohol to sepa-
rate the more easily fusible margaric acid from the less easily fusible
fatty acids.
There remains undissolved, in too small quantity for further exami-
nation, an acid, which melts at 83°, dissolves in stronger alcohol, and contains
81.5 p. c. C., and 13·86 H.
Properties. Benic acid solidifies from fusion in white friable needles,
resembling stearic acid. It melts at 769.
Völcker.
mean.
4.4. C.........
264
77.65
77.53
44 H
44
12.94
12.90
4 0.......
32
9.41
9.57
100.00
100.00
CHHO* .... 340
The above is Strecker's formula (Ann. Pharm. 64, 346). Mulder gives the
formula C42H420¹. — The acid melting at 83° may have the formula C⁹6H⁹O¹ (81·8
p. c. C., 13-4 H.) but on account of its too low melting-point (as compared with
melissic acid), Heintz regards it as a mixture, which may also be the case with
benic acid.
Soda-salt. — A hot alcoholic solution of the salt solidifies to a jelly,
which becomes crystalline when diluted with alcohol, but not on long
standing only.
Völcker.
mean.
44 C …….....
43 H
264
72.92
72.03
•
43
11.88
11.78
3 O......
NaO¹
24
6.63
7.55
31
8.57
8.64
C44H43NaO4
362
100.00
100.00
....
Baryta-salt. Chloride of barium throws down from the alcoholic
soda-salt a precipitate resembling stearate of baryta.
Völcker.
44 C
264
64.78
64.74
43 H .....
43
10.55
10.45
30
24
5.89
6.10
BaO
76.5
18.78
18.71
....
C44H43BaO4
407.5 ...... 100'00
100.00
****
Lead-salt. — Precipitated from the soda-salt by neutral acetate of
lead.
44 C
264
59.59
58.43
43 H........
43
9.70
9.50
3 0......
24
5.42
6.06
РЬО.......
112
25.29
26.01
C44H43Pb04
443
100.00
100.00
....
560
PRIMARY NUCLEUS CH4; BROMINE-NUCLEUS CªBr²H“.
Benate of Ethyl.
C48H4804 C4H6O,C4H4303.
VÖLCKER. J. pr. Chem. 39, 356.
On passing hydrochloric acid gas into an alcoholic solution of benic
acid, the ether is deposited in crystals before the liquid becomes satu-
rated with the gas.
Colourless, translucent, crystalline body, melting at 48° to 49°.
Inodorous.
Völcker.
48 C........
48 H
288
78.26
78.48
48
13.04
12.98
4 O.......
32
8.70
8.54
C4H50,C44H4303
368
100.00
100.00
Bromine-nucleus C44Br2H42.
Bromerucic Acid.
C4Br²H¹²0* = C4Br²H42,04.
R. Orro. Zeitschr. f. Chem. 8, 275; Ann. Pharm. 135, 226.
Formation and Preparation. Erucic acid is covered with water,
and bromine is dropped into the liquid so long as the colour disappears
on brisk agitation. The bromine is absorbed by the acid without
liberation of hydrobromic acid. After pouring off the water and
evaporating the excess of bromine in the air, the bromerucic acid
formed is dissolved in warm alcohol, and crystallised from the cooled
solution in small white nodules, melting at 42° to 43°.
Nodules.
44 C........
2 Br
160
42
53.01
32.13
Otto.
mean.
53.15
31.80
ཉ། སྠཽ ཟླ་རྗེ
42 H
4 O
C4Br2H+201
....
32
498
100.00
100.00
Bromerucic acid does not decompose when kept. — It is converted
into erucic acid by the action of sodium-amalgam on treating its alco-
holic solution acidulated with hydrochloric acid.
Baryta-salt. Thrown down as a white precipitate from the
alcoholic ammonia-salt by acetate of baryta. Melts at 100°, and
decomposes at that temperature, or on exposure to the air, taking up
oxygen and becoming greasy.
ARIBINE.
561
C44Br2H4104
Ba........
C4Br2H*BaO
In vacuo.
Otto.
497
87.89
68.5
12.11
11.80
565.5
100.00
…...
Lead-salt. Plaster-like precipitate, separating from its solution
in a large quantity of boiling absolute alcohol in small white crystals,
which quickly turn rancid in the air.
C44Br2H4104
Pb
C#Br2H41PbO4
Crystals.
Otto.
497
82.7
104
17.3
16.6
........
601
100.0
....
The acid dissolves in alcohol and ether, and is precipitated from the
solution in the form of an oil by water.
COMPOUNDS CONTAINING 46 ATOMS OF CARBON.
Primary Nucleus C4H22; Azo-nucleus C46N4H19.
Aribine.
C46N4H20= C46N4H18, H2.
RIETH (& WÖHLER). Göttinger Nachrichten 1861, 201; Ann. Pharm.
120, 247; N. Ann. Chim. Phys. 64, 485; Rép. Chim. pure 4, 237;
Kopp's Jahresber. 1861, 532; complete: Dissertation über das
Aribine, von R. RIETH, Göttingen, 1861; abstr. Chem. Centr.
1861, 903.
In the bark of Arariba rubra, a Brazilian tree.
Preparation. The bark is exhausted by digestion with hot water
containing sulphuric acid; the extract is concentrated, separated from
deposited sulphate of lime, nearly neutralised with carbonate of soda,
and precipitated with neutral acetate of lead. After removing the
precipitate by filtration, the filtrate is treated with hydrosulphuric
acid to free it from lead and colouring matter remaining in solution,
and afterwards precipitated with carbonate of soda, and shaken
repeatedly with ether, which takes up aribine. The ethereal solution
is mixed with hydrochloric acid, and the hydrochlorate of aribine
thereby precipitated is collected, and purified by crystallisation and
washing with strong hydrochloric acid, after which its aqueous solution
is decomposed by agitation with carbonate of soda and ether. The
aribine purified by this process, repeated several times, is lastly crystal-
lised from ether. It may be obtained in anhydrous and in hydrated
crystals.
Properties.
VOL. XVII.
Colourless, highly lustrous, rhombic pyramids, or
20
562
PRIMARY NUCLEUS C46H22; AZO-NUCLEUS C45N4H¹8.
prisms with angles of 76° 30' and 103° 30'. Melts at 229°, and
solidifies in a crystalline mass. When cautiously heated, it sublimes.
below the melting point in very delicate long needles, but when it is
rapidly heated, empyreumatic products are also formed. It has an
alkaline reaction. Without action on polarised light.
Rieth.
mean.
46 C
4 N
20 H.....
276
78.43
78.33
56
15.89
15.87
20
5.68
........
5.79
C46N4H20
352
100.00
酿​彀
​99.99
When aribine is heated with iodide of ethyl in a water-bath for a
few days, yellow crystals are produced, which are soluble in water,
contain 49.29 p. c. C., and 4.62 H., and are probably formed by the
combination of 2 atoms of ethylic iodide with 1 atom of aribine :
C46N4H20 + 2C+H³I = C46N4H18 (2C+H³),2HI
(calc. 48.82 p. c. C., 4.52 H.). When an alcoholic solution of these
crystals is decomposed with oxide of silver and the solution is evapo-
rated (after removing the iodide of silver) hydrate of biethylaribine
remains as an amorphous, coloured varnish, which forms a crystalline
compound with hydrochloric acid. Alcoholic biethylaribine again
heated with iodide of ethyl yields a brown liquid, or when evaporated,
a black crystalline mass, with a large quantity of free iodine.
Combinations. With Water. A. Hydrated Aribine. - Flat, four-
sided prisms, with oblique end-faces, hollow throughout the entire
length, and open above. The crystals, which are transparent and
shining, effloresce in the air, becoming white and opaque, and lose the
whole of their water of crystallisation at 100°.
Rieth.
C46N4H20
16 HO
Crystals.
mean.
352
70.97
71.59
144
29.03
28.41
496
100.00
100.00
C46N4H20 +16aq
B. Aqueous solution. - Aribine dissolves in 7762 parts of water at
23°, and more freely in hot water. It is deposited from a hot satu-
rated solution, at first in anhydrous and afterwards in delicate feathery
hydrated crystals.
C. Iodine, bromine, and chlorine throw down from dilute hydrochlo-
rate of aribine, brown, yellow, or colourless crystalline needles, which
dissolve on warming the liquid, and appear again on cooling.
D. Aribine combines with acids to form salts which are generally
easily crystallisable, and contain 2 or 4 atoms of acid to 1 atom of
base. From a dilute aqueous solution of the hydrochlorate, caustic
soda and its carbonate, ammonia, and lime-water throw down crystalline
aribine, which dissolves when the liquid is warmed, and makes its ap-
pearance again as it cools. Baryta and strontia-water throw down
insoluble precipitates on warming. Many salts and acids, including
ARIBINE.
563
the following, likewise produce crystalline precipitates [owing, perhaps,
to the fact, that hydrochlorate of aribine is insoluble in saline solutions, as well as in
strong hydrochloric acid (Kr.)]: phosphoric acid, arsenic acid, arsenate of
ammonia, iodide and bromide of potassium, bromate, chlorate, nitrite,
and nitrate of potash, phosphate of soda, chloride of barium, sulphide
of barium, sulphide of strontium, chromate and bichromate of potash,
mercuric chloride, cyanide of potassium, ferrocyanide and ferricyanide
of potassium, cyanate and sulphocyanate of potash, acetate of soda,
and acetate of magnesia. The following salts do not produce precipi-
tates; acetate, oxalate, and binoxalate of ammonia, oxalate of potash,
succinate of ammonia, and acid tartrate of soda. Acetate of ammonia
dissolves the precipitate produced by acetate of soda, and tartaric acid
that formed by neutral tartrate of soda.
Sulphate of Aribine.
A. Bi-acid. Formed from hydrochlorate
of aribine and sulphate of silver.
C46N4H20
2 (HO,SO³)
C46N4H20,2(HO,SO³)
at 120°.
Rieth.
352
78.23
98
21.77
21.41
450
100.00
B. Quadri-acid. Formed by mixing aribine with excess of sul-
phuric acid and washing the resulting salt, which is insoluble in the
excess of acid, with ether and ether-alcohol:
C46N4H 20
4(HO,SO³)
C46N4H20,4(HO,SO³)
Rieth.
352
64.24
196
35.76
35.36
548
100.00
Hydrochlorate of Aribine. - Formed by passing dry hydrochloric
acid gas over aribine, and expelling the excess of acid by a current of
dry air at 100°. Slender needles, easily soluble in water and pre-
cipitable from the solution by strong hydrochloric acid. The salt is
soluble in fusel-oil, but quite insoluble in ether.
Rieth.
C46N4H20
352
82.83
2HCl
73
17.17
16.50
C46N4H20,2HCl .... 425
100.00
Chloroplatinate of Aribine. - Bichloride of platinum throws down
from hydrochlorate of aribine, pale-yellow needles, which do not dissolve
on warming, even after addition of hydrochloric acid.
C46N4H20,2HC1,401_.......
2Pt
C46N4H20,2HC1,2PtC12
Rieth.
567
74.18
197.4
25.82
25.55
764-4
100.00
6.40
Aribine dissolves easily in cold, and more easily in hot alcohol, less
freely in ether, and also in fusel-oil.
202
561 PRIMARY NUCLEUS C46H30; OXYGEN-NUCLEUS C46H20010.
Primary Nucleus C46H30; Oxygen-nucleus C46H20010.
Ononetin.
C46H22O12 C45H20010, H202.
=
20010,H²².
HLASIWETZ. Wien. Acad. Ber. 15, 152.
Formed, together with sugar, by boiling onospin with acids, or
together with formic acid by boiling formonetin.
Onospin is heated with 10 parts of water, and dilute sulphuric acid
is dropped into the solution till turbidity is produced and until the
supernatant liquid deposits oily drops, and again becomes clear. The
ononetin deposited on cooling is purified by crystallisation from
alcohol. — Or, formonetin is boiled with baryta-water, carbonic acid is
passed into the solution, and the precipitate is boiled with alcoholic
sulphuric acid, which dissolves the ononetin.
Properties. Radiated groups of brittle needles, having a high re-
fractive power. Melts at 120°, losing 1·86 p. c. in weight, and solidi-
fying to a crystalline mass on cooling.
at 100°.
Hlasiwetz.
46 C................
22 H......
12 O......
C46H22O12
mean.
276
70.05
69.33
22
5.58
5.72
96
24.37
24.95
394
100.00
100.00
....
.......
The above is Limpricht's formula (Lehrbuch, 623): Hlasiwetz proposes
C48H22O13.
Decompositions. 1. Ononetin heated on platinum-foil evolves vapours
which excite coughing, burns with flame, and leaves an easily com-
bustible charcoal. — 2. Oil of vitriol and peroxide of manganese colour
ononetin a fine carmine-red. 3. Ononetin heated with nitric acid,
melts to a resin, evolving vapours which excite tears, and forming
oxalic acid, together with picric or styphnic acid.-4. The ammonia-
cal solution assumes a dark chrome-green colour in the air, and is
afterwards precipitable by acids in dark-red resinous flocks.
Crystallised ononetin is nearly insoluble in water; when freshly
precipitated by acids, it dissolves to a small extent in boiling water,
from which it crystallises on cooling.
Ononetin dissolves easily in aqueous alkalis. It is precipitated
from its alcoholic solution by basic acetate of lead, but not by other
metallic salts. It is coloured dark-red by sesquichloride of iron.
It dissolves easily in alcohol, and slightly in warm ether.
ONOSPIN.
565
HLASIWETZ.
Formation.
sugar.
Conjugated Compounds of Ononetin.
a. With Formic Acid.
Formonetin.
C48][20012 = CH1O,CHO*.
Wien. Acad. Ber. 15, 160.
Ononin breaks up on boiling into formonetin and
Preparation. Ononin is boiled with dilute sulphuric or hydrochloric
acid till the originally clear solution solidifies to a pulp of flocculent
crystals, which are to be washed with cold water and crystallised from
boiling alcohol. Or the crystalline mass is dissolved in ammonia, and
the filtered solution is precipitated with so much hydrochloric acid
that a portion of the formonetin still remains in solution, together
with the whole of the colouring matter. The gelatinous precipitate
thus obtained is collected, washed, and crystallised from alcohol.
Properties. Small tasteless crystals.
Hlasiwetz.
at 100°
mean.
48 C.......
288
71.29
70.88
20 H....
20
4.95
4.87
12 O.....
96
23.76
24.25
C48H20012
404
100.00
100.00
Hlasiwetz gives the formula C50Н2013.
Formonetin assumes a fine violet colour with oil of vitriol and oxide
of manganese. The solution in aqueous alkalis or in baryta-water breaks
up on boiling into ononetin and a formiate:
C48H20012 + 4HO
=
C46H22012+ C²H²O¹.
It is insoluble in water and is not acted on by aqueous ammonia.
It is not precipitated by sesquichloride of iron or other metallic salts.
It is soluble in boiling alcohol, but nearly insoluble in ether.
b. With Sugar.
Onospin.
С59H34024 = C4³H²2012,C¹²H¹2012.
HLASIWETZ. Wien. Acad. Ber. 15, 147.
566
PRIMARY NUCLEUS C46H30; OXYGEN-NUCLEUS C46H2010.
*
Formation. Ononin, boiled with baryta-water, breaks up into
onospin and formic acid.
Preparation. Ononin is boiled with baryta-water till a pure yellow
precipitate is produced on the addition of more baryta-water; the
liquid is cooled and treated with a current of carbonic acid, or mixed
with sulphuric acid not in excess, so long as a brisk effervescence is
produced; and the precipitate is separated by filtration, washed with a
little cold water, removed from the filter while still moist, and after
neutralisation with a few drops of dilute sulphuric acid, boiled re-
peatedly with water. The hot filtered decoctions solidify on cooling
to a crystalline mass of onospin, which is collected and recrystallised
three or four times from hot water, at last together with animal
charcoal. The liquid, filtered from the carbonate of baryta and onospin, contains
formiate of baryta and sometimes also onospin-baryta, which it deposits in the form
of an amber-yellow resin on cooling. An alcoholic solution of this body, when de-
composed by excess of sulphuric acid and filtered, yields onospin on evaporation.
Properties. Microscopic crystals, drying up to a shining pellicle,
which is slightly electric when rubbed. Nearly tasteless. Melts at
162° and does not undergo further alteration at 200°, or sublimes in
small portion, and solidifies to a translucent, hygroscopic gum, which
is highly electric when rubbed, has a bitterish styptic taste, and crys-
tallises from boiling water.
at 100°.
58 C......
34 H
348
34
60.63
Hlasiwetz.
mean.
60.15
6.04
33.81
ཝཱ ཏི སྒྲ ཇི
24 O......
C58H34024
192
574
5.92
33.45
100.00
100.00
The above is Limpricht's formula. Hlasiwetz proposed C60H34025.
Decompositions. 1. Onospin, when heated on platinum-foil, melts,
burns with flame, and emits a faint odour of sugar. 2. It dissolves
in oil of vitriol with reddish-yellow colour, which changes to carmine-
red on addition of oxide of manganese.
3. It is oxidised by nitric acid,
with formation of oxalic acid. -4. When boiled with dilute hydro-
chloric or sulphuric acid, it dissolves and breaks up into sugar and ono-
netin, which separates in crystals or in oily drops :
-
C58H34024 C46H22O12 + C12H12O12 (Limpricht).
=
In this decomposition, 100 parts of onospin yield, on the average, 29.9
parts of sugar (calc. 31-36 p. c. C12H22O12).
Combinations. Onospin dissolves in all proportions in boiling water
and crystallises from the solution on cooling.
It dissolves easily in aqueous ammonia and in aqueous alkalis, from
which it is precipitated by acids. It crystallises unaltered from its
solution in ammonia.
Onospin-baryta. Occasionally obtained in the preparation of onospin
as a resin containing variable proportions of baryta, It dissolves
easily in alcohol and crystallises from the solution after long standing.
ONONIN.
567
Onospin is not precipitated by metallic salts with the exception of
basic acetate of lead. It does not reduce a boiling solution of nitrate of
silver. It colours sesquichloride of iron a dark cherry-red, even in dilute
aqueous or alcoholic solution. It does not reduce an alkaline solution of
cupric oxide.
It is easily soluble in alcohol, but nearly insoluble in ether.
c. With Formic Acid and Sugar.
Ononin.
C60H34026 C46H21011, C12H22O12,C2HO³.
REINSCH. Repert. 76, 12; 78, 18; Berzel. Jahresber. 23, 506.
HLASIWETZ.
Wien. Acad. Ber. 15, 142; J. pr. Chem. 65, 419; abstr.
Pharm. Centr. 1855, 449 and 470; Pharm. Viertelj. 4, 544; Chem.
Gaz. 1855, 321 and 342; N. Ann. Chim. Phys. 46, 374; Kopp's
Jahresber. 1855, 713.
Discovered by Reinsch in the roots of Ononis spinosa: investigated
principally by Hlasiwetz. - Different from ononide (p. 61).
Preparation. 1. When a decoction of the root is precipitated by
neutral acetate of lead, and hydrosulphuric acid is passed into the
filtrate, sulphide of lead is precipitated, and with it the ononin, which
may be extracted from the washed and dried precipitate by three or
four times repeated boiling with alcohol, and purified by recrystallisa-
tion from alcohol with the help of animal charcoal. The precipitate pro-
duced by neutral acetate of lead, when converted into sulphide of lead and boiled
with alcohol, yields a little more ononin, but not sufficient to compensate for
the alcohol and time employed (Hlasiwetz).. 2. An alcoholic extract of the
root is washed with warm water, and the residue is boiled with alcohol
with addition of oxide of lead, which takes up ononin, and when filtered
and evaporated, leaves it in crystals, which are to be further purified.
The aqueous solutions treated as in 1 yield a little more ononin
(Trommsdorff).-3. The root is boiled with alcohol and the decoction
is filtered hot and concentrated to a syrup, which is then freed by suc-
cessive treatment with water, ether, and alcohol of 60 p. c. from sub-
stances soluble in those liquids. The residue is a pale-brown powder,
a solution of which in boiling alcohol yields crystals of ononin on cool-
ing and evaporation. The crystals are to be washed with cold alcohol
of 75 p. c., which takes up ononide, and recrystallised from boiling
alcohol, with the help of animal charcoal (Reinsch).
Properties. Colourless four-sided needles or lamina; according to
Hlasiwetz inodorous and tasteless, but according to Reinsch they have
a sweetish after-taste. Melts at 235°, undergoing some change and
losing 2.65 p. c. in weight, and solidifying in the crystalline state on
cooling (Hlasiwetz).
568
PRIMARY NUCLEUS C46H34; OXYAZO-NUCLEUS C46N2H2408.
Hlasiwetz.
at 100°.
mean.
60 C.......
360
59.80
59.87
34 H
34
5.64
5.60
26 O......
208
34.56
34.53
CG0H31026
602
100.00
100.00
The above is Limpricht's formula (Grundriss, 680, and Lehrbuch, 622), which as
it contains an even number of atoms, and accounts for the products of decomposition
of the substance, and likewise agrees sufficiently well with the analyses, is preferable
to that of Hlasiwetz, C62H3O27 (Kr.).
Decompositions. 1. Ononin heated on platinum foil melts and burns
with flame (Hlasiwetz).-2. When heated in a glass tube, it yields a
sublimate and leaves a brown residue, which afterwards carbonises
(Reinsch).-3. It forms, with oil of vitrol, a reddish-yellow solution,
which afterwards turns cherry-red, and on addition of oxide of
manganese, a fine carmine-red. - 4. Ít is dissolved by nitric acid, with
yellow colour, and is decomposed, with formation of oxalic acid
(Hlasiwetz), a bitter substance, and a peculiar acid (Reinsch).-5. Its
solution in hot hydrochloric or dilute sulphuric acid breaks up on boiling
into sugar and formonetin, the latter of which crystallises out
(Hlasiwetz):
C60H34026 C48H20012+ C12H12012 + 2HO.
6. Ononin, subjected to prolonged boiling with baryta-water (or
caustic potash), dissolves with yellow colour, emitting a faint aromatic
odour and breaking up into onospin and formic acid (Hlasiwetz):
C60H34026+ 2HO C58H34024 + C²H²0¹.
Combinations. Ononin is insoluble in cold, and but slightly soluble
in boiling water, from which it crystallises on cooling. It is not
affected by chlorine-water, or by ammonia, aqueous sesquichloride of iron
or metallic salts. It is precipitated from its alcoholic solution in white
flocks by basic acetate of lead (Hlasiwetz).
Ononin dissolves in strong alcohol on long boiling. After boiling
for some time with water, it is taken up by moderately strong alcohol.
It is nearly insoluble in ether (Hlasiwetz; Reinsch).
Primary Nucleus C46H34; Oxyazo-nucleus C48N2H2408.
Aricine.
C46N2H2608
=
C46N2H2408,H².
PELLETIER & CORIOL. J. Pharm. 15, 565; N. Tr. 21, 1, 127; Repert.
33, 364.
LEVERKÖHN. Repert. 33, 353.
PELLETIER. Ann. Chim. Phys. 51, 185; Schw. 67, 81; Ann. Pharm.
6, 23.
MANZINI. N. J. Pharm. 2, 95; abstr. Compt. rend. 15, 105; J. pr.
Chem. 29, 42; N. Br. Arch. 32, 48; N. Ann. Chim. Phys. 6, 127.
N. J. Pharm. 2, 313.
F. L. WINCKLER. Repert. 75, 299; 81, 249
Cusconine (Pelletier; Winckler). Cinchovatine (Manzini). — Discovered by
Pelletier & Coriol in 1829.
ARICINE.
569
Occurs in China de Cusco vera (Wiggers, 412), which was investi-
gated by Pelletier & Coriol and by Leverköhn as a spurious calisaya.
In China Jaen palliaa (Wiggers, 402) (Manzini).- Winckler examined
Pelletier's bark, which assumes a green colour with strong nitric acid,
as is the case also with the ethereal extract obtained from it.
Formation. Aricine is formed by treating kinone with nitrate of potash and
oil of vitriol, adding to the product water and zinc, and after 24 hours evaporating
and exhausting the residue with alcohol; the product is turned green by nitric acid
(Schoonbroodt, Par. Soc. Bull. 1, 107; Chem. Centr. 1863, 111). This statement
requires confirmation (Kr.).
Preparation. Aricine is obtained, in the same way as quinine, by
boiling the bark with acidulated water, treating the extract with lime,
and exhausting the lime-precipitate with alcohol of 36°. The alcoholic
extract is filtered hot and the brown filtrate is set aside for a day, when
it deposits the greater part of the aricine in fine crystals, which must
be removed. The mother-liquor is freed from most of the alcohol by
distillation; the black residue is treated with a slight excess of dilute
hydrochloric acid and mixed with a strong solution of chloride of
sodium, which precipitates the colouring matter; and the liquid is
filtered and precipitated by ammonia. The precipitate is redissolved
in hydrochloric acid, and the solution is precipitated by chloride of
sodium, filtered, and again precipitated by ammonia, until the aricine
appears of a straw-yellow colour, after which it is purified by crystalli-
sation from alcohol, with help of animal charcoal (Manzini).
Winckler
submits to distillation the tincture obtained by exhausting the lime
precipitate; dissolves the residual resin in very dilute acetic acid;
decolorises the solution with oxide of lead, basic acetate of lead, and
animal charcoal; precipitates with ammonia; and purifies the product
by crystallisation. In this way the bark yields about 1.4 p.c. of
aricine.
Properties. Thick needles, tasteless at first, afterwards warm and
acid, and having a very bitter taste when dissolved in acids (Pelletier
and Coriol). Very delicate prisms having a vitreous lustre, arranged
in circles (Winckler). According to Manzini, colourless crystals, longer
than those of cinchonine, inodorous, slowly exciting a bitter taste in the
mouth. Has an alkaline reaction. Does not undergo any alteration at
150° and melts at 188° without loss of weight, to a resin which has
the same melting-point when heated again (Manzini). Leverköhn's
aricine was bitter, not alkaline, and not crystallisable, but, like that of
the other chemists, it formed a tremulous jelly with sulphuric acid.
Pelletier.
Manzini.
mean at 120°.
46 C
276
70.05
69-6
69.59
2 N
28
7.09
8.0
7.36
26 H.....
26
6.60
7.0
7.04
80
64
16.26
15.4
16.01
C46N2H2608
394
10000
100.0
100.00
According to Pelletier, C20NH203. Manzini's formula contains 1 at. of hydrogen
more than the one above given, which was preferred by Gerhardt (Traité, 4, 152).-
Isomeric with brucine.
570 PRIMARY NUCLEUS CH¾; OXYAZO-NUCLEUS CªN²H¾Q³,
Aricine gives off stinking empyreumatic products at 190°, leaving
charcoal (Manzini). It dissolves in strong nitric acid with dark-
green colour, and in dilute acid with paler colour (Pelletier & Coriol).
Winckler's aricine exhibits this coloration only when impure.
Aricine is nearly insoluble in water, but easily soluble in dilute
acids, forming for the most part crystallisable salts, which dissolve
even in weak warm alcohol. The salts are precipitated by caustic
alkalis and their carbonates (Manzini). The precipitate is pulverulent,
not resinous (Winckler). The salts are precipitated by ammonia, but
a portion of the aricine remains dissolved in excess of ammonia, from
which it crystallises: the precipitate, which is amorphous at first,
likewise becomes crystalline after a few days. The salts are precipi-
tated by iodide of potassium, bichloride of platinum, chloride of gold,
and tannic acid (Manzini).
Sulphate of Aricine. A. Neutral? —- A neutral solution of aricine
in dilute sulphuric acid solidifies on cooling to a white tremulous jelly,
which dries up to a horny mass on exposure to the air, and is again
converted into a jelly by boiling water. A solution of the salt in
alcohol yields silky needles, dull according to Winckler, resembling
those of sulphate of quinine. The crystals dissolve in warm water
[less easily than sulphate of cinchonine, more easily than sulphate of
quinine (Winckler)], and again gelatinise on cooling. The salt is
insoluble in ether (Pelletier & Coriol).
B. Acid. Flat needles (Pelletier); crystals, obtained by dis-
solving aricine in a slight excess of sulphuric acid. Does not lose
weight at 210° (Manzini). The solution exhibits a blue fluorescence
(Winckler).
46 C
2 N
28 H
10 O
2 S03
C46N2H2608,2 (HO,SO³)
Manzini.
276
56.09
55.59
28
5.69
28
5.69
6.07
80
16.27
80
16.26
16.68
492
100.00
Hydriodate of Aricine.
A solution of aricine in warm dilute acid
yields, on cooling, lemon-yellow needles, very slightly soluble in
cold, easily soluble in warm alcohol. The crystals do not change
at 200°, but cake together at 220°, and melt to a dark mass at 250°
(Manzini).
at 120°
Manzini.
C46N2H2608
HI........
394
75.48
128
24.52
24.54
C46N2H2608,HI .... 522
100.00
Hydrochlorate of Aricine. When aricine is exposed to a current of
hydrochloric acid gas at 120°, 100 parts of it take up 8.52 parts of
hydrochloric acid (1 at. = 9.26 parts HCI). The mass becomes warm,
without melting, assumes a yellow, afterwards dark-orange colour,
and when dissolved in alcohol and evaporated, leaves an amorphous
A solution of aricine in warm aqueous hydrochloric acid
brown gum.
PARICINE.
571
yields, on cooling, crystals which lose their water of crystallisation in
a vacuum, and nothing more at 120° (Manzini).
C46N2H2608
HCI...
C6N2H2O,HC
at 130°.
394
36.5
430.5
....
Manzini.
91.76
8.24
8.33
100.00
Chloroplatinate of Aricine. - Lemon-yellow precipitate, very slightly
soluble in water, but easily soluble in alcohol, from which it crystallises
on spontaneous evaporation (Manzini).
C46N2H2608.......
HC13
Pt
C46N2H2608, HCl,PtCl²
at 120°.
394
Manzini.
65.67
107.5
17.91
98.7
16.42
16.31
600.2
100.00
Aricine dissolves in alcohol more easily than cinchonine, less easily
than quinine (Winckler). It is soluble in ether.
Appendix to Aricine.
Paricine.
F. L. WINCKLER. Repert. 91, 145; 92, 29, and 231; N. Repert. 1,
11.
To be distinguished from aricine. Discovered by Winckler in
1845 in China Jaen fusca from Para (Wiggers, 404), and at first
mistaken for aricine (p. 568), but afterwards found to be an inde-
pendent body. It occurs also in a bark resembling Cortex caribœus
[China de Para rubra? (Kr.)] (Winckler, Repert. 96, 341).
3 0
Preparation. The finely powdered bark is exhausted by thrice boil-
ing it with three times its weight of 80 p. c. alcohol. The extracts thus
obtained are freed from the greater part of the alcohol by distillation,
and the residue is evaporated to dryness, triturated, and digested
with warm hydrochloric acid containing th of the fuming acid, which
leaves a portion undissolved. The dissolved paricine is precipitated
with carbonate of soda, washed, dried, dissolved in ether, and recovered
from the solution by evaporation; then dissolved in very dilute hydro-
chloric acid, treated with animal charcoal, and again precipitated with
carbonate of soda. The portion remaining undissolved in the first treatment
with dilute hydrochloric acid may be freed from a red compound by heating it with
aqueous carbonate of soda, after which acids take up more paricine from the residue.
Paricine thus obtained leaves a slight residue when dissolved in dilute sulphuric
acid.
Properties. Yellow amorphous resinous mass. Hydrate of paricine,
containing 5.03 p. c. of water, precipitated from the acid solutions by
ammonia or alkalis, forms a white, very loose powder. Tastes very
bitter.
572 PRIMARY NUCLEUS C4H¾; OXYAZO-NUCLEUS CN²H¾408.
According to the (preliminary) analyses of Weidenbusch, paricine
is represented by the formula C46N2H2506: the phosphate, hydro-
chlorate and chromate contain, in combination with the amount of pari-
cine represented by this formula, 1 atom of acid and 1 atom of water.
Paricine is coloured greenish-yellow, afterwards a fine dark-green
by nitric acid of sp. gr. 14; also by oil of vitriol, and is decomposed
by the latter acid.
It is wetted with difficulty by water, and dissolves very slightly.
It is soluble in dilute acids (more slowly after drying), forming
colourless or yellow amorphous salts. The sulphate and hydrochlorate
are precipitated from their neutral solutions by hydrochloric, nitric, or
sulphuric acid, the precipitates being soluble in water.
-
Phosphate of Paricine. Precipitated from the hydrochlorate by
phosphate of soda. Resembles the hydrate (Winckler).
14.86 p. c. PO5, and 2.06 p. c. of water (Weidenbusch).
Contains
Sulphate of Paricine. A solution of paricine in warm dilute sul-
phuric acid solidifies on cooling to a firm jelly, which dries up to a
brown, translucent, horny mass, turning opaque when warmed,
triturable to a white powder, and containing, after drying at 100°,
7·79 p. c. of sulphuric acid (Winckler).
Hydrochlorate of Paricine. A solution of paricine in hydrochloric
acid leaves on evaporation a colourless friable resin, which, according
to Weidenbusch, contains 8:53 p. c. of water.
Chromate of Paricine. -- Contains 2.3 p. c. of water, and 16·4 p. c.
of chromic acid (Weidenbusch).
Hydrochlorate of paricine precipitates mercuric chloride (Winckler).
It throws down a yellowish-white amorphous precipitate from iodomer-
curate of potassium (Delffs).
Chloroplatinate of Paricine. Resembles the quinine-salt. Burns
vigorously when heated. Contains 3 p. c. of water, and 15 to 16 p. c.
of platinum (Winckler).
Paricine dissolves easily in alcohol and ether.
Brucine.
C'46N2I2608 = C4N²H²O³,H².
PELLETIER & CAVENTOU. Ann. Chim. Phys. 12, 113; J. Pharm. 2,
529; Schw. 28, 32; Gill. 63, 322; Ann. Chim. Phys. 26, 53.
MERCK.
DUFLOS.
N. Tr. 20, 1, 134.
Schw. 62, 68.
LIEBIG. Pogg. 21, 22, and 487. — Ann. Pharm. 26, 53; 29, 62.
REGNAULT. Ann. Pharm. 26, 20; J. pr. Chem. 16, 267. — Ann. Pharm.
29, 59.
PELLETIER.
Ann. Chim. Phys. 63, 176; Ann. Pharm. 22, 121.
J. Pharm. 24, 159; Ann. Pharm. 29, 53; J. pr. Chem. 14, 180.-
Ann. Chim. Phys. 54, 186.
VARRENTRAPP & WILL. Ann. Pharm. 39, 285.
BRUCINE.
573
DOLLFUSS. Ann. Pharm. 65, 214; Kopp's Jahresber. 1847 and 1848,
629.
STRECKER. Ann. Pharm. 91, 76; N. Ann. Chim. Phys. 42, 366; Kopp's
Jahresber. 1854, 520.
Discovered by Pelletier & Caventou in 1819. -Occurs in the bark
of Strychnos Nux vomica and in false angustura bark; also, together
with strychnine, in Nux vomica, sparingly in Ignatius' beans and in
Upas Tieuté. See p. 480.-A South American arrow poison from
Cuenia, known as Cuba longa, contains brucine, but no strychnine
(Palm, Pharm. Viertelj. 11, 552).
Preparation. 1. From Nux vomica. In the preparation of strych-
nine by the method described at p. 480, brucine remains dissolved,
together with colouring matter, in the alcohol of 34 p. c. employed, and
is obtained as sulphate by evaporating the alcoholic solution to a
syrup, neutralising with cold dilute sulphuric acid, and setting the
liquid aside for some days; the salt then crystallises, and is to be
separated from the black mother-liquor by pressing. The crystals are
dissolved in water, and the solution is decolorised with animal charcoal
and precipitated by ammonia, which throws down a portion of the
brucine, the remainder crystallising from the ammoniacal liquid on
exposure to the air. The crystals are purified by recrystallisation
from boiling alcohol of 80 p. c. (Coriol & Soubeiran, N. J. Pharm. 45,
231).- Wittstein (Darstell. und Prüfung, 215) evaporates the alcoholic
mother-liquor of strychnine to dryness with a quantity of binoxalate
of potash amounting to th of the weight of the nux vomica em-
ployed, then triturates the residue, and digests it for two days with
absolute alcohol at 0°. The undissolved portion is again washed with
ice-cold absolute alcohol so long as it imparts a colour thereto, and is
then dissolved in warm water, heated to volatilise the whole of the
alcohol, and agitated for several days with a quantity of magnesia
equal toth of the weight of the nux vomica employed. The pre-
cipitate thereby produced is collected and exhausted with 90 p. c.
alcohol, and the tincture is concentrated and placed in the cold; the
brucine then collects at the bottom in the form of an oil, which after-
wards crystallises. In this way 10 pounds of nux vomica yield
6 drachms of brucine (Wittstein).
50
1
2. From false Angustura bark. The bark is freed from fat by
ether, and boiled repeatedly with alcohol; the tincture is evaporated
and the residue dissolved in water; the greater part of the colouring
matter is precipitated with basic acetate of lead; the liquid is filtered
and freed from excess of lead by hydrosulphuric acid; and the filtrate
is boiled to throw down a little strychnine, mixed with a quantity of
magnesia equal to th of the bark, again filtered, and evaporated:
a granular mass of brucine then remains, together with colouring
matter. The brucine thus obtained is converted into oxalate by the
addition of oxalic acid, and the salt is treated with ice-cold absolute
alcohol, which takes up colouring matter. The remaining pure oxalate
of brucine is decomposed by evaporating it with magnesia and water,
and the dry mass is exhausted with alcohol and the tincture evaporated
to crystallisation (Pelletier & Caventou).
The hydrated crystals are still to be freed from water by heating.
574 PRIMARY NUCLEUS CH; OXYAZO-NUCLEUS C46N*H*40³.
Properties. Anhydrous brucine melts a little above 100° to a
colourless liquid, which solidifies to a brittle wax on cooling. See
further Hydrated Brucine.
Very small quantities of brucine cautiously heated on platinum
foil in the manner described under strychnine (p. 484), yield on the
superposed glass plate, a whitish deposit, in which round granules
are visible under a magnifying power of 80 diameters; but if the
brucine is too strongly heated, fatty drops also make their appearance.
On addition of water, the granules collect in denser groups without
becoming crystalline: aqueous ammonia likewise produces no crystals
but unites the granules in deep-yellow oily drops. Strong nitric acid
colours the granules deep orange-yellow; dilute nitric, hydrochloric,
or sulphuric acid produces crystalline formations which rapidly dis-
appear. Dilute chromic acid dissolves the granules only slowly and
incompletely, but produces dark-yellow prisms and stars at the edges
of the microscopic drops (Helwig, Anal. Zeitschr. 3, 49).
Dumas &
Pelletier. Liebig. Regnault. Ettling. Strecker.
46 C
276 ...
70·00.... 74·11 ...
69.90
69.95 .... 69.88 .... 70.00
2 N
28
7.10
7.22
5.07
7.07
26 H
26
6.64
80
64
16.26
6.52
12.15
6.66
6.77
6'75 ... 6.70
....
18.37
16.21
C46N2H2608
394
100.00
100.00
100.00
100.00
....
....
....
The above formula was established by Regnault and Dollfus. Earlier formulæ :
C24NH12O3 (Dumas & Pelletier); C32NH1806, afterwards C47N2H27O8 (Liebig);
C48N2H2408 (Regnault); CN2H2507 (Varrentrapp & Will). - Isomeric with
aricine (p. 568).
Decompositions. 1. Brucine heated above its melting point yields
combustible gas and a very little carbonic acid, together with water,
acetic acid, and a large quantity of empyreumatic oil, but no ammonia
(Pelletier and Caventou).-2. When melted on platinum-foil and then
more strongly heated, it takes fire, and leaves a bulky, easily combustible
cinder (Merck).-3. In the decomposition of its salts by electrolysis,
there appears at the positive pole the red colour which is likewise pro-
duced by the action of nitric acid (Pelletier & Couerbe). It behaves in the
-4. It forms a
same way as morphine (xvi, 425) (Hlasiwetz & Rochleder).
peculiar compound with iodine (see below). Bromine forms with it
bromobrucine (Laurent). Bromine-water produces a brown precipitate
in aqueous brucine (Duflos). 5. Chlorine gas passed into water in
which brucine is suspended dissolves the brucine, forming a yellow
neutral liquid which turns acid and assumes a rose-red to blood-red
colour, and afterwards loses its colour and deposits a small quantity
of yellowish flocks. When neutralised with ammonia and evaporated,
it leaves sal-ammoniac, coloured red; from the blood-red solution
ammonia throws down an amorphous, bitter, non-poisonous resin.
Aqueous hydrochlorate of brucine is likewise coloured by chlorine,
without forming an insoluble product, as is the case with strychnine
(Pelletier), so that traces of strychnine may be detected in brucine by
the cloudiness produced on passing chlorine into the solution for ten
minutes (Lepage, J. Pharm. 26, 140). Chlorine-water colours solu-
tions of brucine-salts a fine pale-red, which is changed to yellowish-
brown by ammonia.
6. Brucine is not coloured by cold oil of vitriol, but assumes a yellow
BRUCINE.
575
colour with the hot liquid (Kersting; Guy, Anal. Zeitschr. 1, 92).
See below.-7. On boiling a strong solution of the hydrochlorate with
nitrite of potash, it evolves a large quantity of gas burning with a
green-edged flame (A. W. Hofmann, Ann. Pharm. 75, 368).
8. Brucine assumes a dark-red colour when nitric acid of sp. gr.
1.4 is poured upon it (Pelletier & Caventou), becoming hot and dissolv-
ing, with evolution of combustible gas, the residue solidifies, on
cooling, to an orange-coloured mass, from separation of cacotheline
(Gerhardt). When the cacotheline is allowed to remain in contact
with the nitric acid mother-liquor for a few hours, it is converted into
another chrome-yellow body, which is insoluble in water and explodes
when heated (Gerhardt). — The gas evolved is a mixture of nitrite of
methyl (1 atom of which is produced from 1 atom of brucine), nitric
oxide, and carbonic acid, the last being formed from oxalic acid, which
occurs, together with cacotheline, in the residue. In this reaction
1 atom of brucine yields 4 atoms of carbon in the form of oxalic or
carbonic acid :
C46N2H2608 +5NO6HC40N4H22O18+ C2H30,NO3 + C4H208 + 2NO² + 4HO (Str.).
Brucine.
Cacotheline. Methylic
nitrite.
Oxalic
acid.
:
Gerhardt regarded the combustible gas as nitrite of ethyl, free from nitric oxide
and carbonic acid; and according to Laurent, the gas does not contain carbonic
acid. Liebig, by warming the mixture of acid and brucine, obtained, instead of
nitrite of methyl, a liquid condensable in a freezing-mixture, boiling at 70° to 75°,
not miscible with water, and heavier than dilute nitric acid according to Strecker
this body is probably nitrate of methyl obtained by the employment of more dilute
nitric acid. Laurent condensed the gas obtained from brucine and nitric acid to a
liquid which distilled at 10° to 16°, burned with flame, evolving nitrous fumes, and
contained carbon and hydrogen in the same proportion as nitrite of ethyl. This
body was perhaps a mixture of nitrite and nitrate of methyl (Kr.). See Liebig
(Ann. Pharm. 57, 94, and 58, 234) and Gerhardt, Laurent, and Rosengarten, in the
memoirs referred to under cacotheline (p. 358).
The fine red solution of brucine in excess of nitric acid is decolorised
by hydrosulphuric acid, sulphurous acid, or protochloride of tin; it
turns yellow on warming or on further addition of nitric acid, where-
upon protochloride of tin [and hydrosulphate of ammonia (Fresenius)]
immediately produces a splendid violet coloration and precipitate
(Pelletier & Caventou). Fuming nitric acid dissolves brucine, with
considerable intumescence, forming a red solution: nitric acid of
sp. gr. 1.2 dissolves it with gradually deepening brown-red colour
(Duflos).
When a layer of a solution of brucine in 1,000 parts of water is
placed upon an equal bulk of oil of vitriol, there is formed, in presence
of traces of nitric acid, a rose-red zone which quickly changes to
yellow at the lower edge. This reaction may be employed for the
detection of very small quantities of nitric acid (Kersting, Ann.
Pharm. 125, 254). Brucine covered with oil of vitriol containing
nitric acid, prepared as described at p. 141, vol. xvi, is coloured a
transient red, changing to yellow; the addition of a few drops of
water hastens the formation of the yellow colour. The solution is
again turned red, afterwards yellow by the addition of particles of
oxide of manganese, and assumes a golden yellow colour when nearly
576
PRIMARY NUCLEUS C46H; OXYAZO-NUCLEUS CN2H2÷0³.
neutralized or when supersaturated with ammonia (J. Erdmann, Ann.
Pharm. 120, 188). Brucine prepared from nux vomica is coloured rose-
red, orange, and olive-green by oil of vitrol (containing nitric acid ?):
brucine from false angustura bark exhibits purer colours which
change, not to green but to deep-yellow (Merck). Other oxidising
bodies (see xvi, 141), added to the sulphuric acid solution, pro-
duce a red coloration in the same way as nitric acid (Lefort, Rev.
scient. 16, 355). Permanganate of potash colours the solution in
sulphuric acid red, brown, orange, and yellow (Guy); chromate of
potash colours it dark-green, with evolution of gas; peroxide of lead
produces no effect (Riegel, N. Br. Arch. 58, 279).
9. When 1 part of crystallised brucine is carefully heated with 10
parts of water, 4 parts of oil of vitriol, and oxide of manganese, an
evolution of inflammable vapours, probably of methyl-alcohol, takes
place, attended with frothing of the mass. Peroxide of lead, mer-
curic oxide, and chromate of potash, employed instead of oxide of
manganese, act in the same way, but on warming 1 part of brucine
with bichromate of potash, 2 parts of oil of vitriol, and 2 parts of
water, carbonic and formic acids are also produced (Baumert, Ann.
Pharm. 70, 337).
The volatile product possesses the following properties. It has a suffocating
odour, and like the product formed by the action of nitric acid on brucine, is
colourless, oily, easily inflammable, and burns with a blue, slightly luminous flame
(Liebig, Ann. Pharm. 65, 114). It reduces nitrate of silver, but is not affected by
potash-ley, and is, therefore, free from aldehyde (Rosengarten, Ann. Pharm. 65,
114). When freed from formic acid by rectification over chalk, and dehydrated as
far as possible, without warming, by carbonate of potash, and afterwards by chloride
of calcium, it forms a transparent, colourless liquid, which has an aromatic odour,
burns with blue flame, and throws down metallic silver when boiled with nitrate of
silver and baryta-water, yielding a volatile acid in combination with baryta. It has
the following composition :-
Baumert.
Merck.
a.
b.
a.
b.
2 C
4 H
20
12
....
4
16
37.5
12.5
50.0
....
33.85
12.36
53.79
31.15
34.5
37.8
12.41
12.2
12.4
....
....
56.44
53.3
49.8
....
C2H402
32
100.0
100.00
100.00
100.0
100.0
****
....
....
A
a was rectified once, b twice, over chloride of calcium. The body is, therefore,
methylic alcohol, not quite free from water.
10. Brucine, acted upon by peroxide of lead and dilute sulphuric acid,
yields a brown amorphous body, soluble in alcohol, and a black, or
in thin layers, red, amorphous body, insoluble in alcohol, both of
which are coloured red or yellowish-red by strong nitric acid and by
oil of vitriol (E. Marchand, N. J. Pharm. 4, 28; J. Chim. méd. 20,
367).
11. Brucine forms derivatives with iodide of methyl (Stahlschmidt),
iodide of ethyl (Gunning), and bibromide of ethylene (Schad).-12. It is
not decomposed by the alcoholic fermentation of sugar, or by putre-
faction (Larocque & Thibierge, J. Chim. méd. 18, 689).
Combinations. A. With Water. 1. Hydrated Brucine. - Crystal-
lises on slowly evaporating an alcoholic solution mixed with water in
BRUCINE.
577
transparent oblique four-sided prisms (Pelletier & Caventou), or in
radiated groups of needles (Merck). By rapid evaporation pearly
laminæ, resembling boracic acid, are obtained (Pelletier & Caventou).
-Has a powerful and persistent bitter taste. Poisonous, though less
so than strychnine. - Rotates a ray of polarised light to the left; [a]
in transparent crystals 61.27°, in slightly effloresced crystals =
64.48°, both in alcoholic solution; in solution in hydrochloric acid the
rotation is only 13.97°, but it is restored to the original amount by
ammonia (Bouchardat, N. Ann. Chim. Phys. 9, 213).
Brucine gives off the whole of its water of crystallisation in a
vacuum over oil of vitriol (Strecker), or when heated to 130°, or till it
melts, forming anhydrous brucine.
C46N2H2608
Crystals.
Regnault.
Liebig.
Varrcntrapp
& Will.
394
72
....
84.55
15.45
15.45
16.66
14.60
....
C46N2H2608 + Saq.
466
100.00
•
Or
8 HO...
46 C
2 N
34 H
16 O
C46N2H260 + 8aq.
Varrentrapp
Crystals.
Regnault. & Will.
276
59.22
59.00
28
6.01
6.65
34
7.29
7.29
128
27.48
466
100.00
According to Pelletier & Dumas, brucine crystallised from water contains 18.5
p. c., whilst that crystallised from alcohol contains 13.5 p. c., of water of crystal-
lisation.
2. Aqueous solution. - Brucine dissolves in 850 parts of cold, and
in 500 parts of boiling water (Pelletier & Caventou); in 768 parts of
water at 18.75° (Abl). Crystallised brucine dissolves in 320 parts of
cold, and in 150 parts of boiling water (Duflos).
Brucine is insoluble in ammonia-water (Merck): potash and am-
monia render it less soluble in water. It is precipitated from its
aqueous solution by potash-ley immediately, and by carbonate of
potash on standing for a short time (Duflos).
B. With Iodine. - Tincture of iodine throws down from brucine-
salts a dense kermes-brown or chocolate-brown precipitate, which
dissolves to a pale-brown liquid when heated (Simon, Repert. 65, 194;
v. Planta). The orange-brown precipitate produced by biniodide of
potassium in solutions of acetate of brucine, even when dilute, dis-
solves in caustic potash, but not in acetic acid (Wormley).
A. With 1 atoms of Iodine. Brown precipitate, thrown down
from cold alcoholic brucine by tincture of iodine, not in excess (Pelle-
tier). According to Regnault it crystallises in laminæ.
Pelletier.
2 C46N2H2608
3 I
788
67.41
381
32.59
33.41
2 C46N2H260$,31....
1169
100.00
B. With 3 atoms of Iodine.
VOL. XVIJ,
Brucing turns brown when triturated
2 T
578
PRIMARY NUCLEUS CH; OXYAZO-NUCLEUS C46N2H2409.
with iodine and water, and forms, on boiling, a soft resin, which gives
up only traces to water, dissolves completely in boiling alcohol, forming
a solution which deposits iodobrucine as a brown powder on cooling,
and afterwards yields white crystals of hydriodate of brucine. -Iodo-
brucine turns red with strong nitric acid and with nitrate of silver
(Pelletier). According to Regnault, this compound likewise crystallises
in laminæ.
46 C
2 N
26 H
80
3 I.....
C4&N÷LI260,31
276
28
26
64
381
775
و
Pelletier. Regnault.
35.62
36.14
3.62
3.35
3.55
8.25
49.16
45.60
100.00
C. With Acids. Brucine neutralises acids completely, forming very
bitter, generally crystallisable salts. From aqueous solutions of bru-
cine-salts, the alkalis, magnesia, morphine, and strychnine throw down
the brucine by combining with the acid. The precipitate produced by
caustic potash and its carbonate is dense, pulverulent, and insoluble in
excess of the precipitant: it is converted, by combining with water,
into concentrically arranged needles, visible to the naked eye. Am-
monia throws down oily drops, which dissolve in an excess of ammonia
added at the same time, and crystallise from the solution in needles:
the oily drops are likewise rapidly converted into needles (Fresenius).
When the addition of ammonia produces an evolution of heat, the
brucine is thrown down as an oil, which in a day or two takes up
water and becomes crystalline (Pelletier & Caventou). Bicarbonate of
soda produces in solutions of brucine-salts, after standing for some
time, a deposit of needles, which are insoluble in excess of the precipi-
tant, but dissolve in the carbonic acid set free on adding to the liquid
a quantity of hydrochloric acid insufficient to decompose the whole of
the carbonate. Bicarbonate of soda throws down larger crystals from
acid solutions, but only when the carbonic acid begins to escape
(Fresenius). A solution of brucine in 200 to 500 parts of water con-
taining tartaric acid is not precipitated by alkaline bicarbonates after
addition of tartaric acid (Oppermann).
Carbonate of Brucine. The very easily formed solution of brucine
in water containing carbonic acid deposits crystals free from carbonic
acid, having a pearly lustre and arranged in long feathery forms.
Alkaline carbonates added to brucine-salts likewise precipitate brucine
free from carbonic acid (Langlois, Ann. Chim. Phys. 48, 502; Ann.
Pharm. 100, 374).
Phosphate of Brucine. - Aqueous phosphoric acid neutralised with
brucine does not yield crystals when evaporated: in presence of an
excess of acid, the solution very easily yields large rectangular tables,
the ends of which are formed by truncation-faces; the crystals are
slightly efflorescent in dry air and easily soluble in water (Pelletier &
Caventou). Phosphate of soda produces no precipitate in nitrate of
brucine; it produces slight flocks in the sulphate, and throws down long
thin needles from the hydrochlorate after 12 hours or more (v. Planta).
By concentrating and cooling a solution of brucine in aqueous
phosphoric acid, Anderson (Ann. Pharm. 66, 58) obtained short thick
BRUCINE.
579
prisms which effloresce in the air, melt in their water of crystallisa-
tion at 100°, and solidify to a resinous mass on cooling. They
dissolve in all proportions in hot and somewhat freely in cold water.
Anderson.
92 C
4 N
55 H
19 0
PO5
2 C46N2H260$,3HO,PO5
552
61.61
62.05
******
56
6.25
55
6.14
6.51
152
18.08
71
7.92
896
100.00
By digesting aqueous monosodic phosphate with brucine, short thick
prisms of a double salt having the formula C46N2H260°, NaO,2HO, PO5
are obtained (Anderson).
Hyposulphite of Brucine. Formed in a mixture of brucine, hydro-
sulphate of ammonia, and alcohol on standing in the air. Prismatic
needles which lose 1.79 p.c. of water in a vacuum over oil of vitriol
(1 at. = 1.8 p. c. HO). Dissolves in 105 parts of cold water (How,
Pharm. Centr. 1855, 95).
In a vacuum.
How.
46 C
276
56.67
56.68
2 N
28
5.74
31 H
31
6.36
6.58
15 O
120
24.66
2 S
32
6.57
C46N2H2608,HO,S²O² + 4aq
487
100 00
Sulphate of Brucine.-A. Neutral. Long, apparently four-sided
very bitter needles, easily soluble in water and slightly soluble in
alcohol (Pelletier & Caventou). Loses at 130°, 12 p. c. (Regnault),
12.33 p. c. of water (Varrentrapp & Will) (7 at. = 12.25 p.c. HO).
46 C ......
2 N
27 H
9 0 .....
SO3
C4N2H2O, HO,SO³
Varrentrapp
Dried.
276
Regnault.
& Will.
62.30
61.86
NAS
28
6.32
6.38
27
6.09
6.53
72
40
16.25
16.45
9.04
8.78
8.87
443
100.00
100.00
...
....
The air-dried salt contains 54.14 p. c. C., and 6-62 H. (Liebig) (calc. 54.54
p. c. C., 6·71 H.).
B. Acid. On adding sulphuric acid to a concentrated solution of
the neutral salt, large crystals are rapidly formed from which ether
takes up the excess of acid not required for the formation of the acid
salt (Pelletier & Caventou).
Periodate of Brucine. - Obtained from periodic acid and alcoholic
brucine. Fine colourless needles producing a faint explosion when
heated (Langlois, N. Ann. Chim. Phys. 34, 278). Dissolves easily in
water and alcohol, forming solutions which undergo alteration in the
air (Bödeker, Ann. Pharm. 71, 64).
2 r 2
580 PRIMARY NUCLEUS CH; OXYAZO-NUCLEUS CNHO³.
Iodate of Brucine. Iodic acid and iodate of potash produce
neither coloration nor precipitate in aqueous brucine-salts (Simon ; v.
Planta). The colourless salt obtained by neutralising aqueous iodic
acid with brucine breaks up on evaporation into opaque silky crystals
of a basic salt and hard four-sided prisms of an acid salt (Pelletier).
By dissolving brucine in iodic acid Serullas (Ann. Chim. Phys. 45, 274) obtained a
red liquid which did not yield distinct crystals, according to Pelletier, because he
employed an excess of acid.
Hydriodate of Brucine. - Iodide of potassium throws down from
solutions of acetate of brucine [containingth or more of the salt
(Wormley)] a crystalline precipitate which after washing with water
crystallises from alcohol in silky needles, soluble in a large quantity of
ammonia-water (Merck). Iodide of potassium throws down from the
hydrochlorate or nitrate, needles or lamina, and from the sulphate, hard
prisms (v. Planta). - Transparent, four-cornered laminæ, or very short
prisms obtained from iodide of potassium and sulphate of brucine, or
by neutralising hydriodic acid with brucine. Dissolves more freely in
alcohol than in water (Pelletier).
46 C
2 N
27 H
80
I
C4N²H²O¾‚HI
Crystals.
Pelletier.
276
52.87
53.62
28
5.36
27
5.17
.....
64
12.26
127
24.34
23.57
522
100.00
....
Perchlorate of Brucine. - Pale-yellow shining prisms, obtained by
neutralising dilute aqueous perchloric acid with brucine. The crystals
give off 5.4 p. c. water at 170°, and detonate when more strongly
heated. Dissolves very slightly in cold water and alcohol, and less
freely than the corresponding strychnine-salt in the hot liquids.
(Bödeker, Ann. Pharm. 71, 62; Kopp's Jahresber. 1849, 382).
Chlorate of Brucine. Chlorate of potash does not precipitate nitrate of
brucine (Simon). By dissolving brucine in warm aqueous chloric acid, a
red liquid is obtained, which deposits transparent rhombohedrons.
resembling calc-spar. The crystals may be obtained free from colour
by recrystallisation. Explodes when heated. Dissolves less easily in
water than chlorate of strychnine (Serullas, Ann. Chim. Phys. 45, 280).
Hydrochlorate of Brucine. 100 parts of dry brucine take up 13.06
parts of hydrochloric acid gas, and form a mass soluble without residue
in water (Liebig); at a temperature of 130°, however, only 9.29 parts
of hydrochloric acid are retained (Regnault) (calc. 9.26 parts HCl).—
By dissolving brucine in warm aqucous hydrochloric acid, four-sided
obliquely truncated prisms and needles [small tufts of needles (Reg-
nault)] are obtained on cooling (Pelletier & Caventou). The salt is
permanent in the air, and dissolves very easily in water (Pelletier &
Caventou). It dissolves freely in warm creosote (Reichenbach).
46 C
2 N
27 H
80
Dried.
Regnault.
276
64.11
63.88
28
6.50
6.54
27
6.27
6.81
64
14.86
14.96
35.5
8.26
7.81
100.00
100·00
CL.....
CN²H²ºOº, HCl.... 430·5
BRUCINE.
581
Hydrofluate of Brucine. A solution of brucine in warm, moderately
strong hydrofluoric acid yields on cooling, small, colourless, right
rhombic prisms, which give off 3.34 p. c. of water at 100°. — The salt
dissolves in water, but is nearly insoluble in cold, and but slightly
soluble in boiling alcohol (Elderhorst, Ann. Pharm. 74, 79; Kopp's
Jahresber. 1850, 432).
Nitrate of Brucine. — A neutral solution of brucine in nitric acid
yields on evaporation an amorphous gum; an acid solution readily
yields large, hard four-sided prisms, with dihedral summits. When
heated the salt turns red and black, and then takes fire with slight
explosion (Pelletier & Caventou). Loses 7.23 p. c. of water at 130°
(Regnault) (4 at. 7.32 p. c. HO).
Regnault.
46 C..........
3 N.
27 H
14 0........
Dried.
mean.
276
60.39
60.50
4.2
9.19
8.92
27
5.90
6.06
112
24.52
24.52
100.00
100.00
........
C46N2H2608,HO,NO5.... 457
Phosphantimonic acid (xiv, 227) throws down from aqueous hydro-
chlorate of brucine, even in dilute solutions, a fine rose-red precipitate,
which dissolves when heated, and reappears on cooling, the liquid
then acquiring a deep crimson colour (F. Schulze, Ann. Pharm. 109,
179). Phosphomolybdic acid (xiii, 164) throws down ochre-yellow
flocks (Sonnenschein); an orange-yellow precipitate, insoluble in nitric
acid, but soluble in aqueous ammonia with yellowish-green colour,
turning brown on boiling, and also in alkalis (Trapp, Russ. Pharm.
Zeitschr. 2, 1; Kopp's Jahresber. 1863, 702).
Chromate of Brucine. The neutral and acid chromate of potash
throw down from acetate of brucine (even from solutions containing
onlyth of the alkaloïd) yellow needles, insoluble in acetic acid
(Wormley). Neutral chromate of potash and sulphate of brucine yield
small, pale-yellow prisms, of a neutral salt, which reddens in sunshine.
Chromic acid and brucine form micaceous crystals of an acid salt, easily
decomposed by light (André, N. J. Pharm. 41, 341; Zeitschr. Ch.
Pharm. 5, 651). — Much more easily soluble in water than the cor-
responding strychnine-salts (Horsley).
Brucine partly decomposes the sulphates of iron and copper, forming
double salts (Pelletier & Caventou). — Sulphate of brucine does not
combine with ferric sulphate to form a double salt (Will, Ann. Pharm.
42, 111).
Iodomercurate of potassium throws down from brucine-salts, a white
or yellow powder, which quickly cakes together in curdy masses, not
perceptibly soluble in hydrochloric acid (v. Planta; Delffs). Brucine,
iodide of potassium, and mercuric chloride yield a double compound,
corresponding to that obtained with strychnine (p. 497), somewhat
soluble in water (Groves).
Chloromercurate of Brucine.
Mercuric chloride throws down from
hydrochlorate of brucine (from the sulphate or nitrate only after addi-
tion of chloride of sodium) a dense, opaque precipitate, which turns.
582 PRIMARY NUCLEUS C46H; OXYAZO-NUCLEUS C4N2H2408.
granular on addition of hydrochloric acid or sal-ammoniac (v. Planta).
The previously acid solution is neutral after precipitation with mercuric
chloride (Caillot, Ann. Chim. Phys. 42, 265). Concentrated alcoholic
solutions of mercuric chloride and hydrochlorate of brucine yield small
needles, which dissolve when warmed with more alcohol and hydro-
chloric acid, and are deposited again on cooling (Hinterberger, Ann.
Pharm. 82, 311).
46 C
2 N
27 H
2 Hg....
3 Cl
Hinterberger.
at 100°.
276
39.36
39.31
28
3.99
27
3.85
4:00
200
28.52
27.84
106.5
15.16
64
'9.12
100.00
80
C46N2H260s, HCl + 2HgCl 701.5
....
Terchloride of gold forms with brucine-salts a brownish-yellow preci-
pitate (Merck). The precipitate is reddish grey-brown, and not per-
ceptibly soluble in hydrochloric acid (v. Planta). It is yellow and
amorphous, and perceptible in a solution containing only 6th of
brucine (Wormley).
00
Chloroplatinate of Brucine. Bichloride of platinum throws down
from hydrochlorate of brucine, a dense yellow granular precipitate, not
perceptibly soluble in hydrochloric acid (Robinet; v. Planta). The pale-
yellow amorphous precipitate thrown down from acetate of brucine
quickly becomes crystalline (Wormley). -- Yellow crystalline powder,
very sparingly soluble in cold water (Liebig). It is decomposed by
prolonged boiling with water (Anderson, Ann. Pharm. 96, 205).
C46N2H2608
HC1, C12
Pt
C46N2H2608, HCl, PtCl²
Varrentrapp
& Will.
mean.
Liebig.
mean.
394
65.66
107.5
17.91
98.7
16.43
16.16
16.52
600.2
100.00
!
Chloride of iridium and sodium throws down from brucine-salts an
ochre-yellow or red-brown precipitate insoluble in hydrochloric acid.
(v. Planta).
Hydroferrocyanate of Brucine. - Shining needles, obtained from
ferrocyanide of potassium and nitrate of brucine in the same manner
as the corresponding strychnine salt A. (p. 449). Alcoholic hydro-
ferrocyanic acid throws down from alcoholic brucine, an amorphous,
white, acid precipitate, resembling the compound B obtained from 1
atom of strychnine and 2 atoms of cyanide of iron. -The needles
deposit a blue precipitate when boiled with water (Brandis, Ann.
Pharm. 66, 266).
Needles, dried over chloride of calcium.
Brandis.
mean.
98 C
588
6.4.37
64.22
7 N
98
10.72
56 H
56
6.11
6.52
18 O
144
15.74
Fe.......
28
3.06
2 (C46N2H2608,HCy), FeCy + 2HO
914
100·00
BRUCINE.
583
Hydroferricyanate of Brucine. - Ferricyanide of potassium produces
in hydrochlorate of brucine, on standing for some time, crystals which
turn blue in a vacuum (Dollfuss).-Dark-yellow salt, resembling in
other respects the corresponding strychnine-salt (p. 500) (Brandis).
Platinohydrocyanate of Brucine. -Six-sided rhombic tables, obtained
from platinocyanide of potassium and brucine-salts (Delffs, N. Jahrb.
Pharm. 21, 31).
Hydrosulphocyanate of Brucine. - Sulphocyanide of potassium throws
down from acetate of brucine a white curdy precipitate, which slowly
disappears on heating (O. Henry, J. Pharm. 24, 149). The precipitate
thrown down from hydrochlorate of brucine is granular; nitrate and
sulphate of brucine yield lamine and tables (v. Planta). Sulpho-
cyanide of potassium throws down from dilute hydrochlorate of
brucine, tufts of microscopic, very thin needles (Anderson, N. J.
Pharm. 13, 443). The crystals dissolve easily in pure water, and very
easily in alcohol after pouring off the mother-liquor, in which they are
nearly insoluble on account of the presence of sulphocyanide of potas-
sium (Lepage, J. Pharm. 26, 140). On neutralising a solution of
hydrosulphocyanic acid, not too dilute, with alcoholic brucine, trans-
parent laminæ, are obtained, which do not lose weight or melt at 100°,
and are moderately soluble in water (Dollfuss).
Dollfuss.
48 C
3 N
288
63.57
63.23
42
9.27
27 H
27
5.96
6.13
2 S
32
7.06
80
64
14.14
......
C46N2H2608, CNHS
453
100.00
...t
The salt contains 12.90 p. c. of hydrosulphocyanic acid (calc. 13:02 p. c.)
(Dollfuss).
Oxalate of brucine crystallises in long needles, especially in presence
of excess of acid. Acetate of brucine is very easily soluble, and not
crystallisable (Pelletier & Caventou). — Neutral lactate of brucine dis-
solves brucine (Coriol, J. Scienc. Phys. 3, 247).
Tartrate of Brucine. See p. 216. By dissolving tartaric or anti-
tartaric acid, together with 1 or 2 atoms of brucine, in water or alcohol,
four different salts are obtained.
A
A. Dextrotartrate of Brucine. a. Semi-acid. This salt is imme-
diately deposited, in laminæ, on mixing 2 atoms of alcoholic brucine
with 1 atom of alcoholic tartaric acid. The crystals when prepared
with 95 p. c. alcohol, contain 11 atoms of water. They lose 9.2 per
cent. of water at 100°, and 10 p. c. at 150°, and, therefore, retain
1 atom at 100° (Pasteur).
2 C46N2H26OS
C8H6012
10 HO
Pasteur.
788
75.99
150
14:46
90
8.68
9.20
HO
9
0.87
0.80
2 C46N÷H260,CSH6O2 + 11aq.
1037
100·00
181
PRIMARY NUCLEUS CH; OXYAZO-NUCLEUS CN²H¾Oª.
If in the preparation of this salt the brucine be dissolved in warm
aqueous tartaric acid, large transparent crystals with 16 atoms of
water are obtained on cooling. These crystals lose 15 atoms of water at
100°, and the remaining atom at 150°, at which temperature they
become coloured (Pasteur).
Pasteur.
2 C6N2H2608
CSH6O12
15 HO
HO
2_C*N2H2O,CH'O + 16aq.
788
72.82
150
13.86
135
12:48
12.70
9
0.84
0.52
....
1082
100.00
The sult dried at 100° contains 62.99 p. c. C., and 6.84 H. (Pasteur) (by calc.
63·25 p. c. C., 6·29 H.).
A
b. Mono-acid. This salt is deposited, immediately and completely
as a granular crystalline powder, on mixing the alcoholic solutions of
brucine and tartaric acid. When crystallised from water, it does not
lose water at 100° to 150°, but becomes slightly coloured at 200°
(Pasteur).
Pasteur.
59.83
54 C
2 N
32 H
20 O
C¹¹N²HO³,C³H6O¹2
324
59.55
BU
28
5.14
32
5.88
160
29.43
544
100.00
6.19
Deposited after
B. Antitartrate of Brucine. a. Semi-acid.
some hours, in hard satiny nodules, on mixing solutions of its con-
stituents. It crystallises with the same proportion of water from
alcohol of 95 p. c., and from water. Effloresces more easily than the
dextrotartrate. Loses 27 atoms of water at 100°, and the last atom at
140° (Pasteur).
2 CONFIOS
CSH6O12
27 HO
HO
2 C¹¹6N2H2608,CSII6O12 + 28aq.
Pasteur.
788
66.22
150
12.61
243
20.42
20.66
9
0.75
1.03
1190
100.00
....
b. Mono-acid. Loose silky scales and slender needles, which
crystallise with the same proportion of water from 95 p. c. alcohol and
from water. The salt effloresces easily. It loses 9 atoms of water at
100°, and the last atom at 150°, evolves an odour of caramel at 190°,
and carbonises without melting (Pasteur, N. Ann. Chim. Phys. 38,
472).
CAGN2H2608
CH6O12
9 HO
110
C³N÷H²ºO$,C$II®O¹² + 10aq.
Tartrate of Antimony and Brucine.
the corresponding quinidine-salt (p.
(Stenhouse, Ann. Pharm. 129, 26).
Pasteur.
394 62.16
150
23.66
81
12.77
13.30
9
1.41
1.20
634 100.00
Obtained in the same way as
302). Short brittle crystals
BROMOBRUCINE.
585
54 C
2 N
31 H
22 O
Sb
Crystals.
Stenhouse.
324
47.68
48.03
28
4.12
31
4.56
4.64
176
25.90
120.3
17.74
17.88
679.3
100.00
C46N2H260³,HO,SbO³, C8H+O¹0
Alcoholic picric acid throws down from brucine-salts a yellow or
greenish-yellow precipitate, which dissolves with difficulty in hydro-
chloric, nitric, and acetic acids (Kemp; Wormley, Repert. Chim. pure 2,
430; Chem. News, 1860, 65). Tannic acid, tincture of galls, and infusion
of galls, produce dense, dirty-white precipitates, which dissolve in
acetic acid (Duflos; Wormley), but not in hydrochloric acid (v. Planta).
Tartaric acid prevents the precipitation by tannic acid, but on neutral-
ising the liquid with ammonia a precipitate soluble in excess of am-
monia is thrown down (Oppermann). Brucine behaves in the same
manner as quinine (p. 294) towards oleic acid and olive oil (Attfield).
Picrotoxin with Brucine. On boiling 1 part of brucine with 4 parts
of picrotoxin and water, and filtering, the filtrate solidifies to a mass
of flexible, opaque, white crystals, which may be recrystallised with-
out change. The compound is decomposed by the electric current, and
by alkalis (Pelletier & Couerbe, Ann. Chim. Phys. 54, 186).
3
1
Brucine dissolves very easily in alcohol (Pelletier & Caventou); in
15 parts of alcohol (Cap & Garot); easily in cold alcohol of 20° B.,
and in absolute alcohol (Merck). It is insoluble in ether (Pelletier &
Caventou). Dissolves in 1 parts (Pettenkofer), in 7 parts of chloroform
(Schlimpert); in 70 parts of glycerin (Cap & Garot); in cold creosote
and abundantly in warm picamar (Reichenbach). It dissolves very
slightly in volatile oils, and is insoluble in fat oils (Pelletier & Caventou).
According to M. Pettenkofer, it dissolves in 56 parts, according to
Cap & Garot in 120 parts of fat oil.
Conjugated Compounds and Derivatives of Brucine.
Bromobrucine.
C46N2BrH2508 = C46N2BrII2308, II².
LAURENT. N. Ann. Chim. Phys. 24, 314; Ann. Pharm. 69, 15; J. pr.
Chem. 46, 52; Kopp's Jahresber. 1847 and 1848, 629.
A solution of bromine in weak spirit is poured into an aqueous
solution of sulphate of brucine till 4th to rd of the bromine is thrown
down as a resin; the supernatant liquid is then mixed with ammonia;
the precipitate is dissolved in very weak spirit, and mixed first with
boiling water containing a little alcohol, and afterwards with pure
water, till cloudiness is produced. The liquid deposits, on cooling,
brownish-white needles, which contain 17.5 p. c. of bromine (by cale.
16.91 p. c. Br.), and turn red with nitric acid.
!
1
t
586 PRIMARY NUCLEUS C46H34; OXYAZO-NUCLEUS C4N²Hª¹O³.
Methylbrucine.
C4N2H 2808
CªN²(C²H³)H²³O³‚H².
STAHLSCHMIDT. Pogg. 108, 535; abstr. Chem. Centr. 1860, 216; Repert.
Chim. pure, 2, 135; Kopp's Jahresber. 1859, 398.
Formebrucin.-Obtained only in aqueous solution and in combination with
acids.
Iodide of methyl converts finely powdered brucine, with liberation.
of heat, into hydriodate of methylbrucine, from an aqueous solution of
which the iodine may be separated by the method described under
methylstrychnine (p. 506). The colourless, very bitter solution of
hydrate of methylbrucine thus obtained, assumes a dark-red colour on
standing, more especially when heated, and leaves, when evaporated
over oil of vitriol, a brown syrup, which dissolves easily in water,
evolves carbonic acid with acids, but does not yield crystallisable salts
on account of the partial decomposition of the methylbrucine.
Methylbrucine in the form of sulphate is not poisonous to rabbits in
doses of 10 grains.
Sulphate of Methylbrucine. A. Neutral. Radiated crystals,
having a bitter taste and easily soluble in water and alcohol, obtained
by decomposing hydriodate of methylbrucine with sulphate of silver and
evaporating the solution. The crystals lose 13.9 p. c. of water at 130°
(8 at. 13.61 p. c.).
at 130°.
Stahlschmidt.
C48NHOS,HO ......
SO3
417
40
91.25
8.75
8.57
C¹¹6N³H25 (C¹²H³) 0$,HO,SO³ 457
100.00
....
........
B. Acid. The salt A yields with sulphuric acid indistinct crystals
somewhat less easily soluble than A in water and alcohol.
6·44 p. c. of water at 130° (4 at. = 6·64 p. c.).
Loses
Dried.
Stahlschmidt.
C48N2H2808,2HO
2 SO3
C46N2H25 (C²H³)08,2 (HO,SO³)
426
84.19
80
15.81
15.97
506
100.00
Hydriodate of Methylbrucine. - Dissolves in hot water more easily
than the corresponding salt of methyl-strychnine, and crystallises in
small shining lamine on cooling. The crystals lose 21.47 p. c. of water
over the water-bath (16 at. = 21·2 p. c. HO).
C48N2H2808, H
I
Dried.
Stahlschmidt.
409
76.30
127
23.70
24.22
...
536
100.00
C46N2H25 (C²H³)0º,HI
Hydrobromate of Methylbrucine. - Bromide of potassium throws
down from hydrochlorate of brucine, on standing for some time, a
ETHYLBRUCINE.
587
crystalline precipitate which crystallises from hot water in small shin-
The salt dissolves easily in water and alcohol. — Loses
ing prisms.
8.5 p. c. of water at 130° (5 at. = 8·4 p. c. HO).
Dried.
Stahlschmidt.
C18N2H2808,H
Br.
409
80
83.64
.....
16.36
15.74
C46N2H25 (CH3) 08, HBr
489
100.00
....
Hydrochlorate of Methylbrucine. - Small shining crystals, easily
soluble in water and in alcohol. Loses 16.6 p. c. of water over the
water-bath (10 at. 16.8 p. c. HO).
C48N2H28OS, H
Cl..
C46N2H25 (C²H³)08,HCI
Dried.
Stahlschmidt.
409
92.01
35.5
7.99
8.15
444.5
100.00
Mercuric chloride throws down from hydrochlorate of methyl-
brucine a white curdy precipitate, soluble in water and alcohol, but
insoluble in ether.
Chloroplatinate of Methylbrucine. Yellow precipitate crystallising
from water in fine needles, easily soluble in water and alcohol, insolu-
ble in ether. Contains, at 100°, 16.35 p. c. of platinum (calc. 16.07
p. c.).
Chloroaurate of Methylbrucine.-Orange-yellow precipitate, which
crystallises from a solution in hot water. It is decomposed by
long boiling, with separation of gold. Dissolves with difficulty in cold
water, easily in hot water and hot alcohol. Contains, after drying at
100°, 26.47 p. c. of gold (calc. 26.34 p. c.).
Ethylbrucine.
C'50N2H3008 C46N2(CH)H2308, H³.
=
GUNNING. J. pr. Chem. 67, 46; Kopp's Jahresber. 1856, 516.
Vinebrucin. Known only in combination with water and acids.
Hydriodate of ethyl-brucine, obtained by mixing alcoholic brucine
with iodide of ethyl, yields, when digested with oxide of silver, iodide
of silver and hydrate of ethylbrucine, the latter as a strongly alkaline liquid
which becomes coloured and absorbs carbonic acid when evaporated.
It decomposes ammonia-salts with liberation of ammonia, and the
salts of iron, alumina, and zinc, precipitating the hydrates, and re-
dissolving those of alumina and zinc. It reddens nitric acid like
brucine.
Hydriodate of Ethylbrucine. - Crystallises from a mixture of alco-
holic brucine and iodide of ethyl on standing for some time. It is not
decomposed by caustic potash. Dissolves with moderate facility in
hot alcohol. The salt dried at 100° loses 1.65 p. c. of water at 140°
(1 at.
1·6 p. c.).
588
PRIMARY NUCLEUS CH³; OXYAZO-NUCLEUS C“N²H²O³.
Gunning.
at 100°.
mean.
50 C
2 N
32 H
9 O....
300
53.67
53.25
28
5.01
4.70
32
5.72
5.90
72
12.88
13.27
I
127
22.72
22.88
C46N2 (C+H³) H250$,HI + HO
559
100.00
100.00
....
Chloroplatinate of Ethylbrucine. - Golden-yellow precipitate, crys-
tallising from boiling water.
Gunning.
C50N2H300,HC1, C12
Pt
529.5
84.27
98.7
15.73
15.20
C¹¹N (C¹H³) HOS,HCl,PtCl²
628.2
100.00
....
Compounds obtained from Brucine and Bibromide of Ethylene.
L. SCHAD. Ann. Pharm. 118, 207; J. pr. Chem. 84, 248; Chem.
Centr. 1861, 908; Repert. Chim. pure 4, 46; Kopp's Jahresber. 1861,
542.
Powdered brucine is but slightly attacked by bibromide of ethy-
lene at ordinary temperatures, but dissolves rapidly at 100°, forming
a transparent colourless liquid, which solidifies in a crystalline mass on
cooling. The crystals may be freed from excess of the bibromide by
recrystallisation from boiling water.
The inodorous pearly lamina thus obtained are Schad's hydrated.
Bihydrobromate of Ethylene-brucine or Bromide of Brucine-bromethylene-
ammonium. They dissolve easily in hot water, with difficulty in abso-
lute alcohol, and are insoluble in ether. The aqueous solution is not
precipitated by ammonia or alkalis. The crystals lose 8.56 p. c.
water at 100° (6 at. = 8.49 p. c.).
50 C
2 N
30 H
80
2 Br
C46N2H24 (C4H¹)08,2HBr
Schad.
Dried.
mean.
300
51.54
51.45
28
4.80
3.....
30
5.15
5.27
*******
64
10.99
160
27.52
25.82
582
100.00
****
In contact with silver-salts, the crystals give up half their bromine,
and when heated, the whole of the bromine, as bromide of silver, thus
forming two series of compounds corresponding in every respect to
those obtained in the same way with strychnine (p. 513).
A. Compound containing Bromine. When the crystals are decom-
posed with nitrate of silver, and the filtrate, freed from excess of silver
by hydrochloric acid, is precipitated with bichloride of platinum, yellow
flocks are obtained, which quickly turn crystalline, and contain 13.84
p. c. of platinum. The flocks are represented by the formula
C46N ²II 25 (C¹¹II*Br)0°,HCl,PtCl² (calc. 13·95 p. c. Pt).
2
IGASURINE.
589
B. Hydrate of Ethylene-brucine free from Bromine. [Brucinvinyl-
Ammoniumoxydhydrat (Schad)]. Obtained by digesting the warm
aqueous solution of the above crystals with freshly precipitated oxide
of silver, and evaporating the strongly alkaline filtrate, which takes up
carbonic acid from the air. There remains a brown viscid varnish,
which neutralises acids, forming salts.
Sulphate. — Acid.-Large transparent crystals which effloresce
and decompose in the air. They lose 3.11 p. c. of water at 100° and
the remainder (amounting altogether to 9.35 p. c.) at 130° (2 and 6
at. = 3·1 and 9·4 p.c. HO).
50 C
2 N
at 100°.
Schad.
300
54.15
54.23
28
5.06
34 H
34
6.14
6.40
14 O
112
20.21
2 SO3
80
14.44
14.44
C46N2H2+ (C+H¹) Os,2 (HO,SO³) + 4aq.
554
100.00
Chloroplatinate. Pale lemon-yellow precipitate thrown down from
the hydrochlorate by bichloride of platinum.
Schad.
mean.
50 C....
300
47.90
47.91
2 N
28
4.47
29 F
29
4.63
4.75
80
64
10.22
Pt
98.7
15.76
15.63
3 Cl
106.5
17.02
C¹¹6N2H²¹ (C4H¹) O³,HCl,PtCl²
626.2
100.00
***
Appendix to Brucine.
1. Igasurine.
DESNOIX. N. J. Pharm. 25, 202; Pharm. Centr. 1854, 654; Pharm.
Viertelj. 4, 94. Kopp's Jahresber. 1854, 524.
SCHÜTZENBERGER. Compt. rend. 46, 1234; Instit. 1858, 217; N. J.
Pharm. 35, 31; Rép. Chim. pure, 1, 76; J. pr. Chem. 74, 510; Chem.
Centr. 1858, 557; Chem. Gaz. 1858, 467; Ann. Pharm. 108, 348;
Complete: N. Ann. Chim. Phys. 54, 65; Kopp's Jahresber. 1858,
374.
Occurs in Nux vomica, and remains in solution after the strychnine
and brucine have been precipitated from the boiling extracts by lime.
The filtrate, when concentrated and left at rest for some days, deposits
crystals of igasurine, which are to be dissolved in hydrochloric acid,
decolorized with animal charcoal, and precipitated by ammonia, after-
wards crystallised from alcohol and purified by again dissolving them
in hydrochloric acid and precipitating with ammonia. On agitating
the ammonia-precipitate with the mother-liquor, it takes up water
and becomes crystalline.
590
PRIMARY NUCLEUS C46H3+; OXYAZO-NUCLEUS C46N2H24O8.
The crystals, which contain 10 p. c. water, form feathery groups.
of white silky needles having a very bitter taste and a poisonous
action. They resemble brucine in their behaviour towards reagents,
and rotate a polarised ray of light in the same direction and to nearly
the same extent: they differ from brucine, however, in being pre-
cipitated by bicarbonate of potash, even in presence of tartaric acid;
moreover they are soluble in 200 parts of boiling water, from which
they crystallise very rapidly in cooling, whereas brucine dissolves
only in 500 parts of boiling water and crystallises slowly (Desnoix).
Igasurine behaves towards oleic acid and olive oil in the same way
as quinine (p. 294) (Attfield).
Crystals prepared as above or by concentrating the mother-liquors
of strychnine, and occurring in commerce as brucine, are according to
Schützenberger, a mixture of different bases, of which he found in one
sample as many as five.
A. First Sample. This specimen formed a mixture of very long
and short needles, separable into five bases, the whole of which were
very bitter, poisonous, assumed a red colour with nitric acid like bru-
cine, dissolved in alcohol much more easily than in ether, and formed
casily crystallisable salts.
On boiling this specimen with water, a portion dissolved, whilst the
remainder melted to a semi-fluid resin which dissolved only on boiling
with a very large quantity of water. The latter solution deposited the
whole of the dissolved matter, on cooling, in very large scales, which
were formed of long pearly needles, and retained their form when re-
crystallised-a-igasurine.-The solution formed by the first boiling
with water, decanted at the boiling heat, deposited three bases in suc-
cession on cooling; b-igasurine in separate needles at 85°; c-igasurine
at 45°; and d-igasurine slowly in scales at 30°: from the mother-
liquor, which deposited no more crystals, bichloride of platinum threw
down e-igasurine as platinum-salt.
a-Igasurine. C4N2H2608. Loses 13.2 p. c. of water at 130° (6 at.
= 12·38 p. c. HO). The platinum-salt contains 16.6 p. c. of platinum
(by calc. 16.78 p. c. Pt). Very slightly soluble in water.
b-Igasurine. C36N2H24014. Loses 12.7 p. c. of water at 130° (6 at.
= 12.44 p. c. HO). The platinum-salt contains 16.79 p. c. of platinum
(by calc. 16.84 p. c. Pt). Slightly soluble.
c-Igasurine. CN2H08. Loses 14.06 p. c. of water at 130° (6 at.
= 13.98 p. c. HO). The platinum-salt contains 18.2 p. c. of platinum
(by calc. 18.32 p. c. Pt). Soluble.
d-Igasurine. C34N2H32016. Loscs 117 p. c. of water at 130° (6 at.
12.11 p. c. H10). — Soluble.
e-Igasurine. C36N2H2808. The platinum-salt, C36N2H2608,HCl, PtCl2,
contains 39.7 p. c. C., 5.1 H., and 18-52 Pt (calc. 39.98 p. c. C., 4·81 H.,
18.27 Pt). Easily soluble.
IGASURINE.
591
Analyses by Schützenberger.
Dried at 130°.
b.
a.
C.
d.
OREO
C
N
H
68.78
56.84
64.87
52.2
.....
7.05
7.19
8:00
7.3
6.94
6.54
7.20
8.5
17.23
29.43
19.93
32.0
100.00
100.00
100.00
100.0
Calculations.
a.
b.
C.
d.
44 C
2 N
26 H
80
69.11
36 C
56.86
36 C
65.06
34 C ..
52.04
....
....
....
7.33
....
6.83
16.73
2 N
24 H
7.36
2 N
8.43
....
14 O
6.31
29.47
24 H
7.23
2 N
32 H
7.14
....
8.16
80
19.28
16 O.... 32.66
....
C36N2H24014
C36N2H2408
CN2H20O8
C34N2H32016
B. Second Sample. This specimen contained only one base, which
resembled e-igasurine in point of solubility, and, like it, formed separate
needles. Loses. 14.4 p. c. of water at 130° (6 and 8 at. = 12.61 and
16.14 p. c. HO). With nitrous acid it forms oxyigasurine.
f-Igasurine.
Schützenberzer.
at 130°.
42 C .......
252
67.38
67.22
2 N.....
28
7.48
7.20
30 H.......
30
8.02
7.99
8 0....
64
17.12
17.59
C42N2H3008
374
100.00
100.00
C. Third Sample. On dissolving the sulphate of this specimen in
boiling water, and mixing the solution at 75° with ammonia, g-igasu-
rine was deposited as a fluid resin, after the removal of which,
h-igasurine crystallised in needles, and subsequently i-igasurine in
silky needles.
g-Igasurine. CN2H2O2. Solidifies rapidly, and is obtained from
alcohol, in loose crystals, or on addition of water, in which it dissolves
very slightly, in scales. Loses 11.5 p. c. of water at 130° (6 at.
11.79 p. c.). The platinum-salt contains 15.9 to 16·1 p. c. platinum
(calc. 16-17 p. c. Pt.).
h-Igasurine. C42N2H26012. Loses 7.5 p. c. of water at 130° (4 at.
8.22 p. c.). More easily soluble than g.
i-Igasurine. C40N H26014. Loses 14.56 p. c. of water at 130°
(8 at. 15.04 p. c.). The platinum-salt contains 15.7 p. c. platinum
(calc. 16.12 p. c. Pt.).— Soluble.
According to Schützenberzer, at 130°.
g.
Sch.
h.
42 C
2 N
62.37.. 62.20
6.93.. 6.90
42 C
28 H
6.93.. 6.75
12 0
23.77.. 24·15
2 N
26 H
12 0
Sch.
62.68..62.4
6.97
2.
40 C
Sch.
59-11.. 58*90
2 N
•
6.90.. 6.80
6.47.. 6.6
23.88
26. H
6.40.. 6'49
14 O
27:59.. 27.81
C42N21128012 100-00..100·00
C42N2H26012 100 00
C40N2H260:4 100.00..100·00
592
PRIMARY NUCLEUS C6H3; OXYAZO-NUCLEUS CNH²¹O³.
Oxyigasurine.
SCHÜTZENBERGER. N. Ann. Chim. Phys. 54, 65.
On heating an aqueous solution of sulphate of f-igasurine to boiling
with nitrite of potash, an effervescence takes place, and oxygasurine is
formed. The product is rather more soluble in water than igasurine,
and crystallises from the solution in isolated translucent needles after
12 hours only.
The needles melt in their water of crystallisation at 100°, and lose
13.4 p. c. of water at 130° (8 at. = 13.68 p. c. HO).
13.68 p. c. HO). — The platinum-
salt contains 14.6 p. c. platinum (calc. 14.95 p. c.)
at 130°.
Schützenberger.
42 C...........
252
55.51
55.66
2 N
28
6.17
6.30
30 H
30
6.61
6.74
18 O.....
144
31.71
31.30
C42N2H300'S
454
100.00
100.00
....
...
2. Curarine.
=
H².
C20NH15 C20NH13, H2.
ROULIN & BOUSSINGAULT. Ann. Chim. Phys. 39, 24; abstr. J. Chim.
méd. 4, 71; Berz. Jahresber. 9, 220.
PELLETIER & PETROZ. Ann. Chim. Phys. 40, 213; N. Tr. 19, 2, 107;
Br. Arch. 30, 288.
A. BUCHNER. N. Repert. 10, 167; N. Br. Arch. 110, 19; Kopp's
Jahresber. 1861, 767.
W. PREYER. Zeitschr. Ch. Pharm. 8, 381; N. J. Pharm. [4], 2, 296;
Compt. rend. 60, 1346.
Discovered by Buchner, sen. (Toxikologie, 1827, 249), and afterwards,
in 1828, by Roulin and Boussingault, and prepared pure by Preyer.
Occurs in the arrow-poison of the Indians of the Upper Orinoco, which
is known as Curare or Urari, and is obtained from the sap of some
species of Strychnos. According to Henkel (N. Repert. 10, 164), how-
ever, the following varieties are to be distinguished :—
a. Curare from Guiana, the arrow-poison containing curarine,
occurring in earthern vessels, and prepared from Rouhamon guianensis
and Strychnos cogens.
b. Urari from Strychnos toxifera (Schomburgh), occurring in cala-
bashes. This substance is said not to contain any active constituent
which can be isolated.
c. East Indian arrow-poison containing strychuine, Upas radja or
Tienté.
CURARINE.
593
According to A. Buchner, the distinction between a and b is un-
founded, the curare of the Indians of the Upper Orinoco being essentially
identical with the Urari of the Rio Yupura and Rio Negro, as well as with
the Wurali of Surinam, in support of which view Buchner cites the ex-
periments of Pelikan & Trapp. Milleroux (Compt. rend. 47, 973)
appears to hold the same opinion. Von Martius described as Urari an
arrow-poison in earthen vessels brought by him from Northern Brazil
in 1821. This substance was employed in Buchner's and (as curare)
in Henkel's experiments, also in those of Wittstein (Pharm. Viertelj.
8, 402; N. Br. Arch. 100, 129), who supposed it to contain strychnine
and brucine. This last supposition was contradicted by Wittstein's
own experiments, and was also shown to be erroneous by Buchner
and Henkel.
The bark of Strychnos toxifera appears, from the experiments of
Wittstein, to contain curarine. Preyer found curarine in the fruit
of Paullinia curare, and it is probable that curare is obtained from this
fruit.
Curare is obtained by exhausting the sap and bark of a species of
Strychnos with cold water, and evaporating the extract, together with
another very viscid vegetable extract. It forms a nearly black hygro-
scopic extract, very bitter, soluble for the most part in water, and
contains, besides curarine, fat, brown resin, red colouring matter, gum,
and clay (Boussingault & Roulin). See also Pelletier and Petroz.
is not poisonous when taken internally in small quantities, but quickly
produces death when introduced into wounds (Humboldt, Ann. Chim.
Phys. 39, 30).
It
Preparation of Curarine. Powdered curare is boiled with absolute
alcohol and a few drops of caustic soda; the tincture is freed from
alcohol by distillation, and the residue is mixed with water, which
throws down resin. The solution, filtered from resin, is precipitated
by phosphomolybdic acid, and the precipitate is decomposed by drying
with hydrate of baryta, and afterwards exhausted with absolute
alcohol. From the solution thus obtained, anhydrous ether throws
down white flocks, which rapidly deliquesce to a brown oil in the air,
and rarely crystallise from water, but may be obtained in crystals by dis-
solving them in chloroform and evaporating the solution. Or the
curarine may be obtained as hydrochlorate by precipitating the solution
freed from resin with mercuric or platinic chloride, decomposing
the precipitate by hydrosulphuric acid, and repeating this process
(Preyer).
Roulin & Boussingault dissolve the alcoholic extract of curare in
water, filter from resin, decolorise the solution with animal charcoal,
precipitate with infusion of galls, dissolve the yellowish-white preci-
pitate, after washing, in boiling water containing oxalic acid, boil the
solution with magnesia, evaporate the filtrate, exhaust the residue
with alcohol, and evaporate. Curarine then remains as a pale yellow
syrup, drying up over oil of vitriol to a horny very bitter mass, which
turns turmeric red and litmus blue. - Buchner jun., precipitates the
aqueous extract of curare with neutral acetate of lead, frees the
filtrate from lead by hydrosulphuric acid, and evaporates to a syrup,
which he agitates with soda-ley and chloroform. On evaporating the
chloroform, curarine remains as an amorphous brown mass.
2 Q
VOL. XVII.
594
PRIMARY NUCLEUS C46H3; OXYAZO-NUCLEUS C4N2H2408.
Properties. Colourless four-sided prisms having a slightly alkaline
reaction, very hygroscopic and very bitter (Preyer). Tastes bitter,
though less persistently so than strychnine (Buchner). Much more
poisonous than curare; paralyses the extremities and produces
death without convulsions (Buchner). See also Bernard (N. J. Pharm. [4]
2, 165).
Decompositions. Curarine, when heated, evolves ammoniacal bitter
vapours, and a horny odour. It assumes with oil of vitriol a fine
blue (Preyer), a carmine-red colour (Roulin & Boussing ault).—Strong
nitric acid produces a purple-red (Preyer), a blood-red colour (Roulin &
Boussingault). When mixed with oil of vitriol, and afterwards with
bichromate of potash, curarine assumes a violet colour in the same
manner as strychnine, but the colour, and likewise that produced by
oil of vitriol, is more stable with curarine (Preyer). With curare or
impure curarine, Henkel obtained a brown colour, passing into cherry-
red and violet. Peroxide of lead or ferricyanide of potassium and oil of
vitriol, likewise produce the violet colour.
Combinations. Curarine deliquesces in the air, and dissolves in
water in all proportions (Preyer; Roulin & Boussingault). It forms.
with acids neutral, very easily soluble salts, which turn brown when
warmed. The nitrate, sulphate, hydrochlorate, and acetate crystallise;
the crystalline platinum-salt is thrown down from curarine free from
hydrochloric acid by bichloride of platinum, and corresponds to the
formula C20NH¹,PtCl (Preyer).
15
Curarine dissolves in all proportions in alcohol, and slightly in
anhydrous ether, sulphide of carbon, oil of turpentine, and benzene (Preyer).
Infusion of galls throws down from the aqueous solution a precipitate
soluble in alcohol (Pelletier & Petroz).
3. Conessine or Wrightine.
HAINES. Verhandl. der medic.-physik. Gesellschaft von Bombay 1858;
Schweiz. Pharm. Wochenschr. 1865, 172.
STENHOUSE. Pharm. J. Trans. 1864, 5, 493; Pharm. Viertelj. 14, 301;
Schweiz. Pharm. Wochenschr. 1865, 172.
Neriine. Occurs in the seeds of Wrightia antidysenterica, an East
Indian apocynaceous plant, the Semen Indageer of the druggists (Sten-
house), the extract of which has, according to Husemann, a narcotic
action. It occurs in the bark of the same plant, the Kuda bark of the
bazaars, to the amount of 1th per cent. (Haines).
Preparation. 1. From the seeds. The fatty oil of the seeds is
removed by means of bisulphide of carbon; the residue is digested
with alcohol; the extract is filtered and freed from alcohol by distilla-
tion; the residual mass is exhausted with dilute hydrochloric acid
and the filtrate is precipitated by ammonia. The flocks thus obtained
are purified by washing with cold water (Stenhouse).-2. From the
;
ESERINE.
595
bark. The extract prepared with dilute hydrochloric acid is precipi-
tated by ammonia; the precipitate is exhausted with alcohol, and the
tincture is evaporated to a syrup, which is evaporated to dryness with
neutral acetate of lead and a little ammonia, and afterwards exhausted
with ether. On evaporating the ether, conessine remains as an amor-
phous brown-yellow resin, which softens at 71°, and melts below 100°
(Haines).
Properties. White amorphous powder, having a very bitter (Sten-
house) and also acrid and harsh taste (Haines). Contains 78.3 p. c. C.,
11.2 H.; the conessine in the platinum-salt contained 773 p. c. C.,
11.8 H., and 7.73 N., from which numbers Haines calculated the
formula C25NH220.
Conessine decomposes when heated. With nitric acid it forms
oxalic but no picric acid. It dissolves slightly in boiling water, and
easily in dilute acids, forming amorphous salts. The solution in hydro-
chloric acid yields a flocculent precipitate with mercuric chloride, chloride
of gold, and chloride of platinum (Stenhouse). The amorphous yellow
flocks of the platinum-salt contain 24-05 to 25.06 p. c. of platinum
(Haines). Tannic acid throws down from acetate of conessine, flocks
soluble in hydrochloric acid (Stenhouse).
Conessine dissolves in alcohol, ether, and chloroform (Haines).
According to Stenhouse, it is slightly soluble in boiling alcohol, but
nearly insoluble in ether and bisulphide of carbon.
4. Eserine.
JOBST & HESSE. Ann. Pharm. 129, 115; N. Repert. 13, 80.
AM. VEE & LEVEN. N. J. Pharm. [4] 1, 70; Compt. rend. 60, 1194;
N. Repert. 14, 75.
Physostigmine.-Occurs in the cotyledons (Jobst and Hesse) of the tasteless.
poisonous Calabar bean of Physostigma venenosum, concerning which see Henkel
(N. Jahrb. Pharm. 21, 1). On poisoning by calabar beans and the detection of the
poison, see Edwards (N. Repert. 14, 79; Chem. Centr. 1865, 647).
Preparation. 1. The powdered beans are exhausted with cold
alcohol of 95 p. c."; the tincture is distilled; and the extract is digested
with a strong aqueous solution of tartaric acid. The solution thus
obtained is diluted with water, filtered, supersaturated with bicarbonate
of potash, and again filtered, and the filtrate is shaken up with ether
so long as it gives up eserine. The residue which remains on evapo-
rating the ether is dried over oil of vitriol and exhausted with absolute
ether, which leaves eserine on evaporation. The product is purified
by crystallisation from alcohol and ether, but cannot be completely
freed from red colouring matter (Vee & Leven). - 2. Jobst and Hesse
exhaust the beans with hot alcohol, dissolve the extract in water,
acidify the solution, and precipitate with neutral acetate of lead.
After removing this precipitate, the filtrate is freed from lead by hydro-
sulphuric acid, and evaporated over a water-bath, and the residual
extract is treated with absolute alcohol, which takes up acetate of
2 Q2
596
PRIMARY NUCLEUS CH34; OXYAZO-NUCLEUS CN Hª¹O».
eserine, leaving gum undissolved. A solution of the acetate in cold
water, when shaken with magnesia and ether, gives up to the latter
liquid the eserine, together with fat and colouring matter, to remove
which the decanted ethereal layer is shaken with dilute sulphuric acid,
whereupon the eserine becomes dissolved in the aqueous liquid as sul-
phate, the fat remaining in the ether. The aqueous solution is sepa-
rated, decomposed by magnesia, and freed from eserine by agitation
with ether, which leaves it, on evaporation, as a brown-yellow
amorphous mass (Jobst & Hesse).
Properties. Very thin, rhombic lamina, truncated at the obtuse
angles (Vee & Leven). Its aqueous solution has a slightly burning
taste and a distinctly alkaline reaction. It is extremely poisonous,
producing paralysis of the muscles, loss of motion, and death. Its
aqueous solution, introduced into the eye, produces contraction of the
pupil, even an hour after the death of the animal (Jobst & Hesse).
Contains nitrogen. Melts on platinum-foil, emitting a large quantity
of white fumes.
Eserine dissolves very slightly in water (Vee & Leven), more easily
in aqueous ammonia, and in caustic soda or its carbonate. Biniodide of
potassium throws down from aqueous eserine, a carmine-coloured preci-
pitate (Jobst & Hesse).
Eserine dissolves in acids, forming soluble salts, red and amorphous
(according to Jobst & Hesse), the solutions of which are decolorised
by hydrosulphuric acid. Aqueous eserine throws down sesquioxide
of iron from the sesquichloride.
Mercuric chloride throws down from hydrochlorate of eserine, a
reddish-white amorphous precipitate, easily soluble in hydrochloric
acid, but not in an aqueous solution of the precipitant. Bichloride of
platinum produces a pale-yellow amorphous precipitate, soluble in
hydrochloric acid and in boiling water, and decomposible by an excess.
of hot bichloride of platinum. Terchloride of gold produces a bluish
precipitate, with separation of gold. Tannic acid throws down amor-
phous, reddish-white flocks, soluble in a large quantity of hydrochloric
acid (Jobst & Hesse).
Eserine dissolves easily in alcohol, ether, chloroform, and benzene. It
is thrown down from the ethereal solution by animal charcoal.
5. Oleandrine and Pseudocurarine.
From Nerium Oleander, from which plant Landerer (Repert. 71, 247)
obtained resins, Lucas (N. Br. Arch. 97, 149) a white powder, soluble
in acids and precipitable by tannic acid. An aqueous extract of the
leaves is precipitated with tannic acid; the precipitate is washed with
cold water; and the pseudocurarine is extracted from it by treatment
with aqueous tannic acid. The solution is boiled with oxide of lead,
filtered, evaporated to a syrup, and exhausted with ether, which takes
up a little oleandrine, after which the residue gives up pseudocurarine
to alcohol. The tannate of oleandrine may be freed from adhering
leaf-green by ether.
Pseudocurarine is not volatile and not poisonous. It dissolves in
NARCEINE.
597
water and alcohol, but not in ether. It neutralises acids, forming
amorphous salts, and precipitates mercuric chloride and bichloride of
platinum. Oleandrine is yellow, amorphous, poisonous, and very
bitter. It dissolves very slightly in water, but more freely in alcohol
and ether. It combines with acids, and precipitates solutions of gold
and platinum (Leukowsky, N. J. Pharm. 46, 397).
Primary Nucleus C46H6; Oxyazo-nucleus C4NH27018.
Narceine.
C46NH29018 C46NH27018,H2.
=
$
PELLETIER. Ann. Chim. Phys. 50, 252, and 262; J. Pharm. 18, 607,
and 616; Ann. Pharm. 5, 163; Schw. 67, 311; abstr. Pogg. 27, 659.
– J. Pharm. 21, 573; Ann. Pharm. 16, 47; N. Br. Arch. 5, 158.
COUERBE. Ann. Chim. Phys. 59, 151; Ann. Pharm. 17, 171.
WINCKLER. Repert. 59, 1.
ANDERSON. Trans. Roy. Soc. Edin. 20, 3, 347; Chem. Soc. Qu. J., 5,
257; Ann. Pharm. 86, 182; J. pr. Chem. 57, 358; Kopp's Jahresber.
1852, 537.
0. HESSE. Ann. Pharm. 129, 250; N. Repert. 13, 83.
Discovered by Pelletier in 1832 (J. Pharm. 18, 150; Ann. Pharm. 2,
274).
Source. In opium. Also in the ripe capsules of the blue-seeded
poppy (Winckler). Couerbe obtained 6 drams of narceine from 40
pounds of opium.
Preparation. Narceine is obtained in the treatment of opium,
described at pp. 419-422, vol. xvi. It remains in the filtrate, from
which the greater part of the morphine has been precipitated by
ammonia, and crystallises therefrom after the separation of the meconic
acid and excess of baryta. If the filtrate be neutralised with hydro-
chloric acid, and evaporated to crystallisation, a part of the narceine
crystallises out, while another portion remains in the mother-liquor.
On dissolving about ths of the crystals in water, narceine chiefly
remains undissolved, and may be purified by recrystallisation from
boiling water. A further portion may also be obtained from the
filtrate (Pelletier).
See Anderson's method, xvi, 240. The product is still to be purified by
recrystallisation from a large quantity of boiling water, dissolving in
alcohol, boiling with animal charcoal, and again dissolving in water.
When narceine containing morphine is dissolved in a nearly boiling
solution of very weak caustic potash, and the filtrate is mixed with
acetic acid to slight acid reaction, the narceine crystallises out, whilst
the morphine remains in solution as acetate (Pelletier). Narceine and
meconin may be separated by means of ether, which dissolves only the
latter.
598
PRIMARY NUCLEUS C6H46; OXYAZO-NUCLEUS CNH27018.
From the ripe capsules of the Blue-seeded Poppy. The extract prepared
with boiling alcohol of 80 p. c., when dissolved in boiling water, leaves
behind light-brown flocks of impure narceine, more of which may be
obtained by evaporating the filtrate, and diluting with water; also by
again evaporating the filtrate to an extract, and leaving it to stand;
the narceine is then deposited. The deposits are purified by repeated
crystallisation from boiling alcohol, with help of animal charcoal
(Winckler).
Properties. Narceine is obtained in hydrated crystals which give
up their water with difficulty at 100° (Anderson). Tufts of white
silky needles [or long four-sided right rhombic prisms (Pelletier, Ann.
Chim. Phys. 53, 431)]. Inodorous. Tastes slightly bitter at first, and
afterwards peculiarly styptic (Winckler). Melts at 145 2° (Hesse),
92° (Pelletier) and solidifies to a translucent amorphous mass on cool-
ing. - Rotates a ray of polarised light to the left; [a] r
(Bouchardat & Boudet, N. J. Pharm. 23, 292).
at 110°.
= 66.7°
Pelletier. Couerbe. Anderson. Hesse.
46 C
N
29 H
18 O
....
276 ..
14
59.63
54.02
1444
56.21 ....
59.34
59.29
3.02
4.33
4.76
3.20
29
....
144
6.28
31.07
6.52
35.13
6:64
32.39
6.42
6.49
....
....
31.04
....
....
....
4440
C46NH29018
463
100.00
100.00
....
100.00
100.00
The analyses are given in mean numbers. Pelletier & Couerbe, who do not
state whether they dried their narceine, may have analysed the hydrated alkaloïd
(Kr.). A specimen of narceine from Robiquet, Pelletier, and Caventou's factory,
analysed by Anderson, contained 62 70 p. c. C., 4.22 N., and 6:53 H., corresponding
to the formula C32NH19010.
Decompositions. 1. Narceine, when cautiously heated melts to a
yellow, opaque, oily liquid, which at higher temperatures evolves an
odour of herrings, turns brown, burns with bright-red smoky flame,
and leaves a combustible charcoal (Winckler). It turns yellow at 100°,
and when submitted to dry distillation, yields a little coloured acid
water, a brown tar having an aromatic odour, and white acid needles,
which dissolve in water and alcohol and colour ferric salts blue-
black; probably gallic acid (Pelletier). Narceine heated till it becomes
brown gives up to water the substance which blackens ferric salts (Hesse).-
2. Strong nitric acid dissolves narceine with yellow colour, and
evolves red fumes when heated therewith; the evaporated solution is
bitter, and deposits crystals of oxalic acid (Pelletier; Anderson). In
this reaction no cotarnine or meconin (the products obtained from
narcotine by similar treatment) is obtained (Anderson). Nitric acid of
sp. gr. 1.25 does not colour narceine from poppy capsules, but colours
that from opium pale yellowish-red, both varieties dissolving imme-
diately to a clear greenish-yellow liquid (Winckler). Potash liberates
from the solution in nitric acid a volatile base (Anderson). 3. Oil of
vitriol colours narceine dark red-brown (Winckler); it forms a dark-
red solution, which turns green when warmed (Anderson). Hesse's
narceine is coloured black, or in thin layers, violet, by oil of vitriol.
Oil of vitriol containing nitric acid, immediately colours narceine brown-
red, or with traces of nitric acid, chocolate (Couerbe). A solution in
NARCEINE.
599
oil of vitriol is coloured reddish-yellow by permanganate of potash
(Guy, Anal. Zeitschr. 1, 93).
Combinations.— With Water. - Hydrated Narceine? See above.
Narceine dissolves in 1,285 parts of water at 13° (Hesse); in 375
parts at 14°, and in 230 parts of boiling water (Pelletier), without
previously melting to an oil (Winckler). It dissolves easily in boiling
water, the solution solidifying to a pulpy mass of silky needles on
cooling (Anderson).
Narceine is more easily soluble in ammonia, potash, and soda than in
water; a large quantity of strong potash-ley precipitates it from the
solution in the form of an oil, which afterwards solidifies (Anderson).
Solution of caustic potash of sp. gr. 1.23 colours aqueous narceine
rose-red, and after 24 hours red-brown (Winckler).
Iodine colours narceine greyish-blue and brown-violet (Winckler).
The black-blue compound of narceine with iodine dissolves without
colour in water when boiled therewith, evolving iodine; on cooling, the
solution deposits a blue compound containing iodine, a rose-red com-
pound containing only a little iodine, or white narceine free from iodine,
according to the length of time it has been boiled (Pelletier).
Narceine dissolves in acids, forming crystallisable salts (Pelletier;
Anderson). It forms colourless solutions with vegetable acids, or with
weak mineral acids; also with strong hydrochloric acid, when the
alkaloid is pure (Winckler; Anderson). Pelletier's narceine imme-
diately assumes an azure-blue colour with fuming hydrochloric acid
diluted with one-third of water; in a sufficient quantity of water the
blue compound forms a colourless solution, acquiring only a transient
violet-red colour. On evaporating the colourless solution, there re-
mains a violet-red crust ultimately turning blue, if the narceine has
not been decomposed by too large a quantity of hydrochloric acid. If
the colourless solution be dehydrated by dropping chloride of calcium
into it, the compound is coloured rose-red, violet, and blue; other
dehydrating substances produce a similar effect; a certain quantity of
water, however, is necessary, since narceine assumes with dry hydro-
chloric acid gas an orange colour, turning blue only on addition of a
little water. From the blue solutions which have been decolorised by
the addition of more water, alkalis throw down unchanged narceine.
Oil of vitriol diluted with 4 or 5 parts of water, nitric acid diluted with
2 parts of water, and hydrofluosilicic acid act in the same way as
hydrochloric acid (Pelletier). Winckler's narceine from poppy-cap-
sules did not exhibit the blue colour; narceine from opium showed it,
though only faintly, after being twice recrystallised from alcohol, with
the help of animal charcoal. A saturated aqueous solution of nar-
ceine is not affected by oil of vitriol, iodic acid, nitric acid, oxalic acid,
or basic acetate of lead; iodide of potassium, tartar-emetic, and
nitrate of silver throw down the narceine in needles after 24 hours
(Winckler). Sesquichloride of iron does not colour narceine blue
(Pelletier), but when added to an aqueous solution it produces in 24
hours a crystalline deposit of hydrochlorate of narceine (Winckler).
Sulphate of Narceine. - Crystallises in small prisms from the easily
formed solution of narceine in hot dilute sulphuric acid on cooling
(Hesse). Silky tufts of needles, resembling narceine (Anderson). The
solid salt reddens litmus after prolonged contact with water, but not at
600 PRIMARY NUCLEUS CH; OXYAZO-NUCLEUS C46NH27018.
!
1
first; boiling water also partially resolves it into narceine and sulphuric
acid (Hesse).
Hydrochlorate of Narceine. - Separates from a solution of narceine
in hydrochloric acid of sp. gr. 1·13, on cooling, in white, semi-lustrous
translucent, rhombohedral prisms. The crystals do not redden litmus
after the removal of the free acid, but have a distinctly acid, afterwards
slightly bitter and styptic taste. They become opaque when gently
warmed, and give off their water of crystallisation at 100°. They are
nearly insoluble in cold, but freely soluble in hot water, and in 80 p. c.
alcohol (Winckler). Anderson obtained short, thick, irregular prisms,
having a distinctly acid reaction, and easily soluble in water and
alcohol.
Anderson.
46 C
N
Dried.
276
55.25
55.31
14
2.80
....
30 H
18 O
30
6:00
6.41
144
28.85
Cl
35.5
7.10
7.04
C46NH29018,HCl........ 499.5
100.00
Crystallised.
Winckler.
C46NH29018
463
85.03
85.75
HCI
36.5
6.70
5.92
5 HO
45
8.27
8.33
C46NH29018, HCl + 5aq.
544.5
100.00
100.00
}
Nitrate of Narceine. - Obtained from the hydrochlorate and nitrate
of silver. White, dull, silky, delicate prisms, to be freed from adhering
silver-salt by washing with cold water. Dissolves less freely than
narceine in water (Winckler). From a solution in hot water the salt
crystallises in stars (Anderson).
Chloromercurate of Narceine.-Mercuric chloride renders hydrochlo-
rate of narceine milky, and when more concentrated, or when left to
itself, throws down oily drops, which afterwards crystallise. White,
concentrically arranged, short prisms, which dissolve slightly in boiling
water and in hydrochloric acid, and are not coloured by oil of vitriol.
Chloroaurate of Narceine. Yellow precipitate, which dissolves in
boiling water, and is deposited in the form of an oil on cooling. It is
decomposed by long boiling, with separation of gold (Hesse).
Chlorplatinate of Narceine. -Obtained in the form of a crystalline
powder or small prisms, or from stronger solutions as an amorphous
precipitate, which afterwards crystallises (Hesse; Anderson). Loses
2.73 p. c. of water at 110° (2 at. = 2.61 p. c. HO) (Hesse).
Hesse.
Anderson.
at 100°.
mean.
mean.
46 C
N
30 H
276
41.24
41.05
14
2.09
30
4.48
4.60
16 O
144
21.51
3 Cl
106.5
15.94
Pt
98.7
14.74
14.58
14.52
C46NH29018, HCl + PtCl²
669.2
100.00
COLCHICINE.
601
Narceine dissolves in 800 parts of dilute acetic acid at 13°, and
more freely at higher temperatures, crystallising on cooling (Hesse).
Picric acid throws down from aqueous narceine a yellow oil soluble
in boiling water (Hesse). Tannic acid precipitates aqueous narceine
(Winckler): picrotoxin increases its solubility in water (Pelletier &
Caventou, Ann. Chim. Phys. 54, 186).
Narceine dissolves in 945 parts of 80 p. c. alcohol at 13° (Hesse),
and easily in boiling alcohol, but not in ether.
Appendix to Compounds containing 46 atoms of Carbon.
1. Colchicine.
C34 NH19010.
GEIGER & HESSE. Ann. Pharm. 7, 274; Geiger's Handbuch, 4 ed. 1,
1011.
A. ASCHHOFF; G. BLEY. N. Br. Arch. 89, 1; Pharm. Viertelj. 6,
377.
L. OBERLIN. Compt. rend. 43, 1199; N. J. Pharm. 31, 248; J. pr.
Chem. 71, 112; N. Br. Arch. 96, 192; N. Repert. 6, 301; Pharm.
Viertelj. 6, 555; Complete: N. Ann. Chim. Phys. 50, 108; Kopp's
Jahresber. 1856, 548.
WALZ. N. Jahrb. Pharm. 16, 1.
LUDWIG & PFEIFFER. N. Br. Arch. 111, 3; Kopp's Jahresber. 1862,
383.
M. HÜBLER. N. Br. Arch. 121, 193; Chem. Centr. 1865, 536.
Mistaken for veratrine by Pelletier & Caventou; discovered by Geiger & Hesse
in 1833; investigated most fully by Hübler. According to more recent investiga-
tions it is not an alkaloid, but an indifferent nitrogenous vegetable substance.
Source. In all parts [even in the flowers (Reithner, Pharm. Viertelj.
4, 481)] of Colchicum autumnale, and probably in other species of col-
chicum (Geiger & Hesse). According to J. Müller (N. Br. Arch. 81,
298) Sem. Colchici contains colchicine and a base which is coloured
purple-red by oil of vitriol [apparently colchiceine (Kr.)].
Preparation. 1. From the seeds, which need not be bruised (Hübler).
The seeds are exhausted with hot alcohol of 90 p. c.; the tinctures are
evaporated to a syrup and again diluted with 20 volumes of hot water
and left to cool, whereupon a fatty oil is deposited. After separating
the deposit, the liquid is precipitated with basic acetate of lead; the
precipitate is removed, and also the excess of lead by means of phos-
phate of soda, and the colchicine is thrown down by previously purified
tannic acid, the first and last (less pure) portions of the precipitate
being collected separately, and further treated apart from the middle
portion. The precipitate is washed (by pressing, suspending in water,
collecting, draining, &c.), triturated with oxide of lead and dried; and
if an alcoholic solution of a small portion, tested with sesquichloride of
iron, is found to be free from tannic acid, the whole is boiled with
alcohol. The alcoholic liquid is distilled, and the residual colchicine is
dried over the water-bath and afterwards in a vacuum over oil of
602
PRIMARY NUCLEUS C46H46; OXYAZO-NUCLEUS C46NH27018.
·
vitriol, and is then to be purified by repeated fractional precipitation
with tannic acid (Hübler). The liquids precipitated by tannic acid still contain
colchicine, which may be recovered by precipitating the excess of tannic acid with
basic acetate of lead, and the excess of lead by hydrosulphuric acid, then agitating
the filtrate with animal charcoal, which takes up the colchicine and gives it up to
boiling alcohol. - The tannic acid employed for the precipitations, if it contains
brown colouring matter, as is the case with the commercial acid, must be purified as
follows:-A filtered aqueous solution of the acid is evaporated to dryness with oxide
of lead; and the tannate of lead thus formed is boiled repeatedly with alcohol and
water in succession, afterwards suspended in water and decomposed by hydrosul-
phuric acid (Hübler). — Ludwig and Pfeiffer adopt a process similar to Hübler's.
2. The bruised seeds are exhausted with warm alcohol containing
sulphuric acid; the tincture is shaken up with lime; the filtrate is
neutralised with sulphuric acid and freed from alcohol by distillation;
the residual concentrated aqueous liquid is precipitated by carbonate
of potash; the precipitate is pressed, dried, and exhausted with abso-
lute alcohol; the tincture is decolorised with animal charcoal and eva-
porated; and the product is purified by dissolving it in alcohol, with
the help of animal charcoal. Or the product is dissolved in dilute
sulphuric acid; the solution is decomposed by excess of quick-lime; and
the colchicine is extracted by ether, dissolved in alcohol and allowed
to crystallise, with the addition of a little water (Geiger & Hesse). Are
the crystals colchicine or colchiceine? (Kr.).
A. Aschhoff exhausts the roots with cold water; precipitates the
infusion with basic acetate of lead; neutralises with carbonate of sɔda
not in excess; precipitates with tannic acid; washes and presses the
precipitate, and dissolves it in 8 parts of alcohol; digests the solution
with freshly precipitated sesquioxide of iron; and after complete de-
composition, evaporates the filtrate and purifies the residue by solution
in ether-alcohol.
Properties. Amorphous, brittle, fissured mass, which cakes together
when triturated. Smells slightly aromatic, like hay, and tastes power-
fully and persistently bitter [not acrid (Bley)]. Poisonous; 0.05
gramme killed a dog, but 0·10 gramme did not kill a rabbit, so that it
is probably poisonous only to carnivora (Seidel). See also Schroff (N. Re-
pert. 5, 437; Kopp's Jahresber. 1856, 550); Casper (N. Br. Arch. 81, 1; Pharm.
Centr. 1855, 139). Neutral. Softens at 130°, and melts without loss
of weight at 140° to a transparent brown mass, which is glassy and
brittle after cooling (Hübler). A. Aschhoff, G. Bley, and Ludwig & Pfeiffer
also obtained colchicine as an amorphous neutral mass, but that of Walz and of
Geiger & Hesse crystallised from weak spirit in colourless needles and prisms, and
remained in the form of a varnish on evaporating its solution in stronger alcohol or
ether. Inodorous; does not provoke sneezing, like veratrine; tastes very bitter
and afterwards persistently acrid, not burning; produces vomiting and purging;
4th of a grain kills a young cat in twelve hours. Has a slightly alkaline reaction
(Geiger & Hesse). Geiger & Hesse's crystals cannot be regarded as colchiceine, the
foregoing statements not according sufficiently with the properties of that body
(Kr.).
at 104°.
Hübler.
mean (4).
34 C
N
204
64.35
64.50
14
4.42
4.45
19 H....
19
5.99
6.10
10 O
80
25.24
24.95
C34NH19010
317
100.00
100'00
....
COLCHICINE.
603
The substance lost 4 to 6 p. c. of hygroscopic water on drying (Hübler).
Decompositions. 1. Colchicine burns with a smoky flame on plati-
num-foil, puffing up and leaving a bulky charcoal (Hübler).-2. Chlo-
rine-water produces in aqueous colchicine a slight yellow precipitate,
soluble in ammonia with orange-yellow colour (Aschhoff). 3. Colchi-
cine is converted into colchiceine by dilute sulphuric or hydrochloric acid
(Oberlin; Hübler). See below.
4. Strong nitric acid colours colchicine dark-violet or blue, changing
to olive-green and yellow (Geiger & Hesse). Nitric acid free from
nitrous acid colours it yellow, brown-red, to violet, afterwards brown-
green, and lastly brown-red; fuming nitric acid colours it dark-violet
to indigo-blue, afterwards turning yellow (Aschhoff). - 5. Oil of vitriol,
cautiously poured upon colchicine, assumes a dark-green colour,
changing rapidly to yellow as the colchicine dissolves; a glass rod
moistened with nitric acid and introduced into the yellow liquid pro-
duces a dark-blue zone, changing to violet, brown, and yellow. When
supersaturated with ammonia, the solution assumes a dark brick-red
colour, which is turned yellow by acids, restored by alkalis, and re-
mains fixed (Hübler). Geiger & Hesse's colchicine is coloured yellowish-brown
by oil of vitriol. A solution of colchicine in nitric acid is coloured by oil of vitriol
blue-violet, afterwards brownish-yellow, and ultimately yellow. Chromate of potash
colours the solution in sulphuric acid green (Aschhoff).
6. Colchicine treated with hot potash-ley, yields a brown resin
(Aschhoff). When heated to 100° for a day in a sealed tube with
baryta-water, it is converted into colchiceïne-baryta (Hübler). 7. The
precipitate produced by sulphate of copper in solutions of colchicine
dissolves in caustic potash, forming a solution which turns greenish-
yellow on boiling, without depositing cuprous oxide (Ludwig &
Pfeiffer).
Combinations. Colchicine deliquesces slowly in water and dissolves
in all proportions (Hübler). Geiger & Hesse's colchicine dissolves with mode-
rate facility in water. Tincture of iodine thickens aqueous colchicine with
carmine-red colour. Aqueous mineral acids, especially hydrochloric
acid, added to aqueous colchicine, colour it a deep yellow, and decom-
pose it on long standing, but do not combine with it (Hübler; Asch-
hoff). Geiger & Hesse's colchicine neutralises acids completely, forming salts which
are permanent in the air, partially crystallisable, have a very bitter and harsh taste,
and dissolve easily in water and alcohol. The base is precipitated by alkalis from
concentrated, but not from dilute solutions.
Aqueous alkalis colour solutions of colchicine a deep yellow
(Hübler). An aqueous solution of colchicine is precipitated by car-
bonate of potash (Hübschmann, N. Br. Arch. 95, 332). An equal
volume (not a few drops) of potash-ley produces a yellowish-white
precipitate (Aschhoff). Aschhoff & Bley believe they have obtained
compounds of colchicine with baryta, lime, and magnesia.
Aqueous colchicine is not precipitated by neutral or basic acetate of
lead, sulphate of copper (contrary to the statement of Ludwig & Pfeiffer), or
sesquichloride of iron (Hübler). It yields an orange-yellow precipitate
with phosphomolybdic acid (Sonnenschein). Mercuric chloride throws
down from its concentrated aqueous solution a white curdy precipitate,
soluble in excess of the precipitant and in alcohol (Ludwig & Pfeiffer;
604
PRIMARY NUCLEUS C46H6; OXYAZO-NUCLEUS C4NH7018.
Hübler). Terchloride of gold produces a whitish-yellow precipitate,
soluble in water, alcohol, and excess of the precipitant. Bichloride of
platinum does not precipitate aqueous colchicine (Hübler; Bley), or
throws down from concentrated solutions only a precipitate soluble in
alcohol and in bichloride of platinum (Ludwig & Pfeiffer). According to
Geiger & Hesse, chloride of platinum throws down a yellow precipitate
from aqueous colchicine, but not from its salts. See also Walz on the
reactions of aqueous colchicine (loc. cit.).
Tannate of Colchicine. Aqueous tannic acid throws down curdy
flocks from an aqueous solution of colchicine, even when very dilute.
White amorphous powder, fusible without decomposition above
Hygroscopic; inodorous; less bitter than colchicine. Dis-
solves slightly in cold, more freely in boiling water, and to a less
extent in saline solutions. Easily soluble in alcohol; insoluble in ether
(Hübler). Dissolves in aqueous carbonate of potash, and in acetic
acid (Aschhoff).
210 C
3 N
101 H
98 O........
3 C34NH19010,2C54H22034
Hübler.
57.9 to 58.3
at 104°.
1260
57.61
42
1.92
1.98
101
4.62
4.8 to 4.9
784
35.85
2187
100.00
Hübler supposes the compound to contain 2HO less.
Colchicine dissolves easily in alcohol; according to Hübler, it is in-
soluble, according to Geiger and Hesse soluble in ether. Hübschmann
(N. Jahrb. Pharm. 16, 1) found it soluble in 18 parts of ether of sp. gr.
0.74, and less soluble in absolute ether.
2. Colchiceïne.
C34NH19010 C4NH1906, H.
OBERLIN. N. Ann. Chim. Phys. 50, 108.
LUDWIG & PFEIFFER. N. Br. Arch. 111, 3.
HÜBLER. N. Br. Arch. 121, 193.
Discovered by Oberlin; more fully investigated by Hübler.
to Oberlin, in Colchicum autumnale, but his own experiments
chicine contained therein. undergoes conversion into colchiceîne.
Occurs, according
show that the col-
Formation and Preparation. When an aqueous solution of colchi-
cine, prepared by Geiger and Hesse's process, is mixed with sulphuric
acid, it assumes a yellow colour, and after being heated for some time
throws down, on addition of water, a yellow precipitate of colchiceïne,
which may be crystallised from alcohol or ether. Colchiceïne likewise
crystallises from a solution of colchicine mixed with hydrochloric acid,
after standing in the cold for some weeks; in this case the product is
less coloured and more easily purified than that made with sulphuric
acid (Oberlin). — Hübler dissolves 5 parts of colchicine in 100 parts of
water, and mixes the solution with 5 parts of oil of vitriol previously
diluted with water. The liquid assumes a yellow colour, evolves a
penetrating odour, and when heated turns cloudy from separation of
COLCHICEÏNE.
605
{
resinous drops, after the removal of which, the somewhat concentrated
solution solidifies on cooling to a greenish-yellow crystalline mass,
which is purified by 8 or 10 times repeated crystallisation from water.
A large additional quantity of colchiceïne may be obtained by boiling
the resinous drops with water. - Colchicine is also converted into col-
chiceïne by boiling with baryta-water (p. 603) (Hübler).
The crystals thus obtained are free from the acid employed
(Oberlin). Colchiceïne is formed without the simultaneous formation of
sugar (Ludwig & Pfeiffer), or of any second product; the resin formed
at the same time is to be regarded as a secondary decomposition-pro-
duct of colchiceïne (Hübler). Walz thought he had discovered the formation of
a substance which reduced oxide of copper, and three other bodies.
A part of the resin remains dissolved in the colchiceïne mother-
liquor, and may be precipitated in flocks by exactly neutralising the
liquid with carbonate of soda; or it may be obtained by evaporating
the mother-liquor and exhausting the residue with alcohol. It forms
an amorphous, bitter mass, soluble with deep-red colour in acids,
alkalis, ether, alcohol, and aqueous ammonia, and with blood-red
colour in nitric acid (Hübler; Oberlin).
Properties. Small, white needles collected in nodules, or pearly
laminæ. According to Oberlin and Ludwig & Pfeiffer, it tastes very
bitter; according to Hübler, less bitter than colchicine. Permanent
in the air. Softens when heated, and melts at 155° (Oberlin). Accord-
ing to Oberlin neutral, according to Hübler acid, especially in alco-
holic solution. Not poisonous to rabbits in doses of half a gramme
(Oberlin).
Calc. according to Hübler.
Hübler.
mean, at 100°.
Oberlin.
34 C
N
204
64.35
64.45
62.67
14
4.42
4.50
4.30
19 H
19
5.99
6.10
6.56
10 O
80
25.24
24.95
....
26.47
C34NH19010........
317
100.00
100.00
100.00
Isomeric with colchicine (Hübler).
Decompositions. 1. Colchiceïne assumes a yellow colour externally
when exposed to diffused light; the colourless solution likewise leaves
a yellowish-brown stain when dried on paper (Hübler).—2. It is
coloured by heating to 200°, melts on platinum-foil, and burns (Oberlin).
-3. Chlorine-water throws down white flocks from solutions of colchi-
ceïne (Ludwig & Pfeiffer). — 4. Colchiceïne forms, with oil of vitriol, a
deep-yellow solution, which, when diluted with water and left to
itself, deposits brown flocks (Oberlin). 5. The deep-yellow solution
in strong nitric acid rapidly assumes a violet colour, changing to dark-
red and light-red, and ultimately to yellow (Oberlin). The aqueous solu-
tion is coloured violet, afterwards brown, by nitric acid, yellow by the dilute acid
(Ludwig & Pfeiffer).-6. Colchiceïne, subjected to prolonged boiling with
dilute mineral acids, yields a resin similar to that formed in its prepara-
tion (Hübler).
Combinations.
Colchiceïne dissolves slightly in cold, and more
freely in boiling water. Dilute mineral acids colour the solution yellow;
606 PRIMARY NUCLEUS C46H46; OXYAZO-NUCLEUS CNH27018.
acetic acid does not affect it (Oberlin).
Iodine-water throws down
brown flocks from the aqueous solution (Ludwig & Pfeiffer).
Colchiceïne behaves towards bases like an acid. It dissolves easily
in aqueous ammonia, remaining free from ammonia when evaporated.
It dissolves in potash- and soda-ley, and in aqueous alkaline carbonates,
liberating carbonic acid; the latter solutions, when evaporated, leave
the potash- and soda-salts in the form of yellow fissured varnishes
(Hübler).
Baryta salt. Baryta dissolved in wood-spirit throws down from a
similar solution of colchiceïne, a jelly which dissolves in wood-spirit and
in excess of baryta (Oberlin). The soda-salt throws down from
chloride of barium, amorphous white flocks, which dissolve when
heated, and re-appear on cooling (Hübler). - Colchiceïne is boiled with
baryta-water; the excess of baryta is removed by means of carbonic
acid; the solution is evaporated; and the residue is dissolved in
alcohol, filtered, and evaporated. Amorphous yellow mass, soluble in
alcohol (Hübler).
Hübler.
C34NH1809
BaO
at 100°.
308
76.5
80.10
19.90
18.9
384.5
100.00
....
A
C34NH18Ba010
Colchiceïne-soda throws down from chloride of calcium and chloride
of magnesium white amorphous flocks; it produces with zinc-, lead-,
bismuth-, and murcury-salts, white precipitates, soluble in excess of
the salts, or on boiling, re-appearing as the liquid cools. It forms a
red-brown precipitate with nitrate of cobalt; greenish-brown with
sesquichloride of iron. All these precipitates are soluble in alcohol
(Hübler).· Colchiceïne does not precipitate neutral or basic acetate of
lead, mercuric chloride, nitrate of silver, or tincture of galls. An alcoholic
solution is not precipitated by bichloride of platinum (Oberlin). Ludwig
& Pfeiffer's colchiceïne forms a fine light-yellow precipitate with
chloride of gold and picric acid, dirty dark-brown with bichloride of
platinum, and pale-brown with tannic acid after addition of hydro-
chloric acid, but is not precipitated by mercuric chloride.
Colchiceïne with Cupric oxide. By decomposing the soda-compound
of colchiceïne with sulphate of copper, a yellowish-green precipitate is
obtained, which turns darker and crystalline on boiling, and is easily
soluble in excess of the copper-salt and in alcohol. Or alcoholic col-
chiceïne is boiled with freshly precipitated cupric hydrate, and the
green filtrate is diluted with water and the alcohol driven off, where-
upon the copper-compound is deposited. Microscopic, apparently
quadratic tables and octohedrons. Dissolves slowly in strong aqueous
ammonia and in hot potash-ley (Hübler).
C3+NH¹SO9
CuO
C34NH18CuO10
Hübler.
308
88.56
39.8
11.44
9.36
347.8
100.00
....
According to Hübler, the substance contained an admixture of free colchiceïne.
Colchiceïne dissolves in wood-spirit and in alcohol, from which it crys-
tallises, and less freely in ether. It does not crystallise from its easily
CORYDALINE.
607
formed solution in chloroform (Hübler; Oberlin). It is withdrawn from
its solutions by animal charcoal, which afterwards gives up to alcohol,
not colchiceïne, but a brown bitter mass (Ludwig & Pfeiffer; Hübler).
3. Corydaline.
WACKENRODER. Kastn. Arch. 7,417; Berz. Jahresber. 7,220.
Kastn.
N. Arch. 2, 427. — N. Br. Arch. 49, 153; Kopp's Jahresber. 1847
and 1848, 644.
PESCHIER. Mém. de la Société de Phys. 4, 247; N. Tr. 17, 2, 80.
WINCKLER. Pharm. Centr. 1832, 301; N. Br. Arch. 49, 301.
FR. DÖBEREINER. N. Br. Arch. 13, 64; Ann. Pharm. 28, 288.
RUIKHOLDT. N. Br. Arch. 49, 139; Ann. Pharm. 64, 369; Kopp's
Jahresber. 1847 and 1848, 643.
J. MÜLLER. Pharm. Viertelj. 8, 536.
C. LEUBE, jun. Pharm. Viertelj. 9, 524.
Discovered by Wackenroder in 1826.-Occurs in the roots of Corydalis
tuberosa and C. fabacea (Wackenroder). In smaller quantity in the leaf-sap of the
first plant (Peschier).
Preparation. 1. The coarsely powdered root is twice digested with
water containing hydrochloric acid and pressed; the liquid is left to
itself till it clears, and is then precipitated with carbonate of soda; and
the precipitate is washed so long as it gives up colouring matter, dis-
solved in water containing hydrochloric acid, and again thrown down
by carbonate of soda. The well-washed, dried, and triturated pre-
cipitate is now dissolved by shaking it with freshly rectified oil of tur-
pentine, and the filtered wine-red solution is agitated with water
containing hydrochloric acid, and thereby freed from corydaline. The
oily layer is decanted; the acid solution is filtered through a wet filter
and precipitated with caustic potash; and the precipitate is washed
and dried (Müller).-2. The coarsely powdered root is macerated for
a few days with pure water, and afterwards repeatedly with water
containing sulphuric acid; the liquids are filtered and precipitated by
carbonate of soda; and the precipitates are exhausted with alcohol
(those from the last macerations, being less pure, are treated sepa-
rately). The alcoholic filtrate is evaporated; the residue is dissolved
in dilute sulphuric acid; the solution is filtered from green resin, and
mixed, first with a little potash, which throws down dark-coloured cory-
daline, and, after filtration, with more potash, whereby purer cory-
daline is precipitated (Wackenroder). Or an alcoholic extract of the
root may be exhausted with water; the solution precipitated with basic
acetate of lead in not too great excess; the filtrate freed from lead by
hydrosulphuric acid; and the corydaline precipitated by potash or lime.
Or the root is boiled with water containing hydrochloric acid; the
extract is evaporated to dryness and exhausted with alcohol; the alco-
holic solution is evaporated; the residue taken up by water, which
leaves resin behind; and the corydaline is precipitated from the solu-
tion by caustic potash (Wackenroder).
Winckler frees the sap of the fresh root from albumin by boiling;
precipitates the filtrate with basic acetate of lead; separates the preci-
pitate; and afterwards removes the excess of lead by sulphuric
608
PRIMARY NUCLEUS C6H46; OXYGEN-NUCLEUS CNH018.
acid, and precipitates with ammonia not in excess. The precipitate is
collected, washed with cold water, dried, and exhausted with hot alcohol
of 80 p. c., whereby a dark-green tincture is obtained, which leaves
white crystalline corydaline on evaporation.
Properties. White loose powder, appearing under a magnifying-
power of 125 diameters, to be made up of amorphous granules (Müller;
Leube). According to Wackenroder, it crystallises, on evaporating its
alcoholic solution, in colourless prisms and thin scales. It softens at
60°, and melts completely at 70° [far below 100° (Wackenroder)] to a
translucent wax, without losing weight (Müller). Melted corydaline
floats on water. It is inodorous, and has but little taste alone, but is
very bitter in solution. Its alcoholic solution has an alkaline reaction
(Wackenroder).
Döbereiner.
Ruikholdt.
at 62°.
Müller.
Leube.
at 50°.
mean.
C
OREO
62.18
59.70
74.11
74.18
N
4.32
3.02
3.67
3.62
....
H
6.84
5.90
7.67
7.54
....
26.66
31.38
14.55
14.66
100.00
100.00
100.00
100.00
C34NH22O10 (Döbereiner); CNH27018 (Ruikholdt); C²²N²H5S014 (Müller).
Leube halves this formula.
Decompositions. 1. Precipitated corydaline (and the crystallised
substance to a less extent) assumes a greenish-yellow [lemon-yellow
(Müller)] colour in sunlight, and cannot afterwards be decolorised by
animal charcoal (Wackenroder). — 2. When heated above its melting-
point it turns brown, evolves easily combustible vapours, having an
empyreumatic and ammoniacal odour, and burns with a yellow luminous
flame.-3. It dissolves with yellow colour in strong nitric acid
(Müller); according to Wackenroder and Ruikholdt, it colours the acid
blood-red [on account of the presence of resin (Müller)] and dissolves
without decomposition. 4. Corydaline forms, with oil of vitriol, a
dark-red solution (Müller), which, when evaporated, changes to violet
and black, and carbonises (Wackenroder).
Combinations. Corydaline does not dissolve in water either cold or
boiling (Müller). — With acids it forms salts, which, according to Müller
and Leube, are amorphous, resinous, and easily fusible; according to
Wackenroder, crystallisable for the most part. Caustic alkalis and
their carbonates, as well as ammonia, throw down corydaline from its
salts as a white precipitate, insoluble in excess of the precipitant
(Müller). Wackenroder at one time described cory daline as nearly insoluble in
alkalis, but afterwards stated that it is easily soluble in excess of potash-ley and pre-
cipitable from the solution by sal-ammoniac.
Sulphate of Corydaline. The greenish slightly acid solution leaves
on evaporation a crystalline residue, only partially soluble in water.
The aqueous solution leaves, when evaporated, a greenish-yellow trans-
parent mass, soluble in water, alcohol, and ether (Wackenroder).
CORYDALINE.
609
Hydrochlorate of Corydaline. — A solution of corydaline in excess of
hydrochloric acid leaves, on evaporation, a residue soluble in water,
alcohol, and ether (Wackenroder). By digesting excess of cory-
daline in hydrochloric acid, Wackenroder & Ludwig subsequently
obtained an acid yellowish-green liquid which yielded crystals when
treated with animal charcoal. The crystals are yellowish-green right
rhombic prisms, having a vitreous lustre, very brittle, and neutral;
when dissolved in alcohol of 96 p. c. they are again deposited in the
form of a greyish-yellow crystalline powder. They give off 12.5 p. c.
water at 100°, and 3·02 p. c. more at 145° to 170°, and in the air-dried
state contain 10-78 p. c. of hydrochloric acid (Wackenroder &
Ludwig).
Nitrate of Corydaline. Sulphate of corydaline and nitrate of
baryta yield prismatic crystals, which resinise when too strongly
heated (Peschier). Very dilute nitric acid dissolves corydaline without
decomposition, but the solution reddens and decomposes when evapo-
rated (Wackenroder).
Chloromercurate of Corydaline. - Thrown down from hydrochlorate
of corydaline by mercuric chloride as a white precipitate (Müller),
containing, at 100°, 12.98 p. c. chlorine, and agreeing with the
formula C46NH2907,HCl,HgCl (Leube).
Chloroplatinate of Corydaline. Yellow precipitate containing, at
100°, 16.89 p. c. platinum (Leube).
Terchloride of gold throws down a yellow precipitate from hydro-
chlorate of corydaline (Müller).
Acetate of Corydaline. Strong acetic acid dissolves corydaline
slowly, and leaves on evaporation a crystalline compound, soluble in
water, alcohol, and ether (Wackenroder).
Hydrochlorate of corydaline is precipitated by tannic acid and by
tincture of galls.
Corydaline dissolves in about 9 parts of cold 90 p. c. alcohol, in all
proportions in the hot liquid, and in 2 to 3 parts of ether (Müller).
It is insoluble in oils both fat and volatile (Wackenroder).
2 R
VOL. XVII,
ADDENDA.
Page 199.
Cinchonine.
O. HESSE. Ann. Pharm. cxxxv, 338; Bull. Soc. Chim. 1866, i,
462.
Bihydriodate of Cinchonine, C4°N²H²O²,HI + 2HO, crystallises in
golden-yellow laminæ, gives off its water at 100°, re-absorbs it again
in damp air. Gives by analysis 3·17 p. c. water and 44·31 iodine (calc.
3·09 HO, and 43·64 I.).
Chloroaurate of Cinchonine, C40N2H2402,2HCl,AuCl³. Heavy yellow
powder, melting to a dark-yellow mass at a few degrees above 100°,
and yielding 39-51 p. c. gold (calc. 39.87 p. c.).
Tartrate of Cinchonine and Antimony. This salt contains 2·47 p. c.
water of crystallisation, not 24.77, as stated at page 218; and it is
not efflorescent.
;
Page 220.
Cinchonidine.
HESSE. Ann. Pharm. cxxxv, 333; Bull. Soc. Chim. 1866, i, 460.
This base, the quinidine of Winckler,* is contained in small quan-
tity in all Calisaya barks, and is consequently obtained, together with
quinine, in the preparation of the latter on the large scale. As the
complete separation of quinine from cinchonidine is difficult, com-
mercial cinchonidine almost always contains small quantities of quinine.
According to Koch (Arch. Pharm. cxlii, 34), cinchonidine possesses
febrifugal properties.
Purification. Commercial cinchonidine containing quinine is pre-
cipitated with solution of Rochelle salt, the precipitate is dissolved in
hydrochloric acid, and the solution precipitated with excess of am-
* Hesse retains the name quinidine for this base, and designates the quinidine
of Pasteur (p. 221) as conchinine; but as the base discovered by Winckler is
someric, not with quinine, but with cinchonine, it is more appropriately named
icinchonidine.
CINCHONIDINE.
611
monia. The alkaloids thus obtained are separated as far as possible
by treatment with ether, the quinine being thereby dissolved, together
with a not inconsiderable portion of the cinchonidine; the undissolved
portion, consisting chiefly of cinchonidine, is dissolved in hydrochloric
acid; and the neutral hydrochlorate of cinchonidine thus obtained is
purified by recrystallisation from water.
Properties. Cinchonidine crystallises from alcohol in large anhy-
drous prisms, melting at 206.5° (corrected) to a colourless mass,
which solidifies in the crystalline form at about 190°.
Hesse.
mean.
40 C
240
77.92
77.71
2 N
28
9.09
24 H
24
7.79
7.80
20
16
5.20
308
100.00
C40N2H2402
This formula had not previously been established by direct analysis (see page
222).
Cinchonidine dissolves in 1680 pts. of water at 10°, somewhat
more freely in boiling water.
The salts of cinchonidine are easily prepared either by saturating
the alcoholic solution of the base with an acid, or, in the case of salts
much less soluble than the hydrochlorate, by double decomposition
between that salt and the soda-salt of the required acid.
Hypophosphite of Cinchonidine crystallises in delicate white prisms.
much more soluble than those of the corresponding quinine-salt; it
may be recrystallised from boiling water.
Hyposulphite of Cinchonidine, 2C40N2H2402,S+H2O6+ 4HO. Thin
white prisms, which easily give off their water of crystallisation
amounting to 4.56 —4.83 p. c. (4 at. = 4.70 p. c.) at 110°, but recover
it all on exposure for a short time to moist air. 1 pt. of the salt dis-
solves in 221 pts. water at 10°.
Sulphate of Cinchonidine (comp. p. 224).a. Mono-acid, 2040N2H2402,
S²H³0º + 12HO. Crystallises in white prisms, which give off all their
water, except p. c., on exposure to the air, and the rest (12·92—13·14
p. c. in all) at 100°. One part of the salt dissolves in 97-5 pts. water
at 12°. It is insoluble in ether.
Anhydrous.
Hesse.
C40N2H2402
S2H208
616
86-28
98
13.72
13.56-13·93
2C40N2H2402,S2H2O2
714
100.00
Hydrated.
Hesse.
2 C40N2H2402
616
74.95
S2H208
98
11.92
11.96
12 HO ...
108
13.13
12·92—13·14
2C4N²H²¹O²,S*H³OS + 12aq.
822
100.00
612
ADDENDA.
This
Hesse describes also a modification of the anhydrous salt which is produced
under circumstances not exactly known," and crystallises, from boiling water, in
beautiful colourless prisms, or, when its aqueous solution is left to evaporate at a
moderate temperature, in warty masses containing only traces of water.
anhydrous salt dissolves, according to Hesse, in the same quantity of water as the
hydrated salt, and appears to contain a peculiar alkaloid, inasmuch as when the
alkaloid separated from it, is dissolved in hydrochloric acid, a hydrochlorate is
obtained, which when decomposed by sulphate of soda, yields the original anhydrous
sulphate, and when treated with oxalate of ammonia, yields an anhydrous oxalate of
cinchonidine (p. 613). But if, on the other hand, the hydrochloric solution of the
anhydrous cinchonidine be mixed with sodio-potassic tartrate, and the resulting
tartrate of cinchonidine converted into a sulphate, the sulphate thus produced is
identical in every respect with the hydrated salt a.
b. Bi-acid. A solution of 1 at. of the monosulphate (a) in 1 at.
sulphuric acid, evaporated down to a small bulk, yields this salt in
long, colourless, striated prisms, very efflorescent, and easily soluble
in water and in alcohol. The aqueous solution has a strong acid
reaction, and exhibits a blue fluorescence by reflected light.
crystals give off their water at 120°.
The
€40N2H2402
S2H2OS
10 HO
C40N2H2402,S2H2O + 10aq.
Crystals.
Hesse.
308
62.09
98
19.76
20.26
90
18.15
18.25
496
100.00
This analysis agrees very nearly with that of Winckler (p. 224).
c. Quadri-acid. The solution of the bisulphate in dilute sul-
phuric acid, evaporated over oil of vitriol at ordinary temperatures,
ultimately yields short, solid, colourless prisms of the quadrisulphate,
which dissolve but slowly in cold water, so that they may be easily
freed from excess of acid by washing with cold water. The salt is
insoluble in ether, which, moreover, does not take from it any portion
of the acid. The aqueous solution is strongly acid, and exhibits an
intense blue fluorescence by reflected light.
Hesse.
C40N2H2402
2 S2H208
308
57.04
•
196
36.29
36.16
4 HO....
36
6.67
7.11
C40N2H2402,28 H2O8 + 4aq.
540
100.00
Bihydriodate of Cinchonidine, C4°N²H²¹O²,2HI + 2HO. On adding
a dilute solution of the hydrochlorate to a solution of potassium-iodide
heated to about 50°, the liquid becomes milky, and ultimately deposits
the bi-hydriodate in fine lemon-yellow prisms, which, at 120°, give off
3.17 to 3.22 p. c. water (4HO = 3·09 p. c.).
Hydrochlorate of Cinchonidine, C40N2H2O2, HCl + 2HO. Crystallises
by evaporation in large monoclinic double pyramids, which dissolve in
38.5 pts. water at 10°, in 20 pts. water at 20.1°, and in 325 pts. ether
at 10° (comp. p. 225). The crystals give off 4.87 to 5.11 p. c. water
at 120° (calc. for 2HO. 4.96 p. c.), and yield by analysis 9.85 to
9.94 p. c. chlorine (calc. 9.79 p. c.).
If the solution is concentrated at a high temperature, the salt
finally separates in yellowish oily drops, which, after cooling, gradually
CINCHONIDINE.
613
solidify to a radio-crystalline mass, probably consisting of the anhy-
drous salt. The same product is obtained, though in small quantity,
when the solution is evaporated at a gentle heat.
Nitrate of Cinchonidine crystallises in large colourless prisms, which
melt at about 100° to an oily mass. When the aqueous solution is too
quickly evaporated, the salt likewise separates in the oily form, but if
kept under water, solidifies after a while in crystals. 1 pt. of the salt
dissolves in 70.5 pts. water at 10°. The crystals give off their water
(2 at.) at 110°.
C40N2H2402
NHO6
2 HO
Hesse
Crystals.
308
63
18
79.17
16.21
79.05
78.93
.... ...
4.62
4.80
C40N2H2402,NHO6 + 2aq. 389
100.00
AL
.......
1
Chloroaurate of Cinchonidine, C40N2H2402,2HCl, AuCl³. Obtained by
precipitating a dilute aqueous solution of the hydrochlorate with
chloride of gold, at ordinary temperatures, as a pulverulent mass of a
fine yellow colour, melting with decomposition at about 100°. When
dried over oil of vitriol, it contains 40.04 p. c. gold, the formula re-
quiring 39.87 p. c.
Chloroplatinate of Cinchonidine, C40N2H2O2,2HCl,2PtCl² + 2HO. A
hot acid aqueous solution of the hydrochlorate, mixed with platinic
chloride, deposits this salt after a few seconds as a pale orange-yellow
crystalline powder, or more rarely in small flattened prisms. It is
nearly insoluble in cold, slightly soluble in boiling water, and gives off
its water of crystallisation, 2.07 to 2.42 p. c. (2 at. 2.43 p. c.),
between 120° and 130°. The hydrated salt gives by analysis 26.83
platinum (calc. 26.73 p. c.); the salt dried at 130° gives 27.32 to
27.44 p. c. platinum (calc. 27.40 p. c.).
Hydroferrocyanate of Cinchonidine. Obtained by adding ferro-
cyanide of potassium to the solution of any cinchonidine-salt in dilute
sulphuric acid, as an egg-yellow precipitate consisting of spherical
aggregations. Moderately dilute solutions sometimes yield laminæ,
exactly resembling the corresponding cinchonine-salt. Hence the
reaction given by Bills (p. 214) for the detection of cinchonine may
also be applied to the detection of cinchonidine.
C*H*O*
Acetate of Cinchonidine, C40H24N2O2, C4H4O4 + 2HO. Obtained by
saturating an alcoholic solution of cinchonidine with acetic acid, evapo-
rating, and dissolving the separated salt in a small quantity of water,
in nodular groups of small white needles very soluble in water,
whether cold or hot. It gives off its water of crystallisation, together
with a considerable proportion of its acid, at 100°, so that it is after-
wards only partially soluble in cold water. The air-dried salt gives
by analyis 79.39 p. c. cinchonidine (calc. 79.79 p. c.).
Neutral Oxalate of Cinchonidine. a. Anhydrous. 2040N2H2O2, C4H2O.
Obtained by adding oxalate of ammonia to the hydrochloric acid
solution of the base precipitated from the anhydrous sulphate (p. 612).
Forms small white nodules consisting of concentrically grouped prisms,
which do not lose weight at 110°. Contains 10.18 p. c. oxalic acid,
C4H208 (calc. 10.19 p. c.).
#
.
::
2 R 2
614
ADDENDA.
b. Hydrated, 2040N2H2403, C4H208 + 12HO.-Obtained by precipi-
tation from the ordinary hydrochlorate. Crystallises in long asbesti-
form prisms, which, when in mass, shrink together to an extraordinary
degree on drying in the air. 1 pt. of the hydrated salt dissolves in
252 pts. water at 10°. The air-dried salt gives off 12·72 to 12.87 p. c.
water at 110° (calc. for 12HO = 13-26). The difference arises from
loss of a small quantity of water at ordinary temperatures.
Succinate of Cinchonidine, obtained by saturating an alcoholic
solution of cinchonidine with succinic acid, forms small white prisms,
which retain their water of crystallisation when dried over oil of
vitriol, but give it off at 100°, and dissolve in 582.5 pts. water at
10º.
Hesse.
2C40N2H2402
C$H6OS
4 HO
Crystals.
616
80.00
79.49
118
15.33
36
4.67
4.78-4.85
....
100.00
2C40N2H2402, C8H608 + 4aq. 770
....
Tartrate of Cinchonidine (neutral). - Obtained by double decomposi-
tion from somewhat concentrated solutions, as a white crystalline
precipitate, quite insoluble in sodio-potassic tartrate. Boiling water
dissolves it sparingly, and deposits it on cooling in fine white
prisms. 1 pt. of the salt requires for solution 12.65 parts of water at
10°. Neutral tartrate of cinchonine requires only 35 6 pts. at 16° to dissolve it
(the hydrated salt 33 pts.), so that cinchonine and cinchonidine may easily be sepa-
rated by the different solubilities of their tartrates. The crystals give off their
water completely between 100° and 120°, but recover it all on ex-
posure to moist air.
88 C
4 N
Crystallised.
528
Hesse.
65.83
66.05
56
6.98
58 H
58
7.22
7.33
20 O
160
19.97
204°N2H2402, C8H6O8 + 4aq.
802
100.00
****
...
Or:
Hesse.
2C40N2H2402, C8H608
4 HO
766
36
95.52
4.48
4.45 to 4.93
....
2C40N2H240²,C³H6O8 + 4aq.
802
100.00
....
...t
Tartrate of Antimony and Cinchonidine, obtained like the correspond-
ing cinchonine-salt (p. 218), crystallises in fine white prisms mode-
rately soluble in boiling water, and crystallising in solid prisms on
cooling. Very soluble in alcohol.
Citrate of Cinchonidine. A solution of 1 at. acetate of cinchonidine
and 2 at. citric acid in a small quantity of water, deposits at a certain
degree of concentration colourless prisms, which probably consist of
monobasic citrate of cinchonidine, but decompose when dissolved in
hot water, the solution yielding a salt containing 2 at. cinchonidine to
1 at. citric acid. This bibasic salt is likewise obtained by decomposing
hydrochlorate of cinchonidine with citrate of soda. It gives off 15.39
p. c. water at 120°, and contains 68.31 p. c. cinchonidine.
QUININE.
615
Benzoate of Cinchonidine, CN2H2402, C14H60, crystallises in short
white anhydrous prisms, which dissolve in 340 pts. of water at 10°.—
Gives by analysis 71-82 p. c. cinchonidine (calc. 71.62 p. c.).
Cinchonidine dissolves in 19.7 pts. alcohol at 80 p. c. at 10°, and
in 15.3 pts. at 20°; in 76·4 pts. ether at 10°.
Page 262.
Quinine.
O. HESSE. Ann. Pharm. cxxxv, 325; Bull. Soc. Chim. 1866, i, 459.
Crystallised Quinine, C40NH2O4 + 6HO. Ordinary amorphous
quinine, precipitated from the hydrochlorate by ammonia, gradually
absorbs water if left in the liquid, especially in presence of free am-
monia, and assumes a crystalline aspect. If a considerable excess of
ammonia is present, isolated crystals are formed, which, when mag-
nified, exhibit the form of square prisms with pyramidal summits.
The hydrate gives off all its water when left over oil of vitriol. It
melts at 57°, whereas anhydrous quinine melts only at 176.8°.
Phosphate of Quinine (comp. p. 226). Obtained by decomposing the
hydrochlorate with phosphate of soda. When crystallised from
boiling water, it forms tufts of long needles, soluble in 784 pts. water
at 10°.
Hesse.
Crystals.
2 C40N2H2404
648
72.82
PO5
3 HO
16 HO
71
7.98
8.11
27
3.03
144
16.17
16.05 to 16·52
C40N2H2404, PH308 + 16aq.
990
100.00
-
Bihydriodate of Quinine, C40N2H2404,2HI + 10HO. Obtained in
fine prisms and lamina, on mixing a slightly warmed acid quinine-
solution with iodide of potassium. It gives off a considerable quantity
of water between 30° and 40°, becoming opaque at the same time.
Melts in its water of crystallisation when quickly heated to 100°, and
gives off the whole of it, amounting to 13 51-13.92 (calc. for
10 at. = 13.40) at about 120°. The dehydrated salt gave by analysis
43.63 and 43.86 p. c. iodine, the formula C40N2H2404,2HI requiring
43.79 p. c. When exposed to moist air, it quickly recovers 4 at.
water.
Chlorate of Quinine, 2C4N2H2404, CIIIO + 7HO.- Prepared by
decomposing sulphate of quinine with chlorate of baryta, keeping the
quinine-salt in slight excess, and afterwards removing the excess of
sulphuric acid by digestion with carbonate of baryta. Crystallises in
small mushroom-shaped masses, composed of filiform snow-white
crystals. 1 pt. dissolves in in 78.5 pts. of cold water. Very soluble
in boiling water, and in spirit. Febrifugal (F. C. Tichborne, The
Chemist and Druggist, Sept., 1866, p. 137).
Hydrochlorate of Quinine (comp. p. 282), NII2404,HIC + 4110.—
616
ADDENDA.
Long, asbestiform prisms, which do not effloresce in the air at ordinary
températures, but easily give up their water of crystallisation at 120°.
One part of the salt dissolves in 39.4 pts. water at 10°. Gives by
analysis 8.93-9·05 water and 8.92 chlorine (calc. 8.95 water and 9·08
chlorine).
Arseniate of Quinine, 2040N2H240 As H308 + 16HO.Obtained by
double decomposition with hydrochlorate of quinine and arseniate of
potash. Long white prisms, sparingly soluble in cold, easily in boiling
water. Gives off 15.43 p. c. water at 105° (16HO 15.42 p. c.), and
the salt dried at that temperature give by analysis 10-64 p. c. As0º
(calc. 10.59 p. c.).
=
Oxalate of Quinine (comp. p. 273). -a. Neutral, 2C40N2H2404, C4H2O +
12HO. Long prisms resembling the sulphate, efflorescent and soluble
in 1030 pts. water at 10°. The crystals, heated to 125°, give off
12.76 p. c. water (12 at. 12.76).
=
b. Acid. C4°N²H²40¹,C¹H²O® + 2aq. Obtained by dissolving 1 at.
of the neutral salt and 1 at. oxalic acid in water, and leaving the solu-
tion to evaporate. Small prisms moderately soluble in cold water, and
exhibiting an acid reaction.
C40N2H2404
CчH208
2 HO.....
C40N2H2404, C4H9O8 + 2 aq.
Hesse.
324
75.01
90
20.83
20.60
18
4.16
4.03
U
432
100.00
Succinate of Quinine, obtained by direct combination, forms long
white prisms, which dissolve very easily in boiling water and alcohol,
much less in the same liquids at ordinary temperatures. 1 pt. dissolves
at 10° in 910 pts. water.
2040N2H2404
CHOS
16 HO
2C40N2H2404,CsH6O8 + 16aq.
Hesse.
648
71.21
70.67
118
12.97
144
15.82
15.67 to 15.86
910
100.00
When recrystallised from strong alcohol, or from boiling water
containing an equivalent quantity of succinic acid, it still retains the
same composition and the same amount of water.
Citrate of Quinine (comp. p. 292). a. Bibasic. Obtained either by
saturating quinine with citric acid (p. 292), or by decomposing hydro-
chlorate of quinine with citrate of soda acidulated with citric acid.
When recrystallised from warm water, it forms white, mostly small
prisms, soluble in 930 pts. water at 12°.
Hesse.
2 C40N2H2404
C12HS014
648
67.08
67.33
192
29.88
14 HO....
144
13.04
13.14 to 13.35
2C4N2H2O+,C12H8O14 + 14aq.
984
100.00
....
b. Monobasic, CN²H²¹O*,C¹²II8014. A solution of the bibasic salt
in boiling water, mixed with somewhat more than an equivalent
quantity of citric acid, deposits this salt on cooling in small white
RESINS.
617
prisms, which dissolve with some difficulty in cold and in hot water,
imparting an acid reaction. They contain no water of crystallisation.
Benzoate of Quinine, C40N2H2404,C¹HO4, obtained by direct combi-
nation of quinine and benzoic acid, forms small white anhydrous
prisms, which dissolve in 373 pts. of water at 10°, and give by analysis
72.37 p. c. quinine (calc. 72.64 p. c.).
Eugenate of Quinine, C40N2H2404,C20H1204, is obtained by dissolving
quinine and oil of cloves together in boiling spirit, the liquid as it cools
depositing the salt in fine long silky needles. It dissolves to a slight
extent in boiling water, the undissolved portion melting to an oil,
which solidifies in the crystalline form on cooling. The aqueous solu-
tion, as it cools, also deposits the greater part of the dissolved salt
in small prisms. 1 pt. of it dissolves in 12 pts. of ether at 12°. It is
distinguished from all other quinine-salts in not being decomposed by
ammonia or by caustic potash, dissolving in the alkaline liquid to a
certain amount at the boiling heat, and crystallising on cooling. At
100° it forms a fused yellow mass, and continually gives off eugenic
acid, which, however, cannot be completely removed in this manner.
The salt is anhydrous, and gives by analysis 66.20 p. c. quinine (calc.
66.39 p. c.).
Page 382.
Resins.
The table on the next page gives the results of a recent investiga-
tion by Hlasiwetz and Barth (Ann. Pharm. cxxxiv, 265; Bull. Soc. Chim.
1866, i, 62).
The method adopted for examining the products of decomposition by
potash was as follows: A quantity of the resin, not less than two
pounds, is divided into 8 equal portions, and each portion gradually
added to 3 times its weight of potash-hydrate fused in a silver basin
with a small quantity of water. The resin then melts, and soon forms
with the alkali a homogeneous mass, surmounted by a thick scum;
aromatic vapours are evolved; and the resin is oxidised with evolution
of a large quantity of hydrogen. The operation must be stopped as
soon as this evolution of gas ceases, and the mass when cold, is treated
with about 4 times its weight of water, and then with a sufficient
quantity of sulphuric acid to render the solution acid. A certain
quantity of resinous matter is thereby separated (oxidised resin
analogous to copal) varying in bulk according to the nature of the
original resin. The neutralised liquid, freed from resin and filtered,
is shaken up with ether, the ethereal solution is evaporated to dryness,
and the residue is taken up with water and precipitated by acetate of
lead. This precipitate is washed, suspended in water, and decom-
posed by hydrosulphuric acid, and the liquid filtered and evaporated,
finally yields a crystallised body.
618
ADDENDA.
¿
GUAIAC RESIN
contains:
C-H2604 guaiacic acid.
Yields by dry Distillation.
C38H2206 pyroguaiacin.
C16H1004 creosol.
C¹4H8O4 gaiol.
CROHSO2 guaiacene.
CISH 1006.
DRAGON'S BLOOD
contains:
C40H2004 (?) resin, soluble in
ether, according to John-
ston.
Yields by dry Distillation:
C16H8 metastyrol.
C14HS toluol.
C14H604 benzoic acid.
Oxidised by Potash :
}
Oxidised by Potash.
C¹¹H6O8 protocatechuic acid.
para-oxybenzoic
C28H12014
acid.
protocatechuic
acid.
C18H8O10 (?) the body which
gives a red coloration with
ferric chloride.
C14H6O4 benzoic acid.
CHO
acid.
para-oxybenzoic
C¹4H6O8 protocatechuic acid.
C¹¹2H6O6 phloroglucin.
BENZOÏN
contains:
C70H34O14 (?)
C40H4408-10 (?)
}
C30 H4001-10 (?)
C46H20012
resins.
benzo-cinnamic
acid.
C¹4H604 benzoic acid.
Yields by dry Distillation
C14H6O4 benzoic acid.
C¹²H6O2 phenylic alcohol.
Oxidised by Potash:
C28H12014.
C'18 HSO10 (?).
C4H604 benzoic acid.
C14H60° para-oxybenzoic
acid.
C14H6O6 protocatechuic acid.
C¹²H604 oxyphenic acid.
GALBANUM
contains:
C40H2606 (?) resin.
C20H¹6 oil of galbanum
(gum).
Yields by dry Distillation:
C40H3002.
C¹2H4O4 umbelliferone.
Oxidised by Potash :
C12H604 resorcin.
ALOES
contains:
C34H16014 aloin.
C30H160+ alveretic acid.
Yields by dry Distillation:
C16H12O6 aloïsol.
Oxidised by Potash:
C14HSO4 orcin.
C¹¹¹H60° para-oxybenzoic
acid.
END OF VOL. XVII.

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