bility of its being found to exist in two states, such as many other bases are known to assume. As regards the formula of pilocarpine, Mr. Kingzett sees no reason for abandoning the one he originally assigned to it. His analysis of the free base was conducted with all the refinements of the best methods; and a combustion in vacuo with cupric oxide and metallic copper furnished carbonic anhydride and nitrogen in such quantities as showed the relation of carbon to nitrogen to be as 1 : 6, a requirement which the formula of Harnack and Meyer does not satisfy or explain. The molecular weight of the chloroplatinate calculated from the proportion of platinum found by analysis was 842, which corresponds exactly to the formula C23 H34 N4 04. 2 H Cl. Pt Cl4. 4 4 The analysis of the free base as well as of the chloroplatinate led to C23 H4 N, O, as the simplest formula for pilocarpine. Harnack and Meyer arrive at C11 H16 N2 O2 or C22 H32 N4 O4, showing an apparent difference of CH2 in the two larger formulæ. Until further investigations settle the point in dispute the author is determined to adhere to his own formula. The Alleged Presence of a Second Alkaloid in Jaborandi. A. W. Gerrard. (Pharm. Journ., 3rd series, xi., 608.) The author agrees with Kingzett (see the foregoing article) that Harnack and Meyer's research has not established the presence of a second alkaloid in jaborandi or pilocarpine. These gentlemen are stated to have prepared their new alkaloids from mixed residues obtained from jaborandi leaves and false jaborandi (Piper reticulatum). These, however, are two distinct plants of different natural orders, the latter of which no investigation has yet shown to contain pilocarpine; it is, therefore, obvious that experiments upon such a mixture are of doubtful value. As another inconsistency, the writer points to the fact that in one part of their paper Harnack and Meyer speak of jaborine as contained in jaborandi leaves, while in another part they state that fluid extract of jaborandi is free from jaborine, but that jaborine is produced on evaporating the acidified alcoholic solution. Pilocarpine. A. Poehl. (Bull. de la Soc. Chim. [2], xxxiv., 340.) The author has made analyses of pure pilocarpine as well as of its hydrochlorate and its platinochloride. His results confirm the correctness of Kingzett's formula, C23 H34 N4 04 The alkaloid was prepared by digesting jaborandi leaves in water containing 1 per cent. of hydrochloric acid, treating the infusion with lead acetate, filtering, precipitating the alkaloid from the filtrate by phospho-molybdic acid, washing the precipitate with dilute hydrochloric acid, and finally decomposing it by means of baryta at a temperature below 100° C. Aspidospermine and Paytine. Dr. N. Wulfsberg. (Pharmaceut. Zeitung, 1880, 546.) The alkaloid paytine was discovered by Dr. O. Hesse in 1870 in a white bark of unascertained botanical origin. This bark, known as cortex china alba de Payta, was found by Prof. Flückiger to agree in its anatomical structure with the cinchona barks, but was subsequently ascertained by him not to be a Cinchona, nor a member of the Rubiaces. The author of the present paper, who has recently examined this bark, finds it to correspond so closely with white quebracho bark as to lead him to the conclusion that it is derived from a species of Aspidosperma. He further finds that the alkaloids paytine and aspidospermine show so close an agreement in their general characters and chemical reactions, as published by Hesse and Fraude respectively, and also in the numbers obtained by analysis, that he considers their identity as in the highest degree probable. The Alkaloids of White Quebracho Bark (Aspidosperma Quebracho). Dr. O. Hesse. (Ber. der deutsch. chem. Ges., xiii., 2308.) The author has satisfied himself that Wulfsberg's assertion concerning the identity of Fraude's aspidospermine (from Aspidosperma Quebracho) and Hesse's paytine (from white paytine bark) is incorrect. The investigation leading him to this conclusion has also revealed the existence in quebracho bark of a second alkaloid, which he proposes to call quebrachine. This substance is deposited from an alcoholic solution in white prisms, sparingly soluble in ether, and fusing at 214° C. with partial decomposition. Its formula is C21 H26 N2 O3. It is a strong base capable of neutralizing acids. The sulphate forms four-sided prisms soluble in alcohol and water. The hydrochlorate also crystallizes in prisms which are sparingly soluble in cold, but readily so in hot water. The solution of the alkaloid in pure sulphuric acid has a blue colour, which is greatly intensified by the addition of lead peroxide or potassium bichromate. In these and other reactions it somewhat resembles strychnine and curarine, but differs from these in its action upon frogs. Quebrachine possesses toxic properties. A dose of 0.04 gram proved sufficient to kill a small rabbit. Dr. Hesse states that quebracho bark contains, besides aspidospermine and quebrachine, several other alkaloids upon which he promises to report in a subsequent paper. Alleged Identity of Paytine and Aspidospermine. P. N. A rata. (Journ. Chem. Soc., 1881, 622.) Wulfsberg having stated that paytine, an alkaloid found in a white cinchona bark from Payta, in Peru, is identical with aspidospermine from the bark of Aspidosperma Quebracho, the author points out that the alkaloids obtained from these two sources differ somewhat in composition (the platinochloride of paytine containing 18.73 per cent. platinum, whereas that of aspidospermine contains only 1745 per cent.), and vary considerably in some of their properties and reactions. These differences are shown in the following table : Not coloured by ferric chloride, or by Sulphuric acid produces in solutions strong sulphuric acid. of aspidospermine a wine-red coloration, which disappears after some hours. Mercuric chloride forms an amorphous Precipitated by mercuric chloride in yellow precipitate. Auro-chloride: Purple precipitate, the supernatant liquid exhibiting the same colour. The hydrochloride, hydrate, and nitrate are crystallizable, the sulphate, chromate, oxalate, and picrate are not. white tufts. No crystallizable salts. E. T. Pease. (Journ. Estimation of Nicotine in Tobacco. Amer. Chem. Soc., July, 1880.) The author's estimations of nicotine in leaf and manufactured tobacco were made by titration with Mayer's solution (potassio-mercuric iodide), as directed by Dragendorff (Werthbestimmung eineger starkwirkenden Droguen, 1874, 52). The tobacco was first dried, the portion weighed, then macerated for at least twenty-four hours with water acidulated with sulphuric acid, and the expressed liquid concentrated and filtered. The solution from 2 to 3 grams of tobacco was brought to 50 c.c., and of this 10 c.c. were taken for titration. The end of the reaction was found by filtering a few drops through a very small filter, trying the filtrate on a watch-glass with a drop of the volumetric reagent, and rinsing the filter into the whole solution. The best solution employed contained of a molecular weight of mercuric iodide (made from Hg Cl2+ 6 KI). The precipitate first obtained appears milky when formed, but soon turns black and waxy, and settles to the bottom in a coherent mass. Several of the operations were duplicated, with but very slight differences in results. The end of the precipitation is sharply defined. The six samples of cigars and tobacco thus examined gave the following percentages: 200, 4·05, 3.24, 4·21, 3·94, and 3·93. A short clay pipe, some time in use and partly coloured, was pulverized, macerated in acidulated water, and the solution treated as from tobacco. The result of titration, if due to nicotine, indicated 04779 gram of that alkaloid. The pipe weighed 23-619 grams; therefore 2.02 per cent. of alkaloid was indicated. The alkaloid was also estimated in tobacco smoke, and found to amount to 2:48 per cent. of the tobacco burned. The author suspects, however, that this result may be too high, owing to the possible action of the empyreumatic products on the test-solution. Nicotine Derivatives. A. Cahours and A. Etard. (Comptes Rendus, xc., 275-280, and Journ. Chem. Soc., 1880, 672.) When thiotetrapyridine, C20 H18 N4 S, obtained by the action of sulphur on nicotine (Ibid., lxxxviii., 999, and Year-Book of Pharmacy, 1880, p. 40), is boiled with dilute nitric acid, it gives nicotinic acid (m. p. 228-229°). Thiotetrapyridine when distilled with finely divided metallic copper loses sulphur, and yields a base, isodipyridine, C10 H10 Ng, isomeric with dipyridine, but differing greatly from it in its properties. It is also produced in small quantity by the action of alcoholic potash on thiotetrapyridine at 200°. Isodipyridine is a colourless oil (b. p. 274-275°), having an odour somewhat resembling that of certain mushrooms. It does not solidify at -20°, and its sp. gr. at 13° is 11245. It is insoluble in cold, and only sparingly soluble in boiling water, but easily in alcohol or ether. It unites energetically with hydrochloric acid, but the hydrochloride does not crystallize. The platinochloride (C10 H10 N2 H CI)2 Pt Cl + 2 H2O, crystallizes in deep orange plates of the colour of potassium dichromate. It is decomposed if boiled with water. It was thought probable that if nicotine were submitted to limited oxidation it might yield isodipyridine, thus: C10 H14 N2+ O2 = C10 H10 N2+ 2 H2O. For this purpose pure nicotine was dissolved in dilute potash solution, and oxidized with potassium ferricyanide, and the product distilled. The bases extracted from the distillate by means of ether, when submitted to fractional distillation, were found to consist of isodipyridine with unaltered nicotine. If nicotine in the state of vapour is passed over red-hot porcelain, it is in part decomposed (about 20 per cent.), yielding a gaseous mixture of hydrogen with paraffins and olefines, and a liquid product containing pyridine, picoline, collidine, and new basic substances boiling at temperatures above 250°. A Bromo-derivative of Nicotine. A. Cahours and A. Etard, (Comptes Rendus, xc., 1315-1317. From Journ. Chem. Soc.) One part of nicotine is dissolved in 50 parts of water, and 2 molecules of bromine added for every molecule of nicotine. A yellow flocculent resinous-looking precipitate falls, which, together with the motherliquor, is heated gently to 65-70°, more bromine being added if required. The whole is then filtered and allowed to cool, when an abundant crystallization of the bromo-derivation takes place. The undissolved portion treated separately with water at 70° yields a crystalline deposit similar to the preceding. The crystals are in the form of red needles often more than 1 mm. in length, and are similar in colour to potassium bichromate. They are unalterable in the air, but are decomposed by water at a temperature higher than 70°. When dissolved in concentrated hydrobromic acid, they assimilate a molecule of H Br, forming the hydrobromide of the original derivative. 2 Analysis showed that the formula of the bromo-derivative is C10 H14 N2 Br4. Huber's pentabromide is therefore probably the hydrobromide above mentioned, but the formula given to it by Huber contains three atoms less of hydrogen. The tetrabromo-nicotine is decomposed and destroyed by an aqueous solution of potash. |