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Les diagrammes suivants illustrent la m^thode. rrata o lelure, Id H 32X 1 2 3 1 2 3 4 8 6 ;.,^_ ^ .^e ffj,|i . 44fei&aaNti^(U.fer^W^At4^-- ^i^r'-'W-^^^--:. < tfr ' « i — ^ . i i. y i l " * "; ' ''^?- JWd ' ]|lP^ " M i« ■■ ■M i m ii uin IW — jffj^l^j pit- i r i Nj-j iwi i j»f\ | i^w.i | i l BI, i jj ■f- .M mw^imm»\ : iX; I 'iiHMirtMWWifa»iMtoi>t«i» ■i ^wy i' ■ \'- OUTLINES Modern Chemistry, oi?.<3-^isrio. BASED IN PART UPON RICHES' MANUEL de CHIMIE, Cj ^^ ^, C; GILBER T 'wheeler, .^S^ ^ Professor of Chemistry ,„ t—fc» OTHER WORKS «y PROF. WHEELER. ^■^n.nTj\iiv\TIVE MINERALOGY. A pracllcal guide to til "■"Tmu oJ mSl BpecleB, cb.cliy by pl» H.cal charactcr.B.ic«, A practical guide to the recosul- uBical characmriBiicB. tiou ol miuerui i!n<;v,™=, ^^■—■j -^ .^-•i $1.00. J..T, .i TiisTORr CHARTS. Five in mimher, one each of the fol- lowing: '^l*""*"-'*' p," ' _ 1,, ,,11 ovurTtK) lliietralioui). Wholly MiNKKAi.8, Rooks a"'l/°*?'^^,,,V «- no The Bet 830.00. hand colored pace of cac'.v chart, S'.OO- ^"'■8'-' NATURAL HISTORY PRIMER. A conciso dcBcriptlve work .m /.<>oi.- oov and MiNEBAi-ooY. Price IN PREPARATION. THE CIIEMIriTRY OF BUILDING MATERIALS. -\ C O P Y R I G II T G. GILBEllT WHEELER. 1877. R. PREFACE. recogni- ...8100. )f tho fol- KIIIIATKS; 1, Wholly ...830.00. ; jn 7,(ioi.- ....gioo. important rmHii and MiiBunmH ....82.00. 'S^ Organic chemistry has not as A'et secured in Ameri- can colleges sufficiently lu-oiiounced attention to create a demand for text-books of considerable size or ex- tended scope. In these simple Outlines, therefore, no more has been attempted than this circumstance would appear to warrant. It is hoped that the necessary conciseness in method and form of expression has n(»^t resulted in any important sacrifice of i^erspicuity in thought or arrangement. It would have been easier to prepare a larger work. From the bewildering wealth of results aliorded by the labors of investigators in this branch of science, tlie aj)- propriate selection of that suited to the wants of stu- dents was by no means an easy task. It is assumed in these Outlines that those entering niwn the study of Organic Chemistry have previously made themselves acquainted with Inorganic Chemistry as taught by some modern author, such as Miller or Barker, or have at least become familiar with the gen- eral principles of modern chemical philosophy. The author taking this for gnuited, has not, therefore, en- cumbered the work with a restatement of that which appertains to the theory of chemistry in general. In addition to the organic portion of Riche's Man- uel de Chimie, a translation of which by the author ]'KKKAOK. lias seiTCtl ill part as basis for tlioso Outlines, tlie works of Miller, Fuwiies, Williaiuson, Itoseoe, aiid- iginally work- 3, though the to be found in ed American Sci. [2] xxxi.) ' orlljO. .N"'orlI,N. IV. The marsh gas type fj ,' >> C'v or H^C. H'J Of tlie leading groups of orgjinic bodies, we refer to the hydrogen type: hydrocarbides, aldehvds and the compounds of metals and metalloids vvitii organic radicals. To the water type are referred the alcohols, ethers, men-iiptans and aidiydrides. To the ammonia type belong the amides, amines, and alkalamides, all of which are denominated com- pound ammonias. Marsh-gas is the type to which carbon dioxide is referred, as well as some of the more comjDlex or^ano- metallic bodies. Further details as to the relation of each of these classes of compounds to their respective types will be gwf^n as each particular class is studied. Besides the simple type, Kekule has proposed com- pound types formed by the combination of two of the four types already given. Thus the typos of ammonia and water coirbined serve as a pattern for carbamic and oxamic acids: N"' Carbanilc acid. H H CO" N OxamIc Acid. iifo H ■IWMMMWXMMMIX'Xkl 1 12 I ! ORGANIC ClIKMISTRY. HOMOLOGOUS SKKIKS. The members of a series of compounds winch have the connnon difference of C lU are said to he hornolo- gnus. Two or more such homologous series are termed uologous. The first idea of progressive senes in organic chemistry was enunciated by James Schiol, ot bt. Louis, Mo., in 1842. It was afterwards ^dopted by Gerhardt unchan-ed, save only in name. (lOO-o-l Jo.) Tlie subjoined table will illustrate the nature of these series Each vertical column forms a homologous .cries in which the terms differ by CII,, and each hori- zontal line an isologous series in which the successive terms differ by IIj. The bodies of these last series are designated as the monocarbon, dicarbon group, etc. C H4 C Ha CoH„ C„H, CoHg cJh^ C:,H„ C3H, C,H, C,H,„C,Hs C,He C^H^C.H, CH C,H,oC,H« C.H«C,,H,C,H C„H,, C„H,, C„H,„ C„Hs CeH„ C„H, C«H., The terms of the same homologous series resemble one another in many respects, exhibiting similar trans- formations m.der the action of given re-i.gcnts, and a regular gradation of properties from the lowest to tlie liio-he-st ; thus, of the hydro-carbons, C„ll,nvi. "le low- est terms CII, Cdl,, and Calls, are gaseous at ordinary temperatures, the highest containing 20 or more car- HOMOLOGOUS SERIE.i. 13 liicli have e homolo- ire termed 1 organic el, of St. lo]ited by 100-5-195.) re of these oniologons 1 each hori- successive it series are 3up, etc. C«H, i% vcsenible miUir trans- gents, and a owcrit to the in.2. the low- ^ at ordinary )r more car- bon-iitouis, are solid, while the intermediate com- pounds are liquids, becoming more and more viscid and less volatile, as they contain a greater number of car- bon-atoms, and exhibiting a constant rise of about 20" C. (36° F.) in their boiling points for each addition of Clfa to the molecide. The individual series are given in the following ta- ble, with the names ])roposed for them by A. \Y. Hoffmann: ' E thine CJI, Propine Propone C3H4 Cgll, Quartine Quartone Qiuwtune C4n„ C4H4 c^ii, Quintine Quintoue Quintune C„Hs QHe C,H4 Sextine Sextone Sextune CeHio Cells C„H„ The foi-mul8B in the precedin.L tables represent hydro- carbons all of which are capable of existing in the separate state, and numy of winch have been actually obtained. They are all derived from saturated mole- cules, C„Il2n.2, by abstraction of one or more pairs of hydrogen-atoms. But a saturated hydrocarbon, CII4, for example, may Methane Afethene cir4 CHj Ethane Ethene CJIe 0,\l, Propane Propene C3IIB Callo Quartano Qiuirtene C4ll,0 C4II8 Quintane Quintene CslLa C,H,o Sextane Sextene CoIIu Coll,, 14 ORGANIC CHEMISTRY. dve up 1, 2. 3, or any number of hydrogen-atoms m exchan-e iw other elements; thus marsh gas, CH4. subiccted to the action of chlorine under various cir- cumstances, yields the substitution-products. CH3CI, CHC,C1^ CHCI3 CCI4, which may be regarded as compounds of chlorine with the radicles, (CII3)', (CII.)", (Ctts)'", C'v; and in like manner each hydrocarbon of the series, C„ll2„«, may yield a series of radicles of the forms, (C„IIw)',(CnH.n)", (C3.U-1)'" (CnH.n-.r,&C. each of which has an equivalent value, or combining power, corresponding with the number of hydi-ogen- atoms abstracted from the original hydrocarbon. Those of even equivalence contain even numbers of hydro- gen-atoms, and are identical in composition with those in the table above given ; but those of uneven equiva- lence contain odd numbers of hydrogen-atoms, and are incapable of existing in the separate state, except, uerhaps, as double molecules. These hydrocarbon radicles of uneven equivalence are designated by Hoffmann, with names endmg in yl, those of the univalent radicles being formed trom methane, ethane, &c., by changing the termination i-\ ^. 8 HOMOLOGOUS SERIES. 15 -atoms in gas, CH4. irious cir- CCI4, orine with the series, e forms, combining ' hydrogen- •bon. Those •8 of hyflro- 1 with those ;ven equiva- -atoms, and tate, except, equivalence mding in yl. bnued from termination proached so as to form, when connected witii a powerful battery, an electric arc. The corks through which these rods passed were provided with another opening each, to wliich a tul>e was adapted. Through one of these tubes hydrogen was admitted and through the other the products of the reaction passed as they were formed. The gas was collected in a solution of cuprous chloride in ammonia. A red-precipitate, acetylide of copper was formed, which was thrown upon a filter and treated with hydrochloric acid in a flask, whereuju.n acetylene was set free. Many oi-ganie comjwunds produce acetylene -n subjecting their vapors to the action of electric dis- charges. Acetylene is also produced, as a rule, whenever or- gam'c matter is decomposed by heat. Propebties.— Acetylene is a colorless gas, having a disagreealjle odor. It is moderately soluble in wat'er, and has not been liquified. It is decomposed, at about the temperature at which glass melts, into carbon, iiydrogen, ethylene, ethyl hydride and condensed hydrocarbides, among Avhich Berthelot has found ben- zol. Thenard lias recently obtained it both as a liquid and a vitreous solid. (9 — 78 — 219.) Acetylene burns with a faliginous flame. It de- tonates violently and witho;it residue wlien mixed with ORGANIC CHEMISTRY. 2 5 volumes of oxygen. Cuprous acetylide is an ex- plosive body. It is sometimes formed in brass gas- pipes, and lias been the c^ aise of fatal accidents. ^ Chlorine acts upon acetylene with f f ^^ ^^^'-f^'; there is often detonation accompanied by l.glit O .noderating the action the compound C,II,C1, can he obtained, which, as well as the body ( ,I1.U,, can also be prepared by the action of antimonic chlo- ride up(m acetylene. ,. , • As acetylene is not imcommonly studied m con- nection with inorganic compounds, a more detailed ac count of this hvdrocarbide need not be given here. _ Acetvlene is" the prototype of a homologous seraes of hyd^ocarbides, of which the general tormula is, The following members of this series are known: AUylene, - - " ' ^' ^* Crotonylene, - - " y^* "« Valerylene, " ' ' p S' Rutylene, - - - p'-S'" Beuzylene, - - " ^ib^^^s- I ETHYLENE. 21 is an ex- rass gus- ts. B energy; ^ht. On LCI 2 can onic clilo- [1 in con- etailecl ac- [i here, fous series lula is, ! known: 4 A t8 •28' SECOXD SERIES. General formula, C^Hju. ETHYLENK. Bynonyma: Elayl, Olcflant gas. Formulii Co II.j 8p. Gr. 0.97. Molecular weight, 28. This gas, for no good reason other than custom, is always t^tudied in inorganic clieniistry, usually in con- nection with the consideration of illuminating gas, of which, with methane, it forms a prominent constit- uent. Ethylene is the type of a class of homologous hydro- carbides, of which the general formula is: Each member of the series is related to an alcohol from which it may be obtained on treatment with bodies having a great affinity for water, as sulphuric acid or zinc chloride. C„IL,._,, + 0,-ILO = CJL„. i i ill ! ill ••' ••* i'l 2-2 ORGANIC CHKMISTKY. We note -he following members of tins series : . - - G, H, C;, Hf, - C4 Hs , - - G, Hio Ethylene, - - - Propylene, - - - Butylene, - Amylene, - - " Hexylene, Heptylene, Octylene, - Nonylene, - - " Paramylene, Cetene, - - " " Duodecylenc, - Tridecylene, (Paraffin?)* Tetradecylene, Cg H12 C T 11 1 4 G,,n,, *A. G. Pouchet(60-[3] 4-868) has prepared f-m P^-mn by oxydalion with nitric acid, paraffin ac.d, C-MlUiO-i. fiom whicU he deduces CsmHm as the formula for paraffin. <>. Vj. |j-jx.- ' ."' i series : 6 ^8 [lO [,2 Itc Its ^2 im paraflln, by ^, from which MKTHANE. 2a THIRD SEEIES. GenciMl formula, Cn Hin+a* MKTII^VNE. Discovered by Volta iu I'.TS. Synonyms; Metliyl hydride, Marsh gas, Formenc. Formula CHi or CH3.H. Sp. Or. 0.559. Molecular weight, 16. Permanent gas, not liquiflable, neutral. Not discussed in detail here for tlie same reasons as given under Ethylene. Methane is the first member of the following veiy important liomolog(nis series: C If, methyi hydride, or methiuie. C^ li« ethvl >( " ethiuu'. C3IIH l)ropyl t( " propane. C4 11,0 butyl (( " butane. CsII,. amyl (( " amane. c„ii„ hexvl a " hexano. C,II,„ lieptyl a " he[)tane. f 8 11,8 octvl a " octane. C„II,o nomyl t( " nonane. f ioll« decyl t( " decane. Cnll,, undecvl k( " undecane C12II06 bidecvl u " bidecane. .im\ i^ »tu*» 5r*' 24 OKGANIC fllKMISTKY. Cjsir.a tridecyl '• C,4n:jo tetradecyl " C,,,ir;H pentadecyl" Ciellsj liexadecyl " " tridecane. " tetradeciine. " pentadecane. " hexadeciuie. Nearly all the members of this series have been found ill American petroleum, mixed with members of the preceding, or ethylene, series. Crude petndeum, refined by fractional distillation, is still a mixture of various hydrocarbons. The commercial names given to the products sep- arated at the different boiling points, do not appertidn to chemical compounds, or bodies having a definite composition. Subjoined is a table based on Dr. C. F. Chandler's Report on Petroleum, (100 — '7'2-41) showing the PRODUCTS OF THE DISTILLATION OF CKUDK PETUOLEUM.* H O H a . fc" h > ■A H KAKB. — 3 CUIEr USES. a a s. » = i^ U r- 1 Cymogune OOC. 1 liencrally uncoudoused — used In 1 Ic.u niachliies. .025 18.3 \ Coiidoiiced by Ice and salt— used as ■( an uniL'Bthetlc. (iftsolenc 15^ i .««5 VOfi 48.8 8S.S Used In mnkInK "nlryHH." (Used for oll-clotliB, cleuntiig. ndul- (; NiiplilhH U Nitphllin '■10 .;S4 101. -1 ■< terntlng kerosene, etc. For piilnts A Nuplitlm 1 .~M 148. H ( and varnifhcH, Kciixinu 4 Used to adiillerate kerosene oil. Kcroneno oil or. ,80» ITfi.U Ordinary oil for lumps. MliH'rnI inry Dqiurtment, fo .ud it to con- tain '2^^ jier cent, bituniinous matter. lelebrated sively in various ffico and )iaking a } I'oi- the it to cou- BKNZOL. 27 FOURTH SERIES. Ganeral Ibriuiila C„ Hon^H,. BKNZOL. Synonyms; BenzL-ne, Benzine. Formula C« Ho- Sp. Gr. 0.88. Molecular weight, 78. 8p. Gr of vapor 2.70. Density" " 39. Solid at 4°. Boils at 80.5° Benzol is obtained, witli acetylene and etl.vlene, in tl.e decomposition ot organic t^ubstances bv beat and Its production is especially favored wlR-n the temperat'ire is kept at a high i,oint for some time JUiiyleno and methane form at a tolerably low tempenitnre. Acetylene, which is richer in carbon IS produced at a higher temperature. IUvaoX and especially napthalin, being still more cirboimceous, are tornied at an extremely high temperature. Lerthelot lias i)repared l)en;col syntlieticallv by con- ducting mothaue tribromid., QllWv,, ovei- red-hot coi)j)er: 6(CriBr,)+9CH -C„II,,+9CuBr., - o fr'n. T^' '''' ^""^'^''^••«^ *i« condensed acetylene: I 28 ORGANIC CHEMISTRY boils at 110= " " 139° " " 165= Oric,nnally, benzol was prepared by a pro:.-ess analo- gous to that which fiiriii8he.s methane, i. e., by distill- ing benzoic aeiil with lime, C,n«02+CaO == Ca C Oj+CoHo. At present it is obtained in immense quantities from the tar which is formed as an accessory product in the manufacture of illuminating gas. At the high temperature of the gas-retort other pro- ducts, homologous with benzine, are formed as well; Toluene C^ Hg Xylene tl,, H,„ Cuniene C„ Hia Cymeue Cm Hi 4 and other hvdrocarbides, as napthalin C.oHs, autlira- cene, also various sulphur compounds, notably carnoii bisulphide; several oxygenated compounds, as phenol C„II,f), cresylol C^IIsO ; nitrogenous compounds, as aniline C,H,N, and various members ut its homologous series. , . , -a Benzol is a colorless, neutral licpiid, with a specific gravity of 0.89, almost insoluble in water but soluble in alcohol and ether. It dissolves sulph.ir, phosphorus, lodme, the ditter- ent resins, and fatty substances; this latter property causes it to be employed similarly with con.mercial "benzine" for cleansing purposes. Care must be ta,ven to rub with a piece of cloth having an open texture, r I' III -Jnj BENZOL. 29 3 analo- j distill- ties from jt in the ther pm- as well; , autlira- \\' carlioii \% phenol inpoiincls, ii'S «->t' its a specific ut soluble the differ- ■ jiroperty onimercial st be talven lu texture, that it may remove tlie benzol by absorption, witliout whicli the spot would reappear after evaporation ot the solvent. Benzol burns with a fuliginous flame. Nascent oxy-en gives with it various products, and notably oxalic acid and carbon dioxide. Chlorine and l)romine yield crystalline compounds with benzol. Benzol is the simplest member of a group of bodies known as tlie aromatic oompoumls, of which we shall proceed to describe some of the more important. For distinguishing benzol from the benzine of com- merce, which is made from petroleum, Brandberg recommends to place a small piece of pitdi in a te.-S tube, and pour over it some of the substance to be ex- amined. Benzol will immediately dissolve the jntch to a tar-like mass, while benzine will scarcelv be col- ored. NiTROBEXZOLCJIgXOs. ing This body is obtained by treating benzol with fum nitric acid. CJI«+IIXOa== C6n,(N-0a)+II/). Nitro-benzol is a yellowish oil, crystallizing at 37°, has a sweet taste and an odor which lias led to its use in perfumery under the name of essence of mirbane. Taken internally it acts as a poison. On treatment of nitro-benzol with nascent hydrogen, hydrogen sulphide, or other reducing agent, we oblaiil f" 80 ORGANIC CHEMISTRY, aniltne, which is a colorless liquid, boiling at 182°. It does not act upon litmus, jet combines with the acids, tbnning crystalliziible compounds. Aniline gives with chlorine, bromine and nitric acid products of substitution which are very numerous and well defined. It reacts upon the iodides of niothyl, ethyl, etc., forming the corresponding amines, or bodies constrveted on the type of ammonixi, having one or more of the hi/drogen, atoms replaced hy an organic compound radicle: Aniline Methylaniline Ethyl methylan iline Cell.N N-^II C,II,X ( CJI5 X ■ C Ila III CsIIisX --= N C II, C.2I15 CbIIb or, when free, (€6115)2 , is the radicle phenyl, hence aniline is properly phenylamine. Aniline has, during the last score of years, acquired great importance, as, under the influence of oxydizing bodies, it forms most remarkable tinctorial com- pounds. If a small quantity of aniline is added to a solution of chloride of lime, the liquid is coWred violet, which color disappears in a few moments. In 1858, Perkins obtained, by the action of potassium bichromate and sulphuric acid, a beautiful purple, which is known in Kiria t 182°. ith the ric acid >us and iiothyl, * bodies ' one or >rganie II5 II. JI5 phenyl, icqiiired :ydizing ,1 corn- solution t, which Perkins late and mown in bp:nzol. ;il commerce as 7n,nive. Shortly after, Yergnin obtained a iiijignilicent red coloring matter on heating aniline with tin dichloride. This substance, known under the names of aniline- red, fuchsin, magenta, etc., is now very economi- cally obtained with arsenic oxide in place of the tin dichloride, which is reduced to arseuous oxide by the reaction. iroffmann has shown that aniline-red is .a salt of a colorless base, which he calls rosaniline; this substance has the formula 0^11^,-^,0, or C*ir,,,N3,II,0. In the past few years there have been produced green, yellow and black cohjrs, all originating from aniline. These substances dissolve in alcohol, and dye wool and silk without in any way weakening the fabric. They have a magnificent lustre, but their permanency is not of the highest grade. The consumption of aniline for dyeing has now come to something enormous, amounting in Germany alone to over 15,000 tons per annum. ^ The aniline colors are employed in injecting tissues for microscopic preparations. For a fuller account of the aniline colors, a larger work should be consulted. The history of aniline affords one of the most re- markable instances of the value of scientific chemical reseai-ch, when perseveringly and skillfully applied, for at first few substances seemed to promise less; and the gigantic manufacturing industry at present connected with this compound, in its applications as ;-. 1 i^" 32 OKOANIC ' HEMI.STKV, tinctorial agent, offers a singular contra^st to the early ex])eriinents upon this hotly, when a lew ounces t'ur- nisht'tl a supply which exceeded the most sanguine ex- pectations of tlie early discoverer.-: of this hody. Phionol, CellsO. Synonyms: Hydrate-of phenyl, carbolic acid or phenic acid- It occurs in castoreum, though usually procured iVoni the portions of coal-tar distilling over between 170" and 105'. They are agitated with caustic sodr., water added to separate the insoluble oils, and the phenol dissolved in the alkali is liberated as a crys- talline mass, on decomposing the potassium compound with hydrochloric acid. Salicvlic acid, distilled with an excess of lime, also furnishes phenol; dneOa + CaO = CaCO» + C^HfiO. Ifphenyl-sulphuricacid,^''^^'' j- SO,, obtained by di- rect action of sulphuric acid upoi'. phenol, is heated with potassium hydrate to about 300% potassic ])henol CJIjKO is obtained. Phenol is therefore ol)tained from benzol under the same conditions as alcoiiol is obtained from ethylene, the corresponding hydro- carbide. Piienol crystallizes in handsome needles, fusible at 34= and boiling at IbS". It -s little soluble in water. .m lie early loes t'lir- 'iiiiie ex- ile acid- red tVoiii leii 170- :ic >>»)inids, though only this, the ordinary i)henol, is an iniiiortant body. Heated with concentrated nitric acid, it furnishes yellow, very bitter, crystals of the body known as PicKic or CAienAzro|)liy lactic against scarlet fever. Phenol gives certain reactions of the alcohols ; this >a&*p JjrfirSf N B L i ! 34 ORGANIC CHKMISTUY. somewhat oxiilains the origin of tlie name given it by Berthi'liit, This body is the type of a class of coui- pounds which contains: Cresylol obtained from creosote C-, H-, O Phlon-lol " " " CgllioO Thymol •' " essence of thyme CioHuO. I'lIYSIOI.OOICAL ACTION OF I'HKXOL. Phenol attacks the skin, producing a white stain. It coagulates albumen and is employed with great success as an antiseptic and disinfectant. It is used externally in a diluted state to dress wounds which suppurate, also in many surgic:d case^3. It is sometimes used internally. Large doses of it are ]ioisonous. Carbonate and es^pecially sacchariite of calcium are considered as antidotes for phenol. Grace C'alvcrt has announced that olive or almond oil is a still better antidote. OIL OF Tl'UI'KNTI^^E, 35 \'en it by 3 of com- ite stain, itli great t is used Js which 3ses (if it •Iiiinite of 1. Grace i oil is a FIFTH SERIES. General Formuli,, Cn Iha-i. K8SEXCK, OB OIL OK TUKI'KNTIXK. Formula CioHm. Deiisitj' of vapor compared with air 4.7. Molecular weiglit, 130. Boils at 160. Tm-pentine is extracted from sever.d varieties of the family of oonifem, notably from the pine, fir and larch. Tlie products vary somewhat with the nature of the tree, but they have many common characteristics; their composition is the same, tlieir density is nearly identical and their toiling point very nearly so. Their rotary action on the solar ray varies largely. Isomeric carbides are found in other families of plants, in the aumniiaoem fninily for instance, as the lemons and oranges. These con'tain carbides verv dif- ferent, as evidenced by their odors and other phvsical properties, also different in certain chemical relations, yet liaving the same composition as oil of turpentine.' There are also various polymers of this carbide. This ejitire series of hydrocarbons can be divided into three groups. The tirst contains carbides havinc^ '^4 36 OKGANIC ClIKMISTUY. tlic formula C,„n,6, tlieir boiling points being below 200", and including : Donsity. Boiling at Oil of turpentine, 0.8(5 157" to 160". (( cloves, 0.92 140" " 145". u lemon, 0,85 170" " 175". >( orange, 0.83 175" " 180". u juniper, O.Si about 1 60". ki berganiot, 0.85 " 183". li pepper, O.SG " 167". u elemi, 0.85 '• 180". Tlie carbides of the second group have the formula C.J0II32, their boiling is above 200", they are : Oil of copaiva, 0.91 '• cubebs, 0.93 245". 240". The third group contains the non-volatile carbides, such as Density- Caoutchouc, . - - - 0.!'»3. Gutta-percha, - - - 0.9S. The rotary power, constant for eaeli, varies with the difl'erent species. French oil of turpentine causes the ])lane of polar- ization to deviate to the left; the American variety turns it 13° to the right; oil of lemon causes a devia- tion of 50" to the right; in the case of essence of elemi the deviation amounts to lOO". ISonie of the S99BI OIL UK TUKPENTI-VK. 37 eing below ing at o 160". " 14-5". " 175". " ISO", It 1 60". 183". 167". ISO". the formula e : !45". >40". ile carbides, Density 0.!»2. 0.98. 'ies with the no of polar- •icaii variety uses a devia- :' essence of ioine of the essential oils of the first grouj> contain o.xvgc-n coin- ponuds as well as the carbi)hyd rides. The principal chemical differences between the members of the group ai-o the facility with which they are oxydj^ed and their reaction with hydrochloi-ic acid. Essence of turpentine becomes resinous rapidly when exposed to the air and finally solidifies. Es- sence of lemon becomes viscid after a considerable time. Hydrochloric acid produces, with esscMice of tur])entine, aliipiid and a solid cmpound, having each the same composition, C,oTi,«, IICl, which, after a few M-eeks, becomes a dichlorliydride, (by some denomi- nated a dichl(.rhydrate), C„JI„„2Il('i. Essence of lemon also gives two UicliLrhyd rides at once, one liquid, the other solid. Oil of turpentine may be obtained in a pure state, on distilling the commercial article in a vacuum! Thus obtained, turpentine is colorless, limpid, very volatile, and has a characteristic odor. It is insoluble in water; very soluble in alcohol and ether. It buruo with a snu)l7iyl. If hylciic, at lilt hydro- cry!;?iiV, sylvic, and plmario, C^ll^O.. 42 ORGANIC riI?:MISTRT. This resin constitutes the fixed residue obtained on distilling crude turpentine. It is used for in-eparing varnish, in soldering, and in certain combinations witli the alkalies, called resin-soaps. Subjoined are given the names and the origin of the princijial resins, oleo-resins, gum-resiiis and balsams. With some, the position assigned them in this classi- fication is not definitely settled. RKSINS. Amber is found in the lignites and in the alluvial sands of the J>altie. Arnic'iu, the active principle of Arnica Eoot. Cannabiu, the active principle of Indian Hemp. Castorin, a seci-etion of the Beaver (Castor). Ergotin(f), the active principle of Ergot of common rje. Mastic, a resinous exudation of the Mastic, or Lent- isk tree. Burgundy Pitch, an exudation of the Spruce Fii-, Abies cvcelm. Pyrethrin, the active principle of tlie Pcllito'y root. Eottlerin, a crystalline resin from Kaniala, the min- ute glands which cover the capsules of liottlera tinc- toria. OLKO-KKSINS. Copaiva, a resinous juice of the copaifera officinalis found in Spanish America. Wood-oil, au oleo-resin from the Dipterocarpus turhiiuitns. "w ' t'jfti RESINS, BALSAMS, GUM-RESINS. 43 btained on ])rei)ariTig itions with igin of the <1 balsams, this classi- le alluvial oot. I Hemp. 01'). if common c, or Lent- ^pruco Fir, lito'y root, a, the min- tle?'a tinc- ojfic'inalls terocarpus Elemi, an exudation of an nnkndwn tree, (probablv Cannar'nim commune). Common Frankincense, a concrete turpentine of tlie P.' I) us tmda. Canada balsam, the turpentine of the Balm of Gilead Fii', {Ahles hdmmea). Storax, from the LiquUlamJmr orientale. OUM-RKSINS. Ammoniacum, an exudation of the Dorema ammo- niamiin. Assafoetida, a gum resin obtained 1)v incisioti from the living root of the JS\irthe.v asmfaitida. Gamboge, obtained from the Gavcmia morella. Galbanuin, from the galhanum officinale. My rrh,an exudation of the Balmmodendmn viytrha. , UALSAMS. Benzoin, ol)tained from incisions of the bark of Sty fax benzoin. Balsam of Pern, from the Myro^'ylon Pereirw. Balsam of Tohi, obtained from incisions of the bark ot Myroxylon tuluifera. Caoutchouc is the hardened juice oi Fictis elaMica, Jatropha elastica, Siphonia cithuohu, and other plants' Gutta-perclia is the concrete juice of tlie perclu, (Malay) tree the Isouandra peroha, a sapotaceous plant 44 ORGANIC CIIKMISTUY. ALCOHOLS. GENERAL nKKINITION ANn<"IfAUACTKRISnCS. This name is given to a class of neutral bodies as important as they are numerous. Their essential characteristic is that ot" reacting upon acids so as to form water and. a class of bodies called ctha's. The number of alcohols is very considerable. There are several distinct varieties of alcohol recognized. I. Those built on the type of one molecule of water: C II ' ) \\ i ^' ^^^^y^ "'' 'Jommon alcohol. lolecules of water : O.j, ethylene alcohol or glycol. II. On two molecules of water CJI," ) Ila \ III. On three molecules of water : C H ' ' ' i "ii* ^^3' glvtJerine and thus oil. They may be defined as bodies built on the type of one or more molecules of water having one-half of the hydi'ogen replaced by a hydrocarbide radicle. MOXATOSIK. ALCOHOLS, . or those formed on the type of one molecule of water. i-rMrfiimM,lcohol, Setyl alcohol Octyl alcohol Sexdecyl alcohol Ceryl alcohol Myricyl alcohol (', n« () C^ 11,0 o c„Tr„o SECOND SKUIKS, the type of !-half of the ile. de of water. C„II,.(). Vinyl alcohol Allvl alcohol TlIIRl) SERIKS, C„II,,._,(). ojonieol alcohol G, H4 O CaHeO CioILsO 46 ORGANIC CHEMISTRY. FoiKTir SKKIKS, Benzyl alcohol Xylyl alcohol Cumol alcohol (^yinol alcohol FIfTII SKRIEfi, C„II,.._sO. Cinnyl alcohol Cholesteryl alcohol C:n«o Cs II,oO (\ H,oO C,oIIuO C9 HloO c.«ii«o MoNATOMic Alcohols iiavino tiik Gkxeral Formula, METHYL ALCOHOL, OR WOOD-SPIRIT. CIIjO^^JJ'lo. This substance is found in the liquid obtained on distilling wood. The distillate contains in addition, water, acetic acid, tar, and various oils. In order to extract the methyl alcohol, it is again distilled and that portion which passes over at 90° is collected ; this is diluted with water, the oil which precipitates sepa- rated, and the liquid agitated for a considerable time with olive oil. This oil is then removed, the liquid redistilled several times and oidy that portion collected which jjassea over above 70°. On being again ALCOHOLS. 47 o w uO [44O Formula, ht's lutthyl iil- coliol, nearly ])urc, builiiig at (](!..'»". There arc uther methods of rectiiyiiiII,(). Physiouhucai. A(TI0X. Chlorotbriu is at present very generally used as an UTiesthetic. Opinions as to its manner of acting are divided. Formerly it was thought that the insensi- bility produced was the coniniencement of asphyxia. Since then it has been ascertained that the heart, in case of poisoning by chloroform, immediately loses all power of contraction, and it is now generally admitted that ]>aralysi9 of the muscles and nerves of the heart is produ"('d. As the vapor of chloroform is very dense, care should be taken that in its use, access of air to the lungs be not wholly ])revented, or serious consequences m:iy re- sult. Probably the fatal acciiients that have oos^urred ALCOHOLS. 49 i«l tlistilled II lirst yro- d iiii iigreu- I soluble ill r. I' liuviu'4' ji iliiir, plios- ost's it into - L>II,(). TTiav, in some instances at least, bo attributed to lack of care in this rei^^ard. It is of great iii)])()rtance that the chloroform used should be quite i>iire. In some cases it has been found to have undergone spontaneous decompositioii after exposure to a strong light. It ought to communicate no color to oil of vitriol when agitated with it. The lifjuid itself should be free from color or any chlorous odor. "When a few drops are allowed to evaporate on the hand no unpleasant odor should i-emain. Shuttleworth (^100, 4, 339) states that partially de- composed chloroform can be rectified by agitating it with a solution of sodium hypo-sulphite. used as an acting are le insensi- ' asphyxia. e heart, in ly loses all y admitted ;he heart is 2are should e lungs be es m:iy re- e oot-'urred ORDIXAIIY ALCOHOL. Ethvlic, oij Vixie Alcohol. Formula: C,On+ ii,c)=c,,ir,,(\=cjT,,()«. Glucose. Levuloae. Ill its final fermentation nearly all the siimir is clianged into alcohol and carbon dioxide, C«II,i)«=2C,II,,()+liC0,. This equation accounts for the transformation of O-t ^ to 90 per cent, of the sugar employed, hut besides alcohol and carbon dioxide, succinic acid is always formed as well as -icacid. The same oxidation occurs if diluted fi M'. ; iS exposed to the air in the presence of mother of vinegar, a cryptogamic plant, (Mycodrrma accti). In fact, this is the basis of the manufacture of wine-vin- egar and alcohol. Fuming nitric acid reacts upon alcohol with ex- plosive energy. Aldehyd is formed, also acetic ether, nitrous ether and acetic, formic, glycollic, oxalic and carbonic acids. Alkaline hydrates attack alcohol even in the cold potassium acetate being the chief product formed. If alcoholic vapor is made to pass over lime heated to 250°, hydrogen gas and calcium acetate are produced; the latter is decomposed at a more elevated temperature into marsh gas and water. If silver or mercury is dissolved in nitric acid, and 90 per cent, alcohol added to the cooled solutions, a --i-rr' I -uriiiiai^-itifcua-iji u ORGANIC CHEMISTRY. 11! lively ebullition results, and a crystalline precipitate is deposited which explodes at 185°, or by percussion. This body is the fulminnte of silver or mercury, re- spectively, which is considered as derived from methyl cyanide, CHjCy, by the substitution of 1 molecule of nitryl, and of 1 atom of mercury, or 2 of silver for 3 atoms of hydrogen. The formulae are C(NO,)HffCy; C(N02)Ag,Cy. Potassium attacks absolute alcohol, and is dissolved liberating hydrogen; on cooling, potassium ethylate is deposited. Sodium acts in the same manner. These compounds, if brought in contact with water, regenerate alcohol and the respective alkaline hydrates. Acids attack alcohol and furnish compound ethers, which we will study later. 0/one, according to A. W. Wright, (80— [3]7— 184) oxydizes alcohol to acetic acid. Physiological Action of Alcohol. Uses of Al- cohol.— Alcohol coagulates the blood; injected into the veins it produces instantaneous death. It is a very powerful poison, as are all alcohols of the series CnH2„+>0. Rabuteau (9—81—631) has shown that they are more poisonous in proportion as their mole- cules are complex. Cases hiive been observed where a large dose of alcohol has caused death in half an hour. The worse than worthless character of distilled liciuors as beverages is no longer an open question. With regard to their value as food or medicine, a more authoritative or com])eteut expression of opinion can- nut 1)0 desired than that of the iTiternational Medical Congress, which at its session in Philadelphia in 1876, said : ALCOHOLS. 65 recipitate is percussion. mrcury, re- om methyl nolecule of silver for 3 ^08)HgCy; is dissolved ethylate is ler. These , regenerate und ethers, y to A. W. acetic acid. 5E8 OF Al- ;ed into the is a very the series hown that heir mole- ed where a fan hour. f distilled 1 question, ne, a more )inion can- al Medical ia in 1S76, "1. Alcohol is not shown to have a definite food value by any of the usual methods of chemical analy- sis or physiological investigation. " 2. Its use as a medicine is chiefly that of a cardiac stimuhmt, and often admits of sul).stitution. " 3. As a medicine, it is not well fitted for self-pre- pcription by the laity, and the medical profession is not accountable for such administration, or for the enormous evils arisinji; therefrom. '••i. Tiie purity of alcoholic licpiors is, in general, not fis well assured as that of articles usedf )r medicine should be. The vari(nis mixtures when used as medi- cine, should have delhiite and known composition, and should not be interchanged promiscuously." The dissolving power of alcohol renders it very ser- viceable in the arts. Solutions in this menstruum are called alcohuliG tinctures. Only the purest alcohol ought to be used in pharmacy, though of course, various strengths are requisite, as it should be of a degree to suit the nature of the matter to be dissolved. If the su1)stance to be treated is a re?in, or some substance absolutely insoluble in water, a very concoutrated alco- hol is preferable. A weaker alcohol is made use of, if the nuitter is one that is soluble, both in alcohol and water. Alcohol acts notoidy as a solvent, but also as a 2)re- ventative of decay. This is a ])roperty which renders it especially valuable in the preparation of remedies. » pi« " Iliyl-limn -^r-n ~^ift3^rl'fi^\^ 56 ou(;anic chkmistuy AMYL ALCOHOL. (\M,o 11 O. fli/nonymn: Fouskl (ou Fusei.) Oil, P(rrATo Si'ikit. Tho amylie cuinixMiiuls derive their luune from Ami/lum, starch, the chief constituent of tlie potato. Theyare formeil in sotne proportion in ahnost every in- stance of alcoholic fermentation of 6ui>;ar. Aniylic alcohol is usually prepared on fractionally redistilling the oil which remains when the alcohol, prepared from potatoes, barley, corn, etc., is distilled. The ])ro- duct which comes over at i;J2", is that collected. Cahoiirs and JJ;ilard first established the analoirv, in constitution and i»roperties, of this compound with ordinary alcohol. It is a monatomic alcoh(»l, ffivin"- • 1 • 1 • • ' £3 » With oxKlizing re-agents, valeric acid. C3I [,,(^+0, :^ C,,I1„,0,+ 11,0, Amylic alcohol. Valeric acid. and with acids, coin])ound ethers, as Chloride of amyl, CsIInCl. Acetate of amyl or amyl-acetic ether, ,, .f'k ^ O. CallgO \ 'nffATO SriKIT. r luiine from of tlie ])Otatu. most every in- gav. Amjlic lly redistillincr hoi, prepared ed. Tlie ])ro- luit collected, lie analogy, in inpomid with Icohol, giviiig ■O, cjr„ci. o. ALCOHOLS. M( )XATOMIC ALCOHOLS. Having the general Formula (\,H,,„(). Allymc .a i.coiio. CaHjO = L\1L, , ^^ 57 "{i1 This is a body giving the same reactions as ordinary alcohol. The radicle it contains is the same as tlmt in the triatomic alcohol, glycerine. Among its deriva- tives there are two which are of considerable impor- tance: Allyl sulphide, p'"-- I s f Sulpho-cyanide, ^sljs ) g_ The former is oil of garlic; the latter oil of mustard. (^IL OF (iAKLii; is pi-epared by the following method: allylic alcohol is treated with phosphorus iodide which furnislies allyl iodide C3H5L This iodide is afterwards mixed with an alcoholic solntion of potassium sulphide and the whole is distilled; the product which passes over is identical with the essential oil ol)tained in dis- tilling garlic,onions, assafojtida, etc., with water. OIL OK IICSTAKD. OK SULPHO-CYAMUK OF ALI.YL. This body is ])repared by causing iodide of allyl to react upon ix.tassium sulpho-cyanide, ^'jj U, and may be regarded as sulpho-c-yauic ucid,^JJ }■ S, luiving the *^ m OltGANIC OIIKMISTItY, livdrogoii replaced by tlie radicle tassiuni sul- pho-cya-.iide. It is likewise obtained by the fernienta- tion of mustard seeds. Sul])ho-cyanideof allyl does not exist already formed in black mustard (Shiajns luyro), but according to Bussy, its fornuition is due to a particular ferment. Oil of mustard combines directly with ammonia, forming a crystalline substance called thioshiiuihilnc, CiH^XoS, which, in contact with mercuric oxide, changes into an alkaloid called sinnaniine, of which the composition is C4H0N... It reacts upon lead oxide producing a substance called s'mapoUne whose formula is C;K,,N,(). B( )RNKO CAMl'UOR, OR BOilXEOL C,oHis<^- This body exudes from the dryohalcmoj)>i cmnphora (Borneo). It is crystalline and has an odor between that of camphor and pepper. It fuses at 105°, and boils at about 220". It is dextrogyrate. Heated with nitric acid it furnishes common campln)r CioHsO. DIATOMIC ALCOHOLS OK GLYCOLS, Ordinary Glycol, (CjH^) — 0.— H2=CJIe 0. Propyl " (C,H,,) -O.-IL^C^H^ 0, I alcohol, CslTs. •ritating liiiuid red from iiiiis- 50 be obtaiiu'd ])ntassiuiii siil- y the tenuenta- ah'oady formed it according to dar ferment, kvith ammonia, 7( loshinam In c, lerciiric oxide, nine, of which i])on lead oxide ? whose formula yiops C'iiHj)hora I odor between 3S at 195°, and !. Heated with or CoHeO. !OL8. ,=CAi, 0, o— C,Hs 0., ALCOHOLS. 69 Butyl Glycol, (C,H,) _0,-H„=C,H,„0., Amyl " (C,H,„)-0,-H,-C,H,„0: Hexyl '• (C„H, ,)-()„ -H,=("„H,;o.; Oetyl " (C.H.«)-03-H,=C«H,«o:. TRIA'nmUJ ALCOHOLS. Glycerine, (C3H.)-0;,-H3=C,H,03. TKTRATOMKJ ALCOU0L>i. Erythrite. ((:;,H„)-0,-H,=C,H,„0,. OTUKK COMIM.KX Af.COHOI^. Glucose and its isomeri.les, (C„H,)-0„-H„ =C„H, „0o Manuite, - - (C„H,)-0«-H„=(',H,;o«. Dulcite, - - - (C.H«)-0«-H«-C«H,,Oe. (juercite, ) r, tt /^ ^CH ^ i ^ ORDINARY GLYCOL. Clio =^^^^i)j ' n The discovery of the glycols was an event of great imi)ort.ince. It was aclueved hy Wurtz in 185(5, and the glycol of v/hich we are treating was the lirst discovered. In a flask surmounted by a condenser, two parts of ])otassimn or sodium acetate, are dissolved in weak- alcohol and one ])art of ethylene bromide added. This ' i 60 OROAXIC CIIEMISTBY. mixture islieatofl in a water bath as long as the pre- cipitate of alkaline bromide continues to form, care beina: taik. The alcohol is distilled oft' in a water bath, and the residue afterwards also distilled at a higlier temperature, and that part col- lected which passes over between 140"' and 200° . This portion which contains nionacetic glycol, is heated with a saturated solution of l)aryta until the lic^uid acquires a strong alkaline reaction. The excess of bar^'ta is removed by passing carbon dioxide through the solution which is then filtered and evaporated. The barium acetate is ])recipitated coini)letely by strong alcohol, and the alcohol subseqnentlv removed by dis- tillation. Tlie retort is now heated in an oil bath, and that portion set aside which boils above 150°. This is redistilled and the distillate between 190° and 108° is the product sought. Zeller and Iluefner have lately (18, 10,270) obtained the ]>urest glycol by simply heat- ing a solution of potassium carbonate with ethylene bromide. Glycol is a colorless, odorless liquid, somewhat viscid and having a sweetish tas*?. Its density is 1.12; water and alcohol dissolve it in all proportions. Ether dissolves it with difficulty. It is not oxydized in the air under ordinary con- ditions, but if dilute glycol be made to fall on plati- num black, it becomes heated and is transformed into glycoliG acid. Its equivlence is shown by the follow- ALCOHOLS. (51 as the pro- t(» form, cure le worm well 1 may coiitin- rol is distilled terwanis also that part Ci>l- 1 aoO" . This ol, is lieated til the licjiiid lie excess of xxide through I evaporated, [■el y by stroiijr iioved by dis- oil bath, and 150°. This is 30" and 108° er have lately ' simply heat- kvith ethylene id, somewhat [ts density is I proportions. ordinary con- fall on plati- iisformed into by the follow- ing : glycol attacks siKlium forming two sodiujii glycols; Kali ***^' .NaM^'^- These glycols furnish two ethyl glycols on being heated with ethyl iodide. c^,ii.,r^-* Etliyl-alycol. Dlelhyl.glycol. AVith hydrogen bromide it furnishes two different products according to the number ot molecules of UBr taken. C,lUO^+ HBr - C,UJivO + II,(). Monobromhydric uther. CJI,0, + 2irBr=C.JI,Br+ 2II,0. Kthvluiifc bromide. It is evident tliat mixed ethers may be obtained by treating glycol not with two molecules of the same acid, but with two molecules of ditierent acids. Thus aceto-chlorhydric glycol is formed, ., tt J.-J!' J- O. rr 02 ORGANIC CHEMISTRY These ethers, in the presence of alkalies, are re- formed into their respective acids and glycol, in the .same manner in which ethers of ordinary alcohol regenerate alcohol. Monochlorhydric and aceto-chlorhydric glycol form an exception to this rule; they form oxide of ethylene in presence of alkalies. OXIUK OF KTIIYLKNE, 0,11,0, a polymer of (('.,II,)2(%, is related to glycol as ordinary ether to alcohol. It is not obtained like the latter by the action of hydrogen sulphate on the alcctholic coiiipdund, but is produced by the action of potassa on mono chlorhydric glycol. A solution of potassa is gradually poured iuto chlorhydric glycol i)laced in a glass, or a tubulated retort. KHO + CgHgClO = KCl + H2O + C2H4O. The oxide of ethylene distills over with the water; the latter is absorbed by causing the vapors to pass through a flask containing anhydrous calcium chloride, and the oxide is condensed in a receptacle placed in a refrigerating mixture. It is a colorless, ethereal, fragrant liquid; boiling at 13°. Its density is 0.89. Ethylene oxide is very solu- ble in water, alcohol and ether. It burns with a lumin- ous flame and reduces silver salts. It has the compo- sition biit not the properties of aldehyd, of which it is an isomeride. Ill ALCOHOLS. <)3 lies, iire re- vool, in the mrv alcohol glycol form ) of ethylene Oxide of ethylene is a very remarkable body. It combines directly M-ith oxygen, liydroi;eu, chlorine and bromine, also combineii directly with acids, ofcen even with the disengagement of heat, forming the ethers of glycol and polyethylenic alcohols. This body is there- fore a true non-nitro^euous basic oxide. 1 as ordinary latter by the c compound. Hi on mono- is gradually a glass, or a Ii the water; poi's to pass um chloride, i placed in a 1; boiling at is very solu- rithalumin- 1 the compo- f whicii it is ()4 oh(;a.\ic cjikmistry. TPJ ATOMIC ALCOHOLS OR GLYCERINES. ," i Oruinaky Gi,y( krixe, CaHgO;, =^'{[' | <> • This body, discovered by Scheele, in 1770, and called by him, on aceoiiiit of its sweet taste, the sweet principle of oils, has been specially studietl by Chevreul and by Pelonze. Bei-thelot discovered its real nature and proved it to be a triatoniic alcohol. Glycerine is prepared by decomposing neutral fatty bodies, in the soap and candle industry by alka- lies, or better still by superheated steam. {Tihjhinans 'process.) It is obtained in pharmacy, whenever lead I>laster is prepared and remains in the water with which the latter is washed. It is nmch emi)loyed in pharmacy and perfumery and as a solvent for many substances, ("rude glycer ine may be purified by boiling with ain'nial charcoal and filtering before being evaporated to the rccpiired consistency. The best ])roces8 consists in distilling the crude condensed glycerine in a current of steam. Pas- teur has shown tlnit glycerine is ]>roduced in a very small (pnintity in alcoholic fermentation. AVe owe to Wurtz, a remarlciible synthetical reproduction ofglyccr iiie. Pi(»pyl«.'ue (';,1I,., furriishes an iodide ( ';,II;,I, called iodide of idly]. This bixly produces with bromine the ALCOHOLS. 65 rCEPJXES. I, ■( 1:, » in 1770, and xste, the sweet tnl by Chevreul its real nature josing neutral lustry by alka- . {Tlhjhinaii's tvhenever lead le water with ind pert'uinery ("rude glycer liuial charcoal u tlie rccjnired n distilling the t" steam. Pas- iced in a very 1. AVe owe to ctiou (if gl veer ^ (';,! I ;,!,' called" h bruiiiiue the coinpomid CJI-.nr,, wliich, treated with potassa, or oxide of silver, yields glycerine. CJi^Bra+SKlIO -= 3 KBr.+(l,IIA (jlycerine. Glycerine is a syrupy liquid, colorless, of a sweetish taste and destitute of odor; its density is 1.28 at 15". Sarg has obtained crystals of glycei-ine, whose angles have been measured by Victor Lang (2 l.>2-037). They are rhombic in form and very deli(piesoent. Glyc- ei-ine is soluble in alcohol and water in all pi-opoi-- tions; it is not dissolved by ether. It dissolves alka- lies, alkaline sulphates, chlorides and nitrates, copper sulphate, silver nitrate and many other salts. Glycerine distills at 280°, but is thereby partially decomposed. It may, however, be distilled in a vacuum without cliiinge. It is decomposed nt a tem- perature above 300", and oils, iiiHammable gases, carbon dioxide, and a ])rotiuct Vc-ry iri-itatiiig to the eyes, called acrolein, acrylic aldehyd, are formed; this last substance may be obtained pure by distilling glycerine with sulphuric, or phosjihoric acid. The formula of acrolein is C,l 1,0.,; it is jdso produced in the dry distillation of all fatty bodies wiiich contain glycerine. If glycerine be made to fall drop by drop upon platinum black, it unites, like alcohol and glycol, with ()., and (jlijcer'ic aot'd is formed. C,,Il8(), + O,-{',lI,,0, -1-11,0. The oxidation of the glycerine does not stop here; I ■ i : i : 1 f ,i 6d ORGANIC CIIKMISTUY. there is siibse(iiieiitly formed, acotie, formic, and car- bonic, but cliietiy oxal'c acid. The action of acids on glycerine demonstrates two facts; first, that glycerine is an alcohol; second, that it is a triatomic alcohol. On treating glycerine with hydrochloric acid the first reaction is similar to that between uleohol and this acid, iici+cyiA-t^jr^cio.+ii.o. Monocblo bydric etiier, or Monoclilorliydriii. The continned action of ]))iosphoions perchloride upon glycerine, ov the dichlorliydrate of glycerine, effects the elimination of additional molecules of water and the formation of trichlorhydrin. 3lICl+C:,IIs():,=:C3lI,,Cl , + 8( 11,0) Triciilorhydriu. Bertheltit has studied the acetines, butyrines (tri- butyrine exists in butter), vaierines, a;i(l many other ethers of glycerine. If glycerine is mixed with cohl nitric acid, and sulphuric acid aildcd drop by drop, an oily sul)s,an;e separates out which is ti iiilfroffliicei'inn C;JI.,iNO.V,0:i. This body detonates with great vio- lence. It acts very energetically on the system. A few drops placed on the tongue ]>r.>(luco violent me- grim. Glycerine forms compounds with lime anal- oirctus to those formed by sugar, according to P. Car- les, 1- 174 87). ALCOHOLS. 07 ic, and cur- of acids on t glycerine lie alcohol, cid the first )1 and this pei'chloridc glycerine, [es of water I vi'ines (tri- naiiy otlicr I witli cold by drop, an ivf/Ii/ceri/ie great vio- •ysteni. A violent ine- linio anal- X to P. Car- TsKs. — The uses id' glycerine in the arts, and especially in i)hannacy, are numerous and important, many of which are ba:onate, " borati', " cnrbonntc, " cbloratc, Sulphur, Strycliuia, " nitrate, " BUlpUnte, Urea. Vi'ratria, Zinc chloride, " Iodide. " eulphatc. CIIKMISTUY. 80.00 8.00 60.00 SB.0O 80.00 0.10 0.35 4.00 «.ito 50.00 1.00 60.00 40.00 85.00 "°* - W ? gJ. so.oo 8.00 tiO.OO 9S.00 30.00 0.10 o.« 1.00 •i-i.ao M.OO 1.00 50.00 40.00 .3,V0O KTIIKR,S. 61> ETHERS. .'^iMi'LK i;tiii:es. Etliers arc products l'onne parts, to every 100 of its weight, of a solution of soda liaving a specific gravity of 1.32, and agitated from time to time, dm-ing 4S hours. The ether is decanted hy means of a glass siphon, redistilled and lour-hftlis of the liipiid C(.llected. The remainder may serve for a future operation. This furnishes ordinary etlier. To further purifv, wash with water, decant aiul treat for two dayswith equ'al ])arts of quick lime and fused calcium chloride. Wil- liamscm has clearly shown that etherification takes l)hiee in two stages or successive reactions as follows: CAU + 1 l^SO^ == ] I,() + ^(^TI,)HS()4. EtliylBiilphuric acid. (C JI,)ILS( ), + c,li,( ) _ c,H,o( ) + H,S(),. This explains liow a small quantity of sulphuric acid etherizes a large amount of aicohol, since sul- phuric acid is constantly regenerated. This is con- firmed hy the following experiment. Iodide of etlivl IS made to react upon potassium alcohol; ether \s ohtained as indicated hy the reaction; CJIJ -HC,I1,0K ^ CMI,„0 + KI. Ether is a neutral, volatile li.piid, colorless, having a hunung taste and a strong agreeahle odor. When agitated with water it rises to the surface, hut the water dissolves about one ninth of its own weight of the ether. It is misciMe with alcohol in all in-opor- ^j 72 OliGANIO CIIEMISTKY. I I { i tioiis and with wood spirit. Ether is fre(|iieiit]y udid- terated witli the latter Kubstaiiee. Xext to alcohol it is the most generally employed solvent for organic substances. It dissolves resin, oils and most com- pounds rich in carbon and hydrogen. Bromine; iodine, chloride of gold and corrosive sub- limate are soluble in this li(piid. It dissolves phos- ])borus and sulphur in small quantity. W. Skey, (S — Aug. 3, ' 77,) has shown that contrary to the usual statement in standard works, ether dissolves uota])le quantities of the alkalies. At a red heat it is decom])osed and furnishes carbon monoxide, water, nuirsh gas and acetylene. It is exceedingly inflammable, and burns with a bright flame. Its extreme volatility, the density of its vapor, its insolubility in water and its great inflammability render its use dangerous, and explosions caused by it are of frequent occurrcMice. It should never l)e brought near a fire or light in open vessels. In case ether inflames, it is best, if possible, to at once close the vessel con- taining it, and thus avoid the more serious conse- quences ensuing from an explosion. Exposed to the air it experiences a slow combustion as in the c;5?e of alcohol, and the same compounds are the result. Chlorine acts violently upon it; in moderating the action, the whole or a ])art of the hydrogen may be replaced atom for atom by chlorine. Uses. — It is used in pharmacy in preparing etherial ETHERS. 73 eiitly udul- I iik'ohi>l it for oi'ganic most coin- •ro?ive sub- olves phos- contrary to er dissolves shes carbon rns with a 5 vapor, its tility render by it are of rought near er inflames, vessel con- •ious coiise- osed to the the c;!ve of esult. leratiiig the ijen may be inif etherial tinctures, and as an antispasmodic and stimulant in tlie well-known Hoffmann's anodyne. Its most iniiior- taiit use in medicine is as an anesthetic, than which none is safer or more reliable in efficient hands. It is extensively employed in the laboratory and in photography. COMPOrXD KTUEKS are bodies built up on the type of water, having one half the hydrogen replaced by a hydrocarbide and the other half by a comi)ound radicle containing oxygen, or, in other words, by the radicle of an acid. ACETIC ETHER, (C^H,) ) (C.HgO) O. To prepare this ether 8 parts of very concentrated alcohol are distilled with 7 parts of sulphuric acid and 10 parts of anhydrous sodium acetate, which may be replaced by 20 parts of dry lead acetate. The distil- late is agitated with a solution vt' calcium chloride containing milk of lime, decanted, dried over calcium chloride and finally distilled. Seven parts of water dissolve one part of this body. Alcohol and ether dissolve it in all proportions. It is a solvent for many organic bodies. It is easily de- composed on contact with water. Potassa also effects this decomposition very readily. A pi-olonged action of ammonia transforms it into acetamide and alcohol. 14 OIUI.VNIC CHEMISTRY. M ill OXALIC KTIIKRS. Oxalic acul beiii- a bi])asic acul, furnishes with alcohol two combinations, one lacing acul =vu(l c^M-able ofc.nibinin- with bases ; the other is neutral, C.;li,,< >.• Onlv the latter is of interest. It may be prepared by introdncing four parts of i»0 per cent, alcohol and four parts of oxalic acid into a retort, adding to tins n.ivture three to six parts of sulphuric acid and then rapidly distilling ; the pr..duct is washe.l several tunes, dried/then redistilled, collecting only the lupiid whicii passes over at 1S4". This ether is aromatic, ody, and frraduallv decomp(Jses in water. " Potassium changes it into carbonic ether. If oxalic ether is atjitated with ammoma, a white powder, omnude, and ethyl alcohol are produced. ^^i '.().,+N4n'== 2^(c,n5)'. (»)+nJ, II.; " (h: Oxamide mav be considered as derived from two molecules of ammonia, and belongs to a class ot bodies called tZ/Vn/NV/t'S. . n . ^i It i. a white substance, insoluble m cold water and alcolK .1. Heat> 'd with mercuric oxide it is transtormed into carbon dioxide and urea. (Williamson.) ETHKRS. To iiishes with lud callable ral, C,H,,( ),. be prepared alcohol and ding to this •id and then we ral times, liipiid which tie, oily, tiud er. mia, a white )rodnced. ved from two class of bodies !old water and is transformed ison.) Oxalic ether treated with ammonia in solntion in alcohul t'nrnishes o,f°and a vapor density of <>4-. A red heat decomposes it into ethylene ami hydrochloric acid gas. It is combustible and burns with a green, smoky Hame ; water dissolves the fif- tieth j)artof its volume, alcohol dissolves it completely. MaiiiivMiiib 76 ORGANIC CHEMISTUY. With chlorine it furnij^hes a oomplete and regnlar series of products of substitution whicli an^ not iden- tical, but isonxeric with tlio chlorine products of ethene. Their forinulsB are: C2H4CI2 CoH.tCls C0H..CI4 C,H CI5 C, Cle. IODIDE OF ETUYL OK HYDUOIODIO ETIIEK. aii,i = ^^'^ \ , is obtained on causing alcohol to react ui)ou iodide of phosphorus; the action is violent with white phos- phorus, considerably less so with red pliosphorus. Six hundred grams of concentrated alcohol are intro- duced into a retort witli 140 grains of amorphous phosphorus, and to this mixture 450 grams of iodine are added. The distilling is carried nearly to dryness. The product, condensed in the receiver, is washed with water containing a little potassa ; afterwards with pure water. It is then dried over calcium chloride and again distilled. Iodide of ethyl is a colorless liquid Its density is 1.975. It becomes colored on exposure to light, being slightly decomposed ; it is again rendered colorless on agitating it with an alkaline solution, which absorbs the ETHERS. 77 iind regnlar in^ iu)t iden- products of rniEK. pou iodide of white phos- sphorus. •liol areintro- f amorphous iins of iodine ly to dryness. ; washed with rds witli pure chloride and [ts density is ;o light, being 1 colorless on ch absorbs the acid formed. Itl)urns with a green flame, leaving a resi- due of iodine. Ammouiuni eoni]»ounds in alcoholic, or a.pieous solution, furnish ethylaniine. This amine can he attacked in its turn by iodide of ethyl and yields dietliylaniiiie and oxide of tetrethylaunnonium. The knowledge of these reactions and their api^lication to other iodides are the basis of a general mode for the preparation of oi-gunic ba.-es originated by Ilotihiann. Iodide of etliyl, unlike tlio chloride, is readily decom- jtuscd by solutions of silver nitrate, giving a precipi- tate of silver iodide. CJI,I + AgXO, = (C,ir,0 XO;, + AgL Ci-AXIDK or Ellivr., OIJ CVANUYDRIC ETHEK. This ether is obtained on distilling in an oil-bath 1 })nrt of potassmm cyanide, with 1-5 part of an alkaline suipho-vinute. To the product, redistilled in a bath of salt-water, nitric acid is slowly added in excess ; it is then subjected to another distillation. Finally, it is dried over calcium chloi-ide, and that which passes' over trora 195° to 200" is collected on redistillation. Cyanide of ethyl is a colorless liquid of an alliaceous odor, boiling at Jt7". Cyanide of ethyl is decomposed by potassium hy- drate; ammonia is produced, and the acid obtained corresponds with a higher homologous alcohol. J I 78 ORGANIC CHEMISTRY. CN(C,II5) + 2II,0-- NIl:, + ( -ilUV Propionic iicid. M. Meyer obsen^ed some years ago, that if cyanide of silver is treated with iodide of etliyl, a lii^iiid is forniod, boiling at 82", of an odor which is not that ot ordinary cyanh} k ■ "ic ether. Gautier has shown that this is an isomeric body, and that there are two isomeric series of cyanhydric ethers. Hoffmann has given a dis- tinctive character to these bodies: under the intiuence of the alkalies they jiroduee a ti\ed substance, but this is formic acid and not ammonia, and a volatile substance which is a compound ammonia. CN(C,II5)+2IL()=CII,(), + C,II;, \ N. ^ ' .-^- — II ) Formic acid. Ethylamiue. OeOxVNO-metalt.ic Compounds. Iodide of ethyl attacks the metals and furnibl.-s a class of bodies called organo-metalliG radicles. None of these bodies are found in nature. They are formed from the iodohydric ethers by the substitution of a metal for the iodine: Zn + 2(C,1I,I) - (CoIl5),Zn + Znl,, 2Sn 4- 2(C,Il5l) - (CJIO^Sn + SnI,. Practically these metallic radicles are obtained by various reactions: ORGANO-METALLIC COMPOUNDS. 79 ttcid. hut if cyanide yl, ii li(|iiicl is is TU)t that ot howu that this two isomeric ii\s given a dis- the inrtuence substance, but and a volatile ii. N. lue. :)8. nd furnibl.'-s a iidicles. None liey are formed bstitntion of a Znl,, -Snij. ire obtained by 1. J'.y the action of the metal upon the iodide, for example; 2C,TIJ + Zn=(C,Ilg).,Zn + Znl,. In certain cases, with tin for instance, the reaction is not as distinct, and there is formed in addition tostan- netliyl iodide, staunethyl iodides variously condensed. 2d. The metal is treated with another radicle; thus sodium-ethyl is prepared by the action of sodium upon zinc ethyl, (CJI,)oZn f Xa,=Zn + 2C JI,Xa. 3d. On d(;com[)usin,P=3(C,lI,)Zn + 2PCI3. ith, Stannethyl is obtained by plunging a plate of zinc into a soluble salt of this radicle: the radicle is precijntated in the form of an oily licpiid. Cacodyl, As(Cir;j)2 was the first discovered of thisclass of bodies. It was obtained by Buiisen on distilling arsenous acid with potassium nitrate. The organic radicles combine with mf-talloids with more or less energy ; zinc-ethyl and cacodyl take fire in the air • they also decompose water. The products of oxida- tion vary witlithe luiture of the compounds employed; zinc-ethyl furnishes the Ixidy, CJi/uO, ziuc-ethyl- atc, M'hich, in coutact with water, jiroduces alcohol and oxide of zinc. The metals wliich are, le»s readily oxy- 80 ORGANIC CHEMISTRY. S H dized, such as tin, lead and mercury, give oxides which play tho parts of bases, and these latter com- port themselves like the oxides of the metals they con- tain. Finally, the radicles formed by the elements, phosphorus, arsenic, and antimony, give, with oxy- gen, compounds which generally have the character of acids. Some of the organic derivatives containing phos- phorus are very complex. For instance, J. Auanolf (00-' 75-493) has obtained a body he denominates, methyldiethyJphosphoniumpliemjloxidehjdmte! To prepare zinc-ethyl^ Ave introduce into a flask connected with a condenser inclined in sneh a manner that the vapors find their way back into tho flask, 100 grains iodide of ethyl, 75 grams of zinc, and 6 to 7 grams of an alloy of zinc and sodium, and heat in the water bath until the zinc is dissolved ; then the condenser is incliiR'd as usual, and tho distilling is eflFected over a direct Are, collecting the liquid pro- duct in a flask "illed with dry carbon dioxide. Finallv it is again distilled in this gas, and that col- lected' which passes over from 116" to 120^ All the vessels and all the substances should bo absolutely dry, and it should always be collected and distilled m mcvA^, or in carbon dioxide. It is a colorless liquid, whose density is 1.182, boiling at 118°, inflammable on exposure to the air. With sodium this body furnishes sodium-ethyl, and with chloi-ide of phosijhorus or arsenic, it furnishes triethyl phosphine, P(C..Il5)3, an^l trietliyl arsine, As {6^\^^. ETHERS. 81 give oxides ! latter coin- ;al8 they con- lie elementR, !, with oxy- ) character of ainiiifj ph68- e, J. Auaiuift' lenoiuiuates, yd rate! into a flask leh a manner ;lio flask, 100 , and 6 to 7 and heat in ed ; then the distilling is e liquid pro- )on dioxide, and that col- 20". All the >o absolutely ,d distilled in lorless liquid, inflammable um-ethyl, and !, it furnishes etliyl arsine, Mercury-methyl, treated with iodine, furnishes a liydrocarbide which has the formula ot methyl, Clia. Professors Crafts and Iw-iedel (T2-['i]19-33-l) have prepared a large number of comixuiiuls of silicon with compound radicles, from which they have deduced valuable theoretical considerations. MISCELLANEOUS ETHERS. Formic, butyric, valerianic ether, and other ethers of the tatty series are prepared in the same manner as acetic ether, and liavo the general properties of this ether. The odor of these ethers is agreeai)Ie. Bu- tyric ether has the odor of ]Mne-apple, and \alerianic ether that of ])par> ; (cnanthylic ether has tha aroma of wine, etc. They are used in the nianufaetiire of syrups, flavoring extracts, and for imparting an odor to liquors. If the difference between the points of ebullition of these ethers is examined it will he seen that the addition of the elements (.^ir^ causes an elevation of about 20" in tlie point of ehullition. Kopp hns shown that this fact is a general one and applies to the alcohols, and aeids of the same series, and to the homologous bodies in genei-al. Point of ebullition. - 55" 74" 95" - 119" 133" Formic ether, Acetic " Propioidc " Butyric " Valerianic " Difterence. 19" 2P 14" iA' II^S, as is the case with biatomic mer- captaii.s. One only of each of these two classes will be alluded to here. Ethyl sulphide, or hydrosulphu- ) ., .. C.TI, ) ^ ric ether, ( *-i^^iot? "" (j jj.' .■ S. Ethyl mercaptan, C4H6S=^^-'f|' !- S 41 ) To iirepai-e the sulphide a cuiTent of ethyl chloride, is passed into an alcoholic solution of potassium sulphide. The mercaptan is prepared by the action of potass- ium hydro-sulphide or ethyl sulphide. In either case potassium chloride is formed. K,S +02H,ri=C,H,oS + 2KCl KilS + C.HsCl =C,H6S + K('l. These bodies are afterwards separated by distiilation- Like all the sulphur derivatives of alcohol, they have a nauseous odor. The sulphide boils at 91« the mer- captan at 36°. JnXED KTHKKS containing two different radicles, are obtained by act- .r 1'' :^ II -'Si m ]^^tj^lr.i^j.^k.:Afi^t'^?i. ■ m t ^-f^s m ■ I' •ii' "lit It*,. H;li ! 84 ORGAl^IO CHEMISTRY, ing, for instance, with ethyl iodide upon potassium niethylate, thus : ethyl iodide, potassium potaseinm methyl-ethyl methylate. iodide. etlier. or by acting on hydric methyl sulphate ' jj' ^ SO^ with ethyl alcohol. The following is a list of sume of the moi'e important mixed ethers of the niouiitomic series; TABLE OF MIX1;D ETHERS. UOILING POINT. Methyl-ethyl ether C41sO= ^JJ' J- ^^ + 1^° Methyl ayl-amyletlierCrJInO-cH ^^ ^^^ Ethyl-butyl ether C6Hi40= ^^^^ I O 80" Ethyl-amyl ether C:H,«() = q^ [ O 113« Ethyl-hexyl ether Csll;sO = g^^^ |- O 132- >ii potassium thyl II \^* ist of some of le moiiiitoHiic UOILIXG POINT. +11° 92" D 112° 'J 132" ALDEHYDS. 85 ALDEHYDS. The following are the principal aldehyde, arranged in series Formic aldehyd Ethylir*. aldehyd Propylic aldehyd - Butylic aldeiiyd - Valeric aldehyd (Enanthylic aldehyd - Caprylic aldehyd - Caproic aldehyd liutic aldehyd Ethalic aldehyd AUylic aldehyd (acrolein) G HjO C,H,0 CsTIeO C4H80 C5H.0O CJ1„0 CsIIibO C,oH,oO c„ii,>o C3 H,0 cji,„.,o. Campholic aldehyd (camphor) CioH.fiO se ORGANIC CUEMISTUY. ; < CJI 3n-8 p. Benzoic aldehyd {oil of hitter almonds) Q-, II« O Toluic aklehyd - - - - CgllsO Cuininic aldehyd ... - CioH,.0 Svcocervlic aldehyd - - - CisUsO CellsO. Cinnamic aldehyd {oil of cinnamon) Aldehyds may be regarded as bodies built upon the type of one or more molecules of hydrogen, in which one half the hydrogen atoms are replaced by one or more molecules of an oxidized carbohydride. The formation of aldehyd, (aZcohol <^/A,?/(/rogenated), may be illustrated by the following equation : CoHcO-H., = C2H4O Ethyl alcohol. Ethyl aldehyd. Aldehyds are obtained by the oxydation of alcohols, but thoy are only the first products of oxydation. They are capableof combining with an additional molecule of oxygen, forming acids; hence the aldehyds are inter- mediiito between alcohols and iK'ids. ORDINARY ALDEHYD. c,n40=c,n:,o ) . in This substance is formed by the slow oxydation of alcohol. • CJI«0 Cs lis O C,oTi,.0 CsII^O CellsO. t upon the I, in which by one or e. rogenated), ii: of alcohols, ition. They molecule of Is are iiitev- oxydation of ••"?»- ALDEIIYDS. 87 Alcohol is treated with a mixture of manganese hinoxide, or of potassium bichronuxte, and sulphuric acid, and distilled, care being taken to keep the re- ceiver well cooled. Besides aldehyd, acetyl, acetic ether, acetic acid and water are formed. The product is again distilled, care being taken to collect only that portion M'liich passes over above 60". This liquid is mixed with ether, and, when cool, a stream of drv ammonia gas is caused to i>ass through the solution". Crystals of ammonium aldehyd are formed, C.Il3(XIl4)0, which are decomposed by dilute sul- phuric acid. The mixture is then distilled. Aldehyd is a colorless, very volatile liquid. It is soluble in water, alcohol and ether, and possesses a strong, somewhat stifling odor. The salient property of aldehyd is its avidity for oxygen. If a few drops are poured into water the latter becomes acid; it is therefore a valuable reduc- ing agent. If aldehyd, or ammonium aldehyd, ^\14! I is •^ jN II, f , poured into an ammoniacal solution of silver nitrate, on slightly elevating the temijerature, metallic silver is deposited. This silver adheres to the sidesof the tube, and covei-s it with a mirror-like coating. This prop- erty is the basis of a process of silvering glass globes and other hollow articles of glass. Aldehyd is attacked by chlorine and bromine, and furnishes, by substitution, various products, of which Chlokal CJICI3O, is the most important. J5y. ^^1 ■^=^"ati»^*paa^ji>wT*f«Ki"tMaai^Uiiai'l^aajaiay* m ORGANIC CHEMISTRY. dm to ofchlomU or C,IlCl/) + lI>0.1iasbeen prepared now for several years in very large (juantities, for medicinal purposes. Its name is derived from chlor- ine a^Icohol. Absolute alcohol is saturated, first cold, then hot, with dry chlorine. The litpiid obtained is mixed with its volume of concei ' ated sulphuric acid. The supernatant liquid is decanted, and distilled in an earthern retort, with one-fourth its weight of sulphuric acid. The anhydrous chloral obtained is redistilled twice with calcium carbonate aiul 7 to 8 per cent, of water. The hvdrate is then obtained in handsome crystals, CJICUO + II.O, soluble in water. It has been known for some time that this body is decom- posed in presence of alkalies or alkaline carbonates, into cliloroform and formic acid, CJICl30 + H,0 + KI10=KCHO, + CIICl3+IIA Potassium Chloroform, formiate. Tlie question appeared ])ertinent whether a similar transformation would be affected in the human body, under the action of the alkaline fluids there present, notably those of the blood, and thus develop chloro- form. Liebreich was the first to administer chloral, and he at once obtained the anesthetic efteeta of chlorotorm. His oxperiiiients were repeated in difterent countries, and hydrate of chloral soon came into general use as a hyponotic. ALDEHYDS 89 n prepared ntities, for from chlor- , then hot, ' mixed with icid. The I illed in an )t' sulphuric redistilled per cent, of I handsome er. It has y is decern- carbonates, Dla + II^O. •form. Chloral lijdrate fur medical use must he crystalline and possess the following properties: it should be col- orless, traiis])arent, and have an aromatic odor, a caus- tic taste, readily soluble in water without furnishing drops of oil, also soluble in alcohol, c'lior n ',tJuC benzol, and earbon bisulphide; it should \v r 5ijo to 58", solidify at about 15", boil and volatilize Vtify at 95". With caustic potassa it should fun lo- form, and with sulphuric acid, chloral, withoiu ..ocoui- iiig brown. Its aqueous solution should be neutral and not jiroduce any turbidity with silver nitrate and lutr.c acid. E.xposed to the air it shorld not become moist. Accordingtorecentinvostigationsbyliebreich, [fiO-69-673) chloral produces the opposite phvsiolocal etlects of Btryclmine, hence, these bodies ma'y be used as antidotes one for the other TI.e remaining aldehyds are not sufficiently im- portant for a work of this scope. Camphor has al- ready been considered in connection with turpentine iv a similar umau body, lere present, ^elop chloro- loral, and he ■ chlorotorin. Mit countries, nieral use as ..» A.Ja,M^.^^'^^^^^ OliGANIO CHEMISTRY. ORGANIC ACIDS. ACIDS CONTAININ'i TWO ATOMS OF OXYGEN. FATTY ACID 8KRIKS. Formic acid, Acetic (( Propionic ;( Butyric u Valeric (k Caproic i( CEnanthj , » ' Capryli" ■.i Peli.ijonic a Capno ii Laurie (( Cocci nic u Myristic u Palmitic (( Margaric a Stearic a Arachidic ti Cerotic a Melissic u c„n,„o,. C H,0, C,H4 0, CsHeO, C4II8O, CjIIioO, - cji,A C,IIuO, CsHkO, CJLsOj CioIIaoOj c,,n^o, CialljeOj CyHjsOa CieHj^Oi Ci:H3,0, CisHso^a - C'^II^O, 030x16002. nu-U.di.'.nii,i mMM" "iii j i " -r-l ':ii,-ii.^i:'.'.-'^-,fW--^ -". -y^=*-^??*-T';r^^-"-2v?p*.'? i?^^^^:'fT:}:- " ^^p'rtts^.rs' rr,'n!^l r IMAGE EVALUATION TEST TARGET (MT-3) ^/ '4^4^ :/j fell ^ V^ r '-m^ ■ ^J ^j^ 150 "^^ IfflIBB Photographic Sciences Corporation 23 WEST MAIN STREET WEBSTER, N.Y. MStO (716) 872-4503 CIHM/ICMH Microfiche Series. CIHM/ICMH Collection de microfiches. Canadian Institute for Historical IVIicroreproductlons / Instltut Canadian de microreproductlons historiques I^Wi ORGANIC AOIDS. 91 Acrylic acid Crotouio " Angelic " Pyroterebic " Campholic " Moringic " Physetoleic " Oleic " Doeglic " Erucic " c„ii,„_,o,. CnHin-^iOj. Soi'bic acid Campliiu " C H^Oj C4ll«0,, Cg H10O2 CwHaoOa' C18H34O3 CiaHagOa CaH^aOjj. Cg Hg O2 CioHijOg ABOMATIO ACID 8EBIE8. CnHan-sO^. Benzoic acid Toluic « Xylic " Cuinic " Alpha-cymio acid '-^ntlan— loOji Giimamic acid Pinic " OTHgOa CgHgO, C9 HiqO, OioHijO, CiiHhOj. CsHgO, CjjoHaoOj. :.ji«i<'iM iriMimkiiiiini^itm B ■ n 02 OROANIO CHKMI8TBY. ACIDS CONTAININa THKKE ATOMS OF OXYGEN. C„H,„0: nii^uv^s. Carbonic acid Glycolic " Lactic " .Oxybutyric " Oxyvaleric '' Leucic " (Enanthic " CnH2n_3V-)3. Pyruvic acid Scaminonic " Kicinoleic " CnHjn— it's- Gnaiacic acid Lichenstearic " - Pyromeconic acid CnH-in-sOa. Salicylic acid ■ Anisic " Phloietic ♦' - Oxycnminic " Thyinotic " - C HjOs CaHiOs CsHcO, C^HsOs Cj HjoOg Ce H,,Ob C8H4O3 CigHajOs. Cg Hg Oi C9 HuOs* CBH4O8. C,H,03 C9H:oO, C„H,A CnHiA. ■m re EN. ItoO, l4 03 E4O8. H,03 H:oO, EI„Os. ORGANIC ACIDS. Coumaric acid - - - C9H8O3. ACID8 CONTAININO- FOUR ATOMS OF OXYGEN. 98 Glyceric acid CnH^-aO. CsH^O,. Oxalic acid C,H,0, Malonic (( CsH4 04 Succinic « C4H,04 Pyro tartaric {( C5H8O4 Adipic (( C0H..0O4 Pimelio K C7 HijOj Suberic U CJI„04 Anchoio U C9 HuO, Sebic U C10HJ8O4 Roccellic CnH2„_404. C„H„04. Fumaric acid C4H4O4 Citraconic i( C,Ii«04 Terebic (( CtH,„04 Camphoric (( C,„H„04 Lithofellic (( C»Ha.04. aai^L)iS!.saiMag aiaaeaKaa^,!i i» 94 ORGANIC CHEMISTRY. CnHto-aOj. MelHtic Terechrysic acid C4Ha04 CellsO^. CnH2n_804. Veratric acid CiiH2n_ioO. C9H10O4. Phtalic Insolinic Choloidic acid C8H«04 C9H804 C«IIa804. - CnUjn— uO' Oxynaphthalic acid Piperic " CJT6O4 Cj2H,o04. AOTTd OONTAININO 5, 6, 7 AND 8 A :OMS OF OXYGEN. Tartronic acid Malic " C3H4O, C4HeO,. C„II.,u-405. t Mesoxalic acid CsHjOfl. CnHo„_«05. I604. 10' ,04. BO4 38^4' ,04 I0O4. IF OXYGEN. 4O, A. ORGANIC ACIDS. Cholesteric acid 95 Crocoiiio Comenio Gallic Cholalic acid u u C'nH2n_208. Tartaric acid Quinic " V-'ntlon— I^'r Carballylic acid Aconitic acid Chelidonic Meconic Citric Mncic CnHin-eOa. CnHjn-ioOg. acid ^nHiin-ioOt* acid (( CsHioOs. C5 Hj O5 Ce 11,05 CJIeO, Ca4H4o05. C4H606 CfcHttOe. C,H4 0e C,H4 0, CeHnO, CfiHioOs. Org anio acids are bodies built upon the type of one or more molecxiles of water, hiving one half the hy- drogen replaced by an organic compound radicle con- 9e ORGANIC CHEMISTRY. taining oxygen. There are some acids whose compo- sition is not definitely fixed. We shall first examine the monatomic acids, and study the other series in the order of their atomicity. The organic acids possess tlie general properties of the mineral acids. Many among them, like aceticacid, have a very decided action upon litmus. Generally, they are solid and crystallizable; however, formic, pro^ pionic, butyric acids, etc., are liquid. Acids whose molecules are comparatively simple, are oi-dinarily sol- uble in water— the others are little, or not at all, soluble in this solvent. The monobasic acids are volatile, at least where their molecules are not very complex. The polybasic acids are decomposed by heat. Their salts are ordinarily crystallizable. METHODS OF PREPARATION. I. The acids of the so-called fatty series are ob- tained by the oxidation of the corresponding alcohol, or aldehyd, which latter is the first product of oxida- tion of the respective alcohol. CjHeO -f- 02=C2H4O 4- II2O. V , < Acetic aldehyd. C2H4O-f-Oj=C2H40,. Acetic acid. II. These acids are also produced by the action of alkalies upon the cyanide of the radicle appertaining to the homologous inferior alcoliol. )se compo- it examine jries in the x>pertie8 of acetic acid, Generally, armic, pro- sids whose inarily sol- all, soluble (volatile, at )lex. The Their salts es are ob- ff alcohol, of oxida- action of )ertaining ORGANIC ACIDS. 97 (CH3)CN + KIIO + HaO^^NHs + KCaHaOj Methyl cyauide. PotagBium acetate. III. Acids are likewise formed by the union of the ■elements of carbon monoxide and carbon dioxide with hydrogen carbides and water. The remarkable syn- thesis of formic acid by Berthelot is, according to this method : C0-f-IL0=CH20 2^2- Pelouze has shown that heat, cnrefiilly applied to polyatomic acids, causes them to part with a certain number of molecules of water, of carbon dioxide, or of both, and famishes acids more simple and of a lower equivalence, which he designates by the name oipyro- acids. 2C4HeOe=C,,H804 -\- 2HjO -f- SCO., . Tartaric acid. Pyro-tartaric acid. Of all the series of acids, the most numerous and the most important are those of the so-called fatty series- We shall presently indicate the methods by which they are obtained. Tneir boiling point increases from 16" to 20° with each addition of Cllj to their molecule. Certain of their salts, those of calcium, for instance, are decom- posed by heat, furnishing compounds called acetones. 98 ORGANIC CHEMISTRY. Calcinm acetate. Ordinal y acetone. FORMIC ACID. CH,0,=CH,0 H O. Eed ants made to pass over moistened blue litmus paper produce red stains. Tiie acid secreted by these insects was first obtained by Gehlen, and lias re- ceived the n:;nie oi formio add. I. Berthelot has obtained it from carbon mon- oxide by synthesis. II. It is prepared by distilling a mixture of 10 parts of starch, 30 parts of sulphuric acid, 20 parts of water, and 37 parts of manganese biuoxide in a large retort connected with a condenser. The mass swells considerably, and at first must be heated but gently. The fonnic acid is distilled over and saturated with lead carbonate. The fbrmiate of lead is caused to crystallize m boiling water, then placed in a retort and decomposed by a current of hy- drogen sulphide and thereupon heated; the formic acid is then distilled oif. III. One kilo of glycei-ine, 150 to 200 grains of water and 1 kilo, of oxalic acid are introduced into a retort and heated for 15 iiours at a temperature of about 100°. The oxalic acid is decom]30sed, but only carbon di- oxide is disengaged. "Water is added from time to ACKTIO ACID. 9» lue litmus creted by iiid lias re- bon inon- ture of 10 10 parts of in a large 3t must be tilled over >rmiate of ater, then rent of liy- ormic acid ns of water :o a retort bout 100°. jarbon di- a time to time, and the mixture then distilled until 8 litres have passed over. The glycerine remains unchanged in the retort, and can again be used. Fonnic acid is a colorless liquid, of a very acid re- action, a pungent odor and crystallizing at about 0° and boiling at 104°. It reduces oxide of mercury, furnishing mercury, as a brown powder, also carbon dioxide and water. Its salts are usually soluble, though that of lead is very little soluble in cold water, but quite soluble in boil- ing water. On heating with sulphuric acid, carbon monoxide and water are formed. Exi'KEiMEOT, — Introduce into a test-tube a small quantity of formic acid or a formiate. Add sulphuric acid and heat; a regular liberation of a gas takes place, which may be ignited, producing a blue flame. CH2 02 = CO+HA ♦ i ACETIC ACID. C,HA=CaIl30(^ H \ ^• 8p. Gr. 1.08. Density of vapor 30. Glacial acetic acid melts at 17o; boils at 118". This is the acid of vinegar, and of which it forms the essential part. It is found in the juices of many plants and in certain fluids of the body. It is formed by synthesis from methyl, sodium, or potassium for- 100 OROANIC CIIKMI8TRY. miate, and by the oxidation of acetylene; also by the action of nitric acid upon fatty substances, and by the reaction of potassa ujxtn tartaric, malic and citric acids. It is further produced: I. By the oxidation of alcohol in the following way: "Wine in vat!>, or casks, is placed in a cellar main- tained at a temperature of about 30°; every sixth or eighth day several litres of vinegar are withdrawn and replaced by an etjual quantity of wine. Pasteur has established that the oxydation of alco- hol is produced by a minute plant, the MtjGoderma aceti. In fact, aeetification commenceu only when this plant has been formed in the liquid. If its development is interrupted the oxydation stops; it rendei's the service of taking oxygen frps of the efferves- this acid, the same i a similar it should this test, perliaps more physical than chemical, acetic acid, di- luted with 1000 parts of water, can be readily recog- nized, and with practice, one part in 1500. * ACETATES. Acetic acid is monobasic; there are, however, alka- Ime biacetat^s and some basic acetates of copper and lead. '^ POTASSIUM ACCTATE. This salt, distilled with its weight of arsenous oxide, furnishes a very inflammable liquid, formerly called the "liquor of Cadet," and in wiiich Bun.en has found a radicle spontaneously inflammable, cacodi/l, CjEjaAs^. Potassium acetate forms, as well as sodium acetate, an acid acetate when treated with acetic acid. It is a very deliquescent salt, diflicultly crystallizable. AMJIONIUM ACETATE NHAHsOa, / Is prepared by saturating ammonium carbon- ate with, acetic acid. Its solution constitutes the spirit o/Mindererua ; treated with phosphoric oxide it forms cyanide of methyl. There is also an acid salt, NH4CjH80,CaH40. in compounds of this character, 106 ORGANIC CHEMISTRY. acetic acid must be considered as acting the same part as the water of crystallization in salts. SODIUM ACETATE. NaC^HsOa+SlIjC). This is used in preparing marsh gas and concentrated acetic acid. It is recommended by Tommase (62-72- 23), as a solvent for plumbic iodide, of which two grams are readily dissolved in 0.5 c. c. of a strong sokition of sodium acetate. CALCIUM ACETATE. Ca(C2HAV This salt, subjected to distillation, ftimislies a liquid containing a large proportion of acetone CsHgO- ALUMINUM ACETATE. A1(C,H30,)3. This body is employed at present by dyers, as a mor- dant. It is prepared by causing aluminum sulphate to react upon lead acetate. Lead sulphate, which is insoluble, is separated on filtering the liquid. FEKBIC ACETATE. Tliis salt {pyroUgnite) has been, and is still, somewhat employed for the preservation of wood. ACETATES 107 same part icentrated se (62-72- two grams solution of es a liquid T.O. , as a mor- i sulphate (, which is 1 is still, wood. COPPKR ACETATES. I^omml acetate CAx{C,n,0,), is called verditer. It terms beautiful green crystals (cri/stals of Venus), which, subjected to distillation, furnish acetic aeid mixed with acetone. During this operation, a white sublimate is formed, which deposits in the neck oftheretort. This latter is cuprous acetate, and is car- ned over into the receiver, oxydizes, and changes into cupnc acetate, which colors the distillate blue. There remains in the retort, after this decomposition, very finely divided copper which takes fire when slightly heated in the air. Solutions of this acetate reduce the salts of tne oxide, CuO, and serve to prepare the sub- oxide, CujO. ^ A basic acetate, designated by the name of verdigris 18 obtained by exposing to tlie air sheets of copper moistened with vinegar, or surrounded by the maro of grapes. The metal becomes covered with a greenish incrustation whose formula is, Cu(02H3O2)j,CuO4-6H2O. LEAD ACETATE. The normal acetate Pb(C JI3O,), is prepared by treat- ing litharge with acetic acid in slight excess. This salt, known by the name of sugar of had, crystallizes in oblique rhombic prisms, soluble in two parts of water andeight parts of 95 per cent, alcohol. It has a sweet taste, and is very poisonous. It is employed as a re- 108 ORGANIC CHEMI8TBY. agent, also to prepare aluminum acetate and lead cliro- raate. In digesting acetic acid with an excess of litharge, it furnishes a hexabaeic acetate of lead. If ten parts of normal acetate, with seven partsof litharge are takeuand this mixture digested with 30 parts of water, there are formed minute needles of a tribasic salt P^CallsOj).^} Pb02, HaO. Finally this salt, dissolved in normal ace- tate, gives a sesquibasic acetate, which is deposited in crystals, 2(Pb2C2H302),PbO,Il20. Goulaed's kxtraot is a solution containing a mix- ture of normal and of sesquibasic acetate of lead, which is prepared by boiling 80 i-arts of water, 7 parts of litharge and 6 parts of normal acetate of lead. BUTYKIO ACID. C^HsO,^ AH.O|o. It is usually prepared as follows: a mixture of 10 parts of sugar, 1 part of white cheese, 10 parts of chalk, and some water, is maintained at a temperature of 30" to 35°. First, lactate of lime is formed, which causes the mass to thicken, then that salt changes into buty- rate, disengaging hydrogen and carbon dioxide. When the mixture has become clear, the liquor is evaporated and the butyrate separated with a skimmer. This salt is decomposed by concentrated hydrochloric acid which separates the butyric acid in the form of an oil, which is distilled off. It boils at 163°. It is of a fetid odor, and soluble in water, alcohol and ether. h VALEKIC ACID. 109 lead cliro- itharge, it in parts of itakeuand , there are ormal ace- posited in ing a tnix- I of lead, er, 7 parts ead. [lixture of ts of chalk, ture of 30<* ich causes into buty- de. When evaporated ler. This hloric acid L of an oil, It is of a id ether. Valerianic, or Valeric Acid CgHjoOj = ^s'^'^ I O. It can be obtained by oxydizing amylic alcohol by a mixture of potassium bichromate and sulphuric acid or by distilling valerian root with water acidulated with sulphuric acid. The best method is to boil por- poise oil with water and lime. The oil saponifies and the valerianate of calcium alone is dissolved. This liquid is concentrated and hydrochloric acid added in excess. The valerianic acid separates out in the form of an oil wliich is distilled, and that portion collected which passes over at 175°. Pierre and Puchot have lately devised a process for preparing valeric acid from amyl alcohol. (3-[3]6-40. ) benzoic ACID, C7He02. Density, 61. Density of iu vapor compared with air, 4.27. • . Melts at 120°; boils at 250°. It is obtained by a dry, as also by a wet process. To prepare it by the former method, equal weights of sand and gum benzoin are placed in an earthen ves- sel, the mixture covered with a sheet of filter paper, which is pasted down round the edge, and a long cone of M'hite cardboai-d placed over the whole. The earthen vessel is then heated ovqr a slow fire for two hours, and when cool the cone is removed. The ben- zoic acid is found to have condensed on the interior of the cone in handsome blades, or needles. 110 ORGAXIC 0HEMI8TBT. It is obtained in the wet way, by piilverizing gum benzoin, mixing it with half its weight of lime, and boiling for half an hour in a cast-iron kettle, with six times its weight of water, care being taken to agitate the mixture. It is thrown upon a piece of linen and the residue treated twice with water. The liquids are reduced in volume to two-thirds that of the water used during the first treatment, then saturated with hydro- chloric acid. The benzoic acid sepanitcs out, and is recrystallized from a solution in boiling water. It is also procured from the urine of horbivorous animals. This secretion, evaporated to a small bulk and treated with hydrochloric acid, yieMs a deposit of hippuric acid, which, on being heated with dilute sul- phuric acid, is transformed into benzoic acid. Benzoic acid is also produced on a large scale from naphthalin. Benzoic acid crystallizes in lustrous blades, or need- lesjis little soluble in cold watiT, quite soluble in boiling water, and still more so in alcohol and ether. On passing its vapors through a tube heatod to redness, it is decomposed into benzol and carbon dioxide, C7H,02 = CjHg-}-COj. Chlorine, bromine and nitric acid transform it into substitution products. Chlorbenzoic acid, C7H5CIO. Dinitrobenzoic " C7li4(NO.,)20j. Ammonium benzoate furnishes, on distillation, benr zonitrile C^NHsOa = C^HjN + 2HoO. The alkaline benzoates heated with chloride, or BENZOIC ACID. Ill Zing gum lime, and , with six to Agitate [inen and quids are 'ater used th hydro- lit, and is rbivorous nail bulk leposit of lilute sul- cale from , or need- in boiling lier. On edness, it dioxide, nd nitric ;ion, hen- aridc, or oxychloride of phospliorus, furnish benzyl chloride, which, submitted to the action of potassium benzoate in excess, gives benzoic anhydride, 3(KC,H50j)+POCl8 = 3(C7H50C1)+K3P04. ^ , ' Chloride of benzyl. C,H50C1+KC;HA = C„H,o03+KCl. Benzoic anhydride. The rational formula of benzoic anhydride is, CJI5O),. C:H,0 [ "• Calcium benzoate heated to a high temperature furnishes henzone, Ca(C,n502>j= CaC08+C0(CeH,V Calcium benzoate. Benzooe. Benzoic acid is monobasic, and the benzoates are generally soluble. Benzoic acid taken into the stom- ach, is transformed into hippuric acid. Eolbeand von Meyer have observed that benzoic acid has antiseptic power, though less than salicylic acid, (18-[2J 12-133). ciNNAMio ACID. In Certain balsams there exists an acid called cinnamio acid, wiiose formula is CJIgOa. It exists in the balsams of Peru, benzoin, tolu and in liquid storax. It fuses at 129" and boils at 290°. It 112 ORGANIC CHEMISTKY. has striking features of resemblance to benzoic acid, and is produced like the latter l.y the oxydation of an aldeliyd. This aldehyd is the essence of cinnamoa prepared by distilling cinnamon with water. POLYATOMIC ACIDS. OXALIC ACID. c,ha=^^hI I ^^ PEEPARATioy. In the burdock and sorrel is found an acid salt, commonly called salt of sorrel, which is a mixture of binoxalate and quadroxalate of potas- sium. Sodium oxalate is found in several marine plants, calcium oxalate in the roots of tlie gentian and rhubarb, and in certain lichens. Salt of sonul is extractecl from the burdock {Prunex\ in Switzerland, and in the Black Forest of Germany, by exprtssising the jilfint, clarifying the expressed liquid by boiling with clay, and evaporating ; crystals of salt of sorrel are deposited. The oxalic acid maj' be obtained free by decompos- ing a solution of these crystals with lead acetate ; the oxalate of lead which precipitates is treated with a suitable quantity of sulphuric acid ; the lead is com- jjletely precipitated as lead sulphate ; this is filtered off, and the liquid evaporated and allowed to crys- tallize. At present this acid is chiefly prepared by the action of oxydizing agents upon certain organic substances; the substances best suited for tliis purpose are those OXALIC ACID. 118 izoic acid, tion of ail cinnamon I is found , which is of pcitas- II marine 3 gentian sorrcl is itzerland, xpressing iqiiid l)y of sal t of ieconipos- acetate ; ed with a id is corn- is filtered . to crys- the action hstances ; are those which contain oxygen and lijdrogen in the proportion to form water. One part of starch, or sugar, is l)oiled with eight parts of nitric acid diluted with ten parts of water, until nitrous vapors cease to be disen- gaged, and the liquid then evaporated. The crys- tals of oxalic acid which separate out are freed from the excess of nitric acid, by being several times re- crystallized in water. It is also obtained on a large scale by the action, at a high temperature, of potassa or soda on saw dust. Oxalic acid has been obtained synthetically, by Drechel,on passing carbon dioxide over sodium heated to 320". 2COj+Nai=Na,C204. Properties. — Oxalic acid crystallizes in prisms, which effloresce in the air, and which are very soluble in water and alcohol. It fumes at 98°; at 170° to 180° it is partially sub- limed, but the greater portion is decomposed into cai-- bon monoxide, carbon dioxide, formic aciil and water. 2(C2H A)=CO + 2C0i+C II,0,+II,0. Chlorine, hypochlorous acid, fuming nitric acid and hydrogen peroxide, convert oxalic acid into carbon dioxide. Sulphuric acid causes it to split up into carbon mon- 114 ORGANIC CHEMISTRY. oxide and carbon dioxide, and this reaction is made use of in preparing the former gas. Oxalic acid is bibasic. Normal jiotassiuiu oxalate, K.^=02=C02 . Acid potassium oxalate, KII=02=Cj()2. Uses. — Oxalic acid is employed in removing ink spots from cloth, and in cleaning copper. It owes these }»ro|)ertie8 to the fact that it forms with iron and copper soluble salts, hence it is also employed in calico-works for removing colors. Toxic action of oxalic acid. On account of the use of oxalic acid in tlie arts, and its physical resemblance to cflrtaiu salts, particularly to magnesium sulphate, poisoning wiih it has often occurred, either through design cr imprudence. It acts powerfully upon the system. Tai-dieu men- tions the case of a young man, sixteen years of age, who was poisoned by two grams of this substance. The symptoms observed are similar to those pro- duced by other corrosive agents; great prostration fol- lowed by unconscionsness and a persistent numbness in the lower extremities. The blood of the patient be- comes abnormally red. In cases of poisoning, the acid should be removed from the stomach with promptness, and milk of lime, or magnesium, or ferric hydrate administered. Lime is to be preferred, as it forms a salt completely insol- uble in vegetable acids. ■J SUCCiNlO SOW. 115 made use O2. '2. ving ink wes these id copper ico-works af the use emblance sulphate, through ien men- 8 of age, ance. lose pro- ation fol- lumbness atientbe- removed of lime, 1. Lime ely insoL SUCCINIC ACID. CJI,04 = C4lIA) H,) O,. This acid is produced by the oxydation of butyric acid, and by subjecting amber, succlnum, to dry distil- lation or by the action of iodhydric acid on malic or tartaric acids. Succinic acid crystallizes in rhomboidal prisms which melt at 180° and boil at about 235°, at a higiier tem- perature tliey are decomposed into water and succinic anhydride C4H4OS. It is soluble in 5 times its weight of cold water, soluble in ether and very soluble in alco- hol. It is used in the artificial preparation of malic and tartaric acids. Succinic acid has been found in the fluid of the hydrocele and oi certain hydatids. HALIC ACID. C4H3O2 } f^ Tliis acid, discovered by Scheele in sour apples, is found in many plants; in the berries of the service- tree, in cherries, raspberries, gooseberries, rhubarb, to- bacco, etc. Malic acid is levogyrate, deliquescent and crystallizable; it is soluble in alcohol and fuses at about 100°. At a temperature above 130°, it is decomposed into lii^ 116 ORGANIC CHZiMISTRY. various acids and esY>ed{\l\y paramalio acid, €411404, which i.v identical witli the acid of tlie fumana. It is bibasic like oxaHc acid, but triatoinic and is dis- tinguished from tliis acid by not producing a turbid- ity with calcium compounds. TARTARIC ACID. This acid, obtained from wine tartar by Scheele, in 1770, occurs free and combined with potassium in many vegetable products; in the sorrel, berries of the service-tree and tamarind, in the gherkin, potato, Jerusalem artichoke, etc. The grape is the chief original source of this acid. One method of prepari?!g tartaric acid is to purify crude tartar by dissolving and clarifying with clay, which throws down the coloring matters: then filter- ing and adding calcium carbonate, which precipitates half of the tartaric acid as a calcium salt. 2KHC4H4O«+CaCO3=C.C4H4O8+K2C4H4O«+CO.,+Ha0 Hydro-potassic Calcium Calcium tartrate. Potassium tartrate. carbonate. tartrate. The solution whicli contains the potassium tartrate, is filtered and calcium chloride added : the remainder of the tartaric acid .'s thus precipitated as a tartrate and added to the preceding. cirl^ €411404, ^umai'ia. It and is dis- ig a turbid- y Scheele, in 3otassium in jerries of the •kill, potato, is the chief [ is to purify g with clay, : then filter- precipitates )e+CO,+H,0 lum tartrate, le remainder 18 a tartrate TARTARIC ACID. K AH40e + CaCl2=CaC,H.0« + 2 KCl. Potb88ium tartrate 117 V -^ Culciura tai'trate. These precipitates are washed and decomposed with sulphuric acid, the calcium sulphate is filtered ofij and the liquid evaporated to the point of crystallization. This acid is also called right tartaric, or dextroracemie, as it turns the plane of polarization to the right. Kistner has obtained from certain tartrates a tartaric acid which is optically inactive. This a Id, called jpaz-a- tartario or raoemioaoid, is somewhat less soluble than dextrotartarlc acid, while the reverse is the case with its salts. It contains, moreover, one molecnle of water of crystallization, but does not crystallize, as does the dextrogyrate acid, in hemihedral crystals. Levogyrate tartaric acid is prepared by evaporating a solution of raceraate of cinchonia; the levogyrate tartrate precipitates while the dextrogyrate reiuftins in solution; or a solution of racemic acid is allowed to stand witli a small quantity of calcium phosphate, and a few spores of the PenGilium glaueum; fermenta- tion sets in, which destroys the dextroracemic acid. Dextrotartaric acid crystallizes in beautiful oblique prisms with a rhombic base. Cold water dissolves twice its weight of this acid; alcohol dissolves it with equal facility. It is insoluble in ethei. Tartaric acid melts at about 180°; and furnishes dif- ferent pyrogenous acids, chiefly: TartaHo anhydride, or Tartrelio acid, C4H4O8, and PrjTotartario acid^ CjIIgOi. 118 OROANIO CHEMISTRY. Simpson synthesized pyrotartaric acid and Lebedeff has recently (60-75-100) sliowii th:it this acid is iden- tical with that obtained by heating tartaric acid. Tartaric acid does not precipitate calcium salts. It produces a turbidity with lime water, but an excess of acid dissolves it; by these reactions it may be distin- guished from malic and oxalic acids. Tartrates. Tartaric acid is bibasic. The two tartrates of potassium are : Normal potassium tartrate, KiCJIiOa Hydro " « KC34H50e. This latter salt is obtained by purifying the tartar of wine casks, and is called cream of tartar. It is used in the preparation of black flux, white flnx, potassium carbonate, and tartaric acid, also largely in baking powders. EooHELLE Salt. KNaC4ll408+4a(i. This salt is a double tartrate of potassium and sodium, which was formerly much used as a purgative. It may be pre- pared by mixing in a porcelain disli, 3500 grams of water and 1000 grams of cream of tartar, this is brought to boiling and Kodium carbonate added as long as ef- fervescence is produced. This solution is then filtered and evaporated until it has a density of 1.38. The salt crystallizes in regular rhomboidal prisms; it is soluble in ' Propylglycol. Lactic acid is a colorless, syrupy liquid ; at about 130° it is changed into the anhydride of lactic acid, CflHioOg, and at about 250° it furnishes a crystalline body called lactide whose formula is C3ri40j. Lactic acid posseses the property of dissolving cal- cium phosphate. The lactates are soluble in water. Lactate of iron, (CaHsOg^.Fe, is employed in medicine. UEIC OK LirHIC ACID, CBH4N4O3. Discovei-ed in 1776, by Scheele. This acid exists in human excretions, and in those of the carnivora. In the excretions of herbivora, the uric acid is replaced by hippuric acid. Uric acid is present in normal human urine only in small quantity. The urine of sedentary persons, and of those whose food is very nitrogenous and quite substantial, contains more of this substance than that of individuals who lead an active life, and whose diet is less nourishing. In the latter case the uric acid is oxydized and converted into urea, hence, the proportion of the acid decreases as the quantity of m-eu increases : whereas calculi of 124 OKGANIO CHEMISTRY. nric acid are frequently formed in persons whose diet is very nourisliing, and whose occnpation necessitates but little muscular exertion. The excreta of birds contains a large proportion of uric acid, and that of snakes is formed almost exclusively of this body. This acid may be prepared liy boiling a dilute al- kaline solution with guano, excreta of the boa con- strictor, or uric calculi finely pulverized. The liquid is filtered and the filtrate supersaturated with hydrochloric acid ; the uric acid precipitates in flakes, which become crystalline on standing. The author having had occasion in 1858 to prepare large quantities of uric acid from guano, found that in order to obtain the purest product, as free from coloi^ ing matter as possible, it was preferable to use sod- dium hydrate as a solvent, and carbon dioxide as a pre- cipitant, the latter in sufficient excess to transform the hydrate into bicarbonate. Crystals of uric acid are colorless and odorless. They are nearly insoluble in ether and alcohol. About 1500 parts of boiling water are necessary to dissolve one part of the acid. On distillation uric acid yields urea and other cy- anic compounds. Uric acid heated with water and lead dioxide furnishes urea and a substance called al- lantom, which has been found in the urine of sucking calves. Its formula is C4HJK4O8. The same derivative of uric acid was obtained by the author in 1858, also parabanic acirJ, on heating uric acid with manganese dioxide and sulphuric acid. (80-[2]4:4:-218.) URIC ACID. 125 vhose diet lecessitates a of birds id that of body. I dilute al- > boa coa- jrsaturated iipitates iu to prepare ind thatiu roin coloi- ;o nse sod- ie as a pre- nsfonn the odorless, d alcohol, scessary to other cy- water and I called al- of Bucking Dtained by eating uric tiuric acid. If 1 p;irt of uric add be added to 4 times its weight of nitric acid of a specitic gravity of 1.45, the Bolution being kept cool, small crystals of a substance called alloxan separate out. whose formula is C4H4N2O5+3H2O. Woehler and Liebig obtained from this body a num- ber of very interesting derivations, alloxantin, al- loxanio acid, parabanio acid, thionurio acid, dia- lurio acid, and finally a magnificent purple crystalline Iwdy, murexide. A large number of other deriva- tives have also been obtained by other chemists, t^specially Bayer. The rich color, murexide, is made use of in detecting uric acid. For this purpose, traces of uric acid are heated in a watch glass for a few minutes, with one or two drops of nitric acid ; the ex- cess of acid is evaporated, and the dry residue exposed to the vapors of ammonia, when a pni-ple, or very beautiful rose color, will appear. HIPPURIO ACID C^H^NOa. The urine of herbivora contains a large percentage of this acid, which also exists in a small quantity in human ui'ine. A frugivorous diet augments the pro- jiortion of this body. It is prepared by boiling the fresh urine of the horse (hence the name, from innoi, a horse), or better from that of a cow, with milk of 126 OKGANIO CHEMISTRY. lime, which is than filtered and evapoiated to one- tentii its volume; this is mixed witli a large excess of hydrochloric acid and left to stand 10 or 12 hours. The impure hippuric acid which precipitates is re-dis- solved in soda and re-precipitt,ted with hydrochloric acid. Animal charcoal may be added to the saline so- lution if the brown color still remains. Putrid urine yields only benzoic acid. Dessaignes has prepared this acid artificially by causing zincic glycocol to act on benzoyl chloride. Zn(C2H4N02), -H 2CtI150C1= ZnCl, -J- 2C2H3[NH(C,H50j02. Hippuric acid crystallizes in colorless crystals, which require 600 parts of cold water for their solution, but are very soluble in hot water and alcohol. It is decomposed at 240°, benzoic and cyanhydric acids being found among the products ci' distillation. Under the action of oxydizing agents it lamishes ben- zoic compounds; with nitrons acid it yields heuzo-gly- colic acid. ALKALOIDS. 127 sd to one- ;e excess of 12 hours. is is re-dis- .'d rod 1 lone i saline so- itrid urine ! prepared >col to act crystals, ir solution, I. yanhydric istillation. lishes ben- beuzo-gly- ALKALOIDS. ABTIFICIAl. BASKS OB ALKALOIDS. PRIMARY. CJI,„+3N. Methylamine Ethylainine Propylamine Butylaraine AinylainJne Caprylamine Acetyl amine Allylaraine Cnilon + lN. Cnllin-a -N . Phenylamine, aniline - Toluidine Xylidine Cumidine CH^N CJl^N C3H9X C4H„N Cr.II,3N CeH.N C,H„N CbH„N CJI13N. Flitalidamine CgHsT^. 128 ORGANIC CHEMIST KY. CJI,„_„N. h ' ,■ Naphthalaniine - SECONDARY. - CioHc^f^. f,' ' Dimethylamine - Methylethylainine - Diethylamiue TEKNAKY. C3ll« N ■ C,H„N. Trim ethy lam ine Dimethyletbylamine - Methylethylamjlamiiie - C4H„N PirOSPHINES. • Methylpho8pl)ine Di methyl phosphine Trimethylphosphine - CH5P - C,H,P C3H9P. :-. ARSINE8. Triethylarsine CfiFIisAs. i^ ■ STIBINES. Triethylstibine CeH^Sb. NATURAL ALKALOIDS. 129 PRINCTPAL NATURAL ALKALOIDS. OF IIIK CINCHONAS. Qninia,Quinicia and QiiinidiaCj,H.,,N,0, Ciiiclionia and Cinclionid'a 0,oIL,x',o' ^""»a ■ - - c.«hXo4. OF Ol'ItTM. Morphia Codeia Thebaia Narcotina Papaverine Narceia CnH„N()3 C,9H,iN03 C^H^K O. C30H21NO, OF THE STBYCIINOS. Strychnia Brucia C2iH.^NA ^231128^204. OF THE 80LANACE.B. Nicotina Atropia - Hvosciaminc Solauia C10H14N2 CnHj^NO, CnH23N03 C^sHnN 0x6. OF THE HEMLOCK. Conylia CsH„N. 130 ORGANIC CHEMISTRY. OF PEPPKB. Piperidine AIISCELLANEOUS. Aconitina Veratria Theobromine Caffeia CjHnN. 0.«H4oNO CHgNA CsHioNA. The first organic base isolated was iiioi-phia, obtained in 1816, by Sertuerner. In 1819, Pelletier and Ca- ventou extracted quinia from cincliona bark, and showed that the very active plants used in pharmacy owed their energy to com pounds capable of uniting with the acids, and of forming with them definite crystallizable salts. From that epoch, the number of organic alkaloids has become very considerably augmented; and methods have been discovered by which many of the alkaloids are prepared artificially. It was Fritsche who, in 1840, obtained the first artificial alkaloid on distilling indigo with potassa ; he named it aniline. G«rhardt by similar methods prepared quinole'me, Cahours piperidine^ and, Chantard toluidine. The distillation of organic matter also furnishes al- kaloids. Thus several of them have been obtained from a product of the distillation of bones, the oil of Dippel ; also as products of the distillation of vaiious other organic compounds. COMPOUND AMMONIAS. 131 !5H„N. UNO I52NA tsNA I10N4O,. phia, obtained etier and Ca- •k, and showed acy owed their vith the acids, allizable salts. 3 alkaloids has and methods the alkaloids ache who, in don distilling le. G«rhardt )'me, Cahours \ furnishes al- been obtained es, the oil of don of vaiious A very general method is due to Zinin, which con- sists in causing a reducing substance to act upon nitrous compounds as nitrobenzol, for example. The nitrous compound is introduced into an alcoholic solu- tion of ammonium sulphide, and the mixture allowed to stand; sulphur is soon deposited, and the hydrogen of the hydi'ogen sulphide combines with the oxygen of the nitrous compound. Example: CeH^NO., + 3H,S=2II,0 -F 3S + CJI.N. > , ' Nitrobenzol. For this mode of reduction, as it is not very prac- tical, and is tedious in execution, there is at present substituted the action of iron upon acetic acid, or that of zinc or tin, on hydrochloric acid. Wurtz has given a very interesting method, which has led to the discovery of alkaloids much resembling ammonia, for that reason called compound ammonias. It consists in causing potassa to react upon the cyanic ethers, these bodies being decomposed much like cy- anic acid. Thus methylamine is obtained by the action of potassa upon cyanate oi methyl : CO CH3 N + 2KIIO=K,C03+ H [n. " V Cyanato of mothyl. Potassium carlranate. Methyl- amino. Hofmann made known, very shortly after the pub- 132 ORGANIC CHEMISTRY. lication of Wiirtz' process, a method for the prepara- tion of the cotnponiui ammonias, by which not only a simple equivalent of hydrogen is replaced by the radicles (Oils), (Calls), etc., but all the hydrogen of the ammonia. Hofmann's method consists in causing ammonia to react upon hydrochloric as well as brom- hydric or iodhydric ethers, particularly the latter. Let us take, as an example, iodide of ethyl in con- nection with the study of KTHYLAAONE. Ten to 15 grams of iodide of ethyl and 50 grams of aqua ammonia are heated in sealed tubes of green glass placed in a water bath. The following reaction occurs: CJT,I + XI13=C,HhNI. When the liquid has become homogeneous it is allowed to cool, then decomposed by a solution of po- tassium hydrate, the vapors being collected in water, containing hydrochloric acid. The hydrochloric acid solution is evaporated to dryness, and the residue treated with pure alcohol, which dissolves the chWrhydride of ethylamine and leaves in an insoluble stato the ammo- nium cldoride derived from the excess of ammonia used. The solution of chlorhydride of ethylamine is evaporated to dryness, and the deliquescent crystals obtained decomposed by potassium hydrate, M-ith tho aid of a gentle heat. The volatilized product is con- densed in a cooled I'eceiver. In this reaction there is CLASSIFICATION OF THE ALKALOIDS. 133 he prepara- i not only a ced by the lydrogeii of 9 in causing 11 as brom- latter. liyl in con- grams of green glass tion occurs: leous it is ition of po- 1 in water, chloric acid idue treated rhydride of I the arnmo- >f ammonia hylainine is ent crystals e, M-ith tho hict is con- on there is also formed diethylamine, trietliylamine and oxide uf tetrethyhinimoniuui from which the ethylamine is separated by distillation. It may be obtained more readily by first distilling 1 part potassium cyanate with 2 parts potassium fulphovinate, then by decomposing the cyanic ether obtained with a boiling solution of potassium hydrate contained in a flask connected with a cool receiver. Ethylamine is a limpid liquid, with a strong odor resembling that of ammonia. It has not been solidi- fied. It boils at 18.7", and dissolves in water, producing a very caustic solution. Ethylamine is equally soluble in alcohol and ether. It is combustible, burning with a blue flame, yellow at the margin. It displaces ammonia from its combinations. Its solutions give reactions similar to those of ammonia; for instance, with salts of copper it gives a bluish wliite precipitate, which is dissolved in an excess producing a deep-blue solution. It dift'ers from ammonia in the following reaction: ethylamine precipitates alumina from its salts, and the precipitate is soluble in an excess of ethylamine, which is not the case with ammonia. CLASSIFICATION OF TUE ALKALOIDS, OB ORGANIC BASES. Amines. — Ilofmann has given the names of primary amines, or monamines, to ethylamine, which we have just studied, and the compound ammonias in which a single atom of hydrogen has been replaced by a radicle. 134 ORGANIC CHEMISTRY. r-f:x The same chemist, having prepared ethylamine by the action of ethj-l iodide npon ammonia, subse- quently succeeded iii obtaining diethylamine by similar means. Tlie reaction is the following : N CoH. CoH. 11 |h This hydroiodide obtained, treated with potassium hydrate or lime, furnishes a second base, which is biethylammonia, or diethylamine ; Diethylamine C4lI„N=N A similar compound is. Ethylaniline C8lI„N'=N" C2H5. H These bases have been given the name of secondary amines or imides. The secondary ammonias are attacked by ethyl iodide and other ethers, and u reaction takes place, iden- tical with that which gives rise to the primary and secondary aminer, and tertiary amines, also called nitrlle bases, are thus obtained. AMINES. 135 laniine by nia, subse- ' by similar potassiam , which is secondary hyl iodide ace, iden- rnary and Iso called Snch bodies are: rc,ii, Tnethylamine CeIT.5N=N \ ( '..H,. fCITs Methylethylphenylaraine C9H,3N=X^ (\,II, These bases are related to the alcohols in the same manner as the primary amines. Thus diethylamine is derived from the action of 2 molecules of alcohol on 1 molecule of ammonia and the elimination of 2 mole- cules of water: 2(C,H«0) + NIl3-2H20=C4H„N. In like maimer the ternary amines may be consid- ei-ed as derived from 3 molecules of alcohol and 1 mole- cule of ammonia with the elimination of 3 molecules of water. There are also bodies built upon the type of two and three condensed molecules of ammonia, and are denommated, respectively, di amines and tri-amines; as !(C H y Ternary ethylene diamine IS^ (c,H4); 130 ORGANIC CHEMISTKY. Triethylainine attacks hydroiodic ether, and there i& formed the compound C8HaeXI=N(C2H5)4T. This body treated witli oxide of silver, furnishes an oxy- genated quaternary base, CgHaoNI + Ag HO=Ag I + CsH^iNO. This substance is very caustic, soluble in water and acts as an inorganic alkaline base like potassium hydrate, with which body it is also analagous in com- position. O (CaH,),N l\o. Amides, Alkalamides.— The amides are bodies built upon the type of ammonia, in which one or more of the hydrogen atoms are replaced by an acid compound radicle; thus, acetamide N There are also mixed combinations of amides ard amines, called alkalamides, as acetanilide II^" Cell, CjIIaO. H and there i& 15)4!. This hes an oxy- in water and } potassium ;ou8 in com- bodies built more of the compound amides ard ALKALOIDS. 137 NATURAL ALKALOIDS. Manj of the natural alkaloids appear to possess a composition analogous to that of the compound am- monias. Some are not attacked by iodide of ethvl, and should be classified among the ammoniums, bodied having the same relation to the compound ammonias as does ordmary ammonium hydrate to ammonia. Others are acted upon by iodide of ethyl, and, from the number of bases furnished, it may be ascertained whether they belong to the primary, secondary or ter- nary compound ammonias. The properties of the natural alkaloids in general, resemble those of the artilicial bases or alkaloids, lliey contain nitrogen; those that do not contain oxy- gen are ordinarily volatile, while those with oxygen are non-volatile; they are very soluble in alcohol, ether and chloroform. Certain ones are dissolved by the hydr^carbides, which are now considerably used in the prepa..*ionof the alkaloids. Water does not dissolve any of the artihcial alkaloids, except those having a very low molecular weight, like ethylamine; this liquid, how- ever, dissolves codeia and narceia quite readily. With the exception of quinia and cinchonia, they turn fhe plane of a polarized ray of light to the left. They react like atnrnonia, or potassa, with vegetable 138 ORGANIC CHEMISTRY. II colors, and famish, with platinum bichloride, crystal- lizable double chlorides, little soluble and yellow in color. They combine equally well with auric and mer- curic chlorides. The natural alkaloids have ordinarily a bitter taste. Among their salts the sulphates, nitrates, chlorides and acetates are mostly soluble, while the oxalates, tartrates and tannates are insoluble. Tlie harmless character of tannic acid, and the in- solubility of the compounds formed by it, witli the al- kaloids, render tannin and astringent vegetable sub- stances generally very efficacious antidotes. The precipitates they produce are soluble in acid and alkaline liquids. The alkaloids are partially precipitated from their solutions by potassa, soda and ammonia. Iodine water and solutions of iodine in potassium iodide, precipitate them completely. According to Schultze, the liquid obtained by add- ing antimony perchloride to a solution of phosphoric acid, is a re-agent which precipitates most of the or- ganic bases. A delicate re-agent for the alkaloids is the double iodide potassium and mercury. According to Meyer, the best proportions are 49 grams of potassium iodide and 136 grams of mercury dichloride, to 1 litre of water. It is best to add the re-agent to the solution of the alkaloid, which may be neutral, acid, or even feebly alkaline. It must be borne in mind that the presence of le, crystal- yellow in ic and mer- itter taste. , chlorides B oxalates, ind the in- nth the al- 3table snb- iu acid and from their Kline water precipitate id by add- phosphoric of the or- the doable ' to Meyer, iuin iodide 1 litre of le solution d, or even resence of NIOOTIiVA. 139 sugar, tartaric acid and of albumen may mask the reac- tions ot a number of alkaloids. NICOriNA OB NIOOTYIJA. ^,f \'r '°!u' ""^^^'"^^ ^'■^'" ^^^'^ i^^icofina taba- ^m for this purpose a decoction of tobacco is made, and the hquor evaporated to a syrup. The extract is t^ated with twice its volume of 86 per cent, alcohol, which precipitates the salts present and certain organ! ic substances. ^ 8„hm?.f S''.^''"' "^^""'T '' ^'''^^'^ ^"d *h« residue submitted to a second similar treatment. The alco- tiated solution of potassium hydrate, and the nicotina .barated is re-dissolved in ether. This ethereal solu- S-nT^'^'^'^'.^J" * ^**^'' ^**^'«"d the residue distilled m an oil bath, in an atmosphere of hydrogen Nicotina IS a colorless liquid when pure, remaining liquid at -lOo, boiling at about 246», with decomposf tion. It has the odor of an old pipe. Exposed to the air It becomes brown, then resinous; water, alcohol Kicotina is a powerful base; it fumes when a rod moistened with hydrochloric acid is brought near if It precipitates the metallic oxides, l^icotina requires two molecnles of a monobasic acid for satumtion. The chloride, C.oII„N,i{IIci, is erystallizable, though 140 ORGANIC CHEMISTRY. deliquescent. The hydrogen it contains is not replace- ible by methyl, ethyl, etc. It may be considered as having the rational formula, ^M(05H.)'"; (C5H7)' ' ' being the compound radicle niootyl. Proportion of nicotina in different tobaccos : Havana, Maryland, Virginia, Lothringen, 2.0 per ct. 2.3 « 6.9 « 8.0 « (Schloesing.) TOI8ONINO BY TOBACCO OB BY NICOTINA. The injection of a concentrated decoction of tobacco, causes serious results in a few minutes : intense head- ache is pi-oduced, with nausea and vomiting, violent pain in the abdomen, pallor, and, finally, extreme prostration. An infusion of tea, unroasted coflfee, or any astring- ent substance (pulverized nut-galls, or oak-bark) are the only antidotes known, and they are far from being wholly reliable. The pure nicotina is one of the most dangerous poisons. It manifests itself immediately on being taken, since it is entirely soluble in water. The nervous system is especially affected. Two or three drops sulfice to cause death. ot replace- isidered as tyl. 508 : !r ct. u loesing.) NA. of tobacco, tense liead- ng, violent y, extreme CONIA. 141 f my astring- k-bark) are from being - danfijerous r on being 1 Two or Two drops introduced into the throat of a dog A\-ill ahnost instantaneously canse the following series of symptoms: respiration becomes difiicnlt, the animal staggers, falls without the power of rising again, throws the head back and, in a few moments, is perfect- ly paralyzed, and death ensues. PIPEEIDINE. There has been obtained from the pepper ( Piper longum, Piper nigrum or Piper caudatum\ a body crystallizing in colorless prisms c&Wed pipenne, whose fovmula is CnHisNOs. It is a neutral substance. Wlien distilled with three times its weight of soda- lime it furnishes piperidine, a limpid liquid having the taste of pepper, and also its odor, soluble in water and alcohol, boiling at 106°. Tliis body is alkaline and saturates acids. It con- tains a single atom of hydrogen replaceable by methyl, ethyl, etc. OONIA, CONYLIA. OB CONINE. This body is obtained from hemlock {Conium mac- vlatvm); the crashed seeds are distilled in a large glass retort, with a solution of potasga, or soda^ whereupon an alkaline distillate is obtained. The distilled product is treated with a mixture of two parts of alcohol and one 142 ORGANIC CHEMISTRY. part of ether, which dissolves the sulphate of conia and leaves the insoluble sulphate of ammonium. The ethe- real alcohol is separated by distillation, potassa is added to the residue, and the mixture distilled. Water and conia pass over; the latter is dehydrated with po- tassa, and rectified in vacuo, or in a curretit of hydro- gen gas. Conia is a colorless, oily liquid; emitting an odor of hemlock. Water dissolves it but little, and this better when cold than warm. It is very soluble in al- cohol and ether. It boils at about 210°, yet emits var pors even when cold, for if a glass rod, moistened with- hydrochloric acid, is brought near it, white fumes are produced. It is a monacidic base, voiy alkaline, and forms crystallizable salts. One of its atoms of hydro- gen is replaceable by ethyl or methyl. This base is very poisonous. According to Christi- ason, ten ceTitigrams would suffice to cause death. It is classified among the narcotics; its action is charac- terized particularly by its effect on the organs of respi- ration and the left ventricle of the heart. ALKALOIDS OF THE PAPAVEBAOE^. The seeds of the poppy {Papaver somniferum) yield, on incision, a milky sap, which dries up in a day or two ; this sap, when solidified, constitutes opivm. There are three leading varieties of opium : I. Opium of Smyrna is found in small cakes of 100 to 160 grams, frequently distorted and agglutinated together by reason of their soft nature, and contain 7 OPIUM. 143 'coniaand The ethe- la is added ^ater and with po- of hydro- » an odor and this ible in al- emits va- enedwith* runies are %line, and of hydro- Christi- ith. It is 8 charac- 8 of respi- to 10 per cent, of water. The snrface is brown, but the interior has a fawn color. Sometimes it is found to contain 14 to 15 per cent, of morphia, but in other in- stances only 6 to 6. Good Smyrna opium should con- tain not less than 10 per cent. II. The opium of Constantinople is drier than the preceding. It appears in commerce in flattened, irreg- ular cakes, almost always surrounded with poppy- leaves. It contains 5 to 10 per cent, of morphia. III. The opium of Egypt is still dryer ; it is rarely enveloped in leaves. Its odor is feeble, and it contains ho more than a to 7 per cent, of morphia. Eecently, attempts have been made to cultivate the poppy in Europe, especially in France. Opium contains the alkaloids morphia, codeia, the- beia, papaverine, opianine, narcotine and narceia, an acid combined with these alkaloids called meeonio acid {from firjMcov, a poppy), a crystallized neuti'al substance called meconine, wliich, according to Berthelot, is a complex alcohol, and finally, various gummy and resin- ous compounds. niferum) ) in a day 8 opium. cakes of lutinated contain 7 MOBPHIA OR MORPHINE. Ci:II,9N()3, H,0. Preparation. Ten kilos, of opium are treated re- peatedly with water, and the liquors evaporated to the consistency of a syru o. The mass is redisso'ved in water, filtered, and again evaporated. To the Likewarm liquid are added 1200 144 OKGANIC CHEMISTRY. I iii grams of anhydrous calcium chloride, dissolved in twice its weight of water. A complex precipitate is formed, containing resins, coloring matters, and sul- phate and meconate of calcium, which is thrown upon a filter. The filtered liquid is evaporated over a water-bath. During the concentration, a fresh quantity of meconate of calcium is separated by filtering, and the liquid evaporated to the con?istency of syrup. The liquid is then acidulated with a small quantity of hydrochloric acid, and set aside in a cool place. At the end of a few days, it contains brown crystals of the double chlorhydrate of morphia and codeia, con- taminated with a blackish liquid; these crystals are drained, pressed, and again dissolved in as little boil- ing water as possible. The chlorhydrate, on cooling, deposits crystals, which are again dissolved in hot water and decolored with animal charcoal. After heating to SO" or 85", the solution is filtered, and the liquid, on being concentrated, deposits the double chlor- hydrate in pure white crystals. This salt is again dissolved in boiling water, and the hot liquid treated with ammonia ; the codeia remains in solution, while the morphia is precipitated. This deposit is thrown upon a filter washed with cold water, dried, and dissolved in boiling alcohol ; the morphia separates out in crystals on cooling. It frequently contains some narcotina, from which it is freed by washing once or twice with ether, or chloroform, which dissolves the narcotina, and does not affect the morphia. MORPHIA. 145 dissolved in precipitate is ers, and buI- thrown upon i water bath. / of ineconate d the liquid The liquid is hydrochloric ■own crystals I codeia, con- crystals are as little boil- (, on cooling, olved in hot •coal. After ired, and the double chlor- ater, and the ieia remains tated. This 1 cold water, the morphia from which th ether, or a, and does Pure morphia, (from Morpheus, in allusion to its nar- cotic qualities,) crystallizes in regular prisms witii a rhombic base, is colorless, soluble in 500 parts of boil- ing water, scarcely soluble in cold. Forty to forty-five parts of cold 90 per cent, alcohol are required to dis- solve one part of morphia; it is insoluble in ether. Solutioiis of morphia are very bittei'. Morphia is little soluble in ammonia, while it is dis- solved very readily by alkaline solutions, and even by lime water. Under the action of heat, it fuses in its water of crystallization, the latter escaping, and the alkaloid re- crystallizes on cooling. Morphine is an energeti'* reducing agent, reducing gold and silver salts, setting free the respective metals. It separates the iodine from solutions of iodic acid. If a solution of starch is poured into a test-tube, and a solution of iodic acid and traces of morphia added, the blue color of iodide of starch appears. If morphia is put into a few drops of a concentrated and slightly acid solution of a ferric salt, a beautiful blue color is produced, wliich subsequently changes to green. Morphia, moistened with nitric acid, is colored orange-red, which rapidly changes to yellow. These four reactions are chanvcteristic of morphia. Tf iodine and morphia are mixed in equal propor- tions and the mixture treated with boiling water, a brown liquid is formed which deposits a reddish-brown jiowder called iodomorphia. Morphia fused with al- 146 OKGANIO CUKMISTKY. kalies yields niethylamine. (p. 127). It is attacked by ethyl iodide at 100°, a single molecule of ethyl entering into the group. Morphia forms crystallizable salts, from the solutions of which it is precipitated by the fixed alkalies. Chlokhydbate of moephia, CnHijNOsHCl+sn^O. To prepare this salt, 100 parts of pulverized morphia are treated with a little warm water, then hydrochloric acid is added in sufficient quantity to dissolve the al- kaloid. The solution is afterwards evaporated in a water bath until it crystallizes. This salt is soluble in 20 parts of cold water, very soluble in alcohol. It is the salt of morphia most used, and contains 76 per cent, of morphia. Sulphate op morphia, (C„H,oNOs)jH2S04+6H20 js prepared like the preceding salt, which it resembles in appearance as well as in properties. Moi-phia and its salts are used in very small doses, as in larger doses they are energetic poisons. CoDEiA, CjgllaNOgjIIaO. Discovered in 1832 by Robiqnet. This base, whose name is derived from x^d^ poppy head, exists in the ammoniacal solution obtained in the preparation of morphia. On evaporation the ammonia is driven off and the codeia is precipitated by pot«?sa. Tlie codeia is at first precipitated in the form of a sticky mass which soon becomes pulverescent. It is washed with and dissolved in hydrochloric acid. The liquid is then boiled with washed animal charcoal, and the codeia precipitated with potassa. NABCOTINA. 14T is attacked by ule of ethyl the sohitions Ikalies. sHCl+SHjO. ized morphia hydrochloric solve the al- porated in a water, very lorphia most a. I2SO4+6H2O it resembles small doses, as. i base, whose exists in the eparation of is driven off The codeia sticky mass tvashed with quid is then i the codeia Codeia is crystalline, very soluble in alcohol and ether. It dissolves in 80 parts of cold and in 20 parts of boiling water. Codeia is very soluble in ammonia, and nearly in- soluble in potassa. With chlorine, bromine and ni- tric acid it forms products of substitution. With iodine it furnishes ruby-red crystals, whose formula ia C,8H,iN0aI. Codeia is somewhat used as an anodyne. It is easily distinguished from morphia, since: I. Codeia is soluble in ether and ammonia. II. It is insoluble in solutions of potassa. III. It does not reduce iodic acid or feme salts. IV. Citric acid does not impart to it any color. NARoariNA, C22H2SNO7. Karcotina crystallizes in rhombic prisms. It is al- most insoluble in cold water, somewhat soluble in alcohol, quite so in etlier. It fuses at 170°, and is decomposed before reaching 200°. Dilute nitric acid transforms it into various products of oxydation, the most important of which are meconine^ eotarnine and opianio acid Narcotina unites with acids, but the compounds are decomposed on evaporation. It is distinguished from morphia in that it does not reduce iodic acid and ferric salts, and from codeia in giving with nitric acid a blood red coloration. This substance is also insoluble in potassa and ammonia. It is not as poisonous as morphia. 148 ORGANIC CHEMISTRY. THEBAIA. This alkaloid, sometimes called paramorphia, is the most poisonous of the bases of opium. It is crystallizable, insohible in water, soluble in alcohol and ether. Fuming nitric acid attacks it in the cold, and a yellow liquid is obtained, which be- comes brown on contact with alkalies, and which dis- engages an alkaline vapor. Concentrated sulphuric acid gives it a red hue. PAPAVERINE. This body is crystallizable, insoluble in water, quite soluble in boiling alcohol and ether. It forms crystal- line salts. Under the action of strong sulphuric acid it as- sumes a deep blue color, though Hesse and Drag- eiidorff have recently ascertained that when absolutely pure no color is obtained, the ordinary article found in trade not being pure. NARCEIA. C,3H.«N0b. This alkaloid crystallizes in silky needles, insoluble in ether, soluble in alcohol and boiling water, little soluble in cold water. It forms crystallizable salts. OPIUM. 141^ lorphia, is the er, soluble in attacks it in ed, which be- nd which dis- .ted sulphuric Narceia fuses at 96°, and commences to decompose at about 110°. It is attacked in the cold by concentrated sulphuric acid, a red liquid being produced which rapidly becomes green, especially if slightly heated. The best means of distinguishing narceia is to cause a solution of iodine to act upon the pulverized substance. According to Roussin, the operation is most easily per- formed with one part of iodine and two parts of potas- sium iodide dissolved in ten parts of water. A blue color is produced, which disappears on coming in con- tact with alkalies, or on heating. 1 water, quite forms crystal- ic acid it as- se and Drag- len absolutely article found lies, insoluble water, little :able salts. PIIYSIOIXKJICAL ACmON OF OPIUM. NAECXDTIC POISONS. Opium in small doses is a very highly-prized ano- dyne. Continued use of this substance produces a peculiar state of inebriation, an excited sleep and hal- lucinations of various sorts. The bodies of ojiium-eaters are lean and cadaverous^ their eyes are lustrous, their forms bent; their appe- tite diminishes, and they exist only by increasing the dose of the poison wliich destroys them. In larger doses it is highly poisonous, and acts in a different manner from that of the poisons already studied. It may be considered as the type of the narcotic poisons. It is not unfrequently used for criminal purposes, and the imprudent administration of laudanum and other solutions of this substance often causes serious effects. Claude Bernard has made a careful study of the ac- tion of the various alkaloids ol' opium upon the system, 150 OBOANIO CHEMISTRY and has tabulated their soporific, toxic, and convulsive actions as follows : Toxic. Thebeia, Codeia, Papaverine, Narceia, Morphia, Karcotina. ConTnUlve. Thebeia, Papaverine, ^arcotina, Codeia, Morphia, Karceia, Soporific. Narceia, Morphia, Codeia. With- ont action. Those at the head of each column are the most marked in the respective characteristic action. Subjoined are tabulated the principal chemical characteristics of the opium alkaloids : Uorplii*. Codeia. Narcotina. Tliebeia. Papaverine. Narceia. WATIB. ALCOHOL. Bat little sol- ubia. Soluble. Inaolnble. Insolnble. Insolable. Sliglitl \j eorblo Quite lolable. Very soluble. Soluble. Soluble. Soluble. Soluble. WtBMIL. AXMOHIA. Almoit inaol- uble. Very soluble Soluble. Soluble. Soluble. Inaolable. Nearly insol- ublo. Soluble. Inioluble. Insoluble. Insoluble. Insoluble. QUINIA. 161 nd convulsive QFINIA OR QUININE. C»H.«N,0^3HjO. Soporific. Narceia, Morphia, Codeia. with- ont action. are tlie most ition. >al chemical AXMOHIA. Nearly insol. uble. Soluble. Iniolablei Iiuolnble, luolable, Iniolable. !d in 1820 by Pelleti'ar "a the modem proct This alkaloid was "isr and Caventou. Thr '!owi> by which it is prepared. Yellow Peruvian bark is carefully pulverized and thoroughly mixed with 30 per cent, of its weight of lime, pi-eviously slacked. The mass is then lixiviated three or four times with refined petroleum (petroleum ether) or amylic alcohol, (wood spirit) which dissolves the alkaloids. Nearly inaolnble. Insolnblo. Ineolnble. MrTBIO ACID. BULPBUBIO ACIV. Orange-red color- ation. Orani^e-red color- ation, Blood -red color- ation. Yellow coloration. Colored violet on heating with di- late acid. Colored violet on heating with di- lute acid. Tellow coloration. Red coloration. Dark-blae color- ation. Red color, which becomes green. IODIC ACID. Reduced. la not reduced. Is not reduced. 153 ORGANIC CHEMISTRY The united extracts are agitated with water, acidu- lated with sulphuric acid, making the liquid only sh'ghtly acid. When the solution is completed, animal charcoal is added, and the liquid brought to boiling, filtered while still hot, and allowed to cool. The quinia sulphate which is formed, 2iC.^E^-N^0,), H^SO^-f 7aq., being but slightly soluble, is deposited on cooling. After being allowed to stand 24 hours, the sulphate is collected, expressed and redissolved in as small a quantity of water as possible, containing a few drops of sulphuric acid. The liquid on cooling, deposits crystals, which are dried at 35°. The mother liquors are treated with ammonia, or sodium carbonate, which precipitates a certain quantity of the alkaloid. The precipitate is lightly washed with water, redissolved in dilute sul- phuric acid, boiled with washed animal charcoal, and allowed to cool. A second crop of crystals of quinia sulphate is thus obtained. The mother liquor contains cinchonia sulphate. This sulphate is dissolved in 30 times its weight of boiling water, allowed to cool, and a slight excess of ammonia added. The cinchonia which is precipitated is collected on a filter, and washed with lukewarm leater until the filtmte no longer gives with barium chloride a white precipitate insoluble in acids; it is then dried at a temperature of 30° to 40°. Quinia is white, amorphous and very friable. It I SULPHATES OF QUINIA. 153 I water, acidii- 3 liqaid only lal charcoal is , filtered while linia sulphate ,-f7aq., being ng. , the sulphate n as small a ; a few drops Is, which are treated with )recipltate8 a precipitate is n dilute sul- charcoal, and als of quinia juor contains (solved in 30 [ to cool, and collected on er until the iride a white I dried at a friable. It may be obtained in a crystalline condition, by adding an excess of ammonia to a dilute solution of quinia sulphate, and allowing the solution to stand. This crystallized quinia melts at 57", losing its water of crystallization, solidifies and remelts at 176°. It requires 250 parts of boiling and 460 parts of cold water for its solution. It dissolves in 2 parts of boiling absolute alcohol, 2 parts of chloroform or 50 to 60 parts of ether. Its solutions are very bitter, levogyrate, and for the most part .fluorescent. Heated on platinum foil, quinia swells up and in- flames, leaving a deposit of carbon. Heated with po- tassa it produces hydrogen and quinoleine; (cinchon- lein); it also furnishes a brown compound on being triturated with iodine. Quinia is recognized by the following reactions. It is first saturated with very dilute sulphuric acid and chlorine water; then an excess of ammonia is added, whereupon a green color is obtained. On adding powdered potassium ferrocyanide before the aqua ammonia a rose coloration is produced, which afterwards becomes dark red. Quinia has a basic reaction; it forms with acids crystallizable salts from which the alkalies precipitate quinia. It is a base which saturates two molecules of a monobasic acid. ScLPHATKS OP Quinia. Two sulphates of quinia are known; that obtained by the process we have above 154 OBOANIO CHEMISTBr. described, is the neuti-al sulphate, though generally known as the basic sulphate. Its formula is SCjoHmNA-H^SO.+TIIjO. This salt contains 74.3 per cent, of quinia. It crystallizes in very delicate needles l)elongiiig to the clinorhombic system, and which effloresce in dry air. It dissolves in 30 parts of boiling and 740 parts of cold water; also in 60 jmrts of cold absolute alco- hol. It is very nearly insoluble in ether. Its solu- tions are extremely bitter. It l)econie8 phosphorescent on l)elng heated, and subseqiiently fuses. Heated in the air it burns, leaving a carbonaceous residue. On adding quinia to water acidulated with sulphuric acid, it rapidly dissolves and another sulphate, often called the acid sulphate, is formed, whose formula is It is on account of the difficult solubility of the pre- ceding salt, and the great solubility of this latter one, that we cautioned against the employment of an excess of sulphuric acid in the preparation of quinia. This salt dissolves in 11 parts of water at 12°, and in 9 parts at 18°. Sulphate of quinia, heated to 130° with acidulated water for several hours, is transformed into an isomeric dextrogyrate base called quinieine, which is likewise a febrifuge. Medicinal sulphate of quinia always contains sulphate QUINIA. 15t ^h generally b IS tna. )elongiiig to resce in dry id 740 parts )8olnte alco- •• Its solii- •sphorescent arbonaceoQs tl) sulphuric pliate, often formula is r of the pre- 8 latter one, of an excess inia. at 12°, and ited to 130° transformed quinioine, ins sulphate of cinchonia, and its presence is not considered fraudu- lent, even when it contains 3.5 per cent, of the latter substance, as this salt is necessarily produced in the preparation of quinla. Cinchonia appears to be of Uttle therapeutic value, and is often added to sulphate of quinia. This adulterant is detected by weighing out 0.5 grams of the salt, and adding to it 5 grams of ether The mixture is agitated and 1.5 grams of concentrated ammonia added. If no cinchonia is present, two liquid layers are obtained ; if it is present, a layer of this al- kaloid is formed directly above the ammonia. Good commercial sulphate of quinia should give only a very thin layer. ^ The amount of quinia may be directly determined by decanting and evaporating the ethereal solution and weighing the residue. This result may be verified by replacmg the ether in another determination, by chloroform, wliich dissolves both bases; the residue obtained by the evaporation of this liquid furnishes the weight of the quinia and cinchonia together. Sulphate of quinia sometimes contains sulphate of quinidia; this base is precipitated, together with cin- chonia, by ether. Its presence may be detected by dissolving one gram of the sulphate in 30 grams of boihng water, and adding to the solution ammonium oxalate. Oxalate of quinidia, which is the only soluble oxalate of these bases, remains in solution, and, on fil- tering, a bitter liquid will be obtained, in which the quinidia may be precipitated by ammonia. 156 OROANIO CHEMISTRY. In case sulphate of quinia has been adulterated with calcium sulphate, or other inorganic substance, it may be recognized by a residue which will be obtained on heating the sulphate to redness on platinum foil. Sulphate of quinia sljouid dissolve in 80 per cent, alcohol. If it dissolves in water, but does not dissolve in r.6 per cent, to 60 per cent, alcohol, it may be re- garded as not pure. If adulterated with starch, or fatty bodies, a clear solution cannot be obtained, even in very large quanti- ties of water. Should it contain sugar it will emit an odor of caramel on ignition, and blacken in contact with sul- phuric acid. Quinia sulphate to which salicin, a common adulter- ant, has I Jen added, is colored red by sulphuric acid. Quinia sulphate is chiefly employed in cases of in- termittent fevers. CINCHONIA OB CINCHONINE. . CaoIIaiNjO. Cinchoniawas discovered by Duncan in 1803, though first recognized as an oiganic base by Pelletier and Caventou in 1820. It differs from quinia in containing one atom less of oxygen ; it has never been converted into quinia. It is prepared in the same manner as quinia, but :erated with mce, it may )btained on Ti foil. iO per cent, not dissolve may be re- lies, a clear irge quanti- an odor of 3t with sul- lon adnlter- ' sulphuric iases of in- 303, though jlletier and item less of [uinia. qninia, but CINCHONIA. 167 from the Gray Peruvian Bark. Ciiichonia separates out in crystals on the evaporation of the alcohol with wiiich the calcic precipitate is M'ashed. The crystjils of cinchonia are collected, allowed to drain, and the liquid which runs off will furnish addi- tional crystals on being evaporated. To this mother liquor sulphuric acid is added in excess, and the solu- tion slightly evaporated. The first crystals obtained are sulphate of qt nia, which is leas soluble than sulphate of cinchonia. When nothing remains but a very concentrated mother- liquor, the cinchonia is precipitated by ammonia, a.d freed from quinia by washing with ether. The quinia dissolves, while the cinchonia remains insoluble. The latter crystallizes in brilliant colorless crystals, which are insoluble in cold water and ether, soluble in 2,500 parts of boiling water, in 30 parts of boiling 90 per cent, alcohol, and 40 parts of chloroform. Its solutions are very bitter and dextrogyrate. Cinchonia melts at about 257°; on heating to a slightly higher temperature in a current of nitrogen, or hydrogen, it is completely sublimed. "With chlorine and bromine, it furnishes dichloride and dibromide of cinchonia. With iodine, a yel- low crystalline body is obtained, whose formula is Heated with fused potassa, it produces qumoleine. Cinchonia has an alkaline reaction. It ur»' j> rith acids, forming salts which correspond to the suits of quinia, though generally more soluble. 158 ORGANIC CHEMISTRY. Cinchonia sulphate, heated to about 136°, furnishes the sulphate of an isomeric alkaloid, cinchonieia or cinchonicine. Cinchonia is employed as a febrifuge in Holland, and a few other countries, but its action is regarded as in- ferior to that of quinia. QuiNoiDiNE.— ^?/mw?«a is a base obtained from the last mother-liquor in the preparation of quinia, by precipitation with sodium carbonate. It is olten min- gled with another alkaloid, cinohonidia or cinchoni- dine, and it is this mixture, containing chiefly quinidia, which is called quinoidlne in commerce. Quinidia is isomeric with quinia; it melts at 160". It is difiicultly soluble in water, very soluble in boil- ing alcohol, and slightly soluble in ether. Its solutions are dextrogyrate. Quinidia acts as a iebrifnge. With chlorine and ammonia, it gives the same reactions as quinia, and forms corresponding salts. Quinoidlne contains, as we have said, cinchonidia, a substance isomeric with cinchonia. This body is crys- talline, fusible at about 150°, almost insoluble in water, slightly soluble in ether and chloroform ; boiling alco- hol is the best solvent for cinchonidia. STKYOJINIA. 159 ^36°, furnishes inchonieia or Holland, and egarded as in- iiied from the of quinia, by t is otten min- or cinohoni- iefly quinidia, melts at 160". uble in boil- Its solutions ifnge. With ! reactions tis inchonidia, a body is crys- ible in water, boiling alco- ALKALOIDS OF THE STRYCHNOS. The two chief alkaloids are strychnia and brucia. Desnoix extracted from the nux vomica another alka- loid, which he named igasuria; but according to Schutzenberger, this body is a mixture of several bases. Tliese alkaloids are extracted from the fruit of the Strychnos nux vomica ; from St. Ignatius' beans, fruit of the Strychnoa Ignatii ; from the wood of Coulevre, root of the Sirychn^s eoluhrina ; from the upas, the poison of indi'an arrows, extracted from the Strychnoa tieute; from the False Angiistura Bark, and the bark of the Strychnoa nux vomica, which contains princi- pally brucia. KTRYOHNIA. C,,II.^NA. Nux vomica is pulverized and boiled with three suc- cessive portions of water containing sulphuric acid, and these decoctions evaporated in a water bath. When the liquid is reduced to a small volume, 126 grams ot quicklime slacked to a thin paste are added for each 160 OKQANIO CHEMISTRY. kilo, of mix vomica. The precipitate is collected on a cloth, waslied, dried, and treated with 90 per cent, al- cohol. The alcoholic solution is distilled to three-fourths its volume and left to crystallize. The crystals obtained are chiefly strychnia ; these are allowed to drain, then dissolved in water containing ^ its weight of nitric acid, and the sohuion concentrated in a water bath. The nitrate of brucia remains dissolved and the nitrate of strychnia crystallizes ont. These crystals are re^lissolved in water, animal charcoal added, the solution brought to boiling and then filtered. Ammonia is added to tins liquid, the precipitate washed, dried, and dissolved in boiling alcohol, which deposits the alkaloids on cooling. This method is at present very advantageously sup- planted by the process given for the production of quinia, which, briefly stated, consists in treating the sub- stance with lime directly and employing a solvent for the alkaloids, which is insoluble in water, such as petro- leum or amylic alcohol. Strychnia crystallizes in octahedrons or in prisms of the rhombic system; they are colorless, very bitter, and almost insoluble in water or ether, but readily soluble in ordinary alcohol diluted with 15 per cent, of water. Strychnia treated with potassa furnishes a small qnan- ti ty of quinoleine. lod ide of ethyl produces wi th this base the cx)inpound BBUOIA 161 sollected on a per cent, al- Be-fonrths its tals obtained drain, then ?lit of nitric ater bath, v^ed and the lese crystals 1 added, the ed. I precipitate johol, which ^ously snp- •oduction of tingtliesub. I solvent for ich as petro- in prisms of y bitter, and idily soluble it. of water, small qnan- es with this CaHa(CjH5)NaOJ. Chlorine gas renders even a dilute solution of this alkaloid turbid and the liquid becomes acid; this reaction is characteristic. Bromine also forms deri- vatives by substitution. Iodine combines directly with the molecule of strychnia. Strychnia dissolves in strong sulphuric acid; the so- lution is colorless and becomes dark blue in contact M'ith potassium bichromate or lead dioxide. The color rapidly passes to red and finally to a yellow. Strychnia is colored yellow by hydrogen nitrate only when it contains brucia, a trace of which is suf- ficient to produce the change. Strychnia forms with acids crystallizuble salts. Tlie nitrate CaJIcNA.HNOs crystallizes in fine needles \cry soluble in hot water. Strychnia is among the most powerful poisons, 2 to 3 centigrams being sufficient to canee death. There is believed to be no reliable antidote for strychnia though F. M. Peirce claims that small doses of prussic acid are efiicient for the purpose. (44-'68-336.) BEUCI.V. Ca3H»IfA,4n,0. To obtain this alkaloid the alcoholic liquids from which strychnia has been i-emoved, are saturated with oxalic acid and evaporated. The crystals of oxal- Ate of brucia which are formed, are washed with 95 per 163 ORGANIC CHEMISTRY. cent, alcohol and redissolved in water. The solution is decomposed by lime, the precipitate collected, dried and dissolved in boilujof alcohol; brucia then crystal- lizes out and is purified by two recrystallizations. Crystals of brucia are large and of the clinorhombic system; they are solnble in alcohol, insoluble in ether, but soluble in 850 parts of cold, or 600 parts of boil- ing water. Concentrated sulphuric acid strikes a rose color with brucia which afterwards changes to green. ]Sitric acid colors it red, and if heated it gives off nitrous ether, methyl alcohol and carbon dioxide. Brucia is much less poisonous than strychnia. It may be distinguished from strychnia by its reac- tion with nitric acid. A red color is produced by brucia, which passes to violet on the addition of stannous chloride. This latter coloration does not take place with morphia. Brucia is also one of the best reagents for nitric acid. CcKAEiNA.— From the arrows of the Indians living on the shores of the Amazon and Orinoco, a brown resinous matter is collected, from which ciystais of a substance have been obtained whose poisonous action is exceedingly rapid. Preyer, to whom we owe this discovery, regards its formula as C.oHjsN, and has named it curarina. Tlie Indians of Dutch Guiana poison their arrows with two other substances no less dangerous: tirari and tikunm. These three substances paralyze the ac- tion of the muscles by destroying the motor nerves VKRATRIA. 163 Tlie Bolution llected, dried then crystal- sations. jlinorhombic ible in ether, parts of boil- 86 color with ^ itric acid itroua ether, chnia. by its reac- produccd by addition of ation does 30 one of the dians b'ving CO, a brown I'ystais of a tions action '6 owe tills ^, and has icir arrows oils: tirari lyze the ac- ►tor nerves- (Claude Bernard). It appears that urari, though a fa- tal poison when introduced into the blood by a wound, may yet be swallowed with impunity. DEASnO POISONS. We shall not describe the preparation of the follow- ing alkaloids, on account of their minor importance. The process in general is similar to tliat by which the preceding ones are prepared: The alkaloid is dissolved in an inorganic acid, precipitated by a base, and redis- solved in an appropriate solvent. The roots of the white hellebore ( Veratrum album) and its seeds, furnish an alkaloid called veratria^ C32H53N2O8. It crystallizes in prisms having a rhom- bic base. Tliey are very bitter, insoluble in water, soluble in alcohol and ether, and melt at 115°. Yera- tria is dissolved by strong nitric acid, the solution be- ing violet Sulphuric acid colors it first yellow, then red. Three other poisonous bases, mhadilUa^ eolchinia, and jervia, are found ass«jciated with veratria in the Veratrum album. Jervia, C,>oHj8N2032H2(), (Ger- hardt and Wills' analysis) is white, crystalline and fusible. These bodies are very corrosive poisons, producing great irritation of the alimentary canal, ALKALOIDS OF THE rOISONOUS SOLANACK.K. The belladona, Atropa belladona, and the thorn- apple, i^a^ura «ve. In 1871 a crystalline repared, con- th 3 times its 8 two bodies, washed wilh >sed of these 3d by chloro- proportions, lia grown in 9 subject of Duffield, of t powerfully on. If digi- Lcid and then nes a purple ' to the pro- oduces with )r. to produce I. A niiHi- B, a marked ms produce EMETIA. 167 It ie much to be desired that physicians substitute this crystalline substance, which is invariable, for the amorphous digitalin, which varies greatly, both as to character and effectiveness. Tardieu places digitalin among the hyposthenic poisons. Poisoning by digitalin has often been produced through imprudence. The npm antinr, with which the Indians poison their arrows, is obtained from the Antiaria toxicaria. EMEtlA. This body is obtained from the roots of the ipecac- uanha, Cephcsles ipecacuanhxi; it also exists in the Richardsonia brasiliensia, in the Phaychtria emetica^ and in the roots of the Cainca (madder tribe). These materials, reduced to a nowder, are treated with con- centrated alcohol, and the alcohol then distilled off. The extract is diluted with five times its volume of water, and filtered. To the filtrate 2 per cent, of caustic potassa i- added, and this mixture agitated with chloroform. The chloroform is decanted and distilled ; the emetia crystallizes out. It is dissolved in dilute sulphuric acid, and precipitated from the so- lution with ammonia. A. Glenward (105 -[3] 6—201) gives CisHijjNOa as the formula of emetia. It is amorphous, yellowish, fusible at 50", soluble in water and alcohol. Its solutions are slightly bitter. It is a very weak base, and its salts are not crystalline. A few centigrams suffice to produce vomiting. 168 ORGANIC CHEMISTHY. f ■' CANTJIARIDIN is a very poisono.is crybtalline substance, obtained from bpamsh flies, {Lylta veslcatoria, and other varieties) and has tbe compo.«ition CHA- It is present in nearly all parts of the flies, va.-ying in amount from 5 to 1.2 per ce,.t. R AVolff has of late given this sub- stance a very full investigation. (95, May, '77-102.) CAFFEINE (cAFFEIa) OB THEINE (thEIa). C8HioN,02,H20. Alcohol is added to a mixture of 5 parts coflTee and 1 part slacked lime, until nothing further is dissolved, and the solution distilled. The residue is treated with water, which causes an oil to separate out The watery liquid fnrnishes crystals which are puri- faed by treating with animal chai-coal, and recrystal- lizing in hot water. The extractive matters of the Jcolamut and mate pos- sess the same properties as caffeine. Caffeine crystallizes in flue needles, fusible at 178° and is volatile at a slightly higher temperature. These crystals are but little soluble in ether and cold water yet dissolve very readily in alcohol and boiling water! It IS remarkal)le that the instinct of man should have led hmi to select, as tl;e bases of common bever- 'Jges, just the four or five plants, which out' of many thousands are the only ones, as far as we know, con- taining caffeine. THEOBROMINE. 1G9 ►btained from ber varieties) is preseHt in mnt from 0.5 en this 6ub- 7, '77-102.) eia). ts coffee and is dissolved, 5 is treated jparate out ;h are pnri- d recrystal- id mate pos- )le at 178°, ture. These cold water, iling water, nan should inon bever- it of many know, con- It is recognized b^' boiling with fuming nitric acid ; a yellow li(juid is produced. On being evaporated to dryness, and ammonia added to the residue, a purplo coloration is produced, i-esenibling murexide, (p. 125.) Amallo acid and CholestropJMn are jiroducts of the action of oxidizing agents u])on caffeine; bodies dik- ing this alkaloid to the uric acid group. THEOBKOMINE. There is extracted from th.e caco, Theohroina cacao, a principle crystallizing in microscopic crystals, volatile at 295°, soluble in alcohol and ether, and slightly so in water. It furnishes salts which are decomposed by water. It is called theohromine', its formula is CIL PICBOTOXIN. CsHsO,. From the Indian berry, Cocculus Indieits, there is extracted a white crystalline matter of extreme bitter- ness, called piGrotoxin, {fvom Tttxfx'n bitter roHixhv.) This body is neutral, difficultly soluble in water, and easily soluble in alcohol and ether; its solutions are levogyrate. The physiological action of picrotoxin is analo- gous to that of strychnia, but it differs from it in that it renders the action of the heart slower, and produces vomiting. Prof. J. W. Langley, of Pittsburg, has contributed 1 170 OKGANIO CHEMI8TUV. much to (87-1862) our knowledge of the chemical character of picrotoxin. POLTATDMIO ALKALOIDS. Iliei-e are polyatomic bases which are to the mona- tomic bases what polyatomic alcohols are to monatomic alcohols. They are built upon the type of several molecules of ammonia, or condensed ammoniii, in the same man- ner that polyatomic acids and alcohols are derived from several molecules of water. Cloez obtained the former by the action of ethylene bromide upon potassa dissolved in alcohol. Hoffmaim established their true formula. They are called polyaminea. EXAMPLE. Ethylenic diamine, K, Diethylenic " Triethylenic ( H, ^. C2H4 UREA. 0H4NjO=]^„ POLYATOMIC ALKALOIDS 171 the chemical to the mona- :o monatomic al molecnies e same man- are derived I of ethylene I. They are Eonelle, Jr., was the first to obtain this body in an impure state from urine. Fourcroy and Vanquelin first obtained it pure. Woehler, in 1828, prepared it artificially by a remark- able synthesis, the first attempt to form a body syn- thetically. Urea forms the chief constituent of the urine of mammalia, amounting to nearly one-half of the solid constituent; a small proportion of urea is found in all the fluids of the body. It is an excretory product, as the hydrogen and carbon which have taken their part in the body, escape mainly in the form of water and carbon dioxide, so the nitrogen is eliminated from the system chiefly in the form of urea^ Urea may be extracted from urine by evaporating this liquid to one-tenth its volume and adding, after it has become cold, an excess of nitric acid. Brown crystals of nitrate of urea are formed: these are drain- ed, expressed, resiissolved in water and boiled with animal charcoal. This solution is filtered, and on evaporation it deposits crystals of nitrate of urea. This salt is then dissolved in as small a quantity of water as possible, and the solution treated first with barium carbonate, then with a strong solution of potas- Slum carbonate; urea is set free and barium and potas- smm nitrates formed. The above mentioned salts are added as long as efifervescence is produced; the liquid IS then evaporated to dryness, and the residue treated with absolute alcohol, which dissolves only the urea (J. E. Loughlin, 100-5-362.) 172 ORGANIC CHEMISTRY The synthetic method employed by "Woeliler, con- sists in preparing cyanate of ammonia, which body is isomeric with urea. Cyanate of Ammonium=H4CN20=NH4-Q-CN. This substance changes spontaneously into urea. Heat, upon an earthen plate, 28 parts of potassium ferrocyanide and 14 parts of manganese dioxide, both finely pulverized, and dry until the mixture becomes pasty; when cold, the mass is pulverized and ti^eated with water, and 20 parts of ammonium sulphide added to the liquid, which is now evaporated in a water bath, and the residue treated with boiling alcohol. On evaporating the alcoholic solution, crystals of urea are deposited. Urea is also obtained as a product of other reactions. It crystallizes in prisms of the tetragonal system; these crystals are colorless, without odor, and have a cooling taste. It is soluble in its own weight of water at 15", in an equal weight of boiling alcohol, and in 5 parts of cold 80 per cent, alcohol ; it is difiicaltly soluble in ether. Its solutions are neutral. Urea fuses at 120"; at about 160° it is decomuosed, yielding ammonium carbonate, ammdidef CaOHgNj, and biuret, CjOaHsNj. ■ Oxydizing agents decompose urea. Chlorine also decomposes solutions of urea in the following man- ner: 3Cla + HaO + CH4NaO=6HCl+Na + C08 . Urea heated to 140° with water in scaled tubes, is transformed into ammonia and carbon dioxidf: UREA. 178 Woeliler, con- wliich body is ■ into urea. s of potassium dioxide, both xture becomes d and ti^ated •ulphide added 1 a water bath, alcohol. On als of urea are oduct of other ;he tetragonal lOut odor, and H2O + CH4N20=C03 + 2NPL This transformation likewise occurs when urea is heated with strong sulphuric acid, or fused with po- tassa, also, spontaneously, in presence of the nitro- genous matters of the urine. Urea does not appear to unite with all acids. It has not yet been combined with carbonic, chloric, lactic or uric acids. The nitrate, chloride and oxalate of urea are crystalline. Urea forms combinations with mercury, silver, and sodium oxides, also with mercuric and silver nitrates, etc. rat 15°, in an parts of cold ible in ether. decomposed, le, CsOHsN,, Chlorine also lowing man- fCOj. lied tubes, is oxidf; I 174 ORGANIC CHEMISTBY. NATURAL FAT8 AN^D OILS. Tlie fatty bodies are very widely distributed through- out the vegetable and animal Hngdoms. Some are liquid, others are more or less solid. Certain oils re- main liquid exposed to the air, as olive oil; others oxydize and thicken, as linseed oil, poppy oil, and nut oils; the latter are called negative oils, and are nsed in the manufacture of varnishes, printers' ink, oil cloth, also in paints. Fats and oils are insoluble in water; thev are among the very few bodies which are wholly insoluble in this menstrum; they are also, in general, difficultly soluble in alcohol. They generally dissolve in ether, and the liquid hydro-carbons. Their specific gravity is lesG than that of water. Heat destroys them; acrolein is usually formed associated with other products. Since oil and water repel each other, many other substances may be protected from moisture by simply coating them with oil. Shoe-leather may be rendered water-proof and iron protected from rusting by greas- ing. Wood, saturated with oil, will last for' a long time when buried in moist ground. Stearin ok Stearine, (from arkap, suet) Cj^HnoOe, IS prepared by melting suet in turpentine; the two other proximate principles present, are precipitated, FATS AND OILS. 175 S. ted throuarh- Some are ain oils re- oil; others py oil, and lis, and are •inters' ink, ' are among asoluble in , difficultly 'e in ether, ific gravity lly formed nany other by simply e rendered J by greas- for a long ; the two ecipitated, while the stearine remains in solution. It is separated from the liquid by water, and purified by several re- crystallizations in ether ; it fuses at 71", and solidities at 60°. Berthelot has reproduced stearine synthetically, by heating 3 parts of stearic acid with one part of glyc- erine, in a sealed tube. This synthesis, as well as other researches, estab- lishes the fact that the neutral fats are compound ethers of glyceryl, and the fatty acids. On account of the heat generated by oxidizable oils when exposed to the air, frequent instances of spontaneous combustion occur when cotton rags, or waste soaked with oil, are allowed to remain in a heap. Fats, especially if mixed with nitrogenous matter, become acid, rancid. The chemical nature of this change is not entirely understood. Olein or oleink, is the chief constituent of olive oil and fish oil. Berthelot has shown, by the action of oleic acid on glycerine, that natural oleine is a mix- ture of monoleiue, dioleine, and trioleine. Oleine heated with a small quantity of mercury nitrate, or any other body capable of furnishing nitric oxide, be- comes solid, owing to the transformation of the oloi);3 into an isomeric body, elaidlne. Siccative oils contai. ., instead of oleine, another principle called elaitie. Neutral fatty bodies and other ethers of glycerine are decomposed by alkaline solutions ; a combination with water takes place, glycerine and fatty j..:<'8 are formed. We may take as an example, stearin. p 176 ORGANIC CHEMISTRY. 3KHO+C5,TI„o06=2(KC,8H350,)+CaH803. AlkalieH, therefore, react upon the ethers of glycerine in the same manner as do the ethers of glycol and ordinary alcohol. This reaction is called sapnmficor tion, and soaps are salts formed by stearic, margaric, and oleic acids, with a metal. SOAPS. BIEARINE CANDLES. The only soluble soaps are those whose base is potassa or soda. Soda soaps, those ordinarily in use, are hard, while potassa soaps are soft. On adding to an aqueous solution of soap a solution of a metal, a precipitate is formed which is the soap of the metal emjiloyed ; thus the precipitate which common water produces in soap is a lime soap. Ordinary soap is made by boiling fats of inferior quality -.vith an alkaline solution. When the oil is completely decomposed the soap is precipitated by salt watei', in which soap is insoluble. Stoariiie candles have hitherto been made by saponi- fying suet or tallow with lime in the presence of boiling water. At present the amount of lime employed in the saponification is considerably diminished (amount- ing to only 4 per cent.) by operating at a temperature of 150-. The saponification of fats of inferior quality is also efff^cted by means of sulphuric acid instead of lime; this acid forms with the fatty acids, double or conju- tmmK3-- FATS AND OILS. 177 'sHgOs. of glycerine glycol and saponificor c, margaric, >8e base is irily in use, I adding to a metal, a ' tlie metal imon water of inferior the oil is pitated by by saponi- I of boiling iployed in i (amount- mperatiire lity is also of lime; or conju- gate acids, which are decomposed by water. The de- composition of fats into their constituents, the fatty acids and glycerine, for the manufacture of candles, is at present effected on a large scale by simply heating the fats with steam under pressure, and at a tempera- ture of 260°. This is the celebrated process of the American inventor, Tilghman, to whom the wonder- ful " sand blast " is also due. This decomposition of fats is most remarkable, as, by the same process, only at a lower tempei'ature, Berthelot obtained a result exactly the reverse, caus- ing stearic acid and glycerine to reform stearine by simple direct synthesis. Steajuo acid, OigrijoOa. is crystalline, insoluble in water, soluble in alcohol and ether, and melts at 70°. It unit-ss with the bases ; its alkaline salts alone are soluble. Mai{Gario ob Palmitio acid, C17H34O2, (from fxapyafjov, a pearl, owing to its pearly lustre) is crys- talline. It melts at eO'' and forms salts with the metals. Olkio acid, CigHsjOa, is an oil becoming colored in the air and converted into an acid callec elaidio acid., which is fusible at 44°, in contact with e s.nall qiiantity of hyponitric acid. These three a 'ids, stearic, margaric, and oleic, are those that, with glycerine, constitute most of the natu- ral fats, or glyceryl ethers, V Lead plasikr is essentially a lead-soap compound of plumbic oleate. 178 OKGANIO CHEMISTRY. OROTON OIL. This oil is extracted from the seed of the Croton tiglium of the family of euphorbiacese. The seeds are ground and expressed, or they are treated with ether, which is afterwards driven off by distillation. This oil is yellowish, very bitter, and possessee a disagreeable odor. Alcohol and ether dissolve it. It produces blisters whenever it comes in contact with the skin, and is a drastic poison. Pelletier and Caventou have extracted from this oil an acid body, C4H602, denominated orotonio acid. COD-LIVER OIL. This oil is extracted from the liver of the cod, and several other species of the genus Gadus. Two pro- cesses are employed for its extraction ; either tlie oil is obtained by putrefiactioii, in which case the oil separates out naturally, or the livers are cut in«o small pieces and heated in large pans, then placed in cloth sacks and pressed. It is of a brownish color. A white oil is sometimes sold, which has been bleached by treatment with weak lye and animal charcoal. The efficiency of this latter oil is much less than that of the natural oil. There has been found in this oil 3 to 4 tiionsandths of iodine, and a small quantity of phosphorous ; and its medical qualities are thought to be due to these P the Croton or they are riven off by possesses a solve it. It :'ontact with from this oil io aoid. he cod, and Two pro- ither the oil ase the oil t in?-o small ed in cloth •r. A white ileached by pcoal. The ban that of honsandtha irons ; and le to these WAX. m two snbstances, but it is probable that its efficiency is more frequently due simply to its fatty character. BUTITSB. Ordinm-y Butter. Butter contains stearic, mar- garic, oleic, and butyric acids, and several other proximate neutral principles. Its density is 0.82. It dissolves in 30 per cent, of boiling common alcohol. The odor which it emits on becoming rancid is due to the liberation of fatty acids. " Oleo-margarine'''' is artificial butter, consisting mainly of oleine and margarine obtained from suet or lard. SPEBMACErn. This substance which is formed in peculiar cavities in the head of the 6p3rm whale, and is a neutral fatty bofly sometimes employed in pharmacy. It is an etiier, which, on saponificntion, produces a fatty acid called ethalio acid, and a monatoraic alcohol, ethal. HaO+C3,He40,=C,eTl3,OHO + Cell^O Spermaceti. Bthaltc Acid. WAX. KllMl. Yellow bees-wax is obtained by Hi]l)mittiiig honey- comb to pressure, then fusing the sauie luider boiling water. It is bleached by being cut into tliin cakes and exposed to the air and sunlight. Thus prepared 180 ORGANIC CHEMISTRY ll I- It fuses at 62°. Mixed with 3 per cent, of oil of sweet almonds it forms a cemte, used in pharmacy On being treated with alcohol it separates into two proximate principles: one, soluble in this liquid, is acid a^d is called cerotio ao«f, having the formula C27H51O; the other, which is but slightly soluble is called myricin. The latter is a compound ether, and IS decomposed by bases into an acid, ethaUo acid, and an alcohol, melisaie alcohol, CaoHc^O. CASTOR OIL. This Oil is extracted from the Ricinm vommmcU, a plant of the family of Euphorbiacese. The castor-oil beans are hulled, pulverized, and tlie pasty mass obtained Bubjected to strong pressure. Ihis oil 18 slightly yellow. Its density is 0.926 at 12", a:id it remains liquid at a temperature of -IS » It is very soluble in alcohol, a characteristic which distinguishes it from most other oils. This oil is also an ether of glycerine; the acid which It contains is ricinoleic acid, G^^^O^. SUGARS. 181 It. of oil of pharmacy, ates into two lis liquid, is the formula 7 soluble, is )ounci ether, ethalio acid, 'ommitms, a t^erized, and tig pressure, is 0.926 at ire of -1S<*. ristic which acid which SUGARS. The general name of stigars, by some regarded as polyatomic alcohols, is given to bodies which are capa- ble of fermenting, tliat is, of decomposing directly or indirectly into different products, of which the princi- pal ones are alcohol and carbon dioxide. Fermenta- tion requires tlie presence of certain microscopic plants, and, according to Pasteur, is a phenomenon correlative witii the vital development of these organisms. This, however, has been latterly dis- proved by Tyndall. Sugars may be divided into three classes. In the first are those in which the proportion of hydrogen is more than sufficient to convert the whole of the oxy- gen into water. It contains : Mannite, CaH,,()fi, extracted from manna. Duloite or melampyrite^ CelluOs, found in Mada- gascar. Finite^ CglliaOs, extracted from a Calitbrnian pine tree. Queroite, CgHiaOs, extracted from acorns. These bodied do not fei-ment with beer yeast alone; but in presence of certain ferments and calcium car- bonate they furnish alcohol, carbon dioxide, and hy- drogen. Sugars of the second and third class contain hydro- gen and oxygL'n in the proportions to form water. 182 ORGANIC CHEMISTRY. The second class includes the glucoses, iso-^.^eric bodies, whose general formula is, C,H«0,. Among the'3e are: Ordinary Ghicose or grwpe mga/r. Zevulose, as.socii.red with glucose in the form of inverted sugar. Maltose, obtained fi-onj malt. Galactose, obtained by treating sugar of milk or gums, with dilute adds. ' IJucalin, obtained by the action of maltose on beer yeast. SorUn exists in the berries of the mountain ash. Inosite is foimd in the embryo of young plants and in the fluids of flesh. Lactose or Sugar of MUk. The glucoses may be divided into two series. The first includes those bodies (ordinary glucose, levulose) which, on being oxydized, form saccharic acid, and on being hydrogen ized by means of Podium amalgam, produce mannite. The secora includes those substances (galactose, lactose) wJr/ch, on oxydation produce mucic acid, and on hydro- ^i-enation furnish dulcite. The third class of su- gars contains bodies whose general formula is CijIIaOu, and are called saccharoses, by Berthelot. It contains, besides cane sugar, three bodies called: Melitose, an exudation of certain eucalypti. TreMlose or mycose., extracted from the Turkish manna and certain mushrooms. Melezitose, obtained from an exudation of the larch. The sugars r.f the first two classes are placed by Berthelot among the polyatomic alcohols. MANI^^ITE. 188 68, UOi'cOric Je- Among the form of of milk, or iose on beer tain ash. ►ung plants 368 may be hose bodies » oxjdized, genized by nite. The se, lactose) d on hydro- 1S8 of 8U- [t contains. •ti. le TurloBh ' the larch, placed by MANNITE. Cell^Oe. This body exists naturally in an exudation of vari- ous species of ash {Fraximia rotundlfolia), called inanna, of which it forms the greater portion. It is also found in mushrooms, algae, the sap of mopi fruit trees, onions, asparagus, celery, etc. It nin e pre- pared by dissolving manna in one-half it- ^-t ut water, to which a small quantity of e^g ]« added, and the mixture brought to boiling;, m , .oreu. On cooling, colored crystals are deposited which are expressed and redissolved in hot water. This solution is mixed with animal charcoal, boiled and filtered while hot. The liquid deposits crystals on cooling. Man- nite crystallizes in rhombic prisms and has a sweet taste. It dissolves in seven times its own weight of cold wa- ter, is slightly soluble in alcohol, and insoluble in ether. Its solutions are optically inactive. Mannite fuses at about 165°; at about 200° it yields a certain quantity of a substance called Mannitane, CjIIijOj. It oxydizes in presence of platinum black, fiirnishing a non-crystallizable acid called mannitio acid. Boiling nitric acid converts it into saccharic and oxalic acids. Mannite, treated with a small quantity of nitric acid, is changed into a body insoluble in water, called mtro-mannite, ^^"q «) 1 0«, which may be regarded as a compound ether. Buloite.—Dixlcite is very analogous to mannite, but differs from it, in that it furnishes, with nitric acid, raucic acid. a. T^^? 184 OKGAXIO CUE.MISTBY. GLUCOSKS. CeII,,0«. Tliese compounds may be considered as representa- tive carbohydrates. Ordinary glucose (from yXvnv?, sweet,) or grape sugar, isacrystalline substance, and is found in honey, tigs, and various other fruits, together with anotlier insoluble glucose. It has been found in small quantity in the liver and in most of the fluids of the body. It is obtained by the decomposition of sahcme, tannin, and other substances, which, for this reason, have been named glucosldes. Vegetable cellulose, the envelope of many inverte- brates (chitin and tunicin) and the glyeogenons princi- l)le of the liver furnish glucose on treatment with dilute acids. It is manufactur ,. on .i large scale by the action of starch upon diluto sulphuric acid. Water containing four to eight pi- cent, of sulphuric acid is placed in vats and heated to boiling by means of superheated steam. Before the water boils, starch mixed with water is added, and ebullition maintained as long as a small quantity of the mixture gives a blue reaction with iodine. The sulphuric acid is not changed during this transformation. It is then saturated with ehalk and the liquid allowed to become clear. It is decolored by passing through 3 representa- om yXvHvs, :ance, and is its, together en found in if the fluids nposition of ch, for this ■ny inverte- iions princi- raent with le action of containing phiced in nperheated lixed with s long as a e reaction ged during lid allowed g through I ,»£>...,.*» ■r^jgsgs^rtrs's-KHaKsffi'ffliEfisss!'; 5S«s**i!BS!^>S*^.-S* " V] ^ /a / ^^ IMAGE EVALUATION TEST TARGET (MT-3) 1.0 l^|2^ 12.5 |5o ■^~ M^H *^ 1^ III 2.2 "" !::: !!!!!2.o 1.1 l.'^H 1.8 Photographic Sciences Corporation 1.25 1 1.4 1^ < 6" - 1*- S' 33 WEST MAIN STREET WEBSTER, N.Y. 14580 (716) 872-4503 CIHM/iCMH Microfiche Series. CIHM/ICMH Collection de microfiches. Canadian Institute for Historical MIcroreproductlons / Instltut Canadian de microreproductions historiques 1 GLUCOSES. 185 filters containing animal charcoal and evapoi-ated to a density of 4V Bauine. The glucose crystallizes in compact masses. Often the liquid is evaporated to only 3° B., when a syriip is obtained kno\vn as starch aijrup. Honey treated with cold concentrated alcohol, also furnishes glucose. The crystals of glucose ai-e small, opaque, and ill defined. They are represented' by the formula C«H,jOe,2H20, bnt they may be obtained having the composition CeHiaOg by precipitating the glucose in boiling concen- trated alcohol. The water may also be driven off by heating the glucose to about 100°. Glucose is soluble in a little more than its own weight of water. Weak alcohol dissolves it readily. It is slightly soluble in cold concentrated alcohol. ^ Its solutions turn the plane of polarization to the right. This rotatory power is feeble in the cold. Glucose, heated to about 170°, acts in the same man- ner as mannite. Gelis has demonstrated that it loses a molecule of water; the body formed CeHioOs, is called glucoaane, CcMnO,=CMxo<\ + B.^O. It re- produces glucose on being boiled with acidulated water. If glucose is boiled with dilute nitric acid, saccharic and oxalic acids are formed. Fuming nitric acid forms with glucose a very explosive compound. Hydrochloric acid turns it brown. With dilute sul- phuric acid it furnishes a double acid {auiphoylucio acid)', with strong sulphuric acid, carbon. Glucose oxydized with care, fnrnishes saccharic acid. Heated to 100° with butyric, or various other acids, 186 ORGANIC CHEMISTRY. it loses water, and the glucosane formed reacts upon che acid, forming an ether, saccharide, or dibutyrio glucosane, (0«H«) (C4H;0)Hj [0. Tliis body, as well as other saccharides, are decom- posed under the action of boiling acidulated water, into an acid and glucose. Glucose combines, with sodium chloride, forming several crystalline compounds; it also forms unstable compounds with the metallic bases, CaC.H,oOe BaCeHiiOj, etc. P^ligot has shown that the solutions of these glucos- ates are gradually changed into salts of a special acid called gliudc acid, whose formula is Ci2H,g09. Cnpric acetate boiled with glucose is reduced to the state of suboxide. This action, which is very slow with salts of copper with inorganic acids, becomes rapid and complete in presence of alkalic ^r adding glucose to a solution of copper Bulpha**^ -s salt is not precipitated by potassa. If, however, the liquid is heated, it deposits cuprous oxide. (Trommer's test.) This reaction is more delicate with copper salts, whose acids are reacts upon or dihutyrio , are decom- ilated water, ide, forming rms unstable tliese glucos- special acid duced to the ts of copper complete in to a solution cipitated bj 1, it deposits reaction is le acids are GALACTOSE. 187 organic. A mixture is used of copper sulphate, Rochelle salt and soda (Feliling), or a solution of copper tartrate in potassa. (Barreswil.) Prof. W. S. Haines has ibiind in glycerine a very desirable substitute for the tartrate in Fehling's test. The proportions employed by him for qualitative ex- aminations are: cupric sulphate, 30 grains; potassic hydrate, li drachms; pure glycerine, 2 fluid drachms; distilled water, 6 ounces. LEVTTLOeE, CgH^Oj. This name is given to a variety of glucose, which is found in many fruits. It may be obtained by boil- ing inulin with water, or, better, it can be prepared from cane sugar by the action of dilute acids. It differs from the other sugars in that its rotary power diminishes on heating. GALACTOSE, CgHjjOj. This body is produced by boiling, for two or three hours, sugar of milk with water acidulated with sulphuric acid. It is soluble in water and insoluble in alcohol; nitric acid transforms it into mucio acid. mOSIN, INOSITE OR MUSCLE 8UGAB. C,H,A+2HjO. This substance is found in many animal organs, and 188 ORQANIO CHEMISTRY. is the chief constituent of the liquid which impreg- nates the muscles. It may be prepared by first extracting the creatin from the muscles, then separating the iiiosic acid with baryta. To the liquid is then added a quantity of sulphuric acid sufficient to precipitate the whole of the baryta and the liquid treated with ether, which dis- solves the foreign substances. The aqueous solution is removed and alcohol added to it until a precipitate is formed. Crystals of potas- sium sulphate first separate out, then beautii'ul crystals of inosite. This substance h«s a sweet taste. At a temperature of 100° it loses two molecules of water. It dissolves in one-sixth of its weight of water while it is insoluble in ether and strong alcohol. Inosite is without action upon polarized light. It is not converted into glucose by the action of dilute acids, and does not reduce copper salts. Mixed with milk and chalk it undergoes lactic fermentation. (Page 122.) SACCHAROSES 189 lich irapreg- the creatin iic acid with quantity of wliole of the , which dis- cohol added ftls of potas- til'ul crystals taste. At a es of water, ater while it a light. It on of dilute Mixed with srmentation. SACCHAKOSES. Ordinary Sugar, This body exists in a large number of plants, though it is almost exclusively extracted from the sugar-cane and beet-root. Tlie sngar-cane, Arunde saccharifera, contains 17 to 20 per cent, of sugar. To extract, the juice of the cane is first obtained by expressing. This juice repre- sents 60 to 65 per cent, of the total weight of the cane, and would alter rapidly in the air if care were not taken to bring it rapidly to a temperature of 70°, and adding a quantity of lime. The juice soon becomes covered with foam and deposits difterent albuminoid and other matters, which are precipitated by the lime. It is decanted into pans and rapidly evaporated. The sugar crystallizes out, and the mother liquor is evapo- rated as long as it furnishes crystals. The thick liquid which remains is molasses. The sugar thus obtained is brown sugar, and is subsequently refined. The beet-root most rich in sugar is that of Silesia. It contains about 10 per cent, of sugar. Sugar crys- tallizes in clinorhombic prisms. They may Be readily obtained by slowly evaporating a solution of sugar. 190 OROANIO CHEMISTRY. The crystals of ordinary sugar are very small, as the syrup is made to crystallize quite rapidly. Cold water dissolves three times its weight of sugar; Lot water dissolves it in all proportions, forming a syrupy liquid. It is not dissolved by cold alcohol or ether. Dilute alcohol dissolves it in proportion as it is more or less aqueous. Its solutions are dextrogyrate. Sugar melts at about 180°, and yields a liquid which soUdifies to a vitreous, amorphous mass, called barley sugar, which becomes opaque and crystalline after some time. If sugar is heated a little above this point, it is transformed into glucose and levulosane. CiaHiBOu=OeHiA +0«H,oO,. Levuloiane. At about 190° sugar loses water, becomes brown, and finally furnishes a substance which is commonly known as caramel. According to Gelis three pro- ducts of dehydration are formed, oaratmlam, oara- melene and oarameline. At a temperature of aSO" to 250° sugar is decomposed into carbon monoxide, carbon dioxide, carbohydrides and different empyreu- matic products. Sugar is transformed slowly in the cold, and rapidly at 80", in contact with dilute acids into inverted sugar, which is thus called on account of its inverted action upon polarized light. On pro- longed ebullition the solution is rendered brown and ulmic products are formed. Sugar reacts with barvta water and lime water, forming different compounds called merates or saccharates. SUQAR OF MILK. 191 imall, as the Cold water ; liot water I'Upj liquid, er. Dilute nore or less Sugar melts li solidifies rley sugar, ' some time, point, it is les brown, commonly three pro- 'ane, oara- re of 230" monoxide, empyreu- rly in the lute acids n account On pro- >rown and ith barvta ompounds Tlie solutions of these sucrates are decomposed by carbon dioxide : sugar is reformed. Rousseau makes use of this fact in the manufacture of sugar on a very large scale. Sugar does not ferment immediately in contact with Tbeer veast. to 8UOAB OF HILK, LACTIN OB LACTOSE. CisHaOii + H2O. It is obtained from milk, by precipitating the casein with a few drops of dilute sulphuric acid, filtering and evaporating the liquid. Crystals are deposited, which are purified by re- dissolving and treating with animal charcoal. In Switzerland large quantities of sn^^r of milk are made by evaporating the wkey which remains after the separation of the cheese. The crystals of this body are rhombic prisms. This sugar is insoluble in ether and alcohol, and requires 2 parts of boiling and 6 parts of cold water for its solution. Its solutions are dextrogyrate. At a terri,..ratnre of about 140° it loses H2O, and becomes browii sn: (60° to 180°. In presence of sour milk and chalk it undergoes lactic fermentation. Sugar has been found in a sample of a saccharine matter extracted from the sap of a sapodilla tree, the tree furnishing caoutchouc. 102 ORGANIC OIIEMISTRY Reichardt has obtained (60-'75-807) from a su^ar distinct from ordinary sugar, a body though having the same formula. He names it^am-amJm. HONEY. Honey is produced by the domestic bee (Apis mel- hfica), an insect of the order Hymenoptera. It is separated from the wax by exposing the honey- comb to tlie sun, on wire nets; very pure lioney is thus obtained. "^ Tlie mass which remains is expressed, andtliis prod- uct 18 a second quality of honev, more colored and of a less agreeable taste and odor than the first The comb is then heated with water to remove the remain- derof the honey. The wax thus isolated is melted and run into moulds. Honey owes its sweet taste to several sugars. There is found in it a dexti-oyrgate, crystalhzable glucose, and on removing this sugar there remains a viscid uncrystallizabJe liquid, which contains levnlose. In addition to these, small quan- tities of ordinary sugar have also been found in honey. GLUCOSIDES. This name is given to certain bodies which have the property of forming various products by combin- mg with water, amoi.g which is glucose, or some other sacchanne matter. This change is produced by the action of acids, bases, or by the action of ferments. We cite the fol- lowing, but shall only study the most important: GLUC08IDK8. 193 'om a sugar ugh Laving hin. I (Apis mel- ; the honey- re lioney is 1 tliis prod- olored and Srst. The he remain- is melted eet taste to icti-oyrgate, this sugar aid, which mall quan- found in liich have y combin- ome other of acids, te the fol- tant: Salicin, CisH.gO;, extracted from the bark of the Willow. Amygdalin, CajH^NOn, extracted from the Bitter Almond, Amygdahis covimunis. Orcin, O^IIsOo, extracted from various Lichens. Tiinnin, G^HaOni extracted from the Oak. Phlorizin, CaiHjjOio, extracted from the Apple, Pear, or Cherry tree. Populin, C20H22O8, extracted from Aspen leaves. Arbutin, C13H16O7, extracted from the leaves of the Uva-Ursa. Convolvulin, C31H50O16, extracted from the Convol- vulus orizahensia and mliiedeamis. Jalappin, Q^^Q^^ exti-acted from Convolvulua orizahensu and scammoniu. Saponin, a white amorphous powder whose solution is very frothy and of which the powder is very sternu- tatory, Daphnin, CsiHsaOn, the crystalline matter extracted from the bark of the Ash {Fmxinus excelsior). Cyclamin CaoH240,o, extracted from the tubercles of the Cyclamen europceum. Quinovin, CaotligOg, a resinous, bitter matter, solu- ble in alcohol, existing in the bark of the Quina nova and other cinchonas. Solanin, C43H71NO16. This has already been studied, (page 165). Esculin, C21H.24O13, extracted from the bark of the Horse Chestnut. Qnercitrin, CjgHaoOn, from the bark of the yellow oak {Quercus tinctoria). 194 ORGANIC CHKMISTBy. Coniferin, C.HaOs, from the Larix europaea, etc. Vanillin, from the Vanilla bean, and recently ob- tained artificially (60-74-608). SA Licra, Call igOi + IlaO. This body crystallizes in white needles, fusible at 120°, insoluble in ether, soluble in alcohol and water. These solutions are levogyrate and very bitter. It is used as a febiifuge, but is of little value in well de- fined intermittent fevers. Tt has as a distinguishing chemical character, the pioperty of becoming red with sulphuric acid. Under the action of dilute sulphuric, or hydro, chloric acid, or even with emulsin, salicin is decom- posed. With the latter the reaction is: C.sH.807 + H,0=C«H, A + C^HsOa Glucoge. Saligenln. In contact with cold nitric acid it loses hydrogen, and a body is formed called helicin, Ci^YL^^O-,. When treated with oxydizing agents, it gives off an odor which is identical with that of the essence of meadow sweet {Spirea vlmaria). This body is produced especially when salicin is treated with a mixture of sulphuric acid and potas- sium bichromate, and is also known by the name of hydride ofsalicyl. Its formula is identical with that of benzoic acid, C7H16O2, but it has not the properties of this acid. 8ALICIN. 10ft ropaea, etc recently ob- s, fusible at I and water. i)itter. It is in well de- ici-acter, the icid. , or hjdrou I is decom- \ -I J hydrogen, jives off an essence of 1 salicin is and potas- le name of rizoic acid, I this acid. It is an aromatic liquid, boiling at 196°, and has the property of oxydizing spontaneously, giving rise to an acid called salicylic acid, C7H4O3. Salicin, treated with fused potassa, furnishes potas- sium oxalate and salicylate. Cahours has shown that essence of Gaultheria p'rocumhem, a heath of New Jersey, contains, besides, an isomer of the essence of turpentine, a sweet-scented liquid, boiling at 220°, which is salicylic methyl ether, and is re-converted, in contact with alkalies, into methyl alcohol and sali- cylic acid : it may be produced artificially by treating wood ppirit with a mixture of salicylic and sulphuric acids. Salicylic or oxyhemoio acid has been lately pro- duced by Kolbe (56 -'74 -22), by a remarkable syn- thesis in acting on carbolate of sodium with COj. 2C,H50m + C02=CeTI«0 -i- 0,H403Na,. Sodium phenol. Sodium salicylate of sodium. It has now come to be a very important article in pharmacy and in the arts, on account of its efficiency as an antiseptic, equaling or surpassing carbolic acid (phenol), yet without the unpleasant odor of the latter body, or its toxical qualities. As of considerable im- portance theoretically, it should be stated that Herr- mann has very lately (60-April, "TT) obtained salicylic acid by the action of sodium upon succinic ether. 196 ORGANIC CHEMISTRY. TANNIXS. This is the name given to different principles exist- ing in plants, which are characterized by the following properties: Ist. They give, with ferric salts, a black coloration approaching bine or green. 2d. They precipitate solutions of albuminoid sub- stances, particularly those of gelatine. The principal ones are: Tannin of oak, C^HiaOn. " " cachou (catechin or catechic acid). " " quinqninia (quinotannic acid). " " coffee (caffetannic acid). " " fustic (morintannic acid). Oak tannin is best prepared from gall-nuts which contain much more than does the bark. The nuts &ve pulverized and submitted to the action of commei-- cial sulphuric ether, which is made aqueous. This €ther may be replaced with advantage by a mixture of 600 grams of pure ether, 30 grams of 90 per cent, alcohol, and 10 grams of distilled water for every 100 grams of gall-nuts. After twenty-four hours the apparatus contains two layers of liquid; the upper one is ether, containing but little tannin, while the lower one is a very strong aqueous solution of tannin. The lower layer is removed md evaporated in an inciples exist- the following ack coloration •nmiiioid sub* ic acid), cid). ll-nuts which £. Tlie nuts a of commer- ueous. This a mixture of 90 per cent. 3r for every ur hours the he upper one ile the lower mnin. orated in an TANNIN 197 oven on shallow plates. There remains an amorphous spongy substance, very soluble in water, less soluble in alcohol, and almost insoluble in ether. Tliis residue is very astringent and slightly acid. Solutions of tannin give a white precipitate with tartar emetic. It precipitates solutions of the alkaloids, and coagu- lates blood. With solutions of gelatin it gives a voluminous pre- cipitate, soluble on heating in an excess of gelatin. Tannin forms, with fresh hide, an imputrescible com- pound, which is leather. The art of tanning is based on the action of oak-bark tannin on hides from which the hair has been removed, usually by lime. Gallic acid. In solution, tannin is gradually de- composed, the liquid becoming covered with mould. Carbon dioxide is disengaged and an acid, called gallic acid, is formed. This transformation does not take place if all air is excluded; and the air alone is not sufficient. It requires the presence of a mycelium of a mucedin conveyed to the liquid either by the air or in some other manner. This transformation is, like alcoholic fermentation, a phenomenon correlative with the development and growth of an organism. On boiling tannin with water acidulated witlx hydrechloric or sulphuric acid, it is decomposed into glucose and gallic acid: C^,H«0„H-4HaO=3(C,H605)+C,H,A. Gallic acid. Glucose. 198 ORGANIC CHEMISTRY. GalUc acid is deposited as the liquid becomes cool It 18 purified by redissolvingand treating with animal charcoal, and recrjstallizing. Gallic acid, C,R,0,=^^§^ | o„ crystallizes in silky needles, soluble in three parts of boiling water, but little soluble in cold water. This solution, on standing m the air, becomes altered after a long time, carbon dioxide is disengaged and the solution turns brown- alkalies accelerate this change. ' Gallic acid produces a blue color with ferric salts and precipitates tartar emetic, but does not precipitat^ gelatin when pure, nor the alkaloids. Mixed with pumice-stone and heated to 210° it pro- duces a beautiful sublimate otpyrogaUio acid, carbon dioxide being liberated at the same time. C7HgO5=0AO8+C02. This body occurs in colorless, acicular crystals, fusible at about 115», and soluble in 2.5 parts of water. Its solution absorbs oxygen from the air, in presence of alkalies, and becomes quite brown. It reduces gold and silver salts, and forms unstable compounds with certain acids. It may properly be placed among the phenols. This body is employed in photography, and in the laboratory. Mercadante (47-'r4-484) finds that gallic acid is injurious to vegetation, inasmuch as it combines with the mineral food of the plant rendering it insoluble. Grimaux was the first to consider gallic ftcid aa tetratomic and monobasic (77-620). VEGETABLE CHEMISTRY. 199 Bcomes cool, with animal llizes in silky water, but on standing me, carbon irns brown; ferric salts, ; precipitate 210° it pro- loid, carbon ir crystals, .5 parts of the air, in wn. IS unstable roperly be employed lercadante jnrions to le mineral io acid as VEGETABLE CHEMISTRY. At the moment when the radicle of a plant appears above the ground, its vital phenomena imdergo a marked change. The plant decomposes carbon dioxide, water and certain nitrogenous compounds furnished by the soil, and grows by retaining carbon, hydrogen, uitrogen and a little oxygen, and returns to the air the greater part of the oxygen derived from the carbon dioxide, water and nitrogenous compounds. Bonnet observed, in the last century, that leaves, exposed to the snn in areated water, disengage a gas, which Priestly showed is oxygen. Sennebier discovered that this oxygen is derived from carbon dioxide. De Saussure verified these facts, and demonstrated that this decomposition of carbon dioxide does not take place in the dark, and t>.at the green portions of the plant alone are capable of effecting the change. J. Belluci (9-78-362) has lately shown that, con- trary to former belief, none of the oxygen exhaled by plants is in the form of ozone. ExPEBiKENT.— Place a few leaves in a flask half full of water containing carbon dioxide, "soda water," invert the flask over a glass of water, and expose it to the sun- light, after having covered it, if the sun is very hot, with a sheet of transparent paper; minute bubbles will 200 ORGANIC CHEMISTRY. soon be seen to form on the leaves, as small as the point of a pin, will increase in size, unite and mount to the upper part of the flask. Transfer this gas to a test- tube, and, on examination, it will be found to be oxy- gen. Substitute for this flask an opaque vessel, or per- form the experiment in the dark, and the cprbon diox- ide will not be altered in the least. Wliere do the plants find this carbon dioxide ? Chiefly in the air. Boussingault, in order to demon- strate this, placed under a bell-glass some peas planted in calcined sand; he watered them with pure distilled water, and passed air into the glass; the peas grew, flowered and bore fruit. ISTow the substance of these peas contained carbon hydrogen and nitrogen, in much greater quantity than the seed from which they grew, consequently these constituents were taken from the air and water. ' If, however, the air be made to pass through an alkaline solution before escaping Irora tlie vessel, no carbon dioxide is absorbed, which also proves that the carbon dioxide existing in the air has been removed by the plant. Tlie plant takes up, in the same man- ner, carbon dioxide from the water which passes from the soil into its roots. Plants are also capable of decomposing water, in fact, Collin and W. Edwardd have proved that tlie sub- merged stems of the Polygonum tinctorium and cer- tain mushrooms, exhale hydrogen. On the other hand, Payen has proved that the hy- * drogen exceeds the oxygen in the woody parts of JL 1 VEGETABLE CHEMISTRY. 2U1 I as the point lount to the as to a test- i to be oxy- essel, or per- oprboii diox- ►n dioxide ? r to (lemon- peas planted lire distilled ! peas grew, ined carbon er quantity onsequently and water, through an B vessel, no i^es that the 3n removed same man- passes from y water, in lat the sub- m and cer- • !mt the hy- ly parts of plants, and, indeed, many substances produced by plants, as oils and resins, are very rich in hydrogen. In short, the oxygen contained in the plant would*not be sufficient to oxydize or transform into water the whole of the hydrogen it contains, consequently it must be admitted that water is decomposed by plants. The conditions under which this change takes place have not as yet been determined. The experiment of Boussingault proves, as Ingen- housz has claimed, that the air furnishes the plant with nitrogen; but where does this nitrogen come from? Is it taken by the plant from the free nitrogen of the atmos- phere? or is it derived from the nitric or nitrous acids, or from the ammonia contained in the atmosphere, or, in one word, from the nitrogenous compounds existing in the air? ^ Boussingault has shown that while certain families of plants, principally the common vegetables, derive from the air a large quantity of nitrogen, even taking up free nitrogen, others, the cereals for instance, derive nitrogen chiefly from the soil; for, on causing clover and wheat to grow in calcined sand in presence of air deprived of its nitrogenous compounds, and distilled water, he observed that the clover took up carbon, hy- drogen, water and nitrogen, while it appears that the wheat obtained from the air carbon and water only. Nitrogen, which is present in the air in the form of ammonium nitrate, is absorbed by all plants. Direct experiments have shown that the salts of ammonium, especially ammonium nitrate, constitute an ejicellent 202 ORGANIC CHEMISTRY. compost, and consequently this nitrate can lose its oxy- gen, or become reduced in the plant. Now, it is known that urea and animal excreta are transformed into ammoniacal compounds on exposure to the air; therefore, in order to obtain a good crop, even with plants which take up the nitrogen of the air, it is necessary to employ manures which furnish not only easily assimilated nitrogen, but those which, be- sides, furnish the plant with soluble organic com- pounds and the mineral substances necessary for its development and growth. Of these latter there is re- quired for the plant, potassium and calcium chlorides, sulphates, phosphates, etc. With the four elements, carbon, hydrogen, nitrogen, and oxygen, natrre forms an infinite variety of com- pounds by mysterious methods, to which we have not, as yet, the key, but of which synthetical research gives us some idea. Thus, with carbon dioxide and water, Berthelot produces formic acid; with formic acid he obtains alcohol, and subsequently acetic acid. Pasteur also has shown that glycerine, one of the principles of fat, is produced in the process of fermentation and that a complex acid, succinic acid, is also fonned under the same circumstances. However, we are far from knowing how to produce those substances which nature forms at ordinary temperatures, and with only four elements. What wondrous chemistry is that of the plant, fitted by an all-wise Creator to elaborate with such simple materials, the beauteous violet, the fragrant rose, or the luscious fruit 1 lose its oxy- excreta are ►n exposure good crop, 1 of the air, furnish not which, be- came com- sary for its there is re- 1 chlorides, 1, nitrogen, 5ty of com- e have not, earch gives and water, lie acid he i. Pasteur rinciples of itation and med under e far from lich nature only four hat of the )orate with be fragrant VEGETABLE CHEMISTRY 203 By combining six atoms of carbon with five atoms of water, nature forms either the woody principle, cd- luloae, or the essential constituent of the potato, 8taroh. J3y uniting ten atoms of carbon with sixteen atoms of hydrogen, she produces, in the orange and in the pine, two essences or oils very different in character. By associating the four organic elements she forms the most different substances, the nourishing cere ,1 as well as the most deadly strychnia; and often products as nnhke as these are found side by side in the same plant. Thus the plant is a structure which decomposes car- bon dioxide, water, and compounds of nitrogen; which forms its substance out of carbon, hydrogen, nitrogen, and a part of the oxygen of these compounds, and which exhales oxygen. Hence, chemically, it would be proper to call the plant a reducing apparatus. We should add that the flowers and portions of ' plants not green, also the buds in developing, produce an exhalation of carbon dioxide, and that during ger- mination, and especially during the time of flowering a sensible amount of heat is disengaged. As a result ot this elevation of temperature, there is produced in plants some slight oxydation or combustion, as in the respiration of animals. Hence, we must conclude that plants and animals, m many circumstances at least, deport themselves in a similar manner. Many experimenters, and especially Dutrochet and (iarreau, go further, and say that plants aiid animals 204 ORGANIC CHEMISTRY respire in an identical manner, and according to their theories all living creatures take up oxygen and exhale carbon dioxide. The experiments of Garreau especially deserve at- tention. He placed branches, detached or affixed to the plant, in vessels full of air, and exposed them to a diffiised light. The volume of the air was known and the oxygen absorbed was determined by a special con- trivance ; the carbon dioxide produced was removed by placing in the vessel an alkaline solution of known weight. Thus the variations of these gases were care- fully studied. As a result of his experiments Garreau claimed to have established that both in the dark and in the light, there is an absorption of oxygen and an ex- halation of carbon dioxide, but the amoimt of car- bon dioxide collected does not represent the amount really exhaled, as the greater part is reduced at the moment of liberation. From these facts it would appear that in all living creatures the same phenome- non of respiration takes place, which consists in a consumption of oxygen and an exhalation of carbon dioxide. This phenomenon is associated with another ; viz., assimilation or nutrition. It is here that the differ- ence, indeed a complete opposition, between the two kingdoms is established. The plant grows by re- ducing, under the influence of heat and sunlight, carbon dioxide, water and nitric acid, by accumulating carbon, hydrogen, nitrogeu and by exhaling the greater OBGAKIZED SFBSTANOES. 205 ling to their a and exhale deserve at- :>r affixed to sd them to a I known and special con- gas removed m of known 8 were care- claimed to and in the and an ex- imt of car- tho amount uced at the B it would le phenome- jnsists in a 1 of carbon 3ther ; viz., ; the differ- (en the two ow8 by re- d sunlight, cumulating the greater part of the oxygen. The animal, on the other hand, forma its substance from that of the plant, oxydizing, or consuming, the vegetable products with the oxy- gen of the air exhaled by the plants; it reduces the complex products formed in the vegetable to the state of carbon dioxide, water and ammonia; thus the ani- mals supply the plants with food, receiving in turn nourishment from them. Those desirous of further studying this and other interesting topics relating to Vegetable Chemistry, will find very valuable the woi-ks of Prof. S. W. Johnson, " How Crops Grow," and "How Oops Feed"; also Prof John C. Draper's article in Am. Jour. Sci. and Arts, Nov. 1872, entitled "Growth of Seedling Plants." ORGANIZED StTBSTANCES. Among the chemical substances of which we have spoken certain ones participate more in vital phe- nomena, and have more definite physical structure than do others. These are designated as organized or organisable mibstanoes, the term organio being reserved for the definite compounds studied in organic chemistry. All these substances play an important part in tiie veget- able kingdom, forming the network of vegetable tis- sue, as cellulose or as starch, etc. CELHTLOSE OB OELLTJLIN, (CeHioOg)n. On examining a young plant under the microscope, 206 OBGAino CHEMISTRY. we observe that it is built up of little cells and mi- nute, diaphanous ducts or vessels filled with sap and air. The material of which these tissues are com- posed is called cellulose. The pith of the elder, cot- ton fibre, and paper are almost exclusively composed of this substance. Cellulose is a carbo-hydrate; C.HioO,, in the formula, ordinarily given to it, although a multiple formula at least three times as large, or CigHaoO,, is necessary to explain certain reactions with nitric acid. ExPEEiMEirr. Pure cellulose may be obtained in the following manner: cotton, linen or paper is treated with dilute alkaline solutions, washed and immersed in weak chlorine water; finally it is submitted to the action of various solvents, as water, alcohol, ether and acetic acid until nothing more is dissolved. This substance is solid, white and insoluble. It is destroyed at a red heat, producing carbon and uumer- ous carbohydrides, gaseous and Hquid, which distil over. With monohydrated sulphuric acid it produces a colorless, viscid liquid, which contains, at first, an insoluble substance having the properties of starch and yielding a blue color with iodine. If the action of tlie acid is continued, the whole is dissolved and the sai^e products are obtained as in the case of starch when brought in contact with srilphuric acid, i. e. dextrin and glucose. To separate the latter substance, it is simply necessary to saturate the acid with chalk and evaporate the liquid. Concentrated hydrochloric acid produces the same CELLULOSE. 207 Us and mi- ;h sap and 8 are coin- elder, cot- ^ composed 1O5, ia the I multiple ^isHaoOjj is nitric acid, ned in the eated with ed in weak > action of and acetic ble. It is id uumer- lich distil t produces it first, an starch and ion of tlie the sante ireh when B. dextrin ince, it is ;halk and the same ^ect. If paper be immersed for an instant only in sulphuric acid, diluted with half its volume of water, and carefully washed, it acquires the toughness of pai-chment. Paper thuo prepared is fipequently employed in experiments on dialysis; it is also much used by pharmacists to cover the stoppers of bottles. It is known in commerce as vegetable parchment. OUN COTTON OR PYEOXTLIN. Gun cotton was first made by Schoenbein, in 1846. To prepare it cotton is plunged for two or three minutes into fuming nitric acid, or, better, into a mix- ture of 1 vol. nitric acid (of a density of 1.6), and 2 vols, of strong sulphuric acid; it is then thoroughly washed and dried at a low temperature. The cotton is not changed in appearance other than becoming «omewhat wrinkled. When well prepared it bums completely, leaving no residue. The tem- perature at which it takes fire varies from 100" to 180° according to the manner in which it has been pre- pared. It is cellulose in which from six to nine atoms hydrogen have been replaced by an equivalent quan- tity of the monad radicle NOa that, having the formula CigHaOuONOj, has the greatest explosive energy. Pyroxylin regenerates cellulose in contact with ferrous chloride. K cellulose be considered a sort of alcohol, as claimed by some, pyroxylin would be a nitric ether of this alcohol. Pyroxylin has the advantage over gunpowder of 208 ORGANIC CHEMISTRY. bem^ more easily prepared, and of remaining unaf- fected by moisture, but its cost is relatively greater, and Its shattering power renders its employment dangerous. The term collodion (from «oAA«, glue) is given to a preparation obtained by dissolved gun-cotton in a mixture of 1 part of alcohol and 4 parts of ether, Chas. H. Mitchell has made (62-74-236) a number of experiments, with the view of ascertaining the rela- tive proportions of cotton and acid, together with the proper time of maceration necessary to produce a cotton which should combine the largest yield with the highest explosive power and solubility. The following formula was at length adopted: Eaw cotton, - . , . g p^^s. r^otassium carbonate, . . . j « Distilled water, - . . -^i;^^ « Boil for several hours, adding water to keep up the measure; then wash until free from any alkali, and dry. Then take of— P^fied cotton, . . . . ^ oz. av. JNitrous acid (nitric, saturated with nitrous acid), o ?• f ^Z*^' ■ - - - 4 pints, balphnnc acid, s. g. 1.84, - - .4 « Mix the acids in a stone jar capable of holdino- 2 gals and when cooled to about 80° Fahr., immerse the cot-' ton m small portions at a time ; cover the jar and allow to stand 4 days in a moderately cool place (temp 50° to 70° Fahr.) then wash the cotton in small por^ ning unaf- ly greater, nployment I given to a 3tton in a ether. 1 a number g the rela- r with the produce a f^ield with ted: 2 parts. 1 « ) « Bp up the Ikali, and oz. av. acid), : pints. g 2 gals., ! the cot- 3 jar and !e (temp, lall por- CELLULOSE. 209 tions, in hot water, to remove the principal part of the acid; pack in a conical glass percolator, and pour on distilled water until tlte washings are not affected by solution of barium chloride. Collodion, on spontaneously evaporating, forms a transparent and impermeable membraneous coating, and is much employed in photography, also somewhat in surgery. Cellulose is attacked by chlorine; the use of solu- tions of chloride of lime, and of chlorine, in large quantities in washing, or bleaching, will cause a rapid deterioration of linen or cotton goods. Schweizer has shown that cotton, paper, etc., is very easily dissolved by an ammoniacal solution of copper. Attempts by the author to employ this solution for a *' water-proof " coating of fabrics, as has been suggested, failed to yield a satisfactory result, on account of the liability of the coating to crack and peel off. Peligot has found in the skin of silk worms, and Schmidt has discovered in the envelopes of the Tunicates, a substance, tuniome, which has the com- position and properties of cellulose. Linen, hemp, cotton, wood and paper are all essen- tially cellulose. n 210 ORGANIC CHEMISTRY. AMYLACEOUS SUBSTAN'CES. These substances are almost universaUj present in plants; particularly that known as starch or femla. The potato yields about 20 per cent, of starch. In order to obtain it, this root is grated and the pulp placed upon sieves, arranged one above the other, and through which a streana of water flows. The grains of starch being extremely minute pass through the meshes of the sieve, while the walls of the cells remain behind. The starch is washed, drained,, and dried, first at ordinary temperature, afterwards by the application of a moderate heat. Btaeoh. ^(CeHioOs) probably C^B.^0,,. Flour contains, besides starch, nitrogenous substances, de- nominated gluten; this gluten is capable of ferment- ing, whereupon it becomes soluble, while the starch remains unaltered and insoluble. Under these con- ditions the gluten gradually dissolves, disengaging ammoniacal compounds, hydrogen sulphide and other products of putrefaction. At the end of twenty or thircy days, the gluten having become dissolved, the liquid is removed, and the starch, washed and dried, shrinks into columnar fragments, which are readily pulverized by gentle pressure. ' iT ii -n T j^ :!ES. Ij present ia i otfecula. f starch. In md the pulp he other, and minute pass 3 walls of the hed, drained,, fterwards by )0i5. Flour )stance8, de- I of ferment- e the starch r these con- disengaging ie and other the gluten irnoved, and o columnar by gentle STARCH 211 A more modern method is that employed in France, which is essentially the same as the process cited above, as that used in making potato starch here. The water carries away the starch while the gluten remains be- hind in the form of an elastic mass, which is also util- ized. For this purpose it is incorporated with flour poor in gluten, to be made into macaroni, and for the manufacture of a very nutritive preparation, " granu- lated gluten;" it is also employed, according to the recommendation of Bouchardat, in making bread for persons afflicted with diabetes. Starch, examined with a microscope, exhibits flat- tened ovate granules of different size in various plants, but always very small. Those of the Eohan potato have a length of 0.185 mm.; the smallest are those of the Chenopodiwm, quinoa whose length is 0.002 mm. When starch is heated with water to 70°, the gran- ules increase from 20 to 30 times their original volume, and become converted into a tenacious paste. A small quantity of the starch passes into solution, and to this the name amidin has been given. Starch paste and the solutions of starch have the characteristic property of becoming bine in contact with small quantities of iodine. The liquid becomes colorless at about 70°, but regains its color on cooling. If to this blue liquid a solution of a salt, sodium sulphate for instance, be added, we obtain a dark-blue floculent precipitate. This substance, called starch iodide, is not a chemical com- pound, but a sort of lake, containing variable quanti- ties of iodine difliised throughout the starch and solv- 212 ORGANIC CHEMISTRY. ent. This reaction with iodine is a very valuable test for starch, but is open to several fallacies, and apt to mislead in inexperienced hands. Until lately, it has been claimed that starch is insol- uble in water, and that if water in which starch has been boiled gives with iodine the characteristic reaction of this substance, it is due to particles of starch suffi- ciently minute to pass through the pores of the filter. But the results of the experiments of Maschke and Thenard, show that if starch is heated for some time at 100°, it is partially transformed into a variety solu- ble in water. This substance is colored by iodine; it furnishes, on evaporation, a gummy solid wliich is pre- cipitated by alcohol as an amorphous powder. If we boil starch for a long time with water it is dine; it ill ispre- ter it is 'he pres- iicilitates nstbrma- iiric acid :es place 'minated !e called 8 formed iction of explains iment to nice, the soluble parts of beer yeast, gluten, and many other sub- stances, are capable of producing this transtormation of starch into dextrin and glucose. It has generally been considered that the molecule of starch, in being transft)rmed into glucose simply united with one molecule of water directly, thus: C,Hio05+H80=C6HiA. MusculuB, however, claims to have established that the starch is first transformed into a soluble metamer and this, thereupon, splits up into dextrin and glucose: C„H3oOi5+H20=2CeH,o05+CeHjA^ Dextrin. — v^ Olncose. By further action, the whole of the dextrine becomes converted into glucose, (2-[3]60-203). . ^ ^ , Starch, heated simply to about 160°, is also changed into dextrin. It is attacked by dilute nitric acio, mtrous vapors are given off and difPerent substances are produced, chiefly, however, oxalic acid. If starch is agitated with fuming nitric acid it is dissolved and water precipitates from the solution a nitrous compound which is explosive. The alkalies, in concentrated solutions, when heated with starch disorganize and dissolve it Solutions con- taining t^o to three per cent, of alkali, accelerate the formation of starch paste. 214 ORGANIC CHEMISTRV. Starch is employed in the laundry and therapentio- ally in poultices, injections and baths. Tajaioca is the starch of the root of the Jatropa manihoty called cassava or manioc. Sago is obtained from the pith of various sago palms. Arrow-root is the starch of the Maranta arundi- nacew, and one or two other tropical plants. Salep is obtained trora the Orohts masoula. Inulin. There has been found in the roots of the Jerusalem artichoke, of the chicory, and the bulbs of the dahlia, a substance isomeric with starch, called inulin. LicHENiN. There is extracted from certain lichens and mosses a substance called Uohenin, which has the property of swelling in cold water and of being dis- solved in boiling water. It is prepared by treating Iceland moss with ether, alcohol, a weak solution of potassa, and finally with dilute hydrochloric acid. There exists in the animal organism a variety of starch designated by the name of glycogen. DEXTRIN, OB DEXTBINE:. CjHioOs. To prepare dextrin, starch may be heated with water containing a small quantity of sulphuric or oxalic acid ; the operation should be arrested when the liquid gives with iodine only a wine-colored re- action. FLOUB 215 apentio- Tatropa lis sago xrundi- i of the bulbs of 1, called lichens has the ng dis- ;reating ition of id. riety of d with ario or 1 when red re- For the acids, a small quantity of germinated bar- ley may be substituted, placed in a bag immersed in the liquid. Dextrin thus prepared always contains glucose. It may be obtained free from this substance by heating starch with i its weight of water and Tiftnr of nitric acid. Dextrin is amorphous, slightly yellow, very soluble in water, insoluble in alcohol and concentrated ether. It is used somewhat in preparing bandages in case of fracture, and very extensively as a paste for calico- printers. Dextrin, forms viscid adhesive solutions which are used for the same purposes as gum-arabic. The mu- cilage used bv the U. S. government for postage stamps is composed of dextrin two ounces, acetic acid one ounce, water five ounces, alcohol one ounce. Dextrin may be distinguished from gum-arabic by not being precipitated on adding a dilute solution of lead acetate, and by furnishing with nitric acid a so- lution of oxalic acid and not a precipitate of mucic acid. FLOUE. Amylaceous substances are of great importance as food. Wheat and other cereals are the most import- ant sources of these aliments. Starch, as also sugar and the neutral carbohydrates, are respiratory foods whose principal effect is the pro- duction of heat by being oxidized, or burned, in the body. 216 ORGANIC CHEMISTRY. The composition of four of the leading cereals i& herewith given : 1 GB Dextrin and Olncose. o a 1 II Pi f OD h II Wheat, 14.0 59.5 7 1.7 14 1.2 1.5 Rye, 16.0 57.5 10 3.0 9 2.0 2.0 Oats, 14.0 63.5 8 4.0 12 5.5 4.0 Rice, 14.5 77.0 0.5 7 0.5 0.7 Tlie sticky, elastic substance found with starch in flour is gluten (called also glutin), and is a mixture of \ariou8 proximate compounds but chiefly of three; legvimin, or vegetable casein, fibrin and gelatine. I'lour of good quality is dry and soft to the touch; it f jrms with water an elastic, non-adhesive dough. The value of flour depends largely upon the gluten it contains, though not as stated in most authors upon the percentage of this substance, but upon the quality rather, as shown by recent investigations of R. W. Kunis (26-74-1487). The modern " patent process," originating in Min- nesota, is mainly a method of grinding which intro- duces into the flour more gluten than in older pro- cesses. GUM. CeHioOs. This substance is very widely distributed in the vegetable kingdom. Gums either swell in water or 1 OTTM. 217 ireals is arch in nixture r three; le. J touch; ugh. s ghiten rs upon quality K. W. in Min- 1 intro- er pro- in the ater or are dissolved, imparting to it a mucilaginous consis- tency. From a chemical standpoint they are essentially characterized by giving a precipitate of muoic acid on being boiled with nitric acid, and by precipitating lead subacetate. Gum-arabic, araiiin. This gum exudes from dif- ferent species of acacias, as Acacia arabica, A. sene- galensis, A. vera ; it is obtained from Arabia and Senegal. According to Fremy, gum-arabic is a salt formed by the combination of an acid, gtimmic or arahio acid., with lime and potassa. This acid may be isolated by pouring hydrochloric acid into a solution of gum, and adding alcohol; an am phorous deposit is formed which, dried at 120°, has the formula CgllioOg. This acid is very soluble in water. Its solution is levogyrate, like that of gum-arabic. On being heated to 150° it is transformed into a substance insoluble in water called meta-gummic acid, whose salts are likewise insoluble. Gum-arabic gives with ferric salts an orange-colored, floculent precipitate soluble in acids. Ceeasin. The gum which exudes from cherry and plum trees is a mixture of soluble gummates and in- soluble meta-gummates; hence it is only partially soluble in water. Cerasin becomes soluble on being boiled with water, as the meta-gummates ai-e transformed into gummates by the action of boiling water. These gums heated with dilute sulphuric acid furnish a dextrogyrate sugar. 1 218 ORGANIC CHEMISTRY. Gum-tragacanth often contains starch. Mucilage or Bassorin. There exists in the seeds of the quince and flax, in the roots of the marsh-mal- low and in portions of many other plants, a substance or substances, which, exposed to the action of boiling water, fnniich a thick mucilage, which appears to con- sist of a soluble, together with an insoluble substance. Nitric acid converts this mucilage into mucic and ox- alic acids. Gum and mucilage are frequently em- ployed as emollients, and in syrups, also extensively in confectionery. Pectin Group. Many roots, as the carrot, beet, etc., also green fruits, contain a neutral gelatinous substance, insoluble in water, alcohol and ether, called pectose. It is that which gives to green fruits their harshness. Tliis substance is modilied during the ripening of the fruit and becomes soluble, vegetable jelly, or pectin (from nrjKTii, a jelly), to which Freray assigns the formula CajH48082. Pectin, submitted to the action of a ferment found in 1h9 cellular tissues of vegetables, called pectase, or of cold, very dilute, alkaline solutions, is changed into a gelatinous acid called pectosio aoid, then into another substance likewise gelatinous, which is known by the name of pectio aoid. All these substances are amorphous, and non nitrogenous. Their formulae are not yet definitely determined. According to Fremy, to whom we are indebted for the foregoing facts, the jelly obtained from the current and other fruits is due to the action of the pectase on the laectin of these fruits. LEOUMIN. 219 ) seeds ih-mal- tstance l)oiling to con- istance. \nd ox- ly em- asively t, beet, itinous , called ts their ng the getable which t found iase, or fed into m into known ices are alee are 3ted for current ctase on These substances resemble gums in producing, on boiling with nitric acid, a precipitate of mucic acid. Much doubt still exists respecting the composition of the pectin group. LEGUMIN OR VEGETABLE CASEIN. Legumin is found in most leguminous seeds, such as sweet and bitter almonds, also in beans, peas, etc., the latter containing about 25 per cent. It is con- sidered to be identical with casein by Liebig and "Woehler. It may be obtained by digesting coarsely powdered peas in cold or tepid water for two hours, allowing the starch and fibrous matter to subside, and then filtering the liquid. It forms a clear, viscid solution, which is not coagulated by heat unless albumen is also present, but, like emulsin and unlike albumen, it is precipitated by acetic acid. It is coagulated by lactic acid, also by alcohol; in the latter case the precipitate is redissolved by water. Acetic acid, diluted with 8 to 10 parts of water, is -arefully dropped into the filtered solution obtained above, and the legumin is precipitated; an excess of the acid should be avoided, as this would dissolve th*o precipitate. It falls in the shape of white flakes, and after having been washed on a filter should be dried, pulverized and freed from adhering fat by digestion in ether. Legumin may be obtained from lentils with the same facility as from peas; but it is 220 ORGANIC CHEMISTRY. less easily procured from beans (haricots), in con- sequence of their containing a gummy matter whicli interteres with its precipitation and with the filtration of the liquids. The cnemical properties of legumin are identical with those of casein. Liebiar supposes that grape-juice and other vegetable juices which are deficient in albumen, derive their fermentation power from soluble legumin. This principle is soluble in tartaric acid, and to its pi i:sence he ascribes the tendency of sugar to toim alcoliul and carbon dioxide instead of mucilage and lactic a^jd. VEOETTABLE ALBUMEN. Vegetable albumen is contained in many plant- juices and is deposited in floccuU on applying heat to such liquids. It can also be f -(.ipltated by nitric acid, tannin and mercurio cliloride brecisely tikeanimal albunicn. Vegetable albumen is composed of carbon, hydrogen, nitrogen, oxygen and sulphur. There is no trustworthy formula for this substance. con- which ration mtical ;etable I their This ui and ^id. plant- beat to nitric animal »rbon, ■e is no m f m MK INDEX. PAOE. 86 129 18 Acenapthene, CnUu)— 154.. 38 Acetamide, d Ih NO=S9- • '36 Acetanilide, Cs II» NO=i3S. 130 Acetic oxide C4 He Os =io3 103 Acctochlorhydrlc glycol 63 Acetone, C3 H« 0=e,S. . . .99, 108 Acetyl acetate, C4 N9 Os . . . 103 Acetyl chloride, CjClHsO. 103 Acetyl hydride or aldehyd C2H4 0=44 '■■■ Acetylatninc, C2 H5 N=43.. Acetylene, Ca H2 =26 Acety lide, cuprous 19 Acid.acetic, C2 H4 O5 =60. . 99 Acid, aconitic, C« He Oc =95 174 Acid, acrylic, Cs H4 Oa =72. 9' Acid, adipic, Ce H10O4 =148 9' Acid,alloxanic,C4H4N2 05 125 Acid.alphacymic, CiiHuOa 91 Acid, amalic, Ce H7 Na O4 . . 169 Acid, anchoic, C9 HieOi =188 93 Acid, angelic, C3 Hg O2 =108 91 Acid, anisic, Cs Hb Os = 1 5^- 92 Acid, arable, Ce H10O5 -34^ 2>7 Acid, arichidic, C20H10O2 • • 9" Acid, atropic.Cs Hg Oa =148 164 Acid, benzoic.CT He O2 = 126 91, 109, 126 Acid, benzoglycolic 126 Acid, butyric,C4 H9 Oa . . 9°. »o8 Acid, caffetonnic >96 95 II 33 32 92 PAOE. Acid,camphic, CioHieOao=9' 168 Acid, campholic, C19H18O4 • • 9' Acid, camphoric,CioHi804 41, 93 Acid, caprylic, Cs HieOa • • ■ 9° Acid, caproic,Ce HiaOa = 1 16 90 Acid, capric, CioHaoOa = 172 9° Acid, carballylic, Ce Hs Oa . Acid,carbamic, CIIs NO2 . • Acid, carbazotic,( Picric) CHsNs 07=229 Acid, carbolic.Ce He 0=94. Acid,carbonic,Ca Hs 0=62. Acid, catechic 196 Acid, cerotic, C27HMO...90, 180 Acid, chelidonic, C7 H4 Oe • • 95 Acid, chlorbenzoic.C; H5 CIO = 130.5 '60 Acid, cholalic, C21H40O5 =408 g^ Acid, cholesteric, Cs H 10O5 • • 95 Acid,choloidic,CaiH3804 = 39o 94 Acid, cinnamic, C9 Hg O3 = 148 9'. J" Acid.citraconic C5 He O4 93. '21 Acid, citric, Ce Ha O7. Ha O = 19J-4-18 120, 95 Acid, coccinic, CisHseOa ... 90 Acid, comcnic, Ce H4 O5 • . . 95 Acid, coumaric, C9 Hg O3 . . Acid, croconic, C5 H2 O5 . . Acid, crotonic,C4 He Oa ..91. Acid, cuinic, CjoHiaOa = 164 93 95 178 91 II 222 INDEX. PAGE. Acid, cyanacetic, CaHs(CN) 03=85 103 Acid,cyanhydric,HCN = 27. 161 Acid,dextroracemic 117 Acid.dialuric, C4 H4 Nj O4 135 Acid, dinitrobenzoic, CTH4(NO!j>i02=52i2.., no Acid, doeglic, C19M36O2 = 296 91 Acid, elaidic 177 Acid, erucic, C22H4202 =338. 91 Acid, ethaliCiCieHaaOj =256 179 Acid, ethj'Isulphuric, CaH6HS04=i26 71 Acid, formic, CH2 O2 =50.98, 90 Acid, fumaric,C4 H4 O4 = 1 16 93 Acid, gallic, C7 He O5 . -95. »97 Acid, glucic, Cia Ha O9 =306 186 Acid, glyceric, C3 H« O4 . . . 93 Acid, glycolic, C2 Hi Os .60, 92 Acid, guaiacic, Ce Hg O3 . . . 92 Acid, gummic, C12 H22 On.. 217 Acid, hippuric, C9 HjNOs.. 125 Acid, insolinic, C9 Hs O4 . . . 94 Acid, itaconic, C5 He O4 . . 121 Acid, lactic, CsHeOs-.g^. "2 Acid, lauric, Ci2Ha402 =200 90 Acid, leucic, C« H^Os = 132. 92 Acid, lichenstearic, C9 HuOs 92 Acid, nthic, C5 H4 N4 O3 . . 123 Acid, lithofelUc, CaoH88P4 . . 93 Acid, malic, C4 Hj Os =134 ^'S Acid, malonic, Ca H4 O4 . . . 93 Acid, mannitic 183 Acid, tnargaric, CnHs402 ... I77 Acid, meconic, Cj H4 O. . . . 143 Acid, melissic, CaoHgoOa . . 90 PAGE. Acid, tnellitic, C4 Ht O4 . . . . 94 Acid, mesoxalic, C3 H2 Os . . 94 Acid, tnetagummic 217 Acid, monochloracetic, Ca CI H3 Oa =945 aoi Acid, moringic, Ci5H2a02 . . 91 Acid, morintannic 196 Acid, mucic, Ce Hj Og = 205 95 Acid, myristic, CuHagO-^ ... 90 Acid, cenanthalic, C7 HuOa 90 Acid, cenanlhic, Ci4H2g03 . . 92 Acid, oleic, Ci8H3403 =282. 91 Acid, opianic 127 Acid, oxalic, Ca Ha O4 ■ .93, 1 12 Acid, oxamic, Ca H3 NO3 . . 11 Acid, oxybenzoic, C7 He O3 195 Acid, oxybutyric, C4 Ha O3 92 Acid, oxycuminic, CioHjaOa 92 Acid,oxynapthalic, CioHe O4 94 Acid, oxy valeric, C5 H10O3 . . 92 Acid, palmitic, CieHaaOa .90, 177 Acid, parabanic,C8 Ha N2 Os 125 Acid, paraflnic, C24H4802 . . 23 Acid, paralactic 123 Acid, paramalic, C4 H4 O4 . . 116 Acid, paratartaric 117 Acid, pectic, C16H22O5 =294. 2i8 Acid, pectosic 218 Acid, pelargonic, C9 H18O2 ... 90 Acid, phenic, Ce He 0=94 . . 33 Acid, pheny Isul phuric, Ce He 048=174 33 Acid, phloretic, C9 HioOa . . 93 Acid, phtaliCjCa He O4 = 150 94 Acid, phy8etoric,CieH9oOa .. 91 Acid, picric, Ce Hs (NO2 )3 O 33 PAGE. • 94 •• 94 • 317 .... aoi 2 •• 9« 196 20S 95 )... 90 Oa 90 s .. 92 82. 91 127 •93. 112 3 •. II O3 '95 Os 92 jOs 92 5O4 94 >3.. 9^ 93 177 Os 125 2 •• 23 132 1 •• 116 117 294. 218 • . - 218 )2.. 90 H-- 33 • ••• 3a » •• 92 150 94 h.. 91 )3 33 INDKX. 223 PAOE. Acid, pimelic,C7 H1JO4 93 Acid, pinaric,C,»)H;ii02 =302 41 Acid, pinic, Caol I:»02 = 302 . . 91 Acid,piperic,Ci2Hio04 =218 94 Acid, propionic, C3 Hu Ox 78, 90 Acid, prussic, nCN=27. .. «6i Acid, pyrognllic, Ce He O3 . 198 PAOC. Acid, thionuric, C4HbN03S03=J95--- "S Add, thymotic, CnHuOs •• 9^ Acid, toluic, Cs Ha O2 = 13^' 9' Acid, trichloracetic, HGj CI3 Oa = 163.5 102 Acid, tropic, C9 HioOs =166. 164 Acid', pyroligneous 100 Acid, uric.Cs H4 Ni O3 = 168 123 Acid,pyroineconic,C5H4 08 92 | Acid, valeric or valerianic. Acid, pyrotartaric, C5 Hg O4 = 132 93.117 Acid, pyroterebic,C6 H10O2 . • 9' Acid, pyruvic, C3 H4 O3 -88 92 Acid, quinic, C7 HiaOe =144- 93 Acid, quinotannic 19^ Acid,raceniic,C4 He Oe =15° "7 Acid, ricinolcic, Ci8H3403,92. 180 Acid, roccellic, CnH3204 . • 93 Acid, salicylic, Ct H5 Os i95.32.92 Acid, sarcolactic '22 Acid, scammonic, CisH-^Os 92 Acid, sebic, C10H18O4 =202.. 93 Acid, sorbic, Co U% Oa =112. 9« Acid, stearic, C18H36O2 . .90. '77 Acid, 8uberic,C8 H14O4 = 1 74 93 Acid, succinic, C4 IIe04 93. »i5 Acid, sulphocarbolic, C6H6S04=i74 33 Acid, sulphoglucic 185 Acid, sylvic, C20H90O2 = 302. 41 Acid, tannic, C27H220i7=6i3 196 Acid, tartaric.Ca Ho 0« . ..116, 95 Acid, tartrelic, C4 H4 O5 . . . "7 Acid, tartronic, C3 H4 O5 . . 94 Acid, terebic,CT H10O4 = 158 93 Acid, terechrysic, Ce He O4 94 CeHic02=io2 109, 90 Acid, veratric, C9 HioOs ... 94 Acid, xylic, C9 H10O2 = 150- 9' Acids 95 Acids, aromatic 9' Acids.fatty 90 Acids, general methods of preparation, 9" Acids, organic 9^ Acids, defined..... 95 Acids, polyatomic 112 Acids, pyro 97 Aconitina, C30H47NO7 =533- 1^5 Alcohol, allyl, C3H6O...45, 57 Alcohol, amy lie, C5Hi20.56,45 Alcohol, benzyl, Ct Hs 0= 108 46 Alcohol, butyl, C4 HioO=64 45 Alcohol, eery l.CflHseO = 396 45 Alcohol, cholesteryl 4^ Alcohol, cinnyl, C9H10O.. 46 Alcohol, cuneol 46 Alcohol, cymol, CjoHuO.. 46 Alcohol, melissic, CaoHjaO . . 180 Alcohol, methyl, CH4 O. .45, 46 Alcohol, myricyl, CsoHeaO.. 45 Alcohol, octyl, Cs HwOs 130 45 224 INDEX, FAGZ. Alcohol, ordinary, or ethyl, C2 He 0=46 49 Alcohol, propyl, Cs Hg O.. . 45 Alcohol, sexdecyl, C16H34O. . 45 Alcohol, sextyl, Ce HuO 45 Alcohol, vinyl, C2 He 0=46 45 Alcohol, xylyl.Ca HioO= 122 46 Alcohols, diatomic 58 Alcohols, monatomic 44 Alcohols, polyatomic 59 Alcohols, sulphur 82 Alcohols, selenium 8; Alcohols, tellurium 82 Alcohols, tetratomic 59 Alcohols, triatomic 64 Aldehyds 86 Alizarin, CioHe Os = 174. . . 39 Alkalaniides 136 Alkaloids 127 Allantoin, C4 He N4 Os = 158 124 Alloxan, C4 H4 N2 O5 =160. 125 Alloxantin, Cg H10N4 Oio. . 123 Allyl iodide, Cg H5 1= i63. . 57 Allyl sulphide, Ce IIioS= 114 57 Allyl sulpho-cyanide, C4H5NS=99 57 Allylamine, Cs H7N=:57,.. 127 AHylene, C3 H4 =40 20 Amane, Cs Hi2=72 23 Amber 26, 42 Amides 136 Amidoxypropyl, C3H4(I;H2)0=72 75 Amines 133 Ammelide 172 PAGE. Ammonia aldehydate, C3H4 0NH3=6i 87 Ammonia citrate of iron. .. 121 Ammoniacum 43 Ammonias, compounds 131 Ammonium, cyanate,CH4 N2 172 Ammoniums 137 Ammoniums, quarternary. . 136 Amygdalin, CjoHijrNOn 193 Amyl, acetate, C7 HuOs . . 5^ Amyl, chloride, C5H11CI.. 56 Amyl, hydride, C5 Hi2= 72. 23 Amylamine, C5 Hi3N=87. . 121 Amylene, C5 Hio= 70 23 Anhydride, tartaric, C4H4 0s=i32 117 Aniline 30, 127, 131 Anthracene, Ci4Hio= 178. .29, 39 Arabin Ci2H220n=342 217 Arbutin CisHi607 =284. ... 193 Aricina C2SH26N2 O4 =397. . 129 Arnicin 42 Aromatic compounds 89 Arsines 128 Asphalt 26 Assafoelida 43 AtropiaCnHjsNOs =289. 164,129 Balsams 41 Bases organic, 125 Bases quarternary, 136 Bassorin 218 Belladona 164 Benzene C« He =78 27 Benzine 24 Benzoic aldehyd, C7 He O.. 86 Benzol, Ce Hj =78 27 87 1. .. 121 ... 43 131 4 Na 172 . . . . 137 ry.. 136 193 3.. 56 :i.. .S6 =72. 23 57.. 121 ... 23 117 127. 131 !• -29. 39 ... 217 ... 193 >7-- 129 42 89 * . ■ 128 26 43 . 164,129 ... 41 . . • 125 . . • 136 . ■ . 218 ... 164 ... 37 24 0.. 86 27 INDEX. 226 PAGB. Benzone, C0(C6 H5 )2 = 182 1 19 Benzonitrile C7 H5 Nsiog.. no Benzyl chloride, Q H5 O CI 126 Benzylene, Ci5n28= 208 20 Bidecane, Ci2H»= 1 7° 28 Bidecy 1 hydride, Ci2H26= « 7° 23 Bitumen 26 Biuret, C2 O2 H5 N3 = 1 13 • • 172 Borneol, CioHisO = 1 54 5^ Brandy 52 Brucia, C23H28N 04,4H2 = 394+72 161, 129 Butane C4 Hio=5S 23 Butter Butyl hydride, C4 Hio=58. . Butylamine, C4 HiiN = 73. .. Butylene, C4 Hs =56. . . .20, Cacodyl, (CH 3)2 As 79, Caffeia (caffeine), Cg H10N4 0= 194 130. 168 Campholic alcohol 117 Camphor,artificial,CioHi6HCl 37 Camphor, CioHi60=i52.... 40 Camphor, monochlor, CioH5iC10= 186.5 41 Camphor, oxy-, CioHieOj ... 41 Camphor of Bornco.CioHisO 58 Cantharidin, C5 Hg O3 =95- »3 Propyl i.S Propyl hydride, C3 Ha =44. 23 Propylamine, C3 H9 N = 59 • • '27 Propylene, C3 He =42 22 Proplene iodide,C8H5 I — 168 64 Ptyalin 212 Pyrethrin 42 230 INDEX, PAGE. Pyrolignite io6 Pyroxylin 207 Quercite, Ce HigOa = 164. . . 181 Quercitrin, C!sH3oCn=65o. . 193 Quinia, (quinine) CfflHaiNa Oa =324 — 151, 129 Quinicia, G»Ha4NaOa ..154, 129 Quinidia, CaoIIiiNa Oj =324. 129 Quinidia, oxalate of 155 Quinoidine 158 Quinoleine, (Quinoline), 130. 153.157 Quinovin, C80H48C8 =536... 193 Radicles, defined 14 Radicles, organometallic 78 Radicles, organotnetalloid. . . 81 Reagent, Fehling's 187 Reagent, Haines' 187 Reagent, Trommer's 186 Resins 25, 41 Retinasphalt 25 Retinite 25 Rhigolene 24 Rice 216 Rochelle salt, KNaC4H4 06 4-4aq.... 118 Rosaniline, CaoHaiNs 6=319 31 Rutylene, CioH]8= 138 20 Rye 216 Saccharide 186 Saccharoses,Ci2H230ti = . 189,182 Salicin, CisHisOt =286 194 Saligenin, C^ Hg Oj = 124.. . 194 Saponification 176 Saponine 193 Sinapoline, C7 HijNa 0= 140 58 PAGE. Sinnatnine, C.| Hg Na =82. . 58 Soaps 176 Sodium ethyl, Ca H5 Na= 52 80 Sodium sulphocarbolate, NaC6H6S04=i97 33 Solanidia, (so'.anidine) i6j Solania, (solanine) C43HtiNOi6=8s7.. . 165,129,193 Sorbin, Ce HiaOe = i8o 182 Spermaceti, CajHeiOa =480 179 Spirit of Mindererus 105 Stannethyl 79 Stannethyl iodide 79 Starch 210 Stearin, (stearine) CstHho Oe =890 174 Stearine candles 1 76 Stibines 128 Stibyl 119 Strychia, (strychnine), CaiHaaNa Oa =334. . . 159, 129 Styrol,C8H8=i04 38 Sucrates 190 Sugars 181 Sugar of milk, Ci3Hi40i2i9'.'82 Tannin, Ca7H2aOn=6i8..i96, 193 Tartar emetic, KSbC4 H4 O7 =325 "8 Tetrachloropropyl, CsH3Cl4=i8i IS Tetradecane, Ci4H3o= 198. . . 24 Tetradecyl hydride, C14H30. . 24 Tetradecylene, Ci4H28= >9f>- 22 Tetrethylammonium, N(Ca'H5)4=i3o 133 ThebeiajCigHaiNOs 148, 120 L 29.193 . l82 J 179 . 105 • 79 • 79 . 210 • 174 . 176 .. 128 . 119 INDEX. 231 Theia, (theine) Cg H10N4 Os = 194- • • -168, 130 Theobromine, C7H8N4 02=i8o....i69, 130 Thymol, CioH 140= I so 34 Thiosinnamine, C4H8N2S=ii6 58 Tobacco 140 Toluene, C7 Hg =92 ^^ Toluidine,C7 H9 N = 107.. 127, 130 Trehalose, Ci2H220n= 342- 182 Trichlorhydrin, Cg H5 CI3 . . 66 Trichloroxypropyl, C3H2CIS 0=160.5 IS Tridecane, U13H28- 184 27 Triedecyl hydride, CisHjg. . 24 Tridecylene, Ci3H26= 182 .. . 22 Triethylamine.Ce Hi5N= loi. 135 Triethylarsine, Ce HuA. — 128 PAGB. Triethylenic, diamine, CeHijOa =112 170 TriethyUtibine, CeHwSb... 128 Trimethylainine, C3H9N... 128 Trimethylphosphine.Cs H9 P 128 Tunicine, (Ce HiqOj )x,. . 184, 209 Turpentine, CioHi6= 136 35 Types, organic 10 Wax 179 Whiskey S* Wines 3* Wood-spirit 49 Xylene, C8Hio= 106. 28 Xylidine, C8HiiN=i2i 127 Xylyl alcohol, CsHioOs 122. 46 Zinc, ethyl, (C2H5)2Zn= 213.2 79 Zinc, glycol, Zn(C8 H4 NO2 )i =2i3.2...79, 126 9. "9 • 38 . 190 . 181 91,182 16,193 . 118 •• IS ,. 24 ,. 24 >. 23 ■• 133 \S, 120 *^ f y