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Protoveratridine, C2H4NO. Melts at 265°; non-poisonous. 8. Additional Alkaloids.-Aspidospermine, C2H30NO, and Quebrachine, C1HNO,, are found, along with other alkaloids, in the bark of Aspidosperma Quebracho.

Berberine, Ca0H17NO4.51⁄2 H2O, is found in the root of Berberis vulgaris and Hydrastis canadensis. It forms yellow needles, melting at 120°. When fused with caustic potash it yields quinoline. Associated with it in Hydrastis canadensis is the alkaloid Hydrastine, Ca1H21NO, which forms colorless prisms, melting at 132°, and Canadine, C21H21NO4, which forms white, shining crystals, melting at 134°.

Physostigmine, C15H21N3O2, is found in Physostigma venenosum (Calabar bean). It forms colorless or pinkish crystals, only slightly soluble in water, soluble in alcohol and ether. Two of its salts are now official, Physostigminæ Salicylas, U. S. P., and Physostigminæ Sulphas, U. S. P.

Pilocarpine, CH1NO2, is an alkaloid found in the several varieties of Pilocarpus. It is a crystalline alkaloid first found in Jaborandi leaves, but since made synthetically by Hardy and Calmels from B-pyridine-a-lactic acid by first forming pilocarpidine, C10H1N2O2, and then converting this by the action of methyl iodide into pilocarpine. Two of its salts are official, Pilocarpine Hydrochloras, U. S. P., and Pilocarpinæ Nitras, U. S. P.

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Piperine, CH1NO, (Piperinum, U. S. P.), is obtained from the black and white pepper, in which it is found to the amount of from 7 to 9 per cent. It is a weak alkaloidal base, forming pale yellowish crystals, melting at 130°. When heated with alcoholic potash it is decomposed into Piperidine, CH1N, and Piperic acid, C12H1004. The first of these compounds has already been noticed as hexahydropyridine (see p. 751), and the second is related to the oxyacids of the benzene series, and yields piperonal (see p. 718) by its oxidation.

Piperine can be made synthetically by the action of piperidine on the acid chloride, C12H,O,Cl.

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ANIMAL ALKALOIDS, PTOMAINES, AND LEUCOMAINES.

While it was pointed out as far back as 1820 that symptoms of poisoning would be developed by introducing into an animal products of decomposing and putrefying organic matter, it has only been since 1870, when the Italian Selmi published his studies on cadaveric poisons, that the subject has been fully appreciated.

He gave the name of "ptomaïnes" to these poisonous products of putrefaction. In 1884, Poehl, of St. Petersburg, in the report of a commission appointed to investigate the subject, stated the following conclusions:

1. Putrefaction, fermentation, and other as yet indefinite alterations of albuminous substances are accompanied by the generation of alkaloid-like bodies, - ptomaïnes.

2. These ptomaïnes may be fixed or volatile, fluid or solid, amorphous or crystalline. They show an alkaline reaction, and form salts with the acids like the alkaloids.

3. Some ptomaïnes are tasteless or odorless; others possess an intense bitter taste or aromatic, sweetish odor. Others, again, evolve a cadaveric odor, or resemble conine or nicotine. They are optically inactive bodies. Their color reactions are as various as those of the vegetal alkaloids, and often simulate them.

Gautier, in 1881, announced the presence of toxic alkaloids in the excretions of animals, and gave to them the name of "leucomaïnes." His explanation of their occurrence is as follows: "While four-fifths of the products of animal combustion are aerobic formations, the remaining part of the combustion of the animal economy takes place at the expense of the tissues and is anaerobic, oxygen taking no part in it. In a normal condition of the body a very small proportion of muscular leucomaïnes is found in urine. But if the air that reaches the blood be diminished in quantity, or if the proportion of hæmoglobin be diminished, as in chlorosis or anæmia, or if substances be introduced into the blood which prevent hæmatosis, substances of the character of leucomaïnes or ptomaïnes accumulate in the blood."

Nitrogenous substances, not alkaloids, which are still poisonous are also formed. These have been named "toxalbumens' or

"albumoses."

Among the non-oxygenated liquid ptomaïnes may be enumerated:

Dimethylamine, Triethylamine, Propylamine (see p. 629), These are monamines.

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2

In the class of diamines (see p. 630) we have: Putrescine, CH12N, (tetramethylene-diamine), Cadaverine, CH1N2 (pentamethylene-diamine). These have both been described on p. 630. Isomeric with the last is Neuridine, a non-poisonous ptomaïne from the decomposition of flesh.

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Hydrocollidine, C11H1N, is a very poisonous ptomaïne found by Gautier in decomposing horse-flesh. Collidine, CH1N (tri

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methyl-pyridine), and Parvoline, CH1N (tetramethyl-pyridine), are also found as ptomaïnes.

Tyrotoxicon, CH,N2, found in putrid cheese and in milk and cream after undergoing certain putrefactive changes, also belongs to the non-oxygenated ptomaïnes. It has the composition of the diazo-benzene radical CH ̧.N=N—.

Among the more important oxygenated ptomaïnes we may mention :

Neurine, CH,NO, and Choline, СH1NO, are both derived ammonium hydrates, and are described on p. 630. They are both quite poisonous. Muscarine, CH1NO, first obtained from the fungus Agaricus Muscarius, was found by Brieger in decomposing flesh. Gadinine, C,H1NO, was found in putrid fish. Mytilotoxine, CH1NO,, was obtained from poisonous mussels.

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CHAPTER IX.

THE TERPENES AND THEIR DERIVATIVES.

I. THE TERPENES.

THE terpenes are hydrocarbons of the formula (CH). Both they and the camphors, which are oxygenated derivatives, show a close relationship to the aromatic hydrocarbons, as common camphor, CHO, by the action of certain dehydrating agents yields cymene, C10H14, and terpenes of the formula C10H1 when heated with iodine are oxidized and yield the same hydrocarbon, C10H14 We may therefore consider the terpenes as hydrogen addition compounds of benzene hydrocarbons.*

Characteristic Reactions.-Besides the production of cymene by oxidation, we have other distinctive reactions. The terpenes of the formula C10H18 may add on one or two molecules of a haloid acid (HCl, HBr, HI) or the corresponding amount of bromine, showing that they are unsaturated and that their molecules contain either one or two double linkings of carbon atoms. Many terpenes also form characteristic compounds with nitrous acid, called nitrosites, such as C10H1N,Og. These are crystalline compounds, and may be availed of for the separation of many terpenes. Most terpenes also combine with nitrosylchloride, NOCI, forming nitrosochloride-terpenes. These also are crystalline compounds, which combine with organic bases like benzylamine and piperidine to form nitrolamines.

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Some terpenes form with water crystalline hydrates, as terpinhydrate, C10H1(H2O)2 + H2O. This combination takes place especially in the presence of dilute nitric acid and alcohol. The terpenes frequently polymerize by heating under pressure or by shaking with concentrated sulphuric acid.

Many terpenes are optically active. Frequently a lævo rotatory and a dextro-rotatory modification of the same terpene may be obtained, which, when mixed, yield an optically inactive variety.

*A full discussion of the theoretical views held as to the structural formulas of the terpenes and their derivatives by Professor Ed. Kremers, in which Baeyer's proposed system of nomenclature for these compounds is given, will be found in "Froceedings of the American Pharmaceutical Association, 1894."

The terpenes and the related classes of camphors and essential oils have an antiseptic action.

Classification of Terpenes.-Based upon the differences in chemical formulas, as controlled by molecular weight determinations and analysis of derivatives, we may divide the whole class of terpenes into :

1. Hemiterpenes, CH, such as isoprene, which by polymerization yields dipentene, C10H16, belonging to the next group.

2. Terpenes, C10H18. These are the compounds to which in the narrower sense belongs the class name.

3. Sesquiterpenes, C1H24, include cedrene and cubebene. 4. Diterpenes, C20H24, include colophene.

5. Polyterpenes (C10H18)x, include the polymerized hydrocarbons of caoutchouc and gutta-percha.

Based on the formation of the addition compounds before referred to, due to their unsaturated character, we may divide the special terpenes of the formula C10H16 into three groups:

1. Such as are able to combine with but one molecule of haloid acid, leaving out of consideration cases of polymerization. This group includes pinene and camphene.

2. Such as are able to combine with two molecules of haloid acid but not with nitrous acid. This group includes dipentene, sylvestrene, right and left rotary limonene, and terpinolene.

3. Such as combine with nitrous acid to form nitrosites. This group includes terpinene and phellandrene.

The characters of these terpenes and their addition compounds may be thus given in tabular form:

Description of the Individual Terpenes.-Pinene, C10H10 is the chief constituent of the American and French oils of tur. pentine as well as of juniper oil and eucalyptus oil. Along with