morphothebaïne, together with either methyl or ethyl chloride. By repeating the experiment with hydriodic acid it is shown that methyl iodide is formed, thus:

C19 H21 N O3+2 HI= C17 H17 NO3 + 2 Me I.

15

17

Thebaine, C17 H15 N O (O Me), is therefore the dimethyl ether of morphothebaïne, C17 H15 NO (O H)2.

Morphothebaïne is also characterised as a tertiary base by its combining directly with the halogen-derivatives of the hydrocarbons; its methiodide crystallizes in quadratic tables, the ethiodide in the rhombic form, and the benzochloride in small needles.

Among the products of the decomposition of thebaïne-methylhydroxide are trimethylamine, and a substance of the composition C14 H12 O3, which is probably an oxy-derivative of phenanthrene.

Opium Alkaloïds. P. C. Plugge. (Archiv der Pharm. [3], xxiv. 993-1014; Journ. Chem. Soc., 1887, 280.) Morphine, codeïne, thebaïne, papaverine, narcotine, and narceïne are the most important opium alkaloids. Their physiological action varies from strongly narcotic or sleep-inducing, to strongly exciting or crampproducing; but different observers are not agreed as to the exact order of the members of the series. In the arrangement of the bases according to their poisonous nature, different observers are more nearly in accord. The author examined the reactions of salts of these alkaloids with alkaline salts of organic acids. Morphine, codeïne, and thebaïne, in neutral liquids, react strongly alkaline to litmus, and afford stable salts. Narcotine, papaverine, and narceïne, on the contrary, do not affect litmus paper, and combine only feebly with acids. Thus narceïne sulphate and chloride are slowly decomposed by cold water, more quickly by hot water. It appeared probable from this that solutions of salts of the stronger bases would give no precipitate with alkaline salts of organic acids, whilst in the case of the weak bases, the alkaloïd would be precipitated as such. The following salts were employed: sodium and ammonium acetate, ammonium oxalate, sodium salicylate, sodium potassium tartrate, sodium benzoate and hydrogen sodium carbonate.

Besides the six opium bases, many other alkaloids were examined in the course of the investigation, such as caffeïne, cocaïne, atropine, pilocarpine, coniine, strychnine, brucine, quinine, cinchonine, and cinchonidine; the latter, however, only with sodium acetate. None of these bases were liberated and precipitated; in the case of the cinchona bases, however, it was necessary

to carefully neutralize the sodium acetate with acetic acid, or precipitation took place. With a perfectly neutral solution of sodium acetate, the only alkaloids precipitated are the three weak opium bases, papaverine, narcotine and narceïne. These three bases are also precipitated both by slightly acid and by slightly alkaline acetate solution. Neither of the two solutions exerts any influence on the strong opium bases, consequently the ordinary non-neutralized acetate solution can be used for the separation of the bases with advantage in point of time, and perhaps completeness. Narcotine, papaverine, and narceïne were precipitated as pure bases by all the alkaline salts mentioned previously. Thebaïne was precipitated by sodium salicylate as salicylate, and by hydrogen sodium carbonate. Morphine and codeïne were not precipitated by any of the salts. Arranging the alkaloïds in series, according to their molecular weights, it will be seen that the first three are strong bases, and the last three feeble ones: morphine, C17 H21 N O3; codeïne, C18 H21 N Og; thebaïne, C19 H21 N O3; papaverine, C2 H21 N O; narcotine, C22 H23 N O; narceïne, C22 H29 N O9. Slightly acidified sodium acetate solution will indicate as little as 1 : 40,000 of narcotine in solution. With papaverine, the limit is 1 : 30,000. Narceïne is not nearly so sensitive, the limit being about 1: 600. The precipitation of thebaïne as salicylate gave a limit of about 1: 2,000. For quantitative estimation, narcotine is best precipitated by ammonia, where it is the only substance thrown down by this reagent; sodium acetate has, however, the advantage of precipitating it for qualitative purposes from faintly acid solutions in which all other alkaloïds, excepting papaverine and narceïne, remain in solution. Papaverine and narceïne are also best precipitated quantitatively by ammonia.

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Decomposition-Products of Strychnine. C. Stoehr. (Ber. der deutsch. chem. Ges., xx. 810-814.) In order to obtain evidence on the view of Hanssen that strychnine contains a phenylpyridinegroup as well as a quinoline-group, the author has distilled strychnine with alkali, and obtained, in addition to a hydride of pyridine, not fully examined, y-picoline, identified by analyses of its auro- and mercuro-chlorides, and crystalline form, as also by the melting point of the latter. Experiments to obtain methyl chloride as a product of the decomposition of strychnine were unsuccessful. It is shown that strychnine does not contain a hydroxyl-group, in that by treatment with phosphorus pentachloride the atoms of oxygen remain intact, whilst three hydro

F

gen-atoms are displaced by chlorine to form a trichloro-derivative, C21 H19 Clg N, O, the hydrochloride and sulphate of which crystallize in leaflets.

2

A Derivative of Strychnine. W. F. Loebisch and P. Schoop. (Monatsh. Chem., vii. 609-616.) The products obtained on distilling strychnine with zinc-dust vary according to the temperature; at a lower temperature, one atom of oxygen is removed from the molecule with formation of a compound, C2 H22 N, O, a solid substance, soluble in alcohol with a blue fluorescence, sparingly soluble in dilute acids, insoluble in water. It does not give the strychnine reaction with potassium dichromate and sulphuric acid. At a higher temperature the strychnine molecule is completely decomposed; hydrogen, ethylene, acetylene, and ammonia are evolved, whilst carbazole distils over.

Specific Gravity of Crystalline Strychnine. T. P. Blunt. (Pharm. Journ., 3rd series, xvii. 62.) The gravity was determined in the following manner :-A solution of subacetate of lead was prepared, of such strength that a crystal of strychnine was suspended indifferently in any part of the fluid; the specific gravity of the liquid was found to be 113, which was therefore that of the crystal.

Strychnol. W. F. Loebisch and P. Schoop. (Pharm. Journ., 3rd series, xvii. 352, from Monatshefte für Chemie.)

2

Strychnol or strychnine hydrate, C21 H22 N2 O2+2 H, O, is prepared by boiling strychnine with a mixture of sodium ethoxide and absolute alcohol. The strychnine dissolves with a yellow coloration. On evaporating the mixture to expel the alcohol, a brown oil remains, which in time becomes solid. On dissolving this in water and passing a stream of carbonic anhydride, strychnol separates as a slightly yellow precipitate, which can be further purified by solution in ammonia and reprecipitation. It then forms a white, crystalline mass, consisting of microscopic, wedge-shaped needles; it does not give the strychnine reaction with potassium dichromate and sulphuric acid, but is coloured an intense carminered with sulphuric and nitric acids. At 150° the greater part of the water is lost, but decomposition takes place, and strychnine cannot be obtained from the residue. Strychnol is precipitated from acetic acid solution by the usual alkaloidal reagents; it is very sparingly soluble in cold water, easily in hot. Boiled with dilute acids, or allowed to remain for some time with strong acids, it is dehydrated, and strychnine is formed. Strychnol differs

from strychnine in being very readily oxidized, it even reduces an ammoniacal solution of silver oxide.

The authors point out the close relation between the colour reaction of strychnine and brucine, and also the identity of their respective actions with bromine. Strychnol gives no compounds with ammonia, trimethylamine, or aniline; it dissolves in all these, but any compound formed is dissociated on evaporation.

Strychnine, when heated with aqueous potash, does not yield strychnol in the same way that nitrostrychnine yields xanthostrychnol, but a substance is formed which is probably identical with Gal and Etard's dihydrostrychnine.

The authors have also repeated Goldschmidt's experiments, and have confirmed the formation of indole by fusing strychnine with potassium hydroxide. They also obtained evidence of the presence of butyric acid in the fused mass.

When an alcoholic solution of strychnine is reduced with metallic sodium, an additive product-strychnine hydride-is apparently formed.

19

4

Constitution of Brucine. A. Hanssen. (Ber. der deutsch. chem. Ges., 451-460; Journ. Chem. Soc., 1887, 505.) With the view of throwing further light upon the constitution of brucine, the preparation and composition of kakotheline, originally obtained by Strecker, have been further investigated. To this substance is ascribed the formula C21 H22 N, O,, instead of C20 H22 N4O9, hitherto accepted. When reduced, it yields a base, the analysis of whose hydrochloride pointed to a formula C21 H25 N3 O5, derived from kakotheline by the reduction of one nitro-group and elimination of another. With bromine, kakotheline yields an acid substance, C1, H2, No Or, the platinochloride of which crystallizes in orange-yellow needles, its silver salt in glistening needles; its methyl salt could not, however, be obtained, but the crude product treated with ammonium chloride yielded a base, C19 H22 Me, N2 O7, crystallizing in yellow, sparingly soluble prisms. In this reaction, the acid seems to be analogous to nicotinic acid; and thus it would appear that in kakotheline, as also in brucine, a pyridine grouping is present. The above acid when oxidized with chromic acid yields the base, C16 H18 Ng O4, obtained formerly as a product of decomposition of brucine. According to the author there is present in brucine, besides a quinoline-group, also a dimethoxyphenylpyridine, and in strychnine, a phenylpyridine residue; the stability of brucine seems to indicate a ring-arrangement.

Colchicine. S. Zeisel. Monatsh. Chem., vii. 557-597; Journ. Chem. Soc., 1887, 284.) Previous observations on the composition and properties of colchicine have, for the most part, been very discordant; in this paper a long summary is given. The principal results obtained by the author are as follows: the composition of colchicine is expressed by the formula C22 H25 NO; it combines with chloroform to form a crystalline compound, C22 H25 NO6, 2CH Clg, readily decomposed by water into its components. Colchicine is slightly basic, but its salts, with the exception of an aurochloride, C2 H25 NO6, H Au C14, cannot be obtained from their aqueous solutions. Colchiceïne, formed from colchinine, when heated with a trace of hydrochloric or sulphuric acid, has the composition 2 Ca1 H23 N OG, H2 O. As the difference between the two compounds is one C H, or methylene group, and as methyl alcohol is produced in the decomposition, it follows that colchiceïne is a demethylated colchicine.

22

Colchiceïne possesses at once the properties of a base, as evidenced by the formation of an aurochloride, C21 H23 N O6, H Au Cl. and also those of a monobasic acid, or more probably of a phenol, as shown by the formation of a copper derivative (C21 H22 N O6)2 Cu, and by the readiness with which it dissolves in alkalies. colchicine has no acidic properties, it is probably a methoxyderivative of a compound, of which colchiceïne is the corresponding hydroxy-derivative.

As

It is suggested that the molecular formula of each of the above substances is the double of that given; owing to the complex composition of the substances, the number of hydrogen-atoms is given with a certain reserve.

Sparteine. E. Bamberger. (Liebig's Annalen, ccxxxv. 368376.) The author has re-examined the sulphate, hydriodide, ethiodide, and methiodide of this alkaloid, and has obtained results differing in many instances from those obtained by Mills. Fuller information will be found in the original article.

Ecgonine. C. E. Merck. (Ber. der deutsch. chem. Ges., xix. 3002, 3003.) The author has repeated an experiment made by Calmels and Gossin (abstract, Year-Book of Pharmacy, 1886, 53), and finds that ecgonine, when distilled with almost dry barium hydrate, yields methylamine and not ethylamine as one of the products this corresponds with the behaviour of tropine under like conditions.

Amorphous Cocaine. R. Stockman. (Pharm. Journ., 3rd series, xvii., 861-863.) In isolating cocaine from coca leaves there