UC-NRLF am GIFT OF PnoF. w.D. a / f fe&C44s . OUTLINES BASED IN PART UPON RICHES' MANUEL de CHIMIE, C. GILBERT WHEELER, \ Professor of Chemistry in the University of Chicago. A, S, BARNES & 00,, NEW YORK AND CHICAGO. '877. OTHER WORKS BY PROF. WHEELER. DETERMINATIVE MINERALOGY. A practical guide to the recogni- tion of mineral species, chiefly by physical characteristics. Price $1.00. NATURAL HISTORY CHARTS. Five in number, one each of the fol- lowing: MAMMALIA; BIRDS; REPTILES and FISHES ; INVEKTEBRATKS; MINERALS, ROCKS and FOSSILS. In all, over 700 illustrations. Wholly hand colored Pi ice of each chart, $7.00. The set, $30.00. NATURAL HISTORY PRIMER. A concise descriptive work on ZOOL- OGY and MINERALOGY. Price $1.00. CATALOGUS POLYGLOTTUS, Or classified list of Ihc more important animals, mineral" and fossils in Latin, English, French, German and Spanish; for Scientific Travelers, Collectors, Curators of Museums and others. Price $2.00. IN PREPARATION. THE CHEMISTRY OF BUILDING MATERIALS. COPYRIGHT C. ; G iLB,E,tlt ;.W HEELER. ;:>;>';,'.< 1877. PREFACE. Organic chemistry has not as yet secured in Ameri- can colleges sufficiently pronounced 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 not resulted in any important sacrifice of perspicuity in thought or arrangement. It would have been easier to prepare a larger work. From the bewildering wealth of results afforded by the labors of investigators in this branch of science, the ap- 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 upon 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 granted, 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 237364 PREFACE. has served in part as basis for these Outlines, the works of Miller, Fownes, Williamson, Roscoe, and others have been freely used, while the chemical journals of Europe and America, including their latest numbers, have been consulted and the data which they afforded utilized. For the benefit of any who may care to read the full original papers from which are taken the abridged ex- cerpta of recent articles there are given references, within parentheses, to a list of authorities to be found in the author- s work on Medical Chemistry. Lest any regard the number of characteristic re- actions of the more important compounds as insuffi- cient, it should be stated, that it was not within the plan of the author to adapt this work to the requirements of an analytical manual. Not more than two or three analytical tests are therefore given as a rule, and even this number only in the case of the leading compounds. A similar explanation might be proffered to any who may miss the full technical de- tails relative to certain compounds which are usually given in works on applied, or technological chemistry. Throughout the work, the centigrade thermometer and the metric system of weights and measures are employed, unless otherwise specifically stated. C. GILBERT WHEELER. UNIVERSITY OF CHICAGO, October, 1877. CONTENTS. INTRODUCTORY, - 7 CLASSIFICATION OF ORGANIC COMPOUNDS, 10 HOMOLOGOUS SERIES, - 12 HYDROCARBONS, - 18 ALCOHOLS, - 44 MONATOMIC, 46 DIATOMIC, 58 TRIATOMIC, 64 ETHERS, 69 ALDEHYDS, 85 ACIDS, 90 MONATOMIC, 96 POLYATOMIC, - 112 ALKALOIDS OR BASES, - 127 ARTIFICIAL, 132, 170 " NATURAL, - 137 NEUTRAL FATTY BODIES, 174 SUGARS, - 181 GLUCOSIDES, 193 VEGETABLE CHEMISTRY, 199 CELLULOSE, - 205 STARCH, - 210 DEXTRIN, 214 GUMS, - - 216 ORGANIC CHEMISTRY. rNTEODUCTOEY. Organic chemistry is the science of the compounds of carbon. Only a small number of other elements are met with in natural organic substances; they are hydrogen, oxygen and nitrogen, sometimes also, sulphur, phos- phorus, and very rarely certain other elements. Chemists have succeeded in incorporating most of the elemental substances in organic bodies, yet the larger number even of the artificial compounds include only the four elements first named. Paraffine is found by analysis to contain only carbon and hydrogen, and is therefore called a hydrogen- carbide. The hydrocarbides are compounds so stable and fundamental that some chemists, as Schorlemmer for instance, have even defined organic chemistry as "the chemistry of hydrocarbons and their derivatives." From alcohol, or sugar, we may obtain carbon and water. These bodies therefore are composed of three elements: carbon, hydrogen and oxygen, and are called carbohydrates ; though by some chemists, this term is restricted to those compounds containing car- 8 ORGANIC CHEMISTRY. bon with hydrogen, and oxygen in such proportions as would form water. If albumen is decomposed by heat, the result is not only carbon and water, but also ammonia ; this sub- stance accordingly is nitrogenous. The number of organic bodies is very great. As they are composed of a small number of elements only, it may be concluded that the latter unite in a very great variety of proportions ; it is therefore of much impor- tance to know the molecular grouping of these ele- ments. The mere fact that the kind and number of elements entering into a compound are known, is not sufficient proof that its molecular structure is really determined. Synthesis must often be employed to confirm the results of analysis. Berthelot has specially occupied himself with the synthesis of organic bodies, and has artificially produced a great number of them. Other chemists have experimented in the same direction during the last 15 or 20 years. However, Gerhard t's opinion advanced in 1854; viz., " The vital force alone operates by syn- thesis and reconstructs the edifice demolished by chemical affinity," has ceased to be held as true. ISOMEEISM. Carbon, hydrogen, oxygen and nitrogen are not only capable of uniting in a great variety of proportions, but these elements also furnish numerous isomeric bodies ; these comprise substances which, while com- ISOMERISM. 9 posed of the same elements, have different properties. Sometimes the physical properties alone are different ; we then have physical isomerism. When the chemical properties themselves are modi- fied, this is denominated chemical isomerism. Of the latter, two kinds are recognized. I. Polymerism; cyanogen and paracyanogen are examples of this variety of isomerism ; the latter is to be considered as cyanogen, CN condensed, thus (CN)n ; it is a poly meride of cyanogen. The weight of the molecule of these two substances is therefore dif- ferent. II. Metamerism. At other times the isomerism results from a different grouping of elements in the compound, the molecular weight remaining the same. We will illustrate this by two examples : a) Methyl acetate, and b) Ethyl formiate. Acetic acid = H-0-C 3 H 3 0. Methyl hydrate, or methyl alcohol=H-O-CH 3 . When these two bodies react they furnish water and methyl acetate, CH 3 -O-C 2 H 3 O=<5 3 H 6 2 . Formic acid=H-O-CHO. Ethyl hydrate, or ethyl alcohol=H-O-C 2 H 5 . JN T ow formic acid contains CH 3 less than acetic acid, and hydrate of ethyl contains one molecule of CH 2 more than does hydrate of methyl. As these substan- ces in reacting lose one molecule of water, it is there- fore clear that the compound obtained will have, like the preceding one, the formula C 3 H 6 Oj>. But these 10 ORGANIC CHEMISTRY. two products are not identical substances, for the for- mer treated with alkalies regains the molecule of water which it had lost, reforming acetic acid and methyl hy- drate, while the latter regenerates formic acid and ethyl hydrate. These bodies accordingly differ in the arrangement of their molecule ; they are called metameric bodies* Finally there exist bodies which are isomeric, prop- erly so-called, possessing the same formula, having the same general reactions, the same chemical functions, and which differ only in a very few, chiefly physical, properties : such are oil of turpentine and oil of lemon, each having the formula C 10 H 16 . CLASSIFICATION OF ORGANIC COM- POUNDS. CHEMICAL TYPES. The idea of referring organic bod- ies to some simple model, or type, was originally work- ed out by Laurent and Gerhardt, 18^6-53, though the germs of their ideas 011 classification are to be found in the earlier papers of the distinguished American chemist T. Sterry Hunt. (Am. Jour. Sci. [2] xxxi.) The four principal types are : TT/ \ I. The hydrogen type, TT, > or H 2 . II. The oxide or water type, 5, 1 O' ' orH 2 O. H/ ) III. The nitride or ammonia type,H V N' ' ' orII 3 N. ORGANIC TYPES. 11 BM IV. The marsh gas type ^ ',\ C IV or H 4 C. H'j Of the leading groups of organic bodies, we refer to the hydrogen type: hydrocarbides, aldehyds and the compounds of metals and metalloids with organic radicals. To the water type are referred the alcohols, ethers, rnercaptans and anhydrides. 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 complex organo- metallic bodies. Farther details as to the relation of each of these classes of compounds to their respective types will be given 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 types of ammonia and water combined serve as a pattern for carbamic and oxamic acids: JJ ' ) Carbamic acid. Oxamic Acid. o 12 ORGANIC CHEMISTRY. HOMOLOGOUS SERIES. The members of a series of compounds which have the common difference of CH 2 are said to be homolo- gous. Two or more such homologous series are termed The first idea of progressive series in organic chemistry was enunciated by James Schiel, of St. Louis, Mo., in 1842. It was afterwards adopted by Gerhardt unchanged, save only in name. (100-5-195.) The subjoined table will illustrate the nature of these series. Each vertical column forms a homologous series in which the terms differ by CH 2 , and each hori- zontal line an isologous series in which the successive terms differ by H 2 . The bodies of these last series are designated as the monocarbon, dicarbon group, etc. C H 4 C H 2 Cg-Llg Cg-H.^ Cgllg C 3 H 8 C 3 H 6 C 3 H 4 C 3 H 2 C 4 H 10 C 4 H 8 C 4 H 6 C 4 H 4 C 4 H 2 ^5^-12 C 5 H 10 C 5 H 8 C 5 H 6 C 5 H 4 C 5 H 2 CeH 14 C 6 H 12 C 6 H 10 C 6 H 8 C 6 H 6 C 6 H 4 C 6 H 2 The terms of the same homologous series resemble one another in many respects, exhibiting similar trans- formations under the action of given re-agents, and a regular gradation of properties from the lowest to the highest ; thus, of the hydro-carbons, C n H 2n+ 2, the low- est terms CH 4i C 2 H 6 , and C 3 H 8i are gaseous at ordinary temperatures, the highest containing 20 or more car- HOMOLOGOUS SERIES. 13 bon-atoms, 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 CH 2 to the molecule. The individual series are given in the following ta- ble, with the names proposed for them by A. W. Hoffmann: Methane Methene O I j_4 Jig Ethane Ethene Propane C 3 H 8 Quartane C 4 H 10 Quintane C 5 H 12 Sextane Propene C 3 H 6 Quartene C 4 H 8 Quintene C 5 H 10 Sextene C 6 H 12 Ethine C 2 H 2 Propine 3 H 4 Quartine 4 H 6 Quintine C 3 H 3 Sextine Propone Quartone Quartune 04x14 ^Hjj Quintone Quintune 5 H 6 Sextone CH 5 H 4 Sextune C 6 H 6 The formulae in the preceding tables represent hydro- carbons all of which are capable of existing in the separate state, and many of which have been actually obtained. They are all derived from saturated mole- cules, C n H 2n4 . 2i by abstraction of one or more pairs of hydrogen- atoms. But a saturated hydrocarbon, CH 4i for example, may 14 ORGANIC CHEMISTRY. give up 1, 2, 3, or any number of hydrogen-atoms in exchange for other elements ; thus marsh gas, CH 4 , subjected to the action of chlorine under various cir- cumstances, yields the substitution-products, CH 8 C1, CHCaCla, CHC1 8 , CC1 4 , which may be regarded as compounds of chlorine with the radicles, (CH,)', (CH,)", (OH,)'", 0"; and in like manner each hydrocarbon of the series, C n Ii 2 n+2, ma J yield a series of radicles of the forms, each of which has an equivalent value, or combining power, corresponding with the number of hydrogen- 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, perhaps, as double molecules. These hydrocarbon radicles of uneven equivalence are designated by Hoffmann, with names ending in yl, those of the univalent radicles being formed from methane, ethane, &c., by changing the termination HOMOLOGOUS SERIES. 15 ane into yl ; those of the trivalent radicles by chang- ing the final e in the names of the bivalent radicles, methene, &c., into ylf and similarly for the rest. The names of the whole series will therefore be as follows : CH 4 (CH 8 )' (CH 2 )" (OH)'" Methane Methyl Methene Methenyl C 2 H 6 (C 2 H 5 )' (C 2 H 4 )" (C 2 H 3 )'" Ethane Ethyl Etliene Ethenyl C S H 8 (CaH,)' (C 3 H 6 )" (C 3 H 5 )'" Propane Propyl Propene Propenyl &c. &c. &c. From these hydrocarbon radicles, others of the same degree of equivalence may be derived by partial or total replacement of the hydrogen by other elements, or compound radicles. Thus from propyl, C 3 H 7 , may be derived the following univalent radicles: C 3 H 6 C1 C 8 H 8 01 4 C 3 H 5 Chloropropyl Tetrachloropropyl Oxy propyl C 3 H 2 C1 3 6 C 3 H 6 (CN)' C 3 H 6 (N0 2 ) Trichloroxypropyl Cyanopropyl. Nitropropyl C 8 H 4 (NH a )0 C 3 H 6 (CH 3 ) C 3 H 5 (C 2 H 5 ) 2 Amidoxy propyl Methylpropyl Diethylpropyl. From the radicles above mentioned, all well-defined organic compounds may be supposed to be formed by combination and substitution, each radicle entering into combination, just like an elementary body of the same degree of equivalence. 16 OEGANIO CHEMISTRY. TABLE TO ILLUSTRATE THE ARRANGEMENT OF THE MOKE Series. Hydro- carbons. Sulphides. Chlorides or Haloid Ethers. Alcohols. General Formula. CriH.2n CnH2 + i I tt CnH2+i f s CttH2W+iCl Cnttm+i i. C H2 (C H 3 )2S C H 3 Cl C H 3 HO 2. C2 H4 (C2HS)2S C2HS Cl C2Hs HO 3- C 3 H 6 C 3 H7 Cl C 3 H7 HO 4. C 4 H g C4H 9 Cl C4Ho HO 5. GS Hio (C5Hii)2S CsHiiCl CsHiiHO 6. C 6 Hi2 C 6 Hi 3 HO 7. C 7 Hi 4 8. Cg Hi6 CSHifCl CsHi7HO 9. Cg HiS 10. CioH2o Types H| H } HI II | Hj Hf u H f \ OKGANIC COMPOUNDS. 17 IMPORTANT ORGANIC COMPOUNDS IN HOMOLOGOUS SERIES. Mercaptans. Aldehyde. Acids. Simple Ethers. Compound Ethers. . H \S CnH2n-i O I H I CH2-iO j ~ Hf CnH2/i+i t CnH2w- zO f C H3 HS C H 0,H HO H 02 (C H 3 ) 2 C H 3 C H 02 i. C2Hs HS C2 H3 O,H HC2 H3 02 (C 2H5 , 2 C2H5 C2 H 3 02 2. C3 HS 0,H HC3 HS 0-i C2Hs C3 HS 02 3. C4H 9 HS C4 H7 O,H HC4 H7 O2 C2Hs C4 H7 02 4. CsHnHS Cs H 9 O,H HCS H 9 O2 (CsH 9 )20 CsHuCs H 9 02 5. C6 HiiO,H HC 6 HnO2 C2HS C 6 HiiO2 6. C 7 H, 3 0,H HC7 Hi3O2 C2HS C7 Hi3O2 7. HCg HisO2 C2HS Cg HisO2 8. HC 9 Hi7O2 C2Hs C 9 Hi7O2 9 . 11 ! o Hf CioHi 9 H,0 HCioHi 9 O2 (CioHi 9 )2O C2HS CioHi 9 O2 10. H 1 Hf H | Q H( Hf H / Q 18 ORGANIC CHEMISTRY. CAEEIDES OF HYDKOGEK The origin or preparation of these compounds, also called hydrocarbides, and their properties, physical and chemical, all differ largely. They are unlike the hydrogen combinations studied in inorganic chemistry inasmuch as they possess but feeble chemical energy Among the carbides are: acetylene, marsh-gas or methane, ethylene, oil of tur_ pentine and of lemon, benzol, iiaphthalin, petroleum, caoutchouc, gutta-percha, etc. The hydrocarbides will be divided into six series, they are all built upon the type of a molecule of hy- drogen, or H' ) ir r FIKST SEEIES. General Formula, C n H-2 n _ 2 . ACETYLENE, OB DIHYDROGEN DICARBIDE. Discovered by Davy and composition determined by Berthelct. Formula, C2Ha- Specific Gravity, 0.92. Density, 13. Molecular weight, 26. Direct combination of Carbon and Hydrogen. Up to comparatively recent times it has been con- sidered impossible to unite carbon and hydrogen di- rectly. Berthelot, however, succeeded in doing this in the year 1863. PREPARATION. The apparatus which he employed CARBIDES OF HYDKOGEJS. 19 in this remarkable synthesis, consisted of a glass flask, provided with two lateral tubulures through which passed two metallic rods, terminating in carbon points, and which approached so as to form, when connected with a powerful battery, an electric arc. The corks through which these rods passed were provided with another opening each, to which, a tube 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, whereupon acetylene was set free. Many organic compounds produce acetylene on subjecting their vapors to the action of electric dis- charges. Acetylene is also produced, as a rule, whenever or- ganic matter is decomposed by heat. PROPERTIES. Acetylene is a colorless gas, having a disagreeable odor. It is moderately soluble in water, and has not been liquified. It is decomposed, at about the temperature at which glass melts, into carbon, hydrogen, ethylene, ethyl hydride and condensed hydrocarbides, among which Berthelot has found ben- zol. Thenard has recently obtained it both as a liquid and a vitreous solid. (9 78 219.) Acetylene burns with a fuliginous flame. It de- tonates violently and witho.it residue when mixed with 20 ORGANIC CHEMISTRY, 2.5 volumes of oxygen. Cuprous acetjlide is an ex- plosive body. It is sometimes formed in brass gas- pipes, and has been the cause of fatal accidents. Chlorine acts upon acetylene with extreme energy; there is often detonation accompanied by light. On moderating the action the compound C 2 H 2 C1 2 can be obtained, which, as well as the body C 2 H 2 C1 4 , can also be prepared by the action of antimonic chlo- ride upon acetylene. As acetylene is not uncommonly studied in con- nection with inorganic compounds, a more detailed ac- count of this hydrocarbide need not be given here. Acetylene is the prototype of a homologous series of hydrocarbides, of which the general formula is, The following members of this series are known Allylene, - - C 3 H 4 Crotonylene, - C 4 H 6 Valerylene, - C 5 H 8 Rutylene, C 10 H 18 Benzylene, - C 15 H 28 . ETHYLENE. 21 SECOND SEKIES. General formula, C n H2n. ETHYLENE. Synonyms: Elayl, Olcfiant gas. Formula C 2 H 4 Sp. Gr. 0.97. Molecular weight, 28. This gas, for no good reason other than custom, is always studied in inorganic chemistry, 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: \J n -Lion. 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. 22 ORGANIC CHEMISTRY. We note the following members of this series : Ethylene, - - C 2 H 4 Propylene, - C 3 H 6 Butylene, - - C 4 H 8 Amylene, C 5 H 10 Hexylene, - C 6 H 12 Heptylene, - C 7 H 14 Octylene, - - C 8 H 16 Nonylene, - C 9 H 18 Paramylene, - C 1 H 2 Cetene, - C^H^ Duodecylene, - - ^i2H 24 Tridecylene, (Paraffin?)* C 13 H 26 Tetradecylene, C 14 H 28 . *A. G. Pouchet(66 [3] 4868) has prepared from paraffin, by oxydation with nitric acid, paraffin acid, C^EUsOa, from which he deduces C24H50 as the formula for paraffin. METHANE. THIED SEEIES. General formula, CnH^n^r METHANE. Discovered by Yolta in 1778. Synonyms; Methyl hydride, Marsh gas, Formene. Formula CH 4 or CH 3 , H. Sp. Gr. 0.559. Molecular weight, 16. Permanent gas, not liquifiable, neutral. Not discussed in detail here for the same reasons as givun under Ethylene. Methane is the first member of the following very important homologous series: C H 4 methyl hydride, or methane. C.H, ethyl a " ethane. C S H 8 propyl <.(, " propane. c 4 ri 10 butyl a " butane. C 5 H 12 amyl a " amane. C 6 H 14 hexyl a " hexane. C 7 H 16 heptyl a " heptane. C 8 II 18 octyl tt " octane. C 9 H-20 nomyl tt " nonane. CioH a decyl tt " decane. CnH 24 undecyl a " undecan< Ci 2 H 26 bidecyl tt " bidecane 24 ORGANIC CHEMISTRY. tridecyl " " tridecaiie. tetradecyl " " tetradecane. CisHgj pentadecyl" u pentadecane. C 16 H34 hexadecyl " " liexadecane. Nearly all the members of this series have been found in American petroleum, mixed with members of the preceding, or ethylene, series. Crude petroleum, 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 appertain to chemical compounds, or bodies having a definite composition. Subjoined is a table based on Dr. C. F. Chandler's Heport on Petroleum, (100 '72-41) showing the PRODUCTS OF THE DISTILLATION OF CRUDE PETROLEUM.* NAME. PERCFNTAGE YIELUED. SPECIFIC GKAVITY. BOILING POINT. CHIEF USES. Cymogene Rhigolene .625 0C. 18.3 I Generally uncondcnsed used in 1 ice machines. j Condensed by ice and salt used as Gasolene l 1 /^ .665 48.8 ( an anaesthetic. Used in making "air-gas." C Naphtha B Naphtha (,0" .706 724 82.2 104 4 {Used for oil-cloths, cleaning, adul- teratin ' kerosene, etc. For paints A Naphtha Benzine '" .743 148.8 and varnishes, Used to adulterate kerosene oil. Kerosene oil Mineral sperm Lubricating oil Paraffin 55 19* .804 .817 .833 Solid. 176.6 218.3 301.6 Ordinary oil for lamps. Lubricating machinery. Manufacture of candles. *Rc-arrangedfrom Dr. C. F. Chandler's Report on Petroleum, presented to the Board of Health, of the City of New York, 1870. METHANE. 25 UNSAFE KEEOSENE. Many accidents occur by explosion of lamps, when kerosene oil contains too much of the lighter oils, ben- zine and naphtha. This makes the oil too readily in- flammable, for the lighter oils are driven out by heat- ing (as when a lamp or kerosene stove is burning), and their vapors mixed with the oxygen of the air form a dangerous explosive mixture. There is a law requir- ing manufacturers to keep kerosene oil free from these lighter oils, unfortunately not always faithfully en- forced. The temperature at which kerosene, on heating in an open vessel, emits vapors which readily catch fire on approaching a burning body, is called, technically, the " flash point/' and that at which the kerosene itself inflames is called the ''burning point." FOSSIL KESINS, AND BITUMEN. These substances include amber, re tin asphalt, as- phalt, retinite, and many other allied bodies which are chiefly contained in the tertiary strata. In many in- stances they are the products of the action of an ele- vated temperature upon vegetable bodies; and when this is the case, they form irregular deposits which im- pregnate the strata around. In many cases the bitu- mens occur in regular beds, which appear to have been formed in a manner similar to the deposits of true coal. Certain important building stones have been found to be more or less impregnated with bitumen. Such is the limestone obtained at the artesian well 26 ORGANIC CHEMISTRY. quarry in the city of Chicago, and the celebrated Buena Yista, (Ohio,) sandstone used extensively in Cincinnati; also employed at Chicago in various prominent public buildings, as the post-office and Chamber of Commerce. The author, in making a chemical examination of the latter stone for the United States Treasury Department, found it to con- tain 2.3 per cent, bituminous matter. BENZOL. 27 FOURTH SERIES. General formula Cn H-2n 6. BENZOL. ; Benzene, Benzine. Formula C,jH 6 . Sp. Gr. 0.88. Molecular weight, 78. Sp. Gr. of vapor 2.70. Density " " 39. Solid at 4. Boils at 80.5 Benzol is obtained, with acetylene and ethylene, in the decomposition of organic substances by heat, and its production is especially favored when the temperature is kept at a high point for some time. Ethylene and methane form at a tolerably low temperature. Acetylene, which is richer in carbon, is produced at a higher temperature. Benzol and especially napthalin, being still more carbonaceous, are formed at an extremely high temperature. Berthelot has prepared benzol synthetically by con- ducting methane tribromide, CHBr 3 , over red-hot copper : 6(CHBr 3 )+9Cu=C 6 H 6 -f-9CuBr 2 Benzol may be considered as condensed acetylene: 28 ORGANIC CHEMISTRY Originally, banzol was prepared by a process analo- gous to that which furnishes methane, i. ., by distill- ing benzoic acid with lime, C 7 H 6 2 +CaO = Ca C O 5 +C 6 H 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; viz.: Toluene C 7 H 8 boils at 110 Xylene C 8 H 10 " " 139 Cumene C 9 H 13 " " 165 Cymeue C 10 H 14 " " 180 and other hydrocarb ides, as napthalin C 10 H 8 , anthra- cene, also various sulphur compounds, notably carbon bisulphide; several oxygenated compounds, as phenol C 6 H 6 O, cresylol 7 H 8 O ; nitrogenous compounds, as aniline C 6 H 7 N, and various members of its homologous series. Benzol is a colorless, neutral liquid, with a specific gravity of 0.89, almost insoluble in water but soluble in alcohol and ether. It dissolves sulphur, phosphorus, iodine, the differ- ent resins, and fatty substances ; this latter property causes it to be employed similarly with commercial " benzine" for cleansing purposes. Care must be taken to rub with a piece of cloth having an open texture, 29 that it may remove the benzol by absorption, without which the spot would reappear after evaporation of the solvent. Benzol burns with a fuliginous flame. Nascent oxygen gives with it various products, and notably oxalic acid and carbon dioxide. Chlorine and bromine yield crystalline compounds with benzol. Benzol is the simplest member of a group of bodies known as the aromatic compounds, 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 pitch, in a test tube, and pour over it some of the substance to be ex- amined. Benzol will immediately dissolve the pitch to a tar-like mass, while benzine will scarcely be col- ored. This body is obtained by treating benzol with fuming nitric acid. C.H.+HNO.- C 6 H 5 (N0 2 )+H 6 0. Nitro-benzol is a yellowish oil, crystallizing at 37, has a sweet taste and an odor which has 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 obtain 30 ORGANIC CHEMISTKY. aniline, which is a colorless liquid, boiling at 182. It does not act upon litmus, yet combines with the acids, forming crystallizable 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 methyl, ethyl, etc., forming the corresponding amines, or bodies constructed on the type of ammonia, having one or 'more of the hydrogen atoms replaced by an organic compound radicle: ( C.H. - Aniline C 6 H,N = N { H IH (C 6 H 5 Methylaniline C T H 9 N = N \ H 3 H Ethylmethylaniline C 9 H 13 N CH CH .. C 6 H 5 or, when free, (C 6 H 5 ) 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 colored violet, which color disappears iir a few moments. In 1858, Perkins obtained, by the action of potassium bichromate and sulphuric acid, a beautiful purple, which is known in BENZOL. 31 commerce as mauve. Shortly after, Yerguin obtained a magnificent red coloring matter on heating aniline with tin dichloride. This substance, known under the names of aniline- redy fuchsin, magenta, etc., is now very economi- cally obtained with arsenic oxide in place of the tin dichloride, which is reduced to arsenous oxide by the reaction. Hoffmann has shown that aniline-red is a salt of a colorless base, which he calls rosanilirie; this substance has the formula C^Etl^O, or C^H^N^H^O. In the past few years there have been produced green, yellow and black colors, 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 research, 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 a, 32 ORGANIC CHEMISTRY. tinctorial agent, offers a singular contrast to the early experiments upon this body, when a lew ounces fur- nished a supply which exceeded the most sanguine ex- pectations of the early discoverers of this body. PHENOL, C 6 H 5 0. Synonyms: Hydrate-of phenyl, carbolic acid or phenic acid- It occurs in castoreum, though usually procured from the portions of coal-tar distilling over between 170 and 195. They are agitated with caustic soda, 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. Salicylic acid, distilled with an excess of lime, also furnishes phenol; C 7 H 6 3 + CaO = CaC0 3 + Ifphenyl-sulphuricacid, Vr 5 j- SO 4 , obtained by di- rect action of sulphuric acid upon phenol, is heated with potassium hydrate to about 300, potassic phenol C 6 H 5 KO is obtained. Phenol is therefore obtained from benzol under the same conditions as alcohol is obtained from ethylene, the corresponding hydro- carbide. Phenol crystallizes in handsome needles, fusible at 34 and boiling at 188. It is little soluble in water, PHENOL. 33 very soluble in alcohol and ether. Phenol furnishes with chlorine, bromine and iodine numerous substitu- tion products. Phenol lias come, like alcohol, to have a generic signification, there being a number of analogous com- pounds, though only this, the ordinary phenol, is an important body. Heated with concentrated nitric acid, it furnishes yellow, very bitter, crystals of the body known as PICKIC or CARBAZOTIC ACID. Picric acid is also formed when silk, benzoin, aloes, indigo, etc. , are treated with nitric acid. Tiiis acid is very largely used in dyeing, either di- rectly to produce a yellow color, or, combined with in- digo, to produce a green. Phenol, though called carbolic acid, does not decom- pose the carbonates, or combine with the metals to form true salts. Phenol dissolves in sulphuric acid without coloration, if pure, and forms phenyl-sulphuric acid or sulpho-carbolic acid H which gives definite salts with the metals. One of these, the phenyl-sulphate or sulpho-carbolate of so- dium KaC 6 H 6 SO 4 , is claimed to have valuable proper- ties as a prophy lactic against scarlet fever. Phenol gives certain reactions of the alcohols ; this 34 ORGANIC CHEMISTRY. somewhat explains the origin of the name given it by Berthelot. This body is the type of a class of com- pounds which contains: Cresylol obtained from creosote C 7 H 8 O Phlorylol " " C 8 H 10 O Thymol " u essence of thyme C 10 H U O. PHYSIOLOGICAL ACTION OF PHEXOL. 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 surgical cases. It is sometimes used internally. Large doses of it are poisonous. Carbonate and especially saccharate of calcium are considered as antidotes for phenol. Grace Calvert has announced that olive or almond oil is a still better antidote. OIL OF TURPENTINE. 35 FIFTH SEEIES. General Formula, C n Hgnt. ESSENCE, OR OIL OF TURPENTINE. Formula Density of vapor compared with air 4.7. Molecular weight, 136. Boils at 160. Turpentine is extracted from several varieties of the family of conifera, notably from the pine, fir and larch. The products vary somewhat with the nature of the tree, but they have many common characteristics; their composition is the same, their density is nearly identical and their boiling point very nearly so. Their rotary action on the solar ray varies largely. Isomeric carbides are found in other families of plants, in the aurantiacecB family for instance, as the lemons and oranges. These contain carbides very dif- ferent, as evidenced by their odors and other physical properties, also different in certain chemical relations, yet having the same composition as oil of turpentine. There are also various polymers of this carbide. This entire series of hydrocarbons can be divided into three groups. The first contains carbides having 36 OKGANIC CHEMISTRY. the formula C 10 H 16 , their boiling points being be 500, and including : Density. Boiling at Oil of turpentine, 0.86 157 to 160. a cloves, 0.92 140 "145. it lemon, 0.85 170 " 175. < orange, 0.83 175 " 180. a juniper, 0.84 about 160. a bergamot, 0.85 " 183. u pepper, O.S6 " 167. a elemi, 0.85 " 180. The carbides of the second group have the formula their boiling is above 200, they are : Oil of copaiva, 0.91 245. " cubebs, 0.93 240. The third group contains the non-volatile carbides, such as Density Caoutchouc, - 0.92. Gutta-percha, - 0.98. The rotary power, constant for each, varies with the different species. French oil of turpentine causes the plane of polar- ization to deviate to the left; the American variety turns it 13 to tke right; oil of lemon causes a devia- tion of 50 to the right; in the case of essence of elemi the deviation amounts to 100. Some of the OIL OF TURPENTINE. 37 essential oils of the first group contain oxygen com- pounds as well as the carbohydrid.es. The principal chemical differences between the members of the group are the facility with which they are oxydized and their reaction with hydrochloric 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 essence of turpentine, a liquid and a solid compound, having each the same composition, C 10 H 16 , HC1, which, after a few weeks, becomes a dichlorhydride, (by some denomi- nated a dichlorhydrate), C 10 H 16 ,2HC1. Essence of lemon also gives two dichlorhydrides 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 burno with a smoky flame; on exposure to the air it oxydize,. and becomes resinous. The same effect is produced more rapidly with oxide of lead and some other ox- ides which render the oil siccative and suitable for use in painting. J. M. Merrick (100-4-289) has noticed the circumstance, important in its technical applica- tions, that oil of turpentine attacks metalic lead quite strongly; tin, on the other hand, not at all. Turpen- tine, if exposed to the air, mixed with a solution of indigo, absorbs oxygen and transfers it to the indigo,. 38 OKGANIC CHEMISTRY. which loses its color, yielding a product of oxydation called isatin. Under these circumstances, the turpen- tine does not change, and a given quantity of the es- sence can absorb several hundred times its volume of oxygen, and oxydize an indefinite quantity of indigo. This oxygen is probably the active modification, or ozone. Heated to 300 in a hermetically sealed tube, it changes into two products, one, isomeric, called iso- turpentine, which boils at 1YY, and which exerts a rotatory power of 10 to 15 to the left; the other, a polymer called meta-terebenthene, C^H^ boiling at 360. OTHER SERIES OF HYDROCARBIDES. Cinnamene C 8 H 8 is a very refractive liquid with a density of 0.924, boiling at 146. Styrol which is produced from storax is converted at 205, into a polymeric solid, termed Meta-styrol or Draconyl. If styrol is made to act upon acetylene, or ethylene, at a red heat, there is obtained the very important hydro- carbide naphthalin Ci H 8 . This is a body crystalliz- able in very handsome plates, and is ordinarily obtained from coal tar by distillation between 200 and 300; heavy oils pass over, out of which naphtha- lin crystallizes; on cooling, the mass is pressed and purified by sublimation. It fuses at 79 and distils at 220. Naphthalin is associated in coal tar with a hydro- carbide, beautifully crystallizing in long needles, fus- ing at 93 and boiling at 285. This is acenaphtene ALIZARIN. 39 C 12 H 10 . Another hydrocarbide is also found in this tar, anthracene. Its formula is C 14 H 10 . It forms very diminutive crystalline plates fusing at 210 and boil- ing at 360. Its vapor is extremely acrid. This body has recently enabled chemists to repro- duce the coloring principle of madder; alizarin C I4 H 8 4 . It is obtained on oxydizing anthracene by means of a mixture of bichromate of potassium and sulphuric acid, which gives oxy anthracene C 14 H 8 O 2 . This, with fused potassa, furnishes a combination of potassium and alizarin, from which the latter is pre- cipitated by an acid. It has the form of brilliant bronze-colored needles, identical with natural alizarin obtained from madder. Alizarin sublimes at 215 and is very stable, little soluble in cold water, but readily soluble in boiling water. It is easily dissolved in alcohol, ether and car- bon bisulphide. Its chemical character, not quite well defined as yet, appears to place it among the phenols. (See page 33.) The artificial production of alizarin from anthra- cene, thus furnishing a cheap substitute for madder, the chief dye-stuff used in printing calicoes, is one of the latest and most noteworthy triumphs of organic chemistry. Thousands of acres of land in Europe, especially in Alsatia, now devoted to the culture of madder, may be restored to cereal or other food agri- culture. Before leaving the hydrocarbons proper, it should 40 ORGANIC CHEMISTRY. be stated that compounds of carbon and hydrogen of extra- terrestrial origin have been found in certain met- eorites, by J. Lawrence Smith. (80-76-388.) CAMPHOB. Camphor is usually considered at this point, 0:1 ac- count of its intimate relation to the oxydized essential oils in composition, and to turpentine in many chemical reactions. Berthelot regards camphor as an aldehyd. Ivekule places it among the ketones. Camphor exists" in various parts of the Laurus camphora. To obtain it, the wood is finely divided and heated with water in a metallic vessel, closed by a cover filled with straw. The camphor is condensed in grayish crystals on the straw, forming the crude cam- phor of commerce ; it is afterwards sublimed in a glass retort as a further purification. Camphor is a crystallized body, having a burning taste and an aromatic odor. Its density is 0.99 at 10. It is elastic and with difficulty pulverized, which can, however, be easily effected on moistening with a few drops of alcohol. Water dissolves only about y^Tr part of it ; thrown upon pure water it floats on the surface with a gyratory motion. It is soluble in alco- hol, ether, acetic acid and essential oils ; it is sublimed at ordinary temperatures where kept in close vessels, and deposits again on the cooler side of the recep- tacle. It burns with a smoky flame and oxydizes on being EESINS, BALSAMS, .GUM-RESINS. 41 boiled with nitric acid, yielding camphoric acid C 10 H 16 O 4 which is bibasic. Heated with zinc chloride or anhydrous phosphoric acid, it furnishes Cymol C 10 H 14 . The author found (1-14:6-73) that on treatment of camphor with hypochlorous acid he obtained the -new body, C 10 H 15 C1O, which he denominates monochlor- campJwr\ this, on treatment with alcoholic potassium hydrate, yielded oxy camphor C 10 H 16 O 2 . Camphor is very extensively employed in medicine and pharmacy. RESINS, BALSAMS, GUM-RESINS. These bodies are products of the oxidation of essen- tial or volatile oils. The name of gum-resin is applied to those which contain a gum, and balsam to those which contain essential oils and an acid, usually cin- nainic or benzoic, in addition to the resin which is present in both. A. B. Prescott, the eminent au- thority on proximate analysis, defines balsams as " natu- ral mixtures of volatile oils with their oxidation pro- ducts, resins and solid volatile acids. " They are substances more or less colored, hard and brittle. They are fusible, non- volatile, and burn with a fuliginous flame. They are insoluble in water, gen- erally soluble in alcohol, ether and essential oils. Several of them are acid. This is the case with the most important of them, as the resin of the pine, called colophony, from which three isomeric acids have been obtained ihepinic, sylmc, and pimaric, 42 ORGANIC CHEMISTRY. This resin constitutes the fixed residue obtained on distilling crude turpentine. It is used for preparing varnish, in soldering, and in certain combinations with the alkalies, called resin-soaps. Subjoined are given the names and the origin of the principal resins, oleo-resins, gum-resins and balsams. With some, the position assigned them in this classi- fication is not definitely settled. EESINS. Amber is found in the lignites and in the alluvial sands of the Baltic. Arnicin, the active principle of Arnica Hoot. Cannabin, the active principle of Indian Hemp. Castorin, a secretion of the Beaver (Castor). Ergotin(?), the active principle of Ergot of common rye. Mastic, a resinous exudation of the Mastic, or Lent- isk tree. Burgundy Pitch, an exudation of the Spruce Fir, Abies excelsa. Pyrethrin, the active principle of the Pellitory root. Rottlerin, a cr/stalline resin from Kamala, the min- ute glands which cover the capsules of Rottlera tinc- toria. OLEO -RESINS. Copaiva, a resinous juice of the copaifera offioinalis found in Spanish America. Wood-oil, an oleo-resin from the Dipterocarpm turbinatus. RESINS, BALSAMS, GUM-EESINS. 43 Elemi, an exudation of an unknown tree, (probably Cannarium commune). Common Frankincense, a concrete turpentine of the P'.nus tceda. Canada balsam, the turpentine of the Balm of Gilead Fir, (Abies balsamea). Storax, from the Liquidambar orientale. GUM-RESINS. Ammoniacum, an exudation of the Dorema ammo- niacum. Assafoetida, a gum. resin obtained by incision from the living root of the Narthex assafcetida. Gamboge, obtained from the Garcinia morella. Galbanum, from the galbanum officinale. Myrrh,an exudation of the jBalsamodendronmyrrha. BALSAMS. Benzoin, obtained from incisions of the bark of Styrax benzoin. Balsam of Peru, from the Myroxylon Pereiros. Balsam of Tolu, obtained from incisions of the bark of Myroxylon tuluifera. Caoutchouc is the hardened juice of Ficus elastic^ Jatropha elastica, Siphotiia cahuchu, and other plants. Gutta-percha is the concrete juice of the percTia (Malay) tree the Isonandra percha, a sapotaceous plant. 44 OEGANIC CHEMISTRY. ALCOHOLS. GENERAL DEFINITION AND CHARACTERISTICS. This name is given to a class of neutral bodies as important as they are numerous. Their essential characteristic is that of reacting upon acids so as to form water and a class of bodies called ethers. 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 H ' ) TT 5 \ O, ethyl or common alcohol. II. On two molecules of water : O TT f ' } 2 TT 4 [- O 2 , ethylene alcohol or glycol. III. On three molecules of water : O TT ' ' ' ) I O 3 , glycerine and thus on. "8 ) They may be defined as bodies built on the type of one or more molecules of water having one-half of the hydrogen replaced by a hydrocarbide radicle. MONATOMIC ALCOHOLS, or those formed on the type of one molecule of water, ALCOHOLS. 45 of which ordinary alcohol is the best studied, are characterized by the fact that they contain one atom of oxygen only, and that by reaction with the mono- basic acids they form only a single ether. They in ay be obtained synthetically, as well as by various indirect processes. Subjoined is a classified list of the more important monatomic alcohols: FIRST SERIES, C n H 2+2 0. Methyl alcohol (wood spirit), C H 4 O Ethyl alcohol, (spirit of ,wine) C 2 H 6 O Propyl alcohol C 3 H 8 O Butyl alcohol, - C 4 H 10 O Amyl alcohol, 5 H 12 O Setyl alcohol - C 6 H 14 O Octyl alcohol C 8 H 18 O Sexdecyl alcohol - - C^ED^O Ceryl alcohol C 27 H 56 O Myricyl alcohol - C^H^ O SECOND SERIES, C n II 2n O. Yinyl alcohol C 2 H 4 O Allyl alcohol - C 3 H 6 O THIRD SERIES, * C n H 2n _ 2 O. Eorneol alcohol C 10 H 18 O 46 ORGANIC CHEMISTRY. FOURTH SERIES, Benzyl alcohol C 7 H 8 O Xylyl alcohol - 8 H 10 O Curaol alcohol C 9 H 12 O Cjmol alcohol - - C 10 H U O FIFTH SERIES, OH O ^n-^Sn 8^- Cinnyl alcohol C 9 H 10 O Cholesteryl alcohol - C 26 H44O MONATOMIC ALCOHOLS HAVING THE GENERAL FORMULA, METHYL ALCOHOL, OR WOOD-SPIRIT. CH 4 = ^ 3 | O. 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 only that portion collected which passes over above 70. On being again ALCOHOLS. 47 distilled with calcium chloride ife furnishes methyl al- cohol, nearly pure, boiling at 66.5. There are other methods of rectifying besides the one here given. This body possesses most of the general properties of ordinary alcohol. Under the action of the oxides it furnishes an aldehyd and formic acid. With the acids it produces ethers; viz., with CII / hydrochloric acid, methyl chloride, CH 3 C1= ^ 3 j- ; with acetic acid, methyl acetic ether, C 3 H 6 O 2 =g ^ 3 O j. O. CHLOROFORM, CIIC1 8 . Methyl chloride produces with chlorine a regular series of products of substitution. One of these terms, CHC1 3 , is the very important body, chloroform, dis- covered in 1831 by Soubeiran and Liebig. To prepare this compound, 40 litres of water, 5 kilos of recently slacked lime, and 10 kilos of chloride of lime are heated to 40; 1500 grams of 90 per cent, alcohol are then added and the retort luted with clay. It is now heated for a moment to the boiling point and the fire then at once slackened. The ebullition having ceased there will be found two layers in the receiver. The upper layer is formed of water and alcohol, the lower one is chloroform nearly pure. The latter is washed with water, agitated with a dilute solution of potassium carbonate, or with fused 48 ORGANIC CHEMISTRY. calcium chloride for twenty-four hours, and distilled to four-fifths. Chloroform is a colorless liquid. When first pre- pared it has a sweetish penetrating taste, and an agree- able, ethereal odor. Its density is 1.48; it boils at 60.5, is soluble in alcohol and ether and difficultly so in water. It burns, though not readily; its flame ha vino- a green margin. It dissolves iodine, sulphur, phos- phorus, fatty substances and resins. An alcoholic solution of potassa decomposes it into chloride and formiate : CHC1 3 -f 4KHO 3KC1 -f CHKO 2 -f 2H,O. PHYSIOLOGICAL ACTION. Chloroform is at present very generally used as an anesthetic. Opinions as to its manner of acting are divided. Formerly it was thought that the insensi- bility produced was the commencement of asphyxia. Since then it has been ascertained that the heart, in case of poisoning by chloroform, immediately loses all powerof contraction^ and it is now generally admitted that paralysis of the muscles and nerves of the heart is produced. 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 prevented, or serious consequences may re- sult. Probably the fatal accidents that have occurred ALCOHOLS. 49 may, in some instances at least, be attributed to lack of care in this regard. It is of great importance that the chloroform used should be quite pure. In some cases it has been found to have undergone spontaneous decomposition after exposure to a strong light. It ought to communicate no color to oil of vitriol when agitated with it. The liquid 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 remain. Shuttleworth (100, 4, 339) states that partially de- composed chloroform can be rectified by agitating it with a solution of sodium hypo-sulphite. OKDESTAEY ALCOHOL. ETHYLIC, OR YINIC ALCOHOL. Formula: C->H 6 O. Density of vapor 20. Density .81. Boils at 78.4o. Cannot be solidified. It is prepared by the fermentation of saccharine liquids at a temperature of 25 to 30, in the presence of a small quantity of a ferment. Cane sugar does not directly become alcohol under the influence of a ferment. It is first transformed into two other sugars, glucose and levulose. 50 ORGANIC CHEMISTRY. C 12 H 22 O n + H 2 Glucose. Levulose. In its final fermentation nearly all the sugar is changed into alcohol and carbon dioxide, This equation accounts for the transformation of 94 to 96 per cent, of the sugar employed, but besides alcohol and carbon dioxide, succinic acid is always formed as well as glycerine, and in most cases " fusel oil," consisting chiefly of amyl alcohol. Fermentation is a phenomenon correlative with the development and growth of cells of the fungus Myco- derma (Torula) cerevisice which constitutes yeast. Sometimes the sugar is furnished as a natural product by fruits ; often glucose is produced from the starch of cereals, potatoes, etc., and then changed into alcohol afterwards. Corn is the leading original source in this country. Alcohol obtained by fermentation is concentrated by distillation. This operation is performed in retorts, the construction of which is based upon a principle developed by A. de Montpellier, and improved by Derosne, Dubrunfaut and others. The object is to prevent the distilling over of the water with the alco- hol, and is quite well accomplished by the improved methods now employed. The details are not suited to the scope of this work. The application of this rational method of distilling ALCOHOLS. 51 admits of obtaining liquids containing up to 90 per cent, of alcohol, but it is difficult to go beyond that point of concentration. In order to prepare alcohol more concentrated, sub- stances having a great avidity for water must be used. Calcium chloride is not suitable, as it unites with the alcohol. Anhydrous sulphate of copper, carbon- ate of potassium or quicklime do not produce absolute alcohol. But it is very rare that perfectly anhydrous alcohol is required. Alcohol of 97 per cent, is obtained in treating alcohol of 85 per cent, during two days with lime, or better, with a sixth or seventh part of its weight of dry potassium carbonate, and then distilling. If it is desired to procure absolute alcohol, very concen- trated alcohol is treated with caustic baryta until the liquid is colored yellow and then distilled. Alcohol in fresh bread made with yeast has been found by Bolas (8-27-271) to the amount of .314 per cent. Slices of bread a week old contained .12 to .13 per cent. Absolute alcohol is a colorless liquid, more limpid than water, of an agreeable odor and a burning taste. It boils at 78.4:, is neutral, combustible and burns with a flame but little luminous. It heats on coming in contact with water, and attracts the moisture of the air very rapidly. It contracts upon mixing with water; the max- imum of contraction takes place at a temperature of 15 when 52. 3 vol. of absolute alcohol are mixed with 47.7 vol. of water; instead 100 vol. one obtains 52 . ORGANIC CHEMISTRY 96.3 vol. At the moment of admixture numerous air bubbles escape and the mixture becomes heated. The alcoholic strength of the liquids consumed as "beverages varies considerably. Madeira wines, Malaga " Bordeaux " about 20 per cent. " 14 to 16 " 5 to 12 Shine " " 10 to 12 u California " Y a Cider " 2 to 7 a Beer " 1 to 8 a Spirits are distilled from fermented liquids; brandy from wine ; whisky from a mash of corn or rye ; rum from molasses, etc. They contain abort 50 per cent, of alcohol. The term proof spirits was originally given to al- cohol sufficiently strong to fire gunpowder when lighted. The strength of proof spirits now varies in diiferent localities, and it would be w r ell were this ambiguous designation no longer employed. Alcohol dissolves the caustic alkalies, certain ni- trates, chlorides and other salts, also various gases. With some of these, genuine chemical combinations are produced, and not mere solutions; this is the case with calcium chloride and magnesium nitrate. Alcohol can be mixed with ether in all proportions; it dissolves the resins, essential oils, and a great num- ber of other organic bodies. The chemical properties of alcohol are very inter- ALCOHOLS. 53 esting. Yapor of alcohol is decomposed on passing through a tube heated to redness; hydrogen, marsh- gas, oxide of carbon, small quantities of naphthalin, benzol, and phenol are formed. In presence of air and water it slowly oxidizes and yields acid com- pounds. This action is rapid, if a hot spiral of plati- num is placed in the alcoholic vapor. EXPERIMENT. Place a small platinum spiral in the wick of an alcohol lamp, light and then blow out the flame. It will be seen that the spiral remains incan- descent. Spongy platinum acts still more energetically; if very concentrated alcohol is poured drop by drop into a capsule containing spongy platinum, or platinum black, it will be seen to redden, fumes are produced and an acid liquid is formed containing chiefly aldehyd and acetic acid. The same oxidation occurs if diluted alcohol is exposed to the air in the presence of mother of vinegar, a cryptogamic plant, (Mycoderma aceti). 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 54 ORGANIC CHEMISTRY. lively ebullition results, and a crystalline precipitate is deposited which explodes at 185, or by percussion. This body is the fulminate of silver or mercury, re- spectively, which is considered as derived from methyl cyanide, CH 3 Cy, by the substitution of 1 molecule of nitryl, and of 1 atom of mercury, or 2 of silver for 3 atoms of hydrogen. The formula are C(N0 2 )HgCy; C(N0 2 )Ag 2 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. Ozone,. according to A. W. Wright, (80 1_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 CnEkn+aO. Rabuteau (981631) has shown that they are more poisonous in proportion as their mole- cules are complex. Cases have been observed where a large dose of alcohol has caused death in half an hour. The worse than worthless character of distilled liquors as beverages is no longer an open question. With regard to their value as food or medicine, a more authoritative or competent expression of opinion can- not be desired than that of the International Medical Congress, which at its session in Philadelphia in 1876, said: ALCOHOLS. 55 "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 stimulant, and often admits of substitution. " 3. As a medicine, it is not well fitted for self-pre- scription by the laity, and the medical profession is not accountable for such administration, or for the enormous evils arising therefrom. "4:. The purity of alcoholic liquors is, in general, not as well assured as that of articles used for medicine should be. The various mixtures when used as medi- cine, should have definite 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 alcoholic 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 substance to be treated is a resin, or some substance absolutely insoluble in water, a very concentrated alco- hol is preferable. A weaker alcohol is made use of, if the matter is one that is soluble, both in alcohol and water. Alcohol acts not only as a solvent, but also as a pre- ventative of decay. This is a property which renders it especially valuable in the preparation of remedies. 56 ORGANIC CHEMISTRY. AMYL ALCOHOL. C 5 H 12 = C 5 H n 1 Q II [,- Synonyms: FOUSEL (OR FUSEL) OIL, POTATO SPIRIT. The amylic compounds derive their name from Amylum, starch, the chief constituent of the potato. They are formed in some proportion in almost every in- stance of alcoholic fermentation of sugar. Ainylic alcohol is usually prepared on fractionally redistilling the oil which remains when the alcohol, prepared from potatoes, barley, corn, etc., is distilled. The pro- duct which comes over at 132, is that collected. Cahours and Balard first established the analogy, in constitution and properties, of this compound with ordinary alcohol. It is a monatomic alcohol, giving with oxidizing re-agents, valeric acid. Amylic alcohol. Valeric acid. and with acids, compound ethers, as Chloride of amyl, OsHuCL r\ TT N Acetate of amyl or amyl-acetic ether, (/f^Q !" ' ALCOHOLS. 57 MONATOMIC ALCOHOLS. Having the general Formula C n H 2n O. ALLYLIC ALCOHOL, C 3 H 6 O = C 3 H 5 H This is a body giving the same reactions as ordinary alcohol. The radicle it contains is the same as that in the triatomic alcohol, glycerine. Among its deriva- tives there are two which are of considerable impor- tance : Allyl sulphide, ^ 5 j. S. Sulpho-cyanide, P 3 ]V 5 [ ^* The former is oil of garlic; the latter oil of mustard. OIL OF GARLIC is prepared by the following method: allylic alcohol is treated with phosphorus iodide which furnishes allyl iodide C 3 H 5 I. This iodide is afterwards mixed with an alcoholic solution of potassium sulphide and the whole is distilled; the product which passes over is identical with the essential oil obtained in dis- tilling garlic,onions, assafoetida, etc., with water. OIL OF MUSTARD, OR SULPHO-CYANIDE OF ALLYL. This body is prepared by causing iodide of allyl to react upon potassium sulpho-cyanide, ^ j- S, and may be regarded as sulpho-cyanic acid, " ! S, having the 58 ORGANIC CHEMISTRY. hydrogen replaced by the radicle of allyl alcohol, C 3 H 5 . The product which distills over is an irritating liquid which boils at 145, like the oil prepared from mus- tard directly. This substance may also be obtained by the action of allylic alcohol upon potassium sul- pho-cya:ride. It is likewise obtained by the fermenta- tion of mustard seeds. Sulpho-cyanide of allyl does not exist already formed in black mustard (Sinapis nigra\ but according to Bussy, its formation is due to a particular ferment. Oil of mustard combines directly with ammonia, forming a crystalline substance called thiosinnamine, C 4 H 8 ^N" 2 S, which, in contact with mercuric oxide, changes into an alkaloid called sinnamine, of which the composition is C 4 H 6 N 2 - It reacts upon lead oxide producing a substance called sinapoline whose formula is C 7 K 12 N 2 0. BORNEO CAMPHOK, OR BO3NEOL C 10 Hi 8 O. This body exudes from the dryobalanops camphora (Borneo). It is crystalline and has an odor between that of camphor and pepper. It fuses at 195, and boils at about 220. It is dextrogyrate. Heated with nitric acid it furnishes common camphor C 10 H 6 O. DIATOMIC ALCOHOLS OR GLYCOLS. C n H 2n + 2 2 . Ordinary Glycol, (C 2 HJ 2 H 2 =C 2 H 6 0, Propyl - (C 3 H 6 ) _0 2 -H 2 =C 3 H 8 Q, ALCOHOLS. 59 Butyl Glycol, (C 4 H 8 ) -0 2 -H S =C 4 H 10 S Amyl (C 5 H 10 )-0 2 -H 3 =C 5 H 18 2 Hexyl " (C 6 H I2 )-0 8 -H,=C 6 H 14 2 Octyl (C 8 H 16 )-0 3 -H 2 =C 8 H 18 8 . TRIATOMIC ALCOHOLS. Glycerine, (C 3 H 5 )-0 3 -H 3 =C 3 H 8 (V TETRATOMIC ALCOHOLS. Erythrite, (C 4 H 6 )-0 4 -H 4 =C 4 H 10 4 . ^ OTHER COMPLEX ALCOHOLS. Glucose and its isomerides, (C 6 H 6 ) 6 H 6 ^C^ 2 6 . Mannite, - (C 6 H 8 )-0 6 -H 6 =C 6 H 14 6 . Dulcite, (C 9 H 8 )-0 6 -H 6 =C 6 H 14 6 . Quercite, IT H O - ( CR ^^ i Pinnite, f^iiMfVi T H 2 f ORDINARY GLYCOL. The discovery of the glycols was an event of great importance. It was achieved by Wurtz in 1856, and the glycol of which we are treating was the first discovered. In a flask surmounted by a condenser, two parts of potassium or sodium acetate, are dissolved in weak alcohol and one part of ethylene bromide added. This 60 ORGANIC CHEMISTRY. mixture is heated in a water bath as long as the pre- cipitate of alkaline bromide continues to form, care being taken at the same time to keep the worm well cooled, in "order that the vapors of alcohol may contin- ually flow back into the flask. The alcohol is distilled off in a water bath, and the residue afterwards also distilled at a higher temperature, and that part col- lected which passes over between 140 and 200 . This portion which contains monacetic glycol, is heated with a saturated solution of baryta until the liquid acquires a strong alkaline reaction. The excess of baryta is removed by passing carbon dioxide through the solution which is then filtered and evaporated. The barium acetate is precipitated completely by strong alcohol, and the alcohol subsequently removed by dis- tillation. The 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 198 is the product sought. Zeller and Huefner have lately (18, 10,270) obtained the purest 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 taste. 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 gly colic acid. Its equivlence is shown by the follow- ALCOHOLS. 61 ing : glycol attacks sodium forming two sodium glycols; These glycols furnish two ethyl glycols on being heated with ethyl iodide. C 2 H 4 ) * (C 2 H 5 ) Ethyl-glycol. Diethyl-glycol. With hydrogen bromide it furnishes two different products according to the number of molecules of HBr taken. C a HA+ HBr = C 2 H 5 BrO + H 2 O. Monobromhydric ether. CaH 6 2 + 2HBr-C 2 H 4 Br+ 2H 2 O. Ethylene bromide. It is evident that mixed ethers may be obtained by treating glycol not with two molecules of the same acid, but with two molecules of different acids. Thus C TT aceto-chlorhydric glycol is formed ,p TT Q\pf 62 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. OXIDE OF ETHYLENE, C 2 H 4 O, a polymer of (C 2 H 4 ) 2 O2, is related to glycol as ordinary ether to alcohol. It is not obtained like the latter by the action of hydrogen sulphate on the alcoholic compound, but is produced by the action of potassa on mono- chlorhydric glycol. A solution of potassa is gradually poured into chlorhydric glycol placed in a glass, or a tubulated retort. KHO + C 3 H 5 C10 - KC1 + H 2 + C 8 H 4 0. 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 but not the properties of aldehyd, of which it is an isomeride. ALCOHOLS. 63 Oxide of ethylene is a very remarkable body. It combines directly with oxygen, hydrogen, chlorine and bromine, also combines directly with acids, often even with the disengagement of heat, forming the ethers of glycol and polyethylenic alcohols. This body is there- fore a true non-nitrogenous basic oxide. 64 OKGANIC CHEMISTRY. TEIATOMIC ALCOHOLS OR GLYCERINES. ORDINARY GLYCERINE, C 3 H 8 O 3 = 3 u 5 ' O- . -ti 3 ) This body, discovered by Scheele, in 1779, and called by him, on account of its sweet taste, the sweet principle of oils, has been specially studied by Chevreul and by Pelonze. Berthelot discovered its real nature and proved it to be a triatomic alcohol. Glycerine is prepared by decomposing neutral fatty bodies, in the soap and candle industry by alka- lies, or better still by superheated steam. (Tilghmaii's process.) It is obtained in pharmacy, whenever lead plaster is prepared arid remains in the water with which the latter is washed. It is much employed in pharmacy and perfumery and as a solvent for many substances. Crude glycer- ine may be purified by boiling with animal charcoal and filtering before being evaporated to the required consistency. The best process consists in distilling the crude condensed glycerine in a current of steam. Pas- teur has shown that glycerine is produced in a very small quantity in alcoholic fermentation. We owe to Wurtz, a remarkable synthetical reproduction ofglycer_ ine. Pi opylene C 3 H 6 furnishes an iodide C 3 H 5 I, called iodide of allyl. This body produces with bromine the ALCOHOLS. 65 compound C 3 H 5 Br3 which, treated with potassa, or oxide of silver, yields glycerine. C 3 H 5 Br 3 +3KHO = 3 KBr.+C 8 H 8 O 8 Glycerine. 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 glycerine, whose angles have been measured by Victor Lang (2-152-637). They are rhombic in form and very deliquescent. Glyc- erine is soluble in alcohol and water in all propor- 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 change. It is decomposed at a tem- perature above 300, and oils, inflammable gases, carbon dioxide, and a product very irritating to the eyes, called acrolein* acrylic aldehyd, are formed; this last substance may be obtained pure by distilling glycerine with sulphuric, or phosphoric acid. The formula of acrolein is C 3 H 4 O 2 ; it is also produced in the dry distillation of all fatty bodies which contain glycerine. If glycerine be made to fall drop by drop upon platinum black, it unites, like alcohol and glycol, with O-2 and glyceric acid is formed. C 3 H 8 3 + 0,=C 3 II 6 4 + H,0. The oxidation of the glycerine does not stop here; 66 OKGANIC CHEMISTRY. there is subsequently formed, acetic, formic, and car- bonic, but chiefly oxalic 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 alcohol and this acid, HC1+C 3 H 8 3 =C 3 TT 7 C10 2 +H 2 0. Monochlo:hydric ether, or Monochlorhydriu. The continued action of phosphoious perchloride upon glycerine, or the dichlorhydrate of glycerine, effects the elimination of additional molecules of water and the formation of trichlorhydrin. 3HC1+C 3 H 8 3 =C 3 H 5 C1 3 + 3(H 2 0) Trichlorhydrin. Berthelot has studied the acetines, butyrines (tri- butyrine exists in butter), yalerines, and many other ethers of glycerine. If glycerine is mixed with cold nitric acid, and sulphuric acid added drop by drop, an oily substance separates out which is trinitroglycerine C 3 H 5 (NO 2 ) 3 O 3 . This body detonates with great vio- lence. It acts very energetically on the system. A few drops placed on the tongue produce violent me- grim. Glycerine forms compounds with lime anal- ogous to those formed by sugar, according to P. Car- les, ' 1-174-87). ALCOHOLS. 67 USES. The uses of glycerine in the arts, and especially in pharmacy, are numerous and important, many of which are based upon the solvent power of this compound. Henry Wurtz (31-195-58) has made valuable suggestions as to its economical applications. TABLE SHOWING THE SOLUBILITY OP SOME CHEMICALS IX GLYCERINE, (FROM KLEVER.) ONE HUNDRED PARTS OF GLYCERINE DISSOLVE THE ANNEXED QUANTITIES OF THE FOLLOWING CHEMICALS: Arsenous oxide, 20.00 Arsenic oxide, 20.00 Acid, benzoic, 10.00 " oxalic, 15.00 " taniiic, 50.00 Alum, 40.00 Ammonium carbonate, 20.00 chloride, 20.00 Antimony and potassium tartrate, 5.50 Atropia, 3.00 Atropia sulphate, 33.00 Barium chloride, 10.00 Brucia, 2.25 Cinchonia, 0.50 " sulphate, 6.70 Copper acetate, 10.00 " sulphate, 30.00 Iron and potassium tartrate, 8.00 " lactate, 16.00 " sulphate, 25.00 Mercuric chloride, 7.50 Mercurous chloride, 27.00 Iodine, 1.90 Morphia, 0.45 Morphia acetate, 20.00 chlorhydrate, 20.00 Phosphorus, 0.20 Plumbic acetate, 20.00 Potassium arsenate, 50.00 " chlorate, 3.50 " bromide, 25.00 cyanide, 32.00 iodide, 40.00 Quinia, 0.50 taunate, 0.25 68 ORGANIC CHEMISTRY. Sodium arsenate, 50.00 " bicarbonate, 8.00 " borate, 60.00 " carbonate, 98.00 " chlorate, 20.00 Sulphur, 0.10 Strychnia, 0.25 nitrate, 4.00 " sulphate, 22.50 Urea, 50.00 Veratria, 1.00 Zinc chloride, 50.00 " iodide, 40.00 " sulphate, 35.00 ETHERS. 69 ETHERS. SIMPLE ETHERS. Ethers are products formed by the action of alcohols upon acids. By most chemists they are looked upon as referable to the oxides of metals; thus 2S 3 1 O and ^ 2 S 5 i O, CM 3 ) C 2 JbL 5 j may be regarded as the oxides respectively of methyl and ethyl. They bear the same relation to alcohols that oxides of the metals do to the hydrates. Potassium hydrate KOH. Ethyl hydrate, or ethyl alcohol C 2 H 3 OH. Potassium oxide T ^ i O. & } Ethyl oxide or ethyl ether * O. The simple ethers are mostly liquid. They are very slightly soluble in water, while they are readily soluble in alcohol. Exposed to the action of alkaline solu- tions they regenerate alcohol. C 4 H 8 2 +KHO = C 2 H 6 0+KCoH O 2 . 70 ORGANIC CHEMISTRY. ETHYL ETHER. Synonyms : Vinic ether, sulphuric ether, common ether. 4 H 10 = C * H ' Density .736. Density of vapor, 37. Specific gravity of vapor, 2.586. Boiling point, 35.5. To prepare this compound, sulphuric acid is heated with alcohol in a retort, placed in a sand-bath. The ether distills, its vapor being received in a well cooled condenser, provided with a long tube which cond ucts the uncondensed vapor into a chimney. The cork adapted to the tubulure of the retort is provided with two openings; in one is fixed a ther- mometer, through the other a tube passes which fur- nishes the supply of alcohol. All the connections should close perfectly. When the apparatus i s arranged in this manner, pour TOO grams of 85 percent, or 90 per cent, alcohol into the retort, and add, little by little, 100 grams sulphuric acid of 1.84 sp. gr., then heat. When the thermometer attains 130, cause the alcohol to flow from the upper vessel at a rate sufficient to keep the temperature between 130 and 140. The weight of alcohol capable of being transformed into ether is from 13 to 15 timas the weight of the mixture first in troduced into the retort. The distilled liquid is mixed ETHERS. 71 with 12 parts, to every 100 of its weight, of a solution of soda having a specific gravity of 1.32, and agitated from time to time, during -8 hours. The ether is decanted by means of a glass siphon, redistilled and four-fifths of the liquid collected. The remainder may serve for a future operation. This furnishes ordinary ether. To further purify, wash with water, decant and treat for two days with equal parts of quick lime and fused calcium chloride. Wil- liamson has clearly, shown that etherification takes place in two stages or successive reactions as follows : C 2 H 6 + H 2 S0 4 = II 2 + (C a H 5 )HS0 4 . Ethylsulphuric acid. (C 2 H 5 )HS0 4 + C 2 HeO = C 4 H 10 + H 2 SO 4 . This explains how a small quantity of sulphuric acid etherizes a large amount of alcohol, since sul- phuric acid is constantly regenerated. This is con- firmed by the following experiment. Iodide of ethyl is made to react upon potassium alcohol ; ether is obtained as indicated by the reaction; C 2 H 5 I + C 2 II 5 OK = C 4 H 10 4- KI. Ether is a neutral, volatile liquid, colorless, having a burning taste and a strong agreeable odor. When agitated with water it rises to the surface, but the water dissolves about one ninth of its own weight of the ether. It is miscible with alcohol in all propor- 72 ORGANIC CHEMISTRY. tions and with wood spirit. Ether is frequently adul- terated with the latter substance. Next 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 liquid. It dissolves phos- phorus and sulphur in small quantity. "W. Skey, (8 Aug. 3, '77,) has shown that contrary to the usual statement in standard works, ether dissolves notable quantities of the alkalies. At a red heat it is decomposed and furnishes carbon monoxide, water, marsh 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 occurrence. It should never be 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 case of alcohol, and the same compounds are the result. Chlorine acts violently upon it; in moderating the action, the whole or a part of the hydrogen may be replaced atom for atom by chlorine. USES. It is used in pharmacy in preparing etherial ETHERS. 73 tinctures, and as an antispasinodic and stimulant in the well-known Hoffmann's anodyne. Its most impor- tant 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. COMPOUND ETHERS are bodies built up on the type of water, having one half the hydrogen replaced by a hydrocarbide and the other half by a compound radicle containing oxygen, or, in other words, by the radicle of an acid. ACETIC ETHEK, (r?H r\\ C 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 of 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 prolonged action of ammonia transforms it into acetamide and alcohol. 74 ORGANIC CHEMISTRY. OXALIC ETHEKS. Oxalic acid, being a bibasic acid, furnishes with alcohol two combinations, one being acid and capable of combining with bases ; the other is neutral, C 6 H 10 O 4 . Only the latter is of interest. It may be prepared by introducing four parts of 90 per cent, alcohol and four parts of oxalic acid into a retort, adding to this mixture three to six parts of sulphuric acid and then rapidly distilling ; the product is washed several times, dried, then redistilled, collecting only the liquid which passes over at 184. This ether is aromatic, oily, and gradually decomposes in water. Potassium changes it into carbonic ether. If oxalic ether is agitated with ammonia, a white powder, oxamide, and ethyl alcohol are produced. (C 2 H 5 ) 2 2 1 ' i } II, = Oxamide may be considered as derived from two molecules of ammonia, and belongs to a class of bodies called diamides. It is a white substance, insoluble in cold water and alcohol. Heated with mercuric oxide it is transformed into carbon dioxide and urea. (Williamson.) ETHERS. 75 Oxalic ether treated with ammonia in solution in alcohol furnishes oxamic ether. In this connection the compound of the organic radicles with the haloid elements are usually studied: they are not unfrequently denominated ethers of the hydracids. Their type is a molecule of TT \ hydrogen, H j- . CHLORIDE OF ETHYL OK CHLOKHYDKIC ETHER. Cl f ' This body is formed in small quantity when ethy- lene is made to react upon hydrochloric acid. To prepare it, alcohol contained in a flask sur- rounded by cold water, is saturated with hydrochloric acid 2as and the mixture then distilled. o It is also obtained by pouring into a flask contain- ing 2 parts common salt, a mixture of 1 part alcohol, and 1 part sulphuric acid : it is then gently heated and the ether collected as previously shown. It is a liquid of an agreeable odor, and very volatile, having a boiling point of 12 and a vapor density of 64. A red heat decomposes it into ethylene and hydrochloric acid gas. It is combustible and burns with a green, smoky flame ; water dissolves the fif- tieth part of its volume, alcohol dissolves it completely. 76 ORGANIC CHEMISTRY. With chlorine it furnishes a complete and regular series of products of substitution which are not iden- tical, but isomeric with the chlorine products of ethene. Their formulae are: C 2 H 4 C1 2 Cg-tlgC^ C 2 H,CJ 4 C 2 H C1 5 C 2 C1 6 . IODIDE OF ETHYL OR HYDKOIODIC ETHER. C.H,I = C 2 H 5 1 ? is obtained on causing alcohol to react upon iodide of phosphorus; the action is violent with white phos- phorus, considerably less so with red phosphorus. Six hundred grams of concentrated alcohol are intro- duced into a retort with 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 etlryl 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 acid formed. It burns with a green flame, leaving a resi- due of iodine. Ammonium compounds in alcoholic, or aqueous solution, furnish ethylamine. This arnine can be attacked in its turn by iodide of ethyl and yields diethylamine and oxide of tetrethylammonium. The knowledge of these reactions and their application to other iodides are the basis of a general mode for the preparation of organic bases originated by Hoffmann. Iodide of ethyl, unlike the chloride, is readily decom- posed by solutions of silver nitrate, giving a precipi- tate of silver iodide. = (C.JI 5 ) CYANIDE OF ETHYL OR CYANHYDKIC ETHER. This ether is obtained on distilling in an oil-bath 1 part of potassium cyanide, with 1-5 part of an alkaline sulpho-vinate. 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 chloride, and that which passes over from 195 to 200 is collected on redistillation. Cyanide of ethyl is a colorless liquid of an alliaceous odor, boiling at 97.. Cyanide of ethyl is decomposed by potassium hy- drate; ammonia is produced, and the acid obtained corresponds with a higher homologous alcohol. 78 ORGANIC CHEMISTRY. 3 H 6 2 . Propionic acid. M. Meyer observed some years ago, that if cyanide of silver is treated with iodide of ethyl, a liquid is formed, boiling at 82, of an odor which is not that ot ordinary cyanhydric ether. Gautier has shown that this is an isomeric body, and that there are two isomeric series of cyanhydric ethers. Hoifmann has given a dis- tinctive character to these bodies: under the influence of the alkalies they produce a fixed substance, but this is formic acid and not ammonia, and a volatile substance which is a compound ammonia. H ) CN(C 2 H 5 ) + 2H 2 O= CHA + CJ1 5 V N. TT \ ' J ) Formic acid. Ethylamine. ORGANO-METALLIC COMPOUNDS. Iodide of ethyl attacks the metals and furnishes a class of bodies called organo-metallio 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(O a H 5 I) = (C 2 H 5 ) 2 Zn + ZnI 2 , 2Sn -f- 2(C 2 H 5 I) = (C 2 H 5 ) 2 Sn + SnI 2 . Practically these metallic radicles are obtained by various reactions: ORGANO-METALLIC COMPOUNDS. 79 1. By the action of the metal upon the iodide, for example; 2C 2 H 5 I + Zn=(C 2 H 5 ) 2 Zn 4- Znl a . In certain cases, with tin for instance, the reaction is not as distinct, and there is formed in addition to stan- nethyl iodide, stannethyl iodides variously condensed. 2d. The metal is treated with another radicle; thus sodium-ethyl is prepared by the action of sodium upon zinc ethyl, (C 2 H 5 ) 2 Zn + Na 2 =Zn + 2C 2 H 5 Na. 3d. On decomposing a metalloid compound radicle with a metallic chloride, 3ZnCl 2 + (C 2 H 5 ) 3 P=3(C 2 H 5 )Zn + 2PC1 3 . 4th. Stannethyl is obtained by plunging a plate of zinc into a soluble salt of this radicle: the radicle is precipitated in the form of an oily liquid. Cacodyl, As (CH 3 ) 2 was the first discovered of this class of bodies. It was obtained by Bunsen on distilling arsenous acid with potassium nitrate. The organic radicles combine with metalloids with more or less energy ; zinc -ethyl and cacodyl take fire in the air ; they also decompose water. The products of oxida- tion vary with the nature of the compounds employed; zinc-ethyl furnishes the body, CJI 3 ZnO, zinc-ethyl- ate, which, in contact with water, produces alcohol and oxide of zinc. The metals which are less readily oxy- 80 ORGANIC CHEMISTRY. dized, such as tin, lead and mercury, give oxides which play the 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. Auanoff (60-' 75-493) has obtained a body he denominates, methyldiethylphosphoniumphenyloxidehydrate! To prepare zinc-ethyl, we introduce into a flask connected with a condenser inclined in such a manner that the vapors find their way back into the flask, 100 grams 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 inclined as usual, and the distilling is effected over a direct fire, collecting the liquid pro- duct in a flask Billed with dry carbon dioxide. Finally 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 be absolutely dry, and it should always be collected and distilled in vacua, 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 chloride of phosphorus or arsenic, it furnishes triethyl phosphine, P(C 2 H 5 ) 3 , and trietbyl arsine, As (C 2 H 5 ) 3 . ETHERS. 81 Mercury-methyl, treated with iodine, furnishes a hydrocarbide which has the formula ol methyl, CH 3 . ' Professors Crafts and Friedel (72-[4]19-334) have prepared a large number of compounds of silicon with compound radicles, from which they have deduced valuable theoretical considerations. MISCELLANEOUS ETHEES. Formic, butyric, valerianic ether, and other ethers of the fatty series are prepared in the same manner as acetic ether, and have the general properties of this ether. The odor of these ethers is agreeable. Bu- tyric ether has the odor of pine-apple, and valerianic ether that of pears ; cenanthylic ether has ths aroma of wine, etc. They are used in the manufacture 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 be seen that the addition of the elements CIT 2 causes an elevation of about 20 in the point of ebullition. Kopp has shown that this fact is a general one and applies to the alcohols, and acids of the same series, and to the homologous bodies in general. Point of ebullition. Difference. Formic ether, - - 55 1 q Acetic " - 74: o^o Propionic " - - 95 |t Butyric - 119 fjo Yalerianic" - - 133 82 ORGANIC CHEMISTRY. The boiling point of one of these bodies may accord- ingly be predicted, if that of one of its homologous substances is known. There is a certain close relation between the point of ebullition of an ether and that of the acid whose radicle it contains: Point of ebullition. Difference. Formic acid, 105 ) " ether, - 55 f 50 Acetic acid - 118) u ether, 74 f 44 Propionic acid, - 140 / " ether, - 95 j 45 Butyric acid, - - 163 ether, - - 119 f 44 The solubility in water of the ether formed by homologous acids varies with the molecular weight ; thus formic ether is quite soluble, acetic ether is less soluble, butyric ether is but slightly so, and valerianic ether, which follows it, is nearly insoluble. MERCAPTANS AND THEIR ETHERS. On substituting sulphur, selenium, or tellurium for oxygen in the alcohols of different atomicity, sulphur, selenium, or tellurium alcohols are obtained, which are designated as mercaptans, selenium mercaptans, and tellurium mercaptans. Ethers proper correspond to these as to ordinary al- cohols. These ethers are derived either by the substi- ETHERS. 83 tution of an alcohol radicle for the typical hydrogen, as happens with monatomic mercaptans, or by the elimination of H 2 S, as is the case with biatomic mer- captans. One only of each of these two classes will be alluded to here. Ethyl sulphide, or hydrosulphu- ) n TT c C 2 H 5 ) Q ric ether, f 4Ml b = C 2 H 5 f b ' Ethyl mercaptan, C 4 H 6 S= 2 g 5 j- S. To prepare the sulphide a current 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 2 S +C 2 H 4 C1==C 4 H 10 S + 2KC1 KHS + C 2 H 5 C1=C 2 H 6 S + KC1. These bodies are afterwards separated by distillation- Like all the sulphur derivatives of alcohol, they have a nauseous odor. The sulphide boils at 91 the mer- captan at 36. MIXED ETHERS containing two different radicles, are obtained by act- 84 ORGANIC CHEMISTRY.. ing, for instance, with ethyl iodide upon potassium me thy late, thus : ethyl iodide, potassium potassium methyl-ethyl methylate. iodide. ether. CTT ) or by acting on hydric methyl sulphate j- SO 4 with ethyl alcohol. The following is a list of some of the more important mixed ethers of the monatomic series TABLE OF MIXED ETHEKS. BOILING POINT. Methyl-ethyl ether C 8 H 8 O= Q |[ 3 I O + 11 Methyl-amyl ether C 6 H 14 O = j^ 92 Ethyl-butyl ether C 6 H 14 O = ^ 2 ^ 5 1 O 80 Ethyl-amyl ether C 7 H 16 O = ^ 2 ^ 5 i O 112 Ethyl-hexyl ether C 8 H 18 O = * O 132 ALDEHYDS. 85 ALDEHYDS. The following are the principal aldehyds, arranged in series: C n H 2n O. Formic aldehyd - - C H 2 O Ethylic aldehyd O a H 4 O Propylic aldehyd - - C 3 H 6 O Butylic aldehyd - C 4 H 8 Valeric aldehyd C 5 H 10 O (Enanthylic aldehyd - - C 7 H 14 O Caprylic aldehyd - - C 8 H 16 O Caproic aldehyd CjoH-^O Eutic aldehyd CnH^O Ethalic aldehyd C^H^O C n H 2n . 2 0. Ally lie aldehyd (acroleiri) - C 3 H 4 O C n H 2n4 0. Campholic aldehyd (camphor) C 10 H 16 O 86 ORGANIC CHEMISTRr. Benzole aldehyd (oil of bitter almonds) C 7 H 6 Tolnic aldehyd C 8 H 8 O Cuminic aldehjd - C 10 H 12 O Sycocerylic aldehyd C 18 H 28 O C n H 2n .. 10 O. Cinnamic aldehyd (oil of cinnamon] - C 6 H 8 O. 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, may be illustrated by the following equation: C 2 H 6 0-H 2 C 2 H 4 O Ethyl alcohol. Ethyl aldehyd. Aldehyds are obtained by the oxydation of alcohols, but they are only the first products of oxydation. They are capable of combining with an additional molecule of oxygen, forming acids; hence the aldehyds are inter- mediate between alcohols and acids. ORDINARY ALDEHYD. H This substance is formed by the slow oxydation of alcohol. ALDEHYDS. 87 \ Alcohol is treated with a mixture of manganese binoxide, or of potassium bichromate, 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 which passes over above 60. This liquid is mixed with ether, and, when cool, a stream of dry ammonia gas is caused to pass through the solution. Crystals of ammonium aldehyd are formed, C 2 H 3 (NH 4 )O, 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, VVj f is poured into an ammoniacal solution of silver nitrate, on slightly elevating the temperature, metallic silver is deposited. This silver adheres to the sides of the tube, and covers 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 CHLORAL C 2 IIC1 3 O, is the most important. Hy. 88 ORGANIC CHEMISTRY. drate of chloral, or C 2 HC1 3 O + II 2 O, hasbeen prepared now for several years in very large quantities, for medicinal purposes. Its name is derived from chlor- ine alcohol. Absolute alcohol is saturated, first cold, then hot, with dry chlorine. The liquid obtained is mixed with its volume of concentrated 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 re-distilled twice with calcium carbonate and 1 to 8 per cent, of water. The hydrate is then obtained in handsome crystals, C-^HClsO + H.^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 chloroform and formic acid, Potassium Chloroform. formiate. The question appeared pertinent 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 effects of chloroform. His experiments were repeated in different countries, and hydrate of chloral soon came into general use as a hyponotic. ALDEHYDS 89 Chloral hydrate for medical use must be crystalline and possess the following properties: it should be col- orless, transparent, and have an aromatic odor, a caus- tic taste, readily soluble in water without furnishing drops of oil, also soluble in alcohol, ether, naphtha, benzol, and carbon bisulphide; it should fuse at 56 to 58, solidify at about 15, boil and volatilize completely at 95. With caustic potassait should furnish chloro- form, and with sulphuric acid, chloral, without becom- ing brown. Its aqueous solution should be neutral and not produce any turbidity with silver nitrate and nitric acid. Exposed to the air it shor.ld not become moist. According to recent investigations by Liebreich, (60-69-673) chloral produces the opposite physiolog- ical effects of strychnine, hence, these bodies may be used as antidotes one for the other The remaining aldehyds are not sufficiently im- portant for a work of this scope. Camphor has al- ready been considered in connection with turpentine. 90 ORGANIC CHEMISTRY. OEGAOTC ACIDS. ACIDS CONTAINING TWO ATOMS OF OXYGEN. FATTY ACID SERIES. Formic acid, - C H 2 O 2 Acetic " C 2 H 4 O 2 Propionic " C 3 H 6 O 2 Butyric " C 4 H 8 (X Valeric " C 5 II 10 O 2 Caproic " - C 6 H 12 O 2 (Enanthylic " C 7 H 14 O 2 Caprylic i( C 8 H 16 O 2 Pelargonic " - C 9 H 18 O 2 Capric C JO IL O 2 Laurie " - C 12 H 24 O 2 Coccinic C 13 H 26 O 2 Myristic " - C 14 H 28 O 2 Palmitic " C 16 II 32 O 2 Margaric C 17 H 34 O 2 Stearic C 18 H 36 O 2 Arachidic - " . C2oH 40 O 2 Cerotic O 27 H 54 O 2 Melissic " ORGANIC ACIDS. 91 C a H 2n ...A. Acrylic acid - C H 4 2 Crotonie " C 4 H.O a Angelic " - C 5 H 8 2 Pyroterebic " C 6 H 10 2 Campholic " - C 10 H 18 2 Moringic *' - CtfPIajOa Physetoleic " C 16 H.3oO 2 Oleic C 18 H 34 O 2 Doeglic '' C^IlseO, Erucic " C\ TT C\ \JnSjLjB\J*, Sorbic acid C 6 H 8 O 2 Camphic " C 10 H 16 O 2 AROMATIC ACID SERIES. Benzoic acid C 7 H 6 O 2 Toluic " C 8 H 8 O 2 Xylic " C 9 H 10 2 Cumic 6t - C 10 H 12 O 2 Alpha-cymic acid ( Cinnamic acid C 9 II 8 O 2 Pinic " - 92 ORGANIC CHEMISTRY. ACIDS CONTAINING THREE ATOMS OF OXYGEN, C n H 2n O 3 . Carbonic acid C H 2 O 3 Glycolic " - - C 2 H 4 O 8 lactic " C 3 H 6 O, Oxybntyiic " C 4 H 8 O 3 Oxyvaleric " C 5 H 10 O 8 Leticic " - - C 6 H 12 O 8 (Enanthic " CuBaA- Pyrnvic acid C 3 H 4 O Scammonic " C 13 H 2 8^3 Kicinoleic " CigH^Os Guaiacic acid C 6 H 8 O 3 Lichenstearic " - - C 9 H 14 O 3 . Pyromeconic acid - C 5 H 4 O 3 . C n H 2n _ 8 O 3 . Salicylic acid - - C 7 H 6 O 3 Anisic - C 8 H s O 3 Phloretic " C 9 H :0 O> Oxycuminic " - C 10 H 12 O^ Thymotic u - CnH^Os. OKGANIC ACIDS. 93 Coumaric acid - C 9 H 8 O 3 . ACIDS CONTAINING FOUR ATOMS OF OXYGEN. C n H 2n 4 . Gljceric acid C 3 H (also called acetate of acetyl) or acetic oxide, which boils at 139. Water destroys it, acetic acid being produced. Chloride of acetyl is an irritating liquid, boiling at about 158, decomposable by water into acetic and hydrochloric acids. A derivative of acetic acid of considerable theoretical importance is cyanacetic acid C 3 H 3 NO 2 =C 2 H 3 O ) n CN i ' a crystalline body forming salts with the metals, which have been studied by T. Menies. On acting with sul- phuric acid and zinc on cyanacetic acid, the author [82-67-69] obtained formic and acetic acids and am- monia. VINEGAR. This name is given to the mixture which is obtained by the acetification of wine, whiskey, infu- sion of malt, etc. Good acetic vinegar is of an agree- able taste and aroma. Wood vinegar has a very strong disagreeable taste and odor. It is frequently 104 ORGANIC CHEMISTKY. adulterated with sulphuric acid. An addition of 1 of its weight of this acid is, however, not considered fraudulent, as its presence is regarded necessary to prevent moulding. A ready method of detecting mineral acids, pro- posed by M. Witz (77-75-268), is based upon the use of methyl-aniline, which undergoes no change in con- tact with acetic acid, but promptly changes to a green- ish-blue in presence of the least trace of mineral acid. Vinegar and concentrated acetic acid are employed in medicine as stimulants. An acetate, or acetic acid, can be recognized by heat- ing it slightly with sulphuric acid and alcohol ; a fragrant odor, characteristic of acetic ether, is observed. Heated with sulphuric acid alone, the acetates liberate a vapor which has the odor of vinegar. The following reaction permits of the detection of mere traces of acetic acid; it is saturated with potas- sium carbonate and heated with arsenous oxide in a test tube; fumes and a nauseating odor are given off. The author finds that one of the simplest tests for acetic acid, is to direct a fine, yet powerful stream of water into a test-tube, containing .a few drops of the licjuid to be tested. The very fine, white eiferves- . cence resulting is entirely characteristic of this acid, none of the other ordinary acids producing the same effect. Alcohol should not be present, as it causes a similar effervesence. If the acetic acid is combined it should be set free with a strong mineral acid. By this test, ACETATES. 105 perhaps 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- line biacetates and some basic acetates of copper and lead. POTASSIUM ACETATE. This salt, distilled with its weigh t of arsenous oxide, furnishes a very inflammable liquid, formerly called the "liquor of Cadet," and in which Bunsen has found a radicle spontaneously inflammable, cacodyl, C 4 H 12 As 2 . Potassium acetate forms, as well as sodium acetate, an acid acetate when treated with acetic acid. It is a very deliquescent salt, difficultly crystallizable. AMMONIUM ACETATE ]STH 4 C 2 H 8 2 , Is prepared by saturating ammonium carbon- ate with acetic acid. Its solution constitutes the spirit of Minder erus ; treated with phosphoric oxide it forms cyanide of methyl. There is also an acid salt, OT3 4 C 2 H 3 O,C 2 H 4 O. 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. ]SaC 2 H 3 O 2 +3II 2 0. This is used in preparing marsh gas and concentrated acetic acid. It is recommended by Tommase (52-72- 23), as a solvent for plumbic iodide, of which two grams are readily dissolved in 0.5 c. c. of a strong solution of sodium acetate. CALCIUM ACETATE. Ca(C 2 H 3 2 ) 2 . This salt, subjected to distillation, furnishes a liquid containing a large proportion of acetone C 3 H 6 O- ALUMINUM ACETATE. A1(C 2 H 3 O 2 ) 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. FEEEIC ACETATE. This salt (pyrolignite) has been, and is still, somewhat employed for the preservation of wood. ACETATES 107 COPPER ACETATES. Normal acetate Cn(C 2 H 3 O 2 ) 9 is called verditer. It iorms beautiful green crystals (crystals of Venus), which, subjected to distillation, furnish acetic acid mixed with acetone. During this operation, a white sublimate is formed, which deposits in the neck of the retort. This latter is cuprous acetate, and is car- ried over into the receiver, oxydizes, and changes into cupric acetate, which colors the distillate blue. There remains in the retort, after this decomposition, very finely divided copper which takes lire when slightly heated in the air. Solutions of this acetate reduce the salts of the oxide, CuO, and serve to prepare the sub- oxide, Cu 2 O. A basic acetate, designated by the name of verdigris, is obtained by exposing to the air sheets of copper moistened with vinegar, or surrounded by the marc of grapes. The metal becomes covered with a greenish incrustation whose formula is, Cu(C 2 H 3 O 2 ) 2 ,CuO+6H 2 O. LEAD ACETATE. The normal acetate Pb(C 2 H 3 O 2 ) 2 is prepared by treat- ing litharge with acetic acid in slight excess. This salt, known by the name of sugar of lead, crystallizes in oblique rhombic prisms, soluble in two parts of water and eight parts of 95 per cent, alcohol. It has a sweet taste, and is very poisonous. It is employed as a re- 108 ORGANIC CHEMISTRY. agent, also to prepare aluminum acetate and lead chro- mate. In digesting acetic acid with an excess of litharge, it furnishes a hexabasic acetate of lead. If ten parts of normal acetate, with seven parts of litharge are taken and this mixture digested with 30 parts of water, there are formed minute needles of a tribasic salt Pb(C 2 H 3 O 2 ) 2 , PbO2,H 2 O. Finally this salt, dissolved in normal ace- tate, gives a sesquibasic acetate, which is deposited in crystals, 2(Pb2C 2 H 3 O 2 ),PbO,II 2 O. GOULARD'S EXTRACT is a solution containing a mix- ture of normal and of sesquibasic acetate of lead, which is prepared by boiling 30 parts of water, 7" parts of litharge and 6 parts of normal acetate of lead. BUTYRIC ACID. 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. VALERIC ACID. 109 YALERIANIC, OR VALERIC ACID C 5 H 10 O 2 = 5 9 jj > O. It can be obtained by oxjdizing amjlic 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 which 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] 5-40. ) BENZOIC ACID, C 7 H 6 O 2 . Density, 61. Density of its 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 white cardboard placed over the whole. The earthen vessel is then heated over 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 ORGANIC CHEMISTRY. It is obtained in the wet way, by pulverizing 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 benzole acid separates out, and is recrystallized from a solution in boiling water. It is also procured from the urine of herbivorous animals. This secretion, evaporated to a small bulk and treated with hydrochloric acid, yields 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- les, is little soluble in cold water, quite soluble in boiling water, and still more so in alcohol and ether. On passing its vapors through a tube heated to redness, it is decomposed into benzol and carbon dioxide, 7 H 6 O 2 C 6 H 6 -f-CO 2 . Chlorine, bromine and nitric acid transform it into substitution products. Chlorbenzoic acid, C 7 H 5 C1O. Dinitrobenzoic " C 7 ii 4 (]S"O 2 ) 2 O 2 . Ammonium beazoate furnishes, on distillation, ben- zonitrile C 7 NH 9 O 2 - C 7 H 5 K + 2 FLO. The alkaline benzoates heated with chloride, or BENZOIO ACID. Ill oxychloride of phosphorus, furnish benzyl chloride, which, submitted to the action of potassium benzoate in excess, gives benzoic anhydride, 3(KC 7 H 5 2 )+POC1 3 = 3(C 7 H 5 OC1) + K 3 P0 4 . Chloride of benzyl. C 7 H 5 OC1+KC 7 H 3 2 - C 14 H 10 8 + KCL Benzoic anhydride. The rational formula of benzoic anhydride is, Calcium benzoate heated to a high temperature furnishes 1enzone, Ca(C 7 H 5 2 ) a = CaC0 3 +CO(C 6 H 5 ) 2 . Calcium benzoate. Benzone. Benzoic acid is monobasic, and the benzoates are generally soluble. Benzoic acid taken into the stom- ach, is transformed into hippuric acid. Kolbe and von Meyer have observed that benzoic acid has antiseptic power, though less than salicylic acid, (18-[2]12-133). CINNAMIO ACID. In certain balsams there exists an acid called cinnamic acid, whose formula is C 9 H 8 O 2 . It exists in the balsams of Peru, benzoin, tolu and in liquid storax. It fuses at 129 and boils at 290. It 112 ORGANIC CHEMISTRY. lias striking features of resemblance to benzoic acid, and is produced like the latter by the oxydation of an aldehyd. This aldehyd is the essence of cinnamon prepared by distilling cinnamon with water. POLYATOMIC ACIDS. OXALIC ACID. PREPARATION. 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 the gentian and rhubarb, and in certain lichens. Salt of sorrel is extracted from the burdock (Prunex\ in Switzerland, and in the Black Forest of Germany, by expressing the plant, clarifying the expressed liquid by boiling with clay, and evaporating ; crystals of salt of sorrel are deposited. The oxalic acid may 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- pletely 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 t-ie action of oxydizing agents upon certain organic substances; the substances best suited for this purpose are those OXALIC ACID. 113 which contain oxygen and hydrogen in the proportion to form water. One part of starch, or sugar, is boiled 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. 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 car- bon monoxide, carbon dioxide, formic acid and water. 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 potassium oxalate, K 2 =O 2 =CO 2 . Acid potassium oxalate, KH=O 2 =C 2 O 2 . USES. Oxalic acid is employed in removing ink spots from cloth, and in cleaning copper. It owes these properties 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 the arts, and its physical resemblance to certain salts, particularly to magnesium sulphate, poisoning with it has often occurred, either through design or imprudence. It acts powerfully upon the system. Tardieu 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 unconsciousness 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. SUCCINiC ACID. 115 SUCCINIC ACID. This acid is produced by the oxydation of butyric acid, and by subjecting amber, succinum, 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 higher tem- perature they are decomposed into water and succinic anhydride C 4 H 4 O 3 . 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 ot certain hydatids. MALIC ACID. C 4 H 3 O 2 \ ft H,II 2 f Us This 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 116 ORGANIC CHEMISTRY. various acids and especially paramalic acid, C 4 II 4 O4, which is identical with the acid of the fumaria. It is bibasic like oxalic acid, but triatomic and is dis- tinguished from this 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 preparing tartar ic 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. 2KHC 4 H 4 O 6 +CaCO 3 -CiC 4 H 4 O 6 +K 2 C 4 H 4 O 6 +CO 2 +H,0 Hydro-potassic Calcium Calcium tartrate. Potassium tartrate. carbonate. tartrate. The solution which contains the potassium tartrate, is filtered and calcium chloride added : the remainder of the tartaric acid is thus precipitated as a tartrate and added to the preceding. TARTAKIC ACID. 117 + CaCl 2 =CaC 4 H 4 6 + 2 KCL Potassium tartrate Calcium tartrate. These precipitates are washed and decomposed with sulphuric acid, the calcium sulphate is filtered off, and the liquid evaporated to the point of crystallization. This acid is also called right tartaric, or dextroracemic, as it turns the plane of polarization to the right. Kistner has obtained from certain tartrates a tartaric acid which is optically inactive. This acid, called para- tartaric or racemic acid, is somewhat less soluble than dextrotartaric acid, while the reverse is the case with its salts. It contains, moreover, one molecule of water of crystallization, but does not crystallize, as does the dextrogyrate acid, in hernihedral crystals. Levogyrate tartaric acid is prepared by evaporating a solution of racemate of cinchonia; the levogyrate tartrate precipitates while the dextrogyrate remains in solution; or a solution of racemic acid is allowed to stand with a small quantity of calcium phosphate, and a few spores of the Penoiliuin glaucum; 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 ether. Tartaric acid melts at about 180; and furnishes dif- ferent pyrogenous acids, chiefly: Tartaric anhydride, or Tartrelic acid, C 4 H 4 O 5 , and Pyrotartario acid, C 5 H 8 O 4 . 118 ORGANIC CHEMISTRY. Simpson synthesized pyrotartaric acid and Lebedeff has recently (60-75-100.) shown, that 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, E^CJ^Oo Hydro KC 4 H 5 O 6 . 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 flux, potassium carbonate, and tartaric acid, also largely in baking powders. ROCHELLE SALT. KNaCJ^Oe+^aq. 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 dish, 3500 grams of water and 1000 grains of cream of tartar, this is brought to boiling and sodium 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 rhornboidal prisms; it is soluble in 2J- times its weight of water, but in- soluble in alcohol. TARTAR EMETIC. Tartaric acid forms, with bases, a EMETICS. 119 a class of salts called emetics, the type upon which they are formed being that of tartar emetic. The ordinary tartar emetic has been generally assigned the formula (SbO)'K=O 2 ==C4H 4 O 4 , in which the monad radicle stibyl takes the place of one of the basic hydro- gen atoms. It is prepared by boiling for an hour in 100 parts of water, 12 parts of cream, of tartar, and 10 parts of antimony oxide. This mixture is then filtered, evaporated and allowed to crystallize. This salt crystallizes in rhombic octahedrons ; it has a me- tallic taste, a slight acidity, and is soluble in Imparts of cold, and about 2 parts of boiling water. Crystals of tartar emetic effloresce on exposure to the air. A strip of tin precipitates the antimony as a brown powder. Tannin, and most astringents, precipitate the antimony, hence tartar emetic should not be ad- ministered in connection with this class of bodies. This salt is the most used of the antimony compounds. FERKO -POTASSIUM TARTRATE. Cream of tartar is di- gested with ferrous hydrate for two hours at a tem- perature of 60. For every 100 parts of cream of tar- tar, a quantity of hydrate should be used containing 43 parts of ferrous oxide. The product is filtered, the liquid received in shallow plates, and kept at a temperature of about 45; the salt thus crystallizes in brilliant scales of a garnet red color. It dissolves in water, but is insoluble in strong alcohol. Tartaric acid is often adulterated with alum, potassium bisulphate and cream of tartar ; these substances may 120 ORGANIC CHEMISTRY. all be detected by means of alcohol, in which they are not soluble. Tartaric acid is used in making effervescing drinks, and as a discharge by calico printers. Tartaric acid produces the same toxical effects as oxalic acid, though requiring much larger doses. The blood of the poisoned person becomes red and very fluid. CITRIC ACID. This acid is found associated with oxalic and tartaric acids in many plants. It occurs in cherries, currants, raspberries, oranges and lemons. It is ordinarily extracted from the juice of lemons. This juice is allowed to stand until fermentation com- mences, then filtered and treated with chalk and milk of lime ; an insoluble citrate of calcium is formed, which is decomposed by sulphuric acid; the calcium sul- phate is filtered off and the filtrate evaporated and left to crystallize. Citric acid crystallizes in regular rhombic prisms; it is soluble in three fourths its weight of cold water; this solution, in time, becomes covered with mould. Citric acid is soluble in alcohol and ether. Heated to about 175 it furnishes aconitio acid, n TT n = C 6 H 3 CITKIC ACID. 121 losing H,O on increasing the temperature. Another pyrogenous acid, itaconic acid C 3 H 6 O 4 is formed, which, if heated, is transformed into citraconio acid isomeric with the last mentioned. Oxydizing bodies destroy citric acid, carbon dioxide, acetone, etc., being produced. Fused caustic potassa resolves it into acetic and oxalic acids. C 6 H 8 7 + H 2 0=C 2 H 2 4 + 2C 2 H 4 2 . Oxalic acid. Acetic acid. Citric acid is tetratomic and tribasic. It may be distinguished from oxalic and tartaric acids by its ac- tion on lime water, which it does not precipitate in the cold, but if boiled with an excess of lime water, a pre- cipitate of basic calcium citrate is obtained. MAGNESIUM CITRATE. This salt is prepared by treat- ing magnesium carbonate with a strong solution of citric acid and precipitating this salt with alcohol. It is much used in medicine as a purgative. CITRATE OF IKON. Hydrated ferric oxide is dissolved in a hike-warm solution of citric acid, and the liquid evaporated to dry ness. This body varies in its composition ; it occurs in brilliant amorphous scales, of a g;irnet-red color. AMMONIA CITRATE OF IRON. One hundred grams citric acid are digested for some time with a quantity of ferric hydrate, representing 53 grams of iron, and 16 to 20 grains of aqua ammonia. The liquid is then filtered and evaporated to the consistency of a syrup, 122 ORGANIC CHEMISTRY. and transferred to very shallow vessels which are placed in drying ovens. This substance solidifies in scales, if the temperature at which it is dried is not too high and the layers of liquid are extremely thin. LACTIC ACID. 3 H 6 O 3 = C 3 H 4 ) O3 H,H f U ' This acid was discovered by Scheele, who extracted it from sour milk. It exists in many products after fermentation, as sauerkraut, beet juice, and various vegetables, also nux vomica. It is found in many ani- mal fluids, in the blood and in the fluids which per- meates the muscular tissues. It is to this body that the acid reaction of sour milk is due. Lactic acid extracted from flesh forms, with certain bases, salts which differ in solubility, etc., from those formed with ordinary lactic acid, hence this acid is sometimes called paralac- tic acid, also sarko-laGtic acid, from Gapnos flesh. Lactic acid may be prepared by dissolving sugar of milk in butter-milk, adding chalk to the mixture, and allowing it to stand for eight or ten days at a tem- perature of 30 to 35 The sugar of milk is sometimes replaced by glucose, or cane sugar and fermentation favored by the addi- tion of cheese. A special ferment (tactic ferment) is developed which is transformed into sugar and lactic acid, but the fermentation is arrested as soon as the liquid LACTIC ACID. 123 becomes acid, and it is in order to prevent this acidity that an excess of calcium carbonate or sodium bicar- bonate is always maintained. Wurtz has produced this acid artificially by the action of platinum black on propylglycol. O a + C 3 II 8 2 =C 3 H 6 3 + H 2 0. Propylglycol. Lactic acid is a colorless, syrupy liquid ; at about 130 it is changed into the anhydride of lactic acid, C 6 H 10 O 5 , and at about 250 it furnishes a crystalline body called lactide whose formula is C 3 H 4 O2. Lactic acid posseses the property of dissolving cal- cium phosphate. The lactates are soluble in water. Lactate of iron, (C 3 H 5 O 3 ) 2 Fe, is employed in medicine. UKIC OR LITHIC ACID, C 5 H 4 N 4 O 3 . Discovered 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 urea increases : whereas calculi of 124 ORGANIC CHEMISTRY. uric acid are frequently formed in persons whose diet is very nourishing, and whose occupation 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 by 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 color- 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- lantoin, which has been found in the urine of sucking calves. Its formula is C 4 H 6 N 4 O3. The same derivative of uric acid was obtained by the author in 1858, also parabanic acid, on heating uric acid with manganese dioxide and sulphuric acid. (80-[2]4:4-218.) URIC ACID. 125 If 1 part of uric ac*i:l be added to 4 times its weight of nitric acid of a specific gravity of 1.45, the solution being kept cool, small crystals of a substance called alloxan separate out, whose formula is C 4 H 4 ]Sr 2 O 5 +3H 2 O. Woehler and Liebig obtained from this body a num- ber of very interesting derivations, alloxantin, al- loxanic acid, parabanio acid, thionuric acid, dia- luric acid, and finally a magnificent purple crystalline body, murexide. A large number of other deriva- tives have also been obtained by other chemists, especially 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 purple, or very beautiful rose color, will appear. HIPPTJKIC ACID The urine of herbivora contains a large percentage of this acid, which also exists in a small quantity in human urine. A frugivoroua diet augments the pro- portion of this body. It is prepared by boiling the fresh urine of the horse (hence the name, from innos, a horse), or better from that of a cow, with milk of 126 ORGANIC CHEMISTRY. lime, which is than filtered and evaporated to one- tenth its volume; this is mixed with a large excess of hydrochloric acid and left to. stand 30 or 12 hours. The impure hippuric acid which precipitates is re-dis- solved in soda and re-precipitated 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(C 2 H 4 ]TO 2 ) 2 + 2C 7 H 5 OC1= + 2C 2 H 3 [NH(C 7 H 5 O]O 2 . 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 of distillation. Under the action of oxydizing agents it furnishes ben- zoic compounds; with nitrous acid it yields benzo-gly- colic acid. ALKALOIDS. 127 ALKALOIDS. ARTIFICIAL BASES OR ALKALOIDS. PRIMARY. C n II 2n+3 K Methylamine Ethylamine C 2 Propylamine Butylamine C 4 H n !N" Amylamine C 5 H 13 N Caprylamine - C 8 H 19 N. Acetylamine C 2 H 5 N" Allyiaraine C 3 H 7 N. Plienylamine, aniline - - C 6 H 7 N Toluidine C 7 H 9 JS r Xylidine - C 8 H U N Cumidine - C 9 H 13 K, C n H 2n _ 7 K Phtalidamine - - . - C 8 H 9 N. 128 ORGANIC CHEMISTRY. Naphthalamine - - C 10 H 9 K SECONDARY. Dimethylarnine - C 2 H 7 JS" Methylethylamine - - C 3 H 9 N Diethjlamine - C 4 H n K TEKNAEY. Trimethylamine C 3 H 9 N Dimethylethylamine - C 4 H n ]N" Methylethylamylamine - C 8 H 9 N. PHOSPHINES. Methylphospbine C H 5 P Dimethylphosphine - C 2 H 7 P Trimethylphosphine C 3 H 9 P. AESINES. Triethylarsine C 6 H 15 As. STIBINES. Triethylstlbine - C 6 H 15 Sb. NATURAL ALKALOIDS. 129 PKINCIPAL NATURAL ALKALOIDS. OF THE CINCHONAS. Quinia,Quinicia and QuinidiaC. :o H 24 ]S" 2 O 2 Cinchonia and Cinclionidia O^EL^O Aricina C^H^NA. OF OPIUM. Morphia C 17 H 19 N O 3 Codeia - - C 18 H 21 N O 3 Thebaia C 19 H 21 JST O 3 Narcotina - O.^H^N O 7 Papaverine - C2<)H 21 ]S" O 4 Narceia - OF THE STEYCHNOS. Strychnia Brucia OF THE SOLANACE^E. Nicotina C 10 H 14 N" 2 Atropia - C 17 H a N O 3 Hyosciamine CnH^N O 3 Solania - C 43 H T1 K O 16 . OF THE HEMLOCK. Conylia - C 8 H 15 N. 130 ORGANIC CHEMISTRY. OF PEPPER. Piperidine C 5 H n K. MISCELLANEOUS. Aconitina - C 27 H 40 N O Yeratria - C32H 52 N 2 O 8 Theobromine C 7 H 8 N 4 O 2 Caffeia C 8 H 10 N 4 O 2 . The first organic base isolated was morphia, obtained in 1816, by Sertuerner. In 1819, Pelletier and Ca- ventou extracted quiriia from cinchona bark, and showed that the very active plants used in pharmacy owed their energy to compounds 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. Gerhard t by similar methods prepared quinoleine, Cahonrs 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 various other organic compounds. COMPOUND AMMONIAS. 131 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 hydrogen sulphide combines with the oxygen of the nitrous compound. Example: C 6 H 5 NO a + 3H 2 S=2H 8 O + 3S + C 6 H 7 N. Nitrobenzol. Aniline. For this mode of reduction, as it is not very prac- tical, ar.d 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 of methyl : CO Cyanate Potassium Methyl- of methyl. carbonate. amine. Hofmann made known, very shortly after the pub- 132 ORGANIC CHEMISTRY. lication of Wurtz' process, a method for the prepara- tion of the compound ammonias, by which not only a simple equivalent of hydrogen is replaced by the radicles (CH 3 ), (G,H 5 ), etc., but all the hydrogen of the ammonia. Hof maim' s method consists in causing- o ammonia to react upon hydrochloric as well as brom- liydric or iodhydric ethers, particularly the latter. Let us take, as an example, iodide of ethyl in con- nection with the study of ETHYLAMINE. 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: C 2 II 5 I + OTI 3 = Q,H 8 NI. 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 chlorhydride of ethylamine and leaves in an insoluble state the ammo- nium chloride 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, with the aid of a gentle heat. The volatilized product is con- densed in a cooled receiver. In this reaction there is CLASSIFICATION OF THE ALKALOIDS. 133 also formed diethylamine, triethylamine and oxide of tetrethylammonium 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 mlphovinate, 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 white precipitate, which is dissolved in an excess producing a deep-blue solution. It differs 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 THE ALKALOIDS, OE ORGANIC BASES. AMINES. Hofmann 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. The same chemist, having prepared ethylamine by the action of ethyl iodide upon ammonia, subse- quently succeeded in obtaining diethylamine by similar means. The reaction is the following : ( C 2 H 5 ( C 2 H 5 NlH +C 2 HJ=]^ C 3 H 8 ,HL (H (H This hydroiodide obtained, treated with potassium hydrate or lime, furnishes a second base, which is biethylammonia, or diethylamine ; Diethylamine C A similar compound is, C 6 H 5 Ethylaniline Cs^N^N 1 C 2 H 5 . These bases have been given the name of secondary amines or imides. The secondary ammonias are attacked by ethyl iodide and other ethers, and a reaction takes place, iden- tical with that which gives rise to the primary and secondary amines and tertiary amines, also called nitrile bases, are thus obtained. AMINES. 135 Such bodies are: PC 2 H 5 Triethylamine C 6 II 15 ]N'=E"-[ C 2 H 5 . L QzH-s fCH 3 Methylethylphenylamine CgHigN^N-j C 2 H 5 LC 6 H 5 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 2 H 6 O) + NH 3 2H 2 O=C 4 H n K In like manner the ternary amines may be consid- ered 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 denominated, respectively, di- amines and tri-amines; as ( (0 2 H 4 )" Secondary ethylene diamine N 2 < (C 2 H 4 )", Ternary ethylene diamine N z \ (GJL)". 136 ORGANIC CHEMISTRY. Triethylamine attacks hydroiodic ether, and there is formed the compound C 8 H 2Q 1S T I=]S"(C 2 H 5 ) 4 I. This body treated with oxide of silver, furnishes an oxy- genated quaternary base, ^lSri + Ag HO=Ag I + C 8 H 21 NO. 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 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 1ST There are also mixed combinations of amides and amines, called alJcalamides, as 0,H, acetanilide X ! C 2 H 3 O. H ALKALOIDS. 137 NATURAL ALKALOIDS. Many of the natural alkaloids appear to possess a composition analogous to that of the compound am- monias. Some -are not attacked by iodide of ethyl, and should be classified among the ammoniums, bodies having the same relation to the compound ammonias as does ordinary 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 artificial bases or alkaloids. They 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 hydrocarbides, which are now considerably used in the preparation of the alkaloids. Water does not dissolve any of the artificial alkaloids, except those having a very low molecular weight, like ethylainine; this liquid, how- ever, dissolves cod eia and narceia quite readily. With the exception of quinia and cinchonia, they turn the plane of a polarized ray of light to the left. They react like ammonia, or potassa, with vegetable 138 OEGANiC CHEMISTRY. colors, and furnish, 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. The harmless character of tarmic acid, and the in- solubility of the compounds formed by it, with 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 135 grams of mercury di chloride, 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 NICOTINA. 139 sugar, tartaric acid and of albumen may mask the reac- tions of a number of alkaloids. NICOTINA OR NICOTYLIA. Nicotina is obtained from tobacco (Nicotina taba- cwm.)For this purpose a decoction of tobacco is made, and the liquor evaporated to a syrup. The extract is treated with twice its volume of 85 per cent, alcohol, which precipitates the salts present and certain organ- ic substances. The alcoholic solution is distilled and the residue submitted to a second similar treatment. The alco- holic extract thus obtained, is mixed with a concen- trated solution of potassium hydrate, and the nicotina liberated is re-dissolved in ether. This ethereal solu- tion is evaporated in a water bath, and the residue distilled in an oil bath, in an atmosphere of hydrogen. Nicotina is a colorless liquid when pare, remaining liquid at -10, boiling at about 25, with decomposi- tion. It has the odor of an old pipe. Exposed to the air it becomes brown, then resinous; water, alcohol and ether dissolve it ; its solutions are strongly levogyrate. Nicotina is a powerful base; it fumes when a rod moistened with hydrochloric acid is brought near it ; it precipitates the metallic oxides. Nicotina requires two molecules of a monobasic acid for saturation. The chloride, CioIIuN^IICl, is crystallizable, though 140 ORGANIC CHEMISTRY. deliquescent. The hydrogen it contains is not replace- able by methyl, ethyl, etc. It may be considered as having the rational formula, (C 5 H 7 y ' ' being the compound radicle nieotyl. Proportion of nicotina in different tobaccos : Havana, 2.0 per ct. Maryland, 2.3 " Virginia, 6.9 " Lothringen, 8.0 " (Schloesing.) POISONING BY TOBACCO OK BY NICOTINA. The injection of a concentrated decoction of tobacco, causes serious results in a few minutes : intense head- ache is produced, with nausea and vomiting, violent pain in the abdomen, pallor, and, finally, extreme prostration. An infusion of tea, unroasted coffee, 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 suffice to cause death. CONIA. 141 Two drops introduced into the throat of a dog will almost instantaneously cause the following series of symptoms : respiration becomes difficult, 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. PIPERIDINE. There has been obtained from the pepper ( Piper longum, Piper nigrum or Piper caudatum\ a body crystallizing in colorless prisms called piperine, whose formula is C 17 H 19 NO 3 . It is a neutral substance. "When 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. This body is alkaline and saturates acids. It con- tains a single atom of hydrogen replaceable by methyl, ethyl, etc. CONIA, CONYLIA, OR CONINE. 8 H 15 N. This body is obtained from hemlock (Conium mac- idatum); the crushed seeds are distilled in a large glass retort, with a solution of potassa, or soda, whereupon an alkaline distillate is obtained. The distilled product is treated with a mixture of two parts of alcohol and one 142 OKGAISTIC CHEMISTRY. part of ether, which dissolves the sulphate of coniaand 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 eonia pass over; the latter is dehydrated with po- tassa, and rectified in vacua, or in a current 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 va- 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, very 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 centigrams 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 PAP AVERAGES. The seeds of the poppy (Papaver somniferwn} yield, on incision, a milky sap, which dries up in a day or two; this sap, when solidified, constitutes opium. There are three leading varieties of opium : I. Opium of .Smyrna is found in small cakes of 100 to 150 grams, frequently distorted and agglutinated together by reason of their soft nature, and contain >l OPIUM. 143 to 10 per cent, of water. The surface 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 5 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 no more than 2 to 7 per cent, of morphia. Recently, 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 meconic acid (from/n/KCtfr, a poppy), a crystallized neutral substance called meconine, which, according to Berthelot, is a complex alcohol, and finally, various gummy and resin- ous compounds. MORPHIA OR MORPHINE. C 17 H 19 N0 3 ,H 2 0. PREPARATION. Ten kilos, of opium are treated re- peatedly with water, and the liquors evaporated to the consistency of a syrup. The mass is redissolved in water, filtered, and again evaporated. To the lukewarm liquid are added 1200 144 ORGANIC CHEMISTRY. 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 consistency 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 cblorhydrate 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 80 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 aifect the morphia. MORPHIA. 145 Pure morphia, (from Morpheus, in allusion to its nar- cotic qualities,) crystallizes in regular prisms with 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. Solutions of morphia are very bitter. 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 energetic 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, which subsequently changes to green. Morphia, moistened with nitric acid, is colored orange-red, which rapidly changes to yellow. These four reactions are characteristic of morphia. If 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 powder called iodomorphia. Morphia fused with al- 146 ORGANIC CHEMISTRY. kalies yields methylamine. (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. CHLORHYDRATE OF MORPHIA, C 17 H 19 NO3HC1+3II 2 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 Y6 per cent, of morphia. SULPHATE OF MORPHIA, (C^H^NOg^HoSC^+SILjO is prepared like the preceding salt, which it resembles in appearance as well as in properties. Morphia and its salts are used in very small doses, as in larger doses they are energetic poisons. CODEIA, CisH^JSTOsilljO. Discovered in 1832 by Robiquet. This base, whose name is derived from xGddrj 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 potassa. The 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. NAKCOTINA. 147 Codeia is crystalline, very soluble in alcohol and ether. It dissolves in 80 parts of cold and in 20 parts of boiling water. o 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 i& C 18 H 21 ]TO 3 L 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 ferric salts. IY. Nitric acid does not impart to it any color. NAKCOTINA, Narcotina crystallizes in rhombic prisms. It is al- most insoluble in cold water, somewhat soluble in alcohol, quite so in ether. 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, cotarnine and opianic 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 paramorpliicb, is the most poisonous of the bases of opium. It is crystallizable, insoluble 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- eridorff have recently ascertained that when absolutely pure no color is obtained, the ordinary article found in trade not being pure. NARCEIA. 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. 149 Narceia fuses at 95, 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. PHYSIOLOGICAL ACTION OF OPIUM. NARCOTIC 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 opium-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 which 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 of opium upon the system, 150 ORGANIC CHEMISTRY and has tabulated their soporific, toxic, and convulsive actions as follows : Toxic. Thebeia, Codeia, Papaverine, ISTarceia, Morphia, Narcotina. Convulsive. Thebeia, Papaverine, Narcotina, Codeia, Morphia, Nareeia, Soporific. Narceia, Morphia, Codeia. With- ) out V 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 : WATER. ALCOHOL. ETHER. AMMONIA. Morphia. But little sol- uble. Quite soluble. Almost insol- uble. Nearly insol- uble. Codeia. Soluble. Very soluble. Very soluble. Soluble. Narcotina. Insoluble. Soluble. Soluble. Insoluble. Thebeia. Insoluble. Soluble. Soluble. Insoluble. Papaverine. Insoluole. Soluble. Soluble. Insoluble. Narceia. Slightly sorble Soluble. Insoluble. Insoluble. QUINIA. QUINIA OR QUININE. 151 This alkaloid was discovered in 1820 by Pelletier and Caventou. The following is the modern process by which it is prepared. Yellow Peruvian bark is carefully pulverized and thoroughly mixed with 30 per cent, of its weight of lime, previously slacked. The mass is then lixiviated three or four times with refined petroleum (petroleum ether) or amylic alcohol, (wood spirit) which dissolves the alkaloids. POTASSA. NITRIC ACID. SULPHURIC ACID. IODIC ACID. Soluble. Orange-red color- ation. Colored violet on heating with di- lute acid. Reduced. Nearly insoluble. Orange-red color- ation, Colored violet on heating with di- lute acid. Is not reduced. Insoluble. Blood -red color- ation. Yellow coloration. Is not reduced. Insoluble. Yellow coloration. Red coloration. Insoluble. Dark -blue color- ation. Insoluble. Red color, which becomes green. 152 ORGANIC CHEMISTRY The united extracts are agitated with water, acidu- lated with sulphuric acid, making the liquid only slightly 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, S^^B^NgC^), H 2 SO 4 -|-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 tvater until the filtrate 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 SULPHATES OF QUINIA. 153 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. SULPHATES OF QUINIA. Two sulphates of quinia are known; that obtained by the process we have above 154 ORGANIC CHEMISTRY. described, is the neutral sulphate, though generally known as the basic sulphate. Its formula is This salt contains 74.3 per cent, of quinia. It crystallizes in very delicate needles belonging 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 parts of cold absolute alco- hol. It is very nearly insoluble in ether. Its solu- tions are extremely bitter. It becomes phosphorescent on being heated, and subsequently 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 quinicine, which is likewise a febrifuge. Medicinal sulphate of quinia always contains sulphate QUINIA. 155 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 quinia. Cinchonia appears to be of little 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 replacing the ether in another determination, by chloroform, which 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 boiling 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 ORGANIC 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 should dissolve in 80 per cent. alcohol. If it dissolves in water, but does not dissolve in 56 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 been added, is colored red by sulphuric acid. Quinia sulphate is chiefly employed in cases of in- termittent fevers. CINCHONIA OR CINCHONINE. Cinchonia was discovered by Duncan in 1803, though first recognized as an organic 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 CINCHONIA. 157 from the Gray Peruvian Bark. Cinchonia separates out in crystals on the evaporation of the alcohol with \vlnch the calcic precipitate is washed. The crystals 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 quinia, which is less soluble than sulphate of cinchonia. When nothing remains but a very concentrated mother- liquor, the cinchonia is precipitated by ammonia, and 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 quinoleine. Cinchonia has an alkaline reaction. It unites with acids, forming salts which correspond to the salts of quinia, though generally more soluble. 158 ORGANIC CHEMISTRY. Cinchonia sulphate, heated to about 135, furnishes the sulphate of an isomeric alkaloid, cinchonicia 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. Quinidia 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, cinehonidia or cinchoni- dine, and it is this mixture, containing chiefly quinidia, which is called quinoidine in commerce. Quinidia is isomeric with quinia ; it melts at 160. It is difficultly soluble in water, very soluble in boil- ing alcohol, and slightly soluble in ether. Its solutions are dextrogyrate. Quinidia acts as a febrifuge. With chlorine and ammonia, it gives the same reactions as quinia, and forms corresponding salts. Quinoidine contains, as we have said, cinehonidia, 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 cinehonidia. STKYCHNJA. 159 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. These alkaloids are extracted from the fruit of the Strychnos nux vomica ; from St. Ignatius' beans, fruit of the Strychnos Ignatii ; from the wood of Coulevre, root of the Strychnos colubrina ; from the upas, the poison of indian arrows, extracted from the Strychnos tieute>\ from the False Angustura Bark, and the bark of the Strychnos nux vomica^ which contains princi- pally brucia. STRYCHNIA. 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, 125 grams ot quicklime slacked to a thin paste are added for each 160 ORGANIC CHEMISTRY. kilo, of mix vomica. The precipitate is collected on a doth, washed, 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 fa its weight of nitric acid, and the solution concentrated in a water bath. The nitrate of brucia remains dissolved and the nitrate of strychnia crystallizes out. These crystals are re-dissolved in water, animal charcoal added, the solution brought to boiling and then filtered. Ammonia is added to this 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 Y5 per cent, of water. Strychnia treated with potassa furnishes a small quan- tity of quinoleine. Iodide of ethyl produces with this base the compound BEUCIA 161 C a H 22 (0 2 H 5 )NAI. 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 with 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 cry stall izable salts. The nitrate CoJI^lS^C^HNOg crystallizes in fine needles very soluble in hot water. Strychnia is among the most powerful poisons, 2 to 3 centigrams being sufficient to cause death. There is believed to be no reliable antidote for strychnia though F. M. Peirce claims that small doses of prussic acid are efficient for the purpose. (M-' 68-335.) BEUCIA. To obtain this alkaloid the alcoholic liquids from which strychnia has been removed, are saturated with oxalic acid and evaporated. The crystals of oxal- ate of brucia which are formed, are washed with 95 per 162 ORGANIC CHEMISTRY. cent, alcohol and redissolved in water. The solution is decomposed by lime, the precipitate collected, dried and dissolved in boiling alcohol; brucia then crystal- lizes out and is purified by two recrystallizations. Crystals of brucia are large and of the clinorhombic system; they are soluble in alcohol, insoluble in ether, but soluble in 850 parts of cold, or 500 parts of boil- ing water. Concentrated sulphuric acid strikes a rose color with brucia which afterwards changes to green. ^Nitric 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. CURAKINA. From the arrows of the Indians living on the shores of the Amazon and Orinoco, a brown resinous matter is collected, from which crystals of a substance have been obtained whose poisonous action is exceedingly rapid. Preyer, to whom we owe this discovery, regards its formula as C 10 I1 15 N, and has named it curarina. The Indians of Dutch Guiana poison their arrows with two other substances no less dangerous: urari and tikunas. These three substances paralyze the ac- tion of the muscles by destroying the motor nerves VERATKIA. 163 (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. DKASTIO 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 that 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 ( Yeratrum album) and its seeds, furnish an alkaloid called veratria, CgoHso^Og. It crystallizes in prisms having a rhom- bic base. They 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, sabadillia, colchinia, and jervia, are found associated with veratria in the Veratrum album. Jervia, C. 2 oH, 6 E"2O 3 2H 2 O, (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 POISONOUS SOLANACE^. The belladona, Atropa belladona, and the thorn- apple, Datura stramonium, furnish each an alkaloid 164 ORGANIC CHEMISTRY. called, respectively, atropia and daturia, the formula of which is Cnll^C^. This substance crystallizes in fine needles, which are fusible at about 90, and are partially sublimed at about 135. It is difficultly soluble in water, but very soluble in alcohol and ether. Heated with an oxydizing agent, such as potassium bichromate, or sulphuric acid, it disengages essence of bitter almonds, easily recognizable by its odor, and crystals of benzoic acid are sublimed. With sulphuric acid a violet color is produced, accompanied by a fra- grant odor resembling that of a rose. Hydrochloric acid furnishes two acids with atropia, tropic C 9 H 10 O 3 , and atropic C 9 TI 8 O 2 . Cases of poisoning by atropia are rare, but instances in which persons are poisoned by the berries of bella- dona are of frequent occurrence. The black henbane, Hyosciamus niger, furnishes silky needles of a substance, hyosciamine, which has much resemblance to atropia, but whose action as a poison appears to be less violent. Its physiological action is on the nerves rather than on the muscles. It causes less dilation of the pupil of the eye, and produces a sombre delirium. Belladona and atropia, the datura, the henbane and hyosciamine, as well as the poisonous solanaceae in general, should be classed among the narcotic poisons. Poisoning produced by belladona, and by most of the poisonous solanacese, is characterized by great dila- tion of the pupils of the eyes. The patient is also ACONITINA. 165 seized with vertigo and strange hallucinations followed by a turbulent delirium and convulsions. The face is congested, respiration difficult, and the skin often breaks out in an eruption similar to that in rubeola (measles). No antidote is known for these poisons; an infusion of unroasted coffee, tea, or other astringent substances is recommended, but the use of energetic emetics and purgatives is the most effic'ent method of treatment. The chemical characters of these alkaloids has not been as jet very fully studied. Desfosse has extracted from the woody nightshade, Solanum dulcamara, from the berries of the felon- wort and from the young sprouts of the potato, Sola- numtuberosum, a substance called solanine, 43 H T1 NO 16 , a highly poisonous alkaloid. On being boiled with acids, it furnishes a stronger base solanidine and glucose. ACONITINA. Aconitina is extracted from the monk's-hood, Aconitum napellus, as a colorless amorphous, bitter powder, soluble in alcohol, slightly soluble in ether, and almost insoluble in water. It fuses at 120, and is al- kaline. It is a very active poison. Planta gives its formula as O 30 H 47 ]N T O 7 ( '*). Duquesnel has extracted from the Aconitum napel- lus a crystalline alkaloid, whose formula is 166 ORGANIC CHEMISTRY. DIGITALIN. This substance was long ago obtained in an amor- phous condition from the purple fox-glove. In 1871 ]N T ativelle succeeded in obtaining it in a crystalline form. An extract of fox-glove is first prepared, con- centrated by distillation and dilluted with 3 times its volume of water. A precipitate is formed which contains two bodies, digitalin and digitin. This deposit, washed with boiling alcohol, furnishes crystals composed of these two substances, which are easily separated by chloro- form, as digitalin is dissolved by it in all proportions, while digitin is insoluble. The proportion of digitalin in Digitalis grown in different countries, has been made the subject of special investigation by Prof. S. P. Duffield, of Detroit. (94-1868.) Digitalin is very bitter to the taste. It powerfully irritates the nostrils, and is an active poison. If digi- talin be moistened with strong sulphuric acid and then exposed to the vapors of bromine, it assumes a purple color, which is darker or lighter according to the pro- portions employed. Hydrochloric acid produces with digitalin a very intense emerald green color. One-fourth of a milligram is sufficient to produce the ordinary poisonous effects oi digitalis. A milli- gram produces, in from three to five days, a marked change in the circulation. Three milligrams produce most dangerous effects within 24 hours. EMETIA. 167 It is 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 "ipas antior, with which the Indians poison their arrows, is obtained from the Antiaris toxicaria. EMETIA. This body is obtained from the roots of the ipecac- uanha, Cephceles ipecacuanha; it also exists in the Richardsonia braziliensis, in the Phsychtria emetica, and in the roots of the Cainca (madder tribe). These materials, reduced to a powder, 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 is 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 C^H^CXi 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 CHEMISTRY. CANTHAKIDIN is a very poisonous crystalline substance, obtained from Spanish flies, (Lytta vesicatoria, and other varieties) and has the composition C 5 H 6 O 2 . It is present in nearly all parts of the flies, varying in amount from 0.5 to 1.2 per cent. K. Wolff has of late given this sub- stance a very full investigation. (95, May, '77-102.) CAFFEINE (CAFFEIA) OR THEINE (THEIA). C 8 H 10 N 4 2 ,H 2 0. Alcohol is added to a mixture of 5 parts coffee 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- fied by treating with animal charcoal, and recrystal- lizing in hot water. The extractive matters of the Jcola-nut sndmate 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 remarkable that the instinct of man should have led him to select, as the bases of common bever- ages, just the four or five plants, which out of many thousands are the only ones, as far as we know, con- taining caffeine. THEOBEOMINE. 169 It is recognized by boiling with fuming nitric acid; a yellow liquid is produced. On being evaporated to dry ness, and ammonia added to the residue, a purple coloration is produced, resembling murexide. (p. 125.) Amalic acid and CholestropJian are products of the action of oxidizing agents upon caffeine; bodies link- ing this alkaloid to the uric acid group. THEOBKOMINE. There is extracted from the caco, Theobroma 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 tlieobromine\ its formula is C 7 H & NA. PICEOTOXIN. C 5 H 6 2 . From the Indian berry, Cocculus Indicus, there is extracted a white crystalline matter of extreme bitter- ness, called picrotoxin, (from Tempos bitter ro^ixor.) 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 170 ORGANIC CHEMISTRY. much to (87-1862) our knowledge of the chemical character of pi cro toxin. POLYATOMIC ALKALOIDS. There 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 ammonia, 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. Hoffmann established their true formula. They are called poly amines. EXAMPLE. ( C 2 H/ Ethylenic dianiine, No < H 2 ( O.TV Diethylenic " N 2 \ C 2 H 4 " \ H 2 ( C.H/ Triethvlenic " N 2 \ C 2 H 4 " I C 2 H 4 " IJEEA. POLYATOMIC ALKALOIDS 171 JRouelle, Jr., was the first to obtain this body in an impure state from urine. Fourcroy and Yanquelin 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, re-dissolved 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- sium carbonate; urea is set free and barium and potas- sium nitrates formed. The above mentioned salts are added as long as effervescence 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 Woehler, con- sists in preparing cyanate of ammonia, which body is isomeric with urea. CYANATE OF AMMONiuM=H 4 CE" 2 O=NH4-O-C!N". 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 treated 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 difficultly soluble in ether. Its solutions are neutral. Urea fuses at 120; at about 150 it is decomrjosed, yielding ammonium carbonate, ammelide, C 3 OH 5 N 5 , and fiiuret, C 2 O 2 H 3 N 3 . Oxydizing agents decompose urea. Chlorine also decomposes solutions of urea in the following man- ner : 3C1 2 + H 2 O + CH 4 lSr 2 O-6HCl -1- JST 2 + CO 2 . Urea heated to 140 with water in sealed tubes, is transformed into ammonia and carbon dioxide: UREA. 173 H 2 O + CH 4 ]$r 2 0=C0 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. 174 ORGANIC CHEMISTRY. NATURAL FATS AND OILS. The fatty bodies are very widely distributed through- out the vegetable and animal kingdoms. 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 siccative oils, and are used in the manufacture of varnishes, printers' ink, oil cloth, also in paints. Fats and oils are insoluble in water; they 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 less 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 OR STEARINE, (from Greap, suet) C^H^Ce, is prepared by melting suet in turpentine; the two other proximate principles present, are precipitated, FATS AND OILS. 175 while the stearin e remains in solution. It is separated from the liquid by water, and purified by several re- crystallizations in ether ; it fuses at Tl, and solidifies at' 50. Berth elot 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 witli nitrogenous matter, become acid, rancid. The chemical nature of this change is not entirely understood. OLEIN OK OLEINE, 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 monoleine, 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 oleine into an isomeric body, elaidine. Siccative oils contain, instead of oleine, another principle called elaine. Neutral fatty bodies and other ethers of glycerine are decomposed by alkaline solutions ; a combination with water takes place, glycerine and fatty acids are formed. We may take as an example, stearin. 176 ORGANIC CHEMISTRY. 3KHO+C 57 H 110 6 =3(KC 18 H3 5 2 )+C 3 H 8 3 . Alkalies, therefore, react upon the ethers of glycerine in the same manner as do the ethers of glycol and ordinary alcohol. This reaction is called saponificd- tion, and soaps are salts formed by stearic, margaric, and oleic acids, with a metal. SOAPS. STEARINS 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 employed ; thus the precipitate which common water produces in soap is a lime soap. Ordinary soap is made by boiling fats of inferior quality with an alkaline solution. When the oil is completely decomposed the soap is precipitated by salt water, in which soap is insoluble. Stearine 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 effected by means of sulphuric acid instead of lime; this acid forms with the fatty acids, double or conju- FATS AND OILS. 177 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 temperature, Berthelot obtained a result exactly the reverse, caus- ing stearic acid and glycerine to reform stearine by simple direct synthesis. STEARIO ACID, C^H^C^, is crystalline, insoluble in water, soluble in alcohol and ether, and melts at 70. It unites with the bases ; its alkaline salts alone are soluble. MARGARIC OR PALMITIC ACID, C^H^O^, (from jtapyapov, a pearl, owing to its pearly lustre) is crys- talline. It melts at 60 and forms salts with the metals. OLEIO ACID, Cjgli^Oa, is an oil becoming colored in the air and converted into an acid called elaidic acid, which is fusible at 44, in contact with a small quantity 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. LEAD PLASTER is essentially a lead-soap compound of plumbic oleate. 178 ORGANIC CHEMISTRY. CKOTON 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 possesses 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, C 4 H 6 O 2 , denominated crotonic 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 the oil is obtained by putrefaction, in which case the oil separates out naturally, or the livers are cut into 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 thousandths of iodine, and a small quantity of phosphorous ; and its medical qualities are thought to be due to these WAX. 179 two substances, but it is probable that its efficiency is more frequently due simply to its fatty character. BUTTEB. Ordinary 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. SPERMACETI. This substance which is formed in peculiar cavities in the head of the sp-arm whale, arid is a neutral fatty body sometimes employed in pharmacy. It is an ether, which, on saponifies ti on, produces a fatty acid called ethalic acid, and a monatornic alcohol, ethal. H 2 0+C 33 H 6 A=C 16 H 31 OHO + C^O Spermaceti. Ethalic Acid. E;hal. WAX. Yellow bees- wax is obtained by submitting honey- comb to pressure, then fusing the same under boiling water. It is bleached by being cut into thin cakes and exposed to the air and sunlight. Thus prepared 180 ORGANIC CHEMISTRY it fuses at 62. Mixed with 3 per cent, of oil of sweet almonds it forms a cerate, used in pharmacy. On being treated with alcohol it separates into two proximate principles: one, soluble in this liquid, is acid, and is called cerotic acid, having the formula OjjH^O; the other, which is but slightly soluble, is called myricin. The latter is a compound ether, and is decomposed by bases into an acid, ethalic acid, and an alcohol, melissic alcohol, C^H^O. CASTOR OIL. This oil is extracted from the Ricinus communis, a plant of the family of Euphorbiaceae. The castor-oil beans are hulled, pulverized, and the pasty mass obtained subjected to strong pressure. This oil is slightly yellow. Its density is 0.926 at 12, and it remains liquid at a temperature of 18. 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, CjgH^Os. SUGARS. 181 SUGAES. The general name of sugars, by some regarded as polyatomic alcohols, is given to bodies which are capa- ble of fermenting, that is, of decomposing directly or indirectly into different products, of which the princi- pal ones are alcohol and carbon dioxide. Fermenta- tion requires the presence of certain microscopic plants, and, according to Pasteur, is a phenomenon correlative with 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, C 6 H 14 O (; , extracted from manna. Duleite or melampyrite^ C 6 H 14 O 6 , found in Mada- gascar. Finite, C 6 TI 12 O 5 , extracted from a Californian pine tree. Quercite, C 6 H 12 O 5 , extracted from acorns. These bodies do not ferment 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 oxygen in the proportions to form water. 182 ORGANIC CHEMISTRY. The second class includes the glucoses, isomeric bodies, whose general formula is, C 6 H 12 O 6 . Among these are: Ordinary Glucose or grape sugar. JLevulose, associated with glucose in the form of inverted sugar. Maltose, obtained from malt. Galactose, obtained by treating sugar of milk, or gums, with dilute acids. Eacalin, obtained by the action of maltose on beer yeast. Sorbin exists in the berries of the mountain ash. Inosite is found in the embryo of young plants and in the fluids of flesh. Lactose or Sugar of Milk. 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 sodium amalgam, produce mannite. The second includes those substances (galactose, lactose) which, on oxydation produce mucic acid, and on hydro- genation furnish dulclte. The third class of su- gars contains bodies whose general formula is C^H^On, and are called saccharoses, by Berthelot. It contains, besides cane sugar, three bodies called: Melitose, an exudation of certain eucalypti. Trehalose or mycose^ extracted from the Turkish manna and certain mushrooms. Melezitose, obtained from an exudation of the larch. The sugars of the first two classes are placed by Berthelot among the polyatomic alcohols. MANNITE. 183 MANNITE. C,H U 0, This body exists naturally in an exudation of vari- ous species of ash (Fraxinus rotundifolia\ called manna, of which it forms the greater portion. It is also found in mushrooms, algae, the sap of most fruit trees, onions, asparagus, celery, etc. It may be pre- pared by dissolving manna in one-half its weight of water, to which a small quantity of egg albumen is added, and the mixture brought to boiling and filtered. 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, C 6 H 12 O 5 . It oxydizes in presence of platinum black, furnishing a non-crystallizable acid called mannitic acid. Boiling nitric acid converts it into saccharic and oxalic acids. Mannite, treated with a small quantity of nitric acid, is changed into a bodv insoluble in water, called ('C H ") )" nitro -mannite, (^fr\ \ ( 6 , which may be regarded as a compound ether. Dulcite. Dulcite is very analogous to mannite, but differs from it, in that it furnishes, with nitric acid, mucic acid. 184 ORGANIC CHEMISTRY. GLUCOSES. These compounds may be considered as representa- tive carbohydrates. Ordinary glucose (from y\vH.v$, sweet,) or grape sugar, is a crystalline substance, and is found in honey, figs, and various other fruits, together with another 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 salicine, tannin, and other substances, which, for this reason, have been named glucosides. Vegetable cellulose, the envelope of many inverte- brates (chitin and tunicin) and the glycogenous princi- ple of the liver furnish glucose on treatment with dilute acids. It is manufactured on a large scale by the action of starch upon dilute sulphuric acid. Water containing four to eight per 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 chalk and the liquid allowed to become clear. It is decolored by passing through GLUCOSES. 185 filters containing animal charcoal and evaporated to a density of 41 Baume. The glucose crystallizes in compact masses. Often the liquid is evaporated to only 3 B., when a syrup is obtained known as starch syrup. Honey treated with cold concentrated alcohol, also furnishes glucose. The crystals of glucose are small, opaque, and ill defined. They are represented by the formula C 6 H 12 O 6 ,2H 2 O, but they may be obtained having the composition C 6 H 12 O 6 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 C 6 H 10 O 5 , is called glucosanc, C 6 IL 2 O 6 = C 6 H 10 O 5 + H 2 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 (sulphoglucic acid}\ with strong sulphuric acid, carbon. Glucose oxydized with care, furnishes 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 dibutyric glucosane, (C 6 H 6 ) ) Q (C 4 H 7 0)H 2 f ^' This 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 6 H 10 6 BaC 6 H n O 6 , etc. Peligot has shown that the solutions of these glucos- ates are gradually changed into salts of a special acid called glucic acid, whose formula is Oupric 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 alkalies. On adding glucose to a solution of copper sulphate, this 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 GALACTOSE. 187 organic. A mixture is used of copper sulphate, Rochelle salt and soda (Fehling), or a solution of copper tartrate in potassa. (Barreswil.) Prof. "W". S. Hain^s has found 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, 1^ drachms; pure glycerine, 2 fluid drachms; distilled water, 6 ounces. LEVTJLOSE, C 6 H 12 O 6 . 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, C,H a O, 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-mucic acid. INOSIN, INOSITE OK MUSCLE SUGAR. C 6 H 12 O 6 + 2H 2 O. This substance is found in many animal organs, and 188 ORGANIC CHEMISTKY. 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 inosic 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 beautiful crystals of inosite. This substance has 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 SACCHAEOSES. ORDINARY SUGAR, This body exists in a large number of plants, though it is almost exclusively extracted from the sugar-cane and beet-root. The sugar-cane, Arunde saccharifera, contains 1Y 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 different 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 ORGANIC CHEMISTKY. 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; hot 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 solidifies 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. Ci2H 22 Oii 6 H 12 O 6 + C 6 H 10 O 3 . Levulosane. At about 190 sugar loses water, becomes brown y and finally furnishes a substance which is commonly known as caramel. According to Gelis three pro- ducts of dehydration are formed, caramelane, cara- melene and carameline. At a temperature of 230 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 baryta water and lime water, forming different compounds called sucrates or saccharates. SUGAR OF MILK. 191 The 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 beer yeast. SUGAR OF MILK, LACTIN OR LACTOSE. It is obtained from mirk, 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 sugar of milk are made by evaporating the whey 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 temperature of about 140 it loses H 2 O, and becomes brown at 160 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. 192 ORGANIC CHEMISTRY Keichardt lias obtained (60- 4 75-807) from a sugar distinct from ordinary sugar, a body though having the same formula. He names it para-arabin. HONEY. Honey is produced by the domestic bee (Apis mel- lifica), an insect of the order Hymenoptera. It is separated from the wax by exposing the honey- comb to the sun, on wire nets; very pure honey is thus obtained. The mass which remains is expressed, and this prod- uct is a second quality of honey, more colored and of a less agreeable taste and odor than the first. The comb is then heated with water to remove the remain- der of 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 dextroyrgate, crystallizable glucose, and on removing this sugar there remains a viscid uncry stall izab]e liquid, which contains levolose. 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- ing with water, among which is glucose, or some other saccharine 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: GLTJCOSIDES. 193 Salicin, C 13 H 18 O 7 , extracted from the bark of the Willow. Amygdalin, C^H^NOn, extracted from the Bitter Almond, Amygdalus communis. Orcin, C 7 H 8 O 2 , extracted from various Lichens. Tannin, C 27 H 22 O 17 , extracted from the Oak. Phlorizin, C 21 H 2 4O 10 , extracted from the Apple, Pear, or Cherry tree. Populin, C^H^Og, extracted from Aspen leaves. Arbutin, C 13 H 16 O 7 , extracted from the leaves of the Uva-Ursa. Convolvulin, C 31 H 50 O 16 , extracted from the Convol- vulus orizabensis and schiedeanus. Jalappin, C^H^O^, extracted from Convolvulus orizabensis and scammonia. Saponin, a white amorphous powder whose solution is very frothy and of which the powder is very sternu- tatory. Daphnin, C 31 H 32 O 17 , the crystalline matter extracted from the bark of the Ash (Fraxinus excelsior}. Cyclamin C 20 H 24 O 10 , extracted from the tubercles of the Cyclamen europceum. Quinovin, C 3 oIi 48 O 8 , a resinous, bitter matter, solu- ble in alcohol, existing in the bark of the Quina nova and other cinchonas. Solanin, C 43 H 71 NO 16 . This has already been studied, (page 165). Esculin, CsaH^ds, extracted from the bark of the Horse Chestnut. Qnercitrin, C 29 H 30 O 17 , from the bark of the yellow oak (Quercus tinctoria). 194 ORGANIC CHEMISTRY. Coniferin, C 16 H;>2O 8 , from the Larix europaea, etc. Vanillin, from the Yanilla bean, and recently ob- tained artificially (60-74-608). SALICIN, Ci 3 H 18 O 7 + H 2 O. 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 febrifuge, but is of little value in well de- fined intermittent fevers. It has as a distinguishing chemical character, the property of becoming red with sulphuric acid. Tinder the action of dilute sulphuric, or hydro, chloric acid, or even with emulsin, salicin is decom- posed. "With the latter the reaction is: C 13 H 18 7 + H a O=C 6 H 12 6 + C 7 H A Glucose. Saligenin. In contact with cold nitric acid it loses hydrogen, and a body is formed called helicin, C 13 H 16 O 7 . When treated with oxydizing agents, it gives off an odor which is identical with that of the essence of meadow sweet (Spirea, ulmaria). 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, C 7 H 16 O 2 , but it has not the properties of this acid. SALICIN. 195 It is an aromatic liquid, boiling at 196, and has the property of oxydizing spontaneously, giving rise to an acid called salicylic acid, C 7 H 6 O 3 . Salicin, treated with fused potassa, furnishes potas- sium oxalate and salicylate. Cahours has shown that essence of Gaultfieria procumbens, 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 spirit with a mixture of salicylic and sulphuric acids. Salicylic or oxybenzoic acid has been lately pro- duced by Kolbe (56 -'74 -22), by a remarkable syn- thesis in acting on carbolate of sodium with CO 2 . 2 =C 6 H 6 + C 7 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, '77) obtained salicylic acid by the action of sodium upon succinic ether. 196 ORGANIC CHEMISTRY. TANNINS. This is the name given to different principles exist- ing in plants, which are characterized by the following properties: 1st. 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^H^On. " cachou (catechin or catechic acid). " quinquinia (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 are pulverized and submitted to the action of commer- cial sulphuric ether, which is made aqueous. This ether 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 and evaporated 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. This 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. G-ALLIO 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 with hydrochloric or sulphuric acid, it is decomposed into glucose and gallic acid: C^AT + 4H 2 O=3(C 7 H 6 5 ) + 6 H 12 O 6 - Gallic acid. Glucose. 198 ORGANIC CHEMISTRY. Gallic acid is deposited as the liquid becomes cool. It is purified by redissolvingand treating with animal charcoal, and recrystallizing. O TT O ) Gallic acid, C 7 H 6 O 5 = fr fr f Oft crystallizes in silky needles, soluble in three parts of boiling water, but little soluble in cold water. This solution, on standing in 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 precipitate gelatin when pure, nor the alkaloids. Mixed with pumice-stone and heated to 210 it pro- duces a beautiful sublimate otpyrogallie acid, carbon dioxide being liberated at the same time. C 7 H 6 5 =C 6 H 6 8 +00 2 . 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-' 74-484) 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 acid as tetratomic and monobasic (77-620). VEGETABLE CHEMISTKY. 199 VEGETABLE CHEMISTKY. At the moment when the radicle of a plant appears nbove the ground, its vital phenomena undergo a marked change. The plant decomposes carbon dioxide, water and certain nitrogenous compounds furnished by the soil, and grows bj retaining carbon, hydrogen, nitrogen 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 sun 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 tluit 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. EXPERIMENT. Place a few leaves in a flask half full of water containing carbon dioxide, u 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 carbon diox- ide will not be altered in the least. "Where 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. Now 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 from the vessel, no carbon dioxide is absorbed, which also proves that the carbon dioxide existing in the air has been removed by the plant. The 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. Edwards have proved that the sub- merged stems of the Polygonwn 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 VEGETABLE CHEMISTRY. 201 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? Boussinganlt 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 w r ater 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 excellent 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, nature 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 formed 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 ! VEGETABLE CHEMISTRY 203 By combining six atoms of carbon with five atoms of water, nature forms either the woody principle, cel- lulose, or the essential constituent of the potato, starch. By 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 cereal as well as the most deadly strychnia; and often products as unlike 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 of 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, in many circumstances at least, deport themselves in a similar manner. Many experimenters, and especially Dutrochet and Garreau, go further, and say that plants and 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 diffused 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 amount 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, nitrogen and by exhaling the greater OKGANIZED SUBSTANCES. 205 part of the oxygen. The animal, on the other hand, forms 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 works of Prof. S. "W. Johnson, " How Crops Grow," and "How Crops Feed"; also Prof. John C. Draper's article in Am. Jour. Sci. and Arts, 'Nov. 1872, entitled "Growth of Seedling Plants." ORGANIZED SUBSTANCES. 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 organizable substances, the term organic being reserved for the definite compounds studied in organic chemistry. All these substances play an important part in the veget- able kingdom, forming the network of vegetable tis- sue, as cellulose or as starch, etc. CELLULOSE OK CELLULIN, (C 6 H 10 O 5 ) n . On examining a young plant under the microscope, 206 ORGANIC 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 6 H 10 O 5 , is the formula, ordinarily given to it, although a multiple formula at least three times as large, or C 18 H3oO 15 is necessary to explain certain reactions with nitric acid. EXPERIMENT. 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 numer- ous carbohydrides, gaseous and liquid, 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 the acid is continued, the whole is dissolved and the same products are obtained as in the case of starch when brought in contact with sulphuric 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 effect. 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 parchment. Paper thus prepared is frequently 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. GUN COTTON OR PYROXYLIN. Gun cotton was first made by Schoenbe-in, 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 1.5), 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 -somewhat wrinkled. When well prepared it burns 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 NO 2 that, having the formula C ]8 H 21 O 15 9]^O 2 , has the greatest explosive energy. Pyroxylin regenerates cellulose in contact with ferrous chloride. If 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. being 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 nok\a^ 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 (52-74-235) 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: Raw cotton, . 2 parts. Potassium carbonate, 1 " Distilled water, 100 " Boil for several hours, adding water to keep up the measure ; then wash until free from any alkali, and dry. Then take of Purified cotton, Y oz. av. Nitrous acid (nitric, saturated with nitrous acid), s. g. 1.42, 4 pints. Sulphuric acid, s. g. 1.84, - 4 " Mix the acids in a stone jar capable of holding 2 gals., and when cooled to about 80 Fahr., immerse the cot- tori in small portions at a time ; cover the jar and allow to stand 4 days in a moderately cool place (temp. 50 to Y0 Fahr.) then wash the cotton in small 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 the 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, tunicine, which has the com- position and properties of cellulose. Linen, hemp, cotton, wood and paper are all essen- tially cellulose. 210 OEGANIC CHEMISTRY. AMYLACEOUS SUBSTANCES. These substances are almost universally present in plants; particularly that known as starch orfecula. 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 stream 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. STAECH. a?(C 6 H 10 O 5 ) probably C 18 H3oO 15 . 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 thirty 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. STAKCH 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 Rohan potato have a length of 0.185 mm.; the smallest are those of the GJienopodium, 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 blue 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 diffused 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 which is pre- cipitated by alcohol as an amorphous powder. If we boil starch for a long time with water it is converted into a substance called dextrin. The pres- ence of a small per centage of sulphuric acid facilitates this change, which is soon followed by the transforma- tion of the dextrin into glucose. The sulphuric acid is not at all altered during the reaction. The change ot starch into glucose also takes place when water containing starch, and to which germinated barley has been added, is heated to about 70. This transformation is due to a substance called diastase (from diaffraffis, separation), which is formed in the seed during germination. The production of diastase on the formation of the young shoot, explains how starch becomes soluble and serves as nutriment to the young plant. Theptyalmof the saliva, the pancreatic juice, the STAKCH. 213 soluble parts of beer yeast, gluten, and many other sub- stances, are capable of producing this transformation of starch into dextrin and glucose. It has generally been considered that the molecule of starch, in being transformed into glucose, simply united with one molecule of water directly, thus: C 6 H 10 5 +H 2 0=C 6 H 12 6 . Musculus, 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 18 H3o0 15 + H 8 0=2C 6 H 10 5 + C 6 H 12 O 6 . Dextrin. Glucose. 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 acid, nitrous vapors are given oif and different 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 two to three per cent, of alkali, accelerate the formation of starch paste. 214 ORGANIC CHEMISTRY. Starch is employed in the laundry and therapeutic- ally in poultices, injections and baths. Tagioca, is the starch of the root of the Jatropa manihot, called cassava or manioc. Sago is obtained from the pith of various sago palms. Arrow-root is the starch of the Maranta arundi- nacece* and one or two other tropical plants. Salep is obtained trom the Orchis mascula. 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 lichenin, 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. DEXTKIN, OR DEXTRINE. C 6 H 10 5 . 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. FLOUR 215 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 -jr its weight of water and 1 2 tf 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 by 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. FLOUK. 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 eifect 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 is- herewith given : Ill I I! 9 Wheat, 14.0 59.5 7 1.7 14 1.2 1.5 Eye, 16.0 57.5 10 3.0 9 2.0 2.0 Oats, 14.0 53.5 8 4.0 12 5.5 4.0 Eice, 14.5 77.0 0.5 7 0.5 0.7 The sticky, elastic substance found with starch in flour is gluten (called also glutin), and is a mixture of various proximate compounds but chiefly of three; legumin, or vegetable casein, fibrin and gelatine. Flour of good quality is dry and soft to the touch; it forms 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. C 6 H 10 O 5 . This substance is very widely distributed in the vegetable kingdom. Gums either swell in water or GUM. 217 are dissolved, imparting to it a mucilaginous consis- tency. From a chemical standpoint they are essentially characterized by giving a precipitate of mucic acid on being boiled with nitric acid, and by precipitating lead subacetate. GUM-ARABIC, ARABIN. 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, gummic or arable acid, with lime and potassa. This acid may be isolated by pouring hydrochloric acid into a solution of gum, and adding alcohol; an amphorous deposit is formed which, dried at 120, has the formula C 6 H 10 O 5 . 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 are transformed into gummates by the action of boiling water. These gums heated with dilute sulphuric acid furnish a dextrogyrate sugar. 218 ORGANIC CHEMISTRY. Gum-tragacanth often contains starch. MUCILAGE OR BASSOKIN. 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, furnhh 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. This substance is modified during the ripening of the fruit and becomes soluble, vegetable jelly, or pectin (from Ttrjuri^^ a jelly), to which Fremy assigns the formula CgjH^Oga. .Pectnij submitted to the action of a ferment found in tli3 cellular tissues of vegetables, called pectase, or of cold, very dilute, alkaline solutions, is changed into a gelatinous acid called pectosio acid, then into another substance likewise gelatinous, which is known by the name of pectic acid. 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 -oectin of these fruits. LEGUMIN. 219 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 carefully dropped into the filtered solution obtained above, and the legumin is precipitated; an excess of the acid should be avoided, as this would dissolve tbe 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 which interferes with its precipitation and with the filtration of the liquids. The cnemical properties of legumin are identical with those of casein. Liebig 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 presence he ascribes the tendency of sugar to toi-rn alcohol and carbon dioxide instead of mucilage and lactic acid. VEGETABLE ALBUMEN. Vegetable albumen is contained in many plant- juices and is deposited in fiocculi on applying heat to such liquids. It can' also be precipitated by nitric acid, tannin and mercuric chloride brecisely like animal albumen. Vegetable albumen is composed of carbon, hydrogen, nitrogen, oxygen and sulphur. There is no trustworthy formula for this substance. INDEX. PAGE. Acenapthene, Ci 2 Hio=i54. . 38 Acetamide, C 2 HS NO=59- . 136 Acetanilide, Cs K NO 135. 130 Acetic oxide C4 H 6 O 3 =102 103 Acetochlorhydric glycol 63 Acetone, C 3 H 6 0=58 99, 108 Acetyl acetate, C4 N 9 Os . . . 103 Acetyl chloride, C 2 C1H 3 O. 103 Acetyl hydride or aldehyd, C 2 H 4 0= 44 86 Acetylamine, C 2 HS N=43.. 129 Acetylene, C 2 H 2 =26 18 Acetylide, cuprous 19 Acid,acetic, C 2 H4 Os =60. . 99 Acid, aconitic, CG HG OG =95 174 Acid, acrylic, C 3 H4 O 2 =72. 91 Acid, adipic, CG HioO4 =148 91 Acid, alloxanic, C4 H4 N 2 Os 125 Acid, alpha-cymic, QiHyOg 91 Acid, amalic, CG HT N 2 04 . . 169 Acid, anchoic, Cg HieO4 =188 93 Acid, angelic, C.5 HS O 2 =108 91 Acid, anisic, Cs I Is Os =152. 92 Acid, arabic, CG HioOs 342 217 Acid, arichidic, C-2oH4oO2 . . 90 Acid, atropic.Cg HS O 2 =148 164 Acid,benzoic,C7 HG O 2 =126 91, 109, 126 Acid, benzoglycolic 126 Acid, butyric,C4 H 8 O 2 . . 90, 108 Acid, caffetannic 196 Acid, camphic, Acid, carapholic, CigHisC^ . . 91 Acid, camphoric,CioHisO4 41, 93 Acid, caprylic, Cg Hi 6 O 2 ... 90 Acid, caproic,C6 Hi 2 O 2 = 1 16 90 Acid, capric, CioH 2 oO 2 =172 90 Acid, carballylic, CG H 8 OG . 95 Acid, carbarn ic, CHs NO 2 . . . u Acid, carbazotic,( Picric) CH 3 N 3 07=229 33 Acid, carbolic, CG H 6 = 94. 32 Acid, carbonic, C 2 H 3 O = 62. 92 Acid, catechic 196 Acid, cerotic, CsTHsjO . . .90, 180 Acid, chelidonic, CT H4 OG .. 95 Acid, chlorbenzoic,C? HS CIO = 130.5 .... 160 Acid, cholalic, C24H 4 oO5 =408 95 Acid, cholesteric, C 8 HioO 5 . . 95 Acid,choloidic,C 2 4H 38 O4 = 3oo 94 Acid, cinnamic, Cg II 8 O 2 = 148 91, in Acid,citraconic, Cs HG 04 93, 121 Acid, citric, C 6 Us O7.Ha O = 192+18 .- 120, 95 Acid, coccinic, dsIIscOa ... 90 Acid, comcnic, CG H4 Os .. . 95 Acid, coumaric, Cg H 8 O 3 . . 93 Acid, croconic, Cs II 2 Os . . 95 Acid, crotonic,C4 HG O 2 ..91, 178 Acid, cumic, CioHi 2 O 2 =164 91 222 INDEX. PAGE. Acid, cyanacetic, C 2 H 3 (CN)0 2 =85 103 Acid,cyanhydric,HCN = 27. 161 Acid,dextroracemic 117 Acid, dialuric, C4 H4 N 2 04 125 Acid, dinitrobenzoic, CT H 4 (NO 2 ) 2 O 2 =212... no Acid,doeglic, CigH 36 O 2 =296 91 Acid, elaidic 177 Acid, erucic, QzHgOg =338. 91 Acid, ethalic, CieHsaOg =256 179 Acid, ethylsulphuric, C 2 H 5 HS0 4 =i26 71 Acid, formic, CH 2 O 2 =50.98, 90 Acid, fumaric,C4 H4 O 4 = 1 16 93 Acid, gallic, CT H 6 O 5 . .95, 197 Acid, glucic, Ci2 H 8 Og =306 186 Acid, glyceric, C 3 H 6 O 4 . . . 93 Acid, gl y colic, C 2 Hi O 3 . 60, 92 Acid, guaiacic, Ce Us O 3 . . . 92 Acid, gummic, Ci 2 H^ On.. 217 Acid, hippuric, Cg Hg NO 3 .. 125 Acid, insolinic, Cg HS O 4 . . . 94 Acid, itaconic, Cs He O 4 . . 121 Acid, lactic, C 3 He O.s ..92, 122 Acid, lauric, C^H^Oo, =200 90 Acid, leucic, Ce Hi 2 O 3 =132. 92 Acid, lichenstearic, Cg Hi 4 Os 92 Acid, lithic, C 5 H4 N 4 O 3 . . 123 Acid, lithofellic, C2oH36O 4 . . 93 Acid, malic, C& He Os =134 115 Acid, malonic, Cs H 4 O 4 ... 93 Acid, mannitic. . . . , 183 Acid, margaric, CnHgiC^ . . . 177 Acid, meconic, CY H 4 O. . . . 143 Acid, melissic, CsoHeoOa . . 90 PAGE. Acid, mellitic, C 4 H^ 64 . . . . 94 Acid, mesoxalic, Cg H 2 Os . . 94 Acid, metagummic 217 Acid, monochloracetic, C 2 Cl HS O 2 =94.5 201 Acid, moringic, CisH 2 8O 2 . . 91 Acid, morintannic 196 Acid, mucic, CQ HS Os =205 95 Acid, myristic, C^HasO^o ... 90 Acid, cenanthalic, CT HuOg 90 Acid, cenanthic, CuH-^Os . . 92 Acid, oleic, Ci8H 34 O 2 =282. 91 Acid, opianic 127 Acid, oxalic, C 2 H 2 O 4 . ..93, 1 12 Acid, oxamic, C 2 HS NOs . . n Acid, oxybenzoic, Cy HQ Os 195 Acid, oxybutyric, C 4 HS Os 92 Acid,oxycuminic, CioHi 2 Os 92 Acid,oxynapthalic, CioHe O 4 94 Acid, oxyvaleric, Cs HioOs .. 92 Acid, palmitic, CieHsoO^ .90, 177 Acid, parabanic,Cs H 2 No Os 125 Acid, parafinic, C 2 4H 4 gO 2 . . 23 Acid, paralactic 122 Acid,paramalic, C 4 H 4 O 4 . . 116 Acid, paratartaric 117 Acid, pectic, CieH 22 Os =294. 218 Acid, pectosic 218 Acid, pelargonic, Cg HisO 2 ... 90 Acid, phenic, Cg H 6 0=94. . 32 Acid, phenylsulphuric, C 6 H 6 4 8=174 32 Acid, phloretic, Cg HioOs . . 92 Acid, phtalic,Cs H 6 O 4 =150 94 Acid, physetoric, CieHsoO-^ . . 91 Acid, picric, C 6 H 3 (NO 2 ) s O 33 INDEX. 223 PAGE. Acid, pimelic, CT HnO 93 Acid, pinariCjCaoHgoOa =302 41 Acid, pinic, CaoHsoOs = 302 . . 91 Acid, piperic, Ci2HioC>4 =218 94 Acid, propionic, C 3 HG Oo 78, 90 Acid, prussic, HCN=27. . . 161 Acid, pyrogallic, CG H 6 O 3 . . 198 Acid, pyroligneous 100 Acid, pyromeconic, C 5 H4 O 3 92 Acid, pyrotartaric, Cs H 8 04 = i3 2 93, "7 Acid, pyroterebic, CG HioOg . . 91 Acid, pyru vie, Cs Ih O 3 88 92 Acid,quinic, Ci HioOc =144- 93 Acid, quinotannic 196 Acid,racemic,C4 H 6 OG =150 117 Acid, ricinoleic, CisH^Os, 92, 180 Acid, roccellic, Ci7Hs-)O4 . . 93 Acid, salicylic, CT H 5 O 3 195,32,92 Acid, sarcolactic 122 Acid, scammonic, CisH-^Os 92 Acid, sebic, Ci Hi 8 O4 =202.. 93 Acid, sorbic, C c I Is Og =112. 91 Acid, stearic, CisHsoOa . .90, 177 Acid, suberiCjCs Hi 4 O4 =174 93 Acid, succinic, C4 HG 0493, 115 Acid, sulphocarbolic, C 6 H 6 S0 4 =i74 33 Acid, sulphoglucic 185 Acid, sylvic, QoHsoOo =302. 41 Acid, tannic, C 2 7lI>2Oi7=6iS 196 Acid, tartaric,C.i HG OG . ..116, 95 Acid, tartrelic, C 4 H 4 O 5 . . . 117 Acid, tartronic, Qj H 4 Os . . 94 Acid, terebic,C: HioO4 =158 93 Acid, terechrysic, CG HG O 4 94 PAGE. Acid, thionuric, Ci H 5 NO 3 SOs =195 125 Acid, thymotic, QiHuOs .. 92 Acid, toluic, Cs HS Og =136 91 Acid, trichloracetic, HC 2 C1 3 O 2 =163.5 JO 2 Acid, tropic, Cg HioOs =166. 164 Acid, uric,Cs H4 N 4 Os = 168 123 Acid, valeric or valerianic, CG HioO2 =102 109, 90 Acid, veratric, Cg HioOs ... 94 Acid, xylic, Cg HioO2 =150. 91 Acids 95 Acids, aromatic 91 Acids, fatty 90 Acids, general methods of preparation, 96 Acids, organic 90 Acids, defined 95 Acids, polyatomic 112 Acids, pyro 97 Aconitina, C3oH47NO 7 =533. 165 Alcohol, allyl, C 3 H 6 O...45, 57 Alcohol, amylic, Cs 11120.56,45 Alcohol, benzyl, CT H 8 O=io8 46 Alcohol, butyl, C 4 H ]0 O = 6 4 45 Alcohol, eery 1,C27H5 6 O = 396 45 Alcohol, cholesteryl 46 Alcohol, cinnyl, Cg HioO . . 46 Alcohol, cuneol 46 Alcohol, cymol, CioHuO.. 46 Alcohol, melissic, CsoHe2O. . 180 Alcohol, methyl, CH 4 O. .45, 46 Alcohol, myricyl, CsoHcsO.. 45 Alcohol, octyl, Cs Hi 8 O=i3o 45 224: INDEX. PAGE. Alcohol, ordinary, or ethyl, C 2 H 6 = 4 6 49 Alcohol, propyl, Cs HS O.. . 45 Alcohol, sexdecyl, CieHaiO.. 45 Alcohol, sextyl, CQ HuO 45 Alcohol, vinyl, C 2 H 6 = 46 45 Alcohol, xylyl,Cs HioO= 122 46 Alcohols, diatomic 58 Alcohols, monatomic 44 Alcohols, polyatomic. 59 Alcohols, sulphur 82 Alcohols, selenium 82 Alcohols, tellurium 82 Alcohols, tetratomic 59 Alcohols, triatomic 64 Aldehyds 86 Alizarin, QoHe Os =174. . . 39 Alkalamides 136 Alkaloids 127 Allantoin, C 4 H 6 N 4 O 3 = 158 I2 4 Alloxan, C 4 H 4 N 2 Os =160. 125 Alloxantin, Cg HioN 4 OIQ. . 123 Allyl iodide, C 3 H 5 I = 168 . . 57 Allyl sulphide, C 6 HioS= 1 14 57 Allyl sulpho-cyanide, C 4 HsNS=99 57 Allylamine, Cs Ht N = 57... 127 Allylene, Cs H 4 =40 20 Amane, Cs Hi 2 = 72 23 Amber 26, 42 Amides 136 Amidoxypropyl, C 3 H 4 (NH 2 )O=72 75 Amines 133 Ammelide 172 PAGE. Ammonia aldehydate, C 2 H 4 ONH 3 =6i 87 Ammonia citrate of iron. . . 121 Ammoniacum 43 Ammonias, compounds 131 Ammonium, cyanate,CH 4 N 2 172 Ammoniums 137 Ammoniums, quarternary. . 136 Amygdalin, CaoH^N On . . . . 193 Amyl, acetate, CT Hi 4 Os . . ,56 Amyl, chloride, CsHnCl.. 56 Amyl, hydride, Cs Hi2=72. 23 Amylamine, Cs HisN = S7. . 121 Amylene, Cs Hio=7o 23 Anhydride, tartaric, C 4 H 4 05=132 117 Aniline 30,127, 131 Anthracene, Ci 4 Hio=i78. .29, 39 Arabin C^H^On = 342 217 Arbutin dsH^C^ =284 193 Aricina CasH^Ng O 4 =397. . 129 Arnicin .... 42 Aromatic compounds 89 Arsines 128 Asphalt 26 Assafoetida 43 AtropiaCnHssNOs =289.164,129 Balsams 41 Bases organic, 125 Bases quarternary, 136 Bassorin 218 Belladona 164 Benzene Ce He =78 27 Benzine 24 Benzoic aldehyd, C 7 H 6 O.. 86 Benzol, C 6 H 6 = 78 27 INDEX. 225 PAGE. Benzene, CO(Ce H 5 ) 2 =182 119 Benzonitrile CT HS N=iO9.. no Benzyl chloride, C 7 H 5 O Cl 126 Benzylene, Ci5H 2 8=2oS 20 Bidecane, Ci 2 H 2 6= 170 28 Bidecy 1 hydride, Ci 2 H 26 = 1 70 23 Bitumen 26 Biuret, C 2 O 2 H 3 N 3 = 1 13 i7 2 Borneol, CioHi 8 O =154 58 Brandy 52 Brucia, Caa H 26 N O 4 , 4H 2 O = 394+72 161, 129 Butane C 4 Hio=s8 23 Butter 179 Butyl hydride, C 4 H 10=58. . 23 Butylamine, C 4 HnN = 73- .. 128 Butylene, C 4 H 8 =56 20, 22 Cacodyl, (CH 3 ) 2 As 79, 105 Caffeia (caffeine), C 8 Hi N 4 O= 194 130, 1 68 Campholic alcohol 117 Camphor,artincial,CioHi 6 HCl 37 Camphor, CioHi6O = i52.. . . 40 Camphor, monochlor, CioH 5 iClO = 186.5 41 Camphor, oxy-, CioHi 6 O 2 ... 41 Camphor of Bornco,CioHi 8 O 58 Cantharidin, C 5 H 6 O 2 =98. 168 Candles, 176 Cannabin... 42 Caoutchouc, (C 5 H 8 ) x ..., . .36, 43 Caprylamine, C 8 Hi9N=i29. 127 Caramel, CtaHisOg ?=3o6. . 190 Caramelaae, 190 Caramelene, 190 Carameline, 190 PAGE. Carbo-hydrates, defined, .... 7 Carbonic ether, Cs HioOs . . 74 Casein, vegetable, 219 Castor oil, 180 Castorin, 42 Cellulose, (cellulin,) (Ci 8 H 30 5 ) 202 Cerasin 217 Cetene, CnH 22 = 154 23 Chitin 184 Chloral, C 2 C1 3 HO= 147.5 . . 87 Chloral hydrate, C 2 HCl+2HO=6o.5+63... 88 Chloroform, CHCls =119.5. 47 Chloropropyl,C 3 H 6 1 = 77.5 15 Cholesterophan, Cs He N 2 Os 169 Cinchonia, (cinchonine) C 20 H 24 N 2 = 308 129, 156 Cinchonicia, (cinchonicine) CaoH24N2 2 =308 158 Cinchonidia, (cinchonidine) C 20 H 24 N 2 = 308 158, 129 Cinnamene, C 8 H 8 =104.. . . 38 Codeia, CisH-^NOs =299.146,129 Colchinia 163 Collodion 208 Colophony 41 Compound ammonias 131 Conia, (conine), C 8 Hi5N.i4i, 129 Conicine, C 8 iri 5 N=i25 . . . . 129 Coniferin, Ci6H 22 Os =342 . . 193 Convolvulin, CsiHsoOie 193 Conylia, C 8 Hi 5 N=i25. .141, 129 Cotarnine 147 Cream of Tartar, C 4 H 5 KOe 116 Creatin, C 4 H 9 N 3 O-> = 131 . 188 226 Creosote 34 Cresylol, C 7 H 8 O=io8 . .. 29, 34 Crotonylene, C 4 HG =54. . . . 20 Cumene, Cg IIio=i2o. 28 Cumidine, C 9 IIi3N=i35 127 Cuprous acctvlide, Cu 4 C 4 II 2 0=319.6 20 Cui-ari 163 Curarina 162 Cyanopropyl, C 3 H 6 (CN). . . 15 Cyclamin, C^U24OiQ= 424 . . 193 Cymene, Ci Hi 4 = 134 2 ^ 3 s Cymogene, 24 Cymol, CioHi4=i34 41 Daphnin, CaiHaiOn 193 Daturia, (atropia) CnH^NOs =289 164, 129 Decane, CioH-22 142 24 Dextrin, CG HioOs =162.212,214 Diastase 212 Diethylamine, C 4 HnN=y3. 128 Diethylpropyl, C 3 H5(C 2 H 5 )2=99 15 Diethylenic diamine, C 4 Hi N 2 =86 170 Digitalin 166 Digitin 166 Dimethylphosphine,C 2 H 7 P 128 Draconyl 38 Dulcite, (dulcose) C 6 IIi-iO 6 =126 183, 181 Duodccylene, Ci2ll24= 168. . 23 Elaidine 175 Elaine 175 Elayl, C 2 H 4 =28 21 Elemi 43 PAGE. Emetia, CisH-^NOs =248. . . 167 Emetics 119 Ergotin 42 Ery thrite, C 4 Hi O 4 49 Esculin, QjiHojOis 193 Essence of mirbane, C 6 H 5 N0 2 =i23 29 Essence of thy me,CioHi 6 34 Essential oil of cloves,C 1( )Hi6 37 Essl. oil of bergamot 37 Essl. oil of copaiba, CsoHss. . 37 Essl. oil of cubebs, CjjoHgg.. . 37 Essl. oilofelemi, CioHi 6 =i36 37 Essl. oil of juniper, QoHig. . . 37 Essl. oil of lemon, Collie 37 Essl. oil of orange, CioII 16 . .. 37 Essl. oil of pepper, CioHie ... 37 Ethal, CieHwQz =258 179 Ethane, C 2 H 6 =30. . . .13, 15, 23 Ethene, Co H 5 =29 13, 15 Ether acetic, C 2 H 5 C 2 H 8 O a =88 73 Ether, butyric, C 6 Hi 2 C>2 =11681 Ether, chlorhydric, C 2 H 5 Cl. 75 Ether, common, C 4 HioO = 74 70 Ether, cyanhydric, Cs H 5 N . 77 Ether, ethyl, C 4 HIQ= 74 70 Ether, formic, C% HQ O 2 ==74. Si Ether, hydroiodic, C 2 H 5 I. . 76 Ether, hydrosulphuric, C 4 Hio*S=90 83 Ether, cenanthylic, 81 Ether, oxalic, CG IIioO 4 = 146 74 Ether, oxamic, C 4 H 7 O 3 N. 117 Ether, sulphuric, C 4 HioO. . 70 Ether, valerianic, 81 INDEX. 227 PAGE. Ether, vinic, C4 HioO = 74. . . 70 Ethers 69 Ethers, simple 69 Ethers, compound 73 Ethers, miscellaneous Si Ethers, mixed 38 Ethine, C 2 H 2 =26 13 Ethyl, C 2 Hs =29 15 Ethyl chloride, C 2 H 5 Cl .. . 75 Ethyl cyanide, C 2 H 5 CN.. . 77 Ethyl formiate, C 2 HG O 2 . . . 9 Ethylglycol, C 4 H 9 O 2 =89. 61 Ethyl-hcxyl ether, C 8 HisO.. 84 Ethyl hydride Co 1 1 5 = 30 . . . 23 Ethyl iodide, C 2 H 5 1 = 156.. 76 Ethyl mercaptan, 4 H 6 S,.. 83 Ethylmethylaniline, Cg HisN 30 Et-hyl oxide C 4 HioO = 14... . 69 Efchyl sulphide C 4 HioS = 90.. 83 Ethylamine, C 2 H 7 N. . . 132, 127 Ethylene, C 2 H 4 =28 21 Ethylene bromide, C 2 H 4 B 2 61 Ethylene chloride,C 2 H 4 C1 2 76 Ethylene oxide, C 2 H 4 O.. . . 62 Eucalin, C 6 HioOe 180 182 Fats 174 Fatty acid series 90 Fermentation, acetic 100 Fermentation, alcoholic. .49, 181 Fermentation, gallic 197 Fermentation, lactic 122 Ferrocyanide of potassium, K 4 F e C 6 N 6 =36S 172 Flour 215 Formene, CH 4 =16 23 Frankincense 43 PAGE. Fulminates 54 Fusel, or fousel oil 56 Galactose, C 6 Hi 2 O 6 187, 182 Gas, illuminating 21 Gasolene 24 Glucosane, CG H^Oe = 180 . 185 Glucose, C 6 IIiijOc = iSo. 182, 184 Glucosides 192, 184 Gluten 216 Glycerin, Ca HS Os =92. ... 64 Glycocol, Zincic, Zn(C 2 H 4 NO 2 ) 2 =213.2. 126 Glycogcn, CG HioOs =162. . 214 Glycol, amyl, 5 Hi 2 O 2 = 104 59 Glycol, butyl,C 4 HioOg =90. 59 Glycol, diethyl, C 6 Hi 4 O 2 . . 61 Glycol, ethyl, C 4 1 1 9 O 2 =89 61 Glycol, hexyl,C 6 H 4 O 2 = 1 18 59 Glycol, monochlorhydric. .. 62 Glycol, octyl,C 8 Hi 3 O 2 = 146 59 Glycol, ordinary, C 2 HG Og ... . 59 Glycol, propyl, C 3 II 8 O^ .58, 123 Grape sugar 182 Guano 124 Gum, CG HjoOs = 162 216 Gum arabic 217 Gum resins 41 Gun-cotton 207 Helicin, dsH^O? =283 194 Heptyl hydride, CT HI=7i6... 193 Jerria, C2oH 4 6N 2 O 3 =362.. . 163 Kerosene 24 Kctones 40 Lactide, C$ H4 O 2 =72 123 Lactose or lactin, CiaHaiOi2=342 . . .191, 182 Leather 197 Legumin 219 Levulosan, CG HioO.5 = 162.. 190 Levulose,C 6 Hi 2 O 6 =180.187,182 Lichenin 214 Madder 39 Maltose, C 6 HiaO 6 = 180 182 Mannitane, CG H^Os =164.. 183 Mannite, C 6 Hi 4 O 6 =182.181,183 Marsh-gas, CH4 = 16 23 PAGE. Meconine, 143, 147 Melampyrite, CG H^O 6=184 181 Melezitose, Ci2H22Oi3=374-. 182 Melitose, Ci2H^Oi2=365 182 Mercaptans 82 Metamerism 9 Metaterebenthene, CsoHss. . 38 Metastyrol, 38 Methane, CH 4 = 16 13, 15, 23 Methenyl, CH=i3 15 Methyl, CH 3 =15 15 Methyl acetate, 63 H 6 Og ... 9 Methyl chloride, CH 3 Cl.. . . 47 Methyl cyanate, Ca HS NO.. 131 Methyl hydride, CILi =16.. 23 Methylamine, CH 5 N. . . 127, 131 Methylethylamine, C 3 H 9 N 128 Methylphosphme, CH 5 P. . . 128 Methylpropyl, C 3 H 6 (CH 3 ). 15 Molasses 189 Monamines 133 Monochlorcamphor, CioH 15 C10 = S6. 5 41 Monochlorhydrin, C 3 H 7 C10 2 = 110.5 66 Morphia, (Morphine) Ci-H 19 N 03=285 143,129 Murexide,C 8 HS N 6 OG =284 125 My cose, Ci^H^OiisJ^. . . . 182 Naphtha 24 Naphthalamine, CioHg N. . . 128 Naphthalin, CioH 8 =128.. .27, 38 NarceiajC^HogNOg =463.148,129 Narcotina, C22H23NOr =413 129 Nicotina, CioHi4N 2 = 162 . 139,129 Nicotyl, C 5 H 7 =67 140 INDEX. 229 PAGE. Nicotylia,CioHi 4 N 2 =162.139,129 Nitrile bases 124 Nitrobenzol, C 6 H 5 NO 2 .... 29 Nitroglycerine, C 3 H 5 (NO 2 ) 3 O 3 =227 ... 66 Nitryls or cyanhydric ethers, 134 Nonane, Cg HSO= 128 23 Nonyl hydride, Cg H20= 128. 23 Nonylene, Cg His=i26 22 Octane, Cs His=ii4 23 Octyl glycol, Cs Hi 8 O 2 =146 59 Octyl hydride, Cs H\8= 1 14. . 23 Octylene, Cs Hie=ii2 22 Oils, fatty 174 Oils, essential 36 Olein, C 5 7Hio4 OG =884 175 "Oleomargarine" 179 Oleo-resins 42 Opium 142 Orcin, C? HS O 2 =124 193 Organizable substances 205 Organometallic compounds, 78 Oxamide, C 2 H4 O> No =92, 74 Oxanthracene, Cyllg O 2 ... . 39 Oxycamphor, CioIIitjOo, =168 41 Para-arabin 192 Plants, respiration of. 201 Plants, nutrition of 204 Polyamines . . 170 Polymerides 9 Polymerism, 9 Populin, QaoH^Os =390. . . . 193 Potassium, binoxalatc 114 Potassium, ferrocyanide, KiF e CeN 6 =368 172 Paraffin, Co 4 H 5 = 338 ... .22 24 PAGE. Papaverine, C2oH2iNO4 .129, 148 Paramorphia, CigHaiNOs ... 148 Paramylene, CioH2o= 140. . . 22 Pectin 218 Pectose 218 Pentadecane 0^32=212. . . 24 Pentadecyl hydride, CisH^. 24 Petroleum 24 Phenol, C 6 H 6 O = 94 32 Phenol, potassic C 6 H 5 KO.. 32 Phenol, trinitric C 6 H 3 (NO 2 )3 = 229 30 Phenyl, CG H 5 =77 30 Pheny 1 hydrate,C C H 6 O = 94 32 Phenylamine, CG H 7^=93. 127 Phlorizin, C2iH24Oio=436. . . 193 Phlorylol, C 8 Hi O=i22 34 Phosphines 128 Phtalidamine, Cs Hg N=ii9 127 Picrotoxin, C 3 H 6 O 2 =98... 169 Pinite, C 6 H 12 O5 = 164 in Piperidine, C.5 HnN=85..i3o, 141 Piperine, CnHigNO 3 =285.. .141 Pitch, Burgundy 42 Potassium, formiate 88 Propane, C 3 H 8 =44 ... 13, 15, 23 Propenyl, C 3 HS =41 15 Propine, C 3 H4 =40 13 Propone, C 3 H 2 =38 13 Propyl 15 Propyl hydride, C 3 HS =44- 23 Propylamine, C 3 Hg N = 59. . 127 Propylene, C 3 HG =42 22 Proplene iodide,C 3 HS I = i68 64 Ptyalin 212 Pyrethrin 42 230 INDEX. Pyrolignite 106 Pyroxylin 207 Quercite, C 6 Hi 2 O 3 = 164. . . 181 Quercitrin, C^U.g[)Cn=6^o. . 193 Quinia, (quinine) C2oH24N 2 O 2 =324 151, 129 Quinicia, C2oH24N 2 O 2 . . 154, 129 Quinidia, C2oH24N 2 O 2 =324. 129 Quinidia, oxalate of 155 Quinoidine 158 Quinoleine, (Quinoline), ' 130, I53>i57 Quinovin, CsoH 48 C8 = 536. . . 193 Radicles, defined 14 Radicles, organometallic 78 Radicles, organometalloid. .. Si Reagent, Fehling's 187 Reagent, Haines' 187 Reagent, Trommer's 186 Resins 25, 41 Retinasphalt 25 Retinite 25 Rhigolene 24 Rice 216 Rochelle salt, KNaC 4 H 4 O 6 +4 aq .... 118 Rosaniline, CsoH^Ns = 319 31 Rutylene, CioHi 8 = 138 20 Rye 216 Saccharide 186 Saccharoses, Ci 2 H22On = . 1 89, 1 82 Salicin, Ci 3 Hi 8 O 7 =286 194 Saligenin, C7 H 8 O 2 =124.. . 194 Saponification 176 Saponine 193 Sinapoline, C 7 Hi 2 N 2 0=140 58 PAGE. Sinnamine, C 4 H 6 N 2 =82. . 58 Soaps 1 76 Sodium ethyl, C 2 H 5 Na=52 So Sodium sulphocarbolate, NaC 6 H 6 S0 4 =i 9 7 33 Solanidia, (solanidine) 165 Solania, (solanine) C43H7iNOi6=857.. .165,129,193 Sorbin, Ce Hi 2 O 6 = 180 182 Spermaceti, C32H6 4 O 2 =480 179 Spirit of Mindererus 105 Stannethyl 79 Stannethyl iodide 79 Starch 210 Stearin, (stearine) Cs-Hno 06=890 174 Stearine candles 176 Stibines 128 Stibyl 119 Strychia, (strychnine), C 2 iH 22 N 2 6 2 =334. . . 159, 129 Styrol, C 8 H 8 = 104 38 Sucrates 190 Sugars 181 Sugar of milk, Ci 2 H;> 4 Oi 2 . 191,182 Tannin, C 27 H2 2 Oi 7 =6iS.. 196, 193 Tartar emetic, KSbC 4 H 4 O 7 =325 118 Tetrachloropropyl, C 3 H 3 Ci 4 =i8i 15 Tetradecane, Ci 4 Hso= 198. . . 24 Tetradecyl hydride, Ci 4 II 3 o. . 24 Tetradecylene, Ci 4 H28=i96. 22 Tetrethylammonium, N(C 2 H 5 )4=i3o 133 Thebeia,Ci 9 H 2 iNO 3 148, 120 INDEX. 231 PAGE. Theia, (theine) C 8 Hi N 4 O 2 = 194- - 168 > J 30 Theobromine, C 7 HS N 4 O2 = 180. . . . 169, 130 Thymol, CioHi4O= 150 34 Thiosinnamine, C 4 H 8 N 2 S=ii6 58 Tobacco 140 Toluene, C? H 8 =92 28 Toluidine,C7 H 9 N= 107.. 127, 130 Trehalose, Ci2HooOn = 342. . 182 Trichlorhydrin, Cs H 5 Cls . . 66 Trichloroxypropyl, C 3 H 2 C1 3 O= 160.5 15 Tridecane, CisHss 184 27 Triedecyl hydride, CisHsg. . 24 Tridecylene, Q 3 Ho 6 = 182 ... 22 Triethylamine,C 6 Hi S N= 101 . 135 Triethylarsine, C 6 Hi 5 A s .... 128 PAGE. Triethylenic, diamine, CG Hi2O-2 =112 170 Triethylstibine, C 6 Hi 5 Sb ... 128 Trimethylamine, Cs Hg N... 128 Trimethylphosphine,C3 Hg P 128 Tunicine, (Ce HioOs ) x ,. . 184, 209 Turpentine, CioHi 6 = 136 35 Types, organic 10 Wax 179 Whiskey 52 Wines 32 Wood-spirit 49 Xylene, C 8 Hio=io6 28 Xylidine, C 8 HnN=i2i 127 Xylyl alcohol, C 8 Hi O= 122. 46 Zinc, ethyl, (C 2 H 5 ) 2 Zn = 213.2. 79 Zinc, glycol, H4 NO 2 }z =21^.2...^, 126 RETURN CIRCULATION DEPARTMENT TO -^ 202 Main Library LOAN PERIOD 1 HOME USE 2 3 4 5 6 ALL BOOKS MAY BE RECALLED AFTER 7 DAYS 1 -month loans may be renewed by calling 642-3405 6-month loans may be recharged by bringing books to Circulation Desk Renewals and recharges may be made 4 days prior to due date DUE AS STAMPED BELOW UNIVERSITY OF CALIFORNIA, BERKELEY FORM NO. DD6, 60m, 12/80 BERKELEY CA 94720 $ H W ffi U ,$1 1 a cr . : a O w J w w ffi 5 H o -4- "^ S ' .1 oQ . o C S . e sj^ - w =".".- ^g 013-0 Tof s d"oMt. Q W H c/3 aj ^5 p ^f ^f rC fO vo