YEAR-BOOK OF PHARMACY.

PART I.
CHEMISTRY.

Hyoscine. A. Ladenburg. (Ber. der deutsch. chem. Ges., xiii., 1549-1554.) The author has previously stated that hyoscyamine, the crystallizable alkaloid of Hyoscyamus niger, is accompanied by an amorphous base, which remains in the mother-liquor after the crystallization of the former. It is obtained from this mother-liquor in the form of a brown syrup, and may be purified by conversion into the aurochloride and subsequent regeneration. The name "hyoscine," which he gives to this new base, had previously been applied by him to a body obtained from hyoscyamine by the action of barium hydrate (see Year-Book of Pharmacy, 1880, p. 26); but as this body proved identical with tropine, the corresponding decomposition product of atropine, he now proposes to apply the name hyoscine to the second alkaloid naturally occurring in henbane. When hyoscine is acted upon by barium hydrate, it yields tropic acid and a base isomeric with tropine, for which the name "pseudotropine" is suggested.

The reactions of hyoscine are similar to those of hyoscyamine. Potassio-mercuric iodide produces a light yellow amorphous precipitate with acid solution of hyoscine, and mercuric chloride an amorphous precipitate. In its physiological action hyoscine resembles atropine.

The paper concludes with the following summary of the mydriatic alkaloids ::

9

1. Atropine, C17 H23 N Og, splits up into tropic acid, C, H10 03, and tropine, C, H15 NO.

2. Hyoscyamine, C17 H23 N O3, yields tropic acid, C, H10 O3, and tropine, Cg H1 NO.

15

3. Hyoscine, C17 H23 NO3, splits up into tropic acid, C, H10 O3, and pseudotropine, Cg H15 NO.

4. Homatropine (a secondary product), C16 H21 N Og, decomposes into amygdalic acid, Cg Hg Og, and tropine, C. H15 N O.

The three natural mydriatic alkaloids are therefore isomeric. The Mydriatic Alkaloids. A. Ladenburg. (Chemiker Zeitung, 1881, No. 9.) So far as is known at present, only three mydriatic alkaloids occur naturally, viz., atropine, hyoscyamine, and hyoscine, all of which correspond to the formula C17 H23 NOg. Atropine occurs in Atropa Belladonna and Datura Stramonium, hyoscyamine in Atropa Belladonna, Datura Stramonium, Hyoscyamus niger, and Duboisia myoporoides, and hyoscine in Hyoscyamus niger.

Duboisine is identical with hyoscyamine, and daturine appears to be a mixture of atropine and hyoscyamine.

The decomposition products mentioned in this paper are the same as those referred to in the preceding abstract.

Tropeïnes. A. Ladenburg. (Ber. der deutsch. chem. Ges., xiii., 1081-1088.) This paper is a continuation of the author's previous report on a series of artificial alkaloids produced by the action of dilute hydrochloric acid on salts of tropeine (Year-Book of Pharmacy, 1880, p. 25). The bases of this kind now described by him are the following:-hydroxybenzoyltropeïne, parahydroxybenzoyltropeïne, orthohydroxybenzoyltropeïne, benzoyltropeïne, phthalyltropeïne, atropyltropeïne or anhydrotropeïne, cinnamyltropeïne, and oxytoluyltropeïne or homatropeïne. The last named alkaloid possesses mydriatic properties fully equal to those of atropine.

Synthesis of Tropic Acid. A. Ladenburg and L. Rügheimer. (Ber. der deutsch. chem. Ges., xiii., 2041.) In a previous investigation the authors have established the close relation between hydratropic, atrolactic, atropic, and tropic acids, and have shown that these acids may be successfully converted one into the other. They have now succeeded in producing atrolactic acid synthetically by treating acetophenone with phosphorus pentachloride, heating the resulting dichlorethylbenzol with alcoholic solution of potassium cyanide, distilling off the alcohol, boiling the residue with barium hydrate, then acidifying the product with hydrochloric acid, and purifying the acid thus separating by recrystallization. The resulting atrolactic acid can be converted into atropic acid by the action of hydrochloric acid, the product yielded in this manner being perfectly identical with atropic acid obtained from tropic acid. Atropic acid, as previously stated, is readily convertible into tropic acid; and the synthesis of tropic acid is thus fully accomplished.

Atropine. L. Pesci. (Gazz. Chim. Ital., x., 425-430. From Journ. Chem. Soc.) The atropine was prepared from dry belladonna leaves by exhausting them with cold water, evaporating the extract at a gentle heat, and, after mixing the syrupy mass with soda solution, agitating with benzene to extract the alkaloid. The benzene solution was then agitated with dilute sulphuric acid, and the acid solution after addition of an alkali was in like manner agitated with chloroform. On mixing the chloroform solution with an equal volume of light petroleum (benzolene), and allowing it to evaporate spontaneously, the liquid soon becomes filled with long colourless needles of pure atropine. The mother-liquors contain a small quantity of another alkaloid. Pure atropine, C17 H23 N O3, melts at 106-108. A table of its reactions is given: with picric acid it produces a yellow precipitate even in presence of sulphuric acid; with concentrated sulphuric acid no coloration in the cold, but a yellow tinge appears on heating; on adding water a pleasant odour of roses is evolved.

Atropine is not altered by boiling with a saturated solution of tartaric acid.

Action of Nitric Acid on Atropine.-If atropine is strongly heated with nitric acid, it yields picric acid; but if it is gradually added to fuming nitric acid, maintained at about 50°, it dissolves with a slight yellow coloration which subsequently disappears. neutralising the product and extracting with ether, an oily base is obtained soluble in chloroform. With dilute sulphuric acid, it yields a crystalline sulphate having an odour of hawthorn; the sulphate is readily soluble in boiling water, but only sparingly in the cold. The platinochloride is crystalline, and, unlike that of atropine, is but sparingly soluble in hydrochloric acid. The aurochloride is a yellow amorphous precipitate, whilst that of atropine crystallizes readily in tufts of needles. There are also many other points of difference in its reactions from those of atropine. In its physiological effects, it does not cause dilation of the pupil, and it does not appear to be poisonous.

A New and Characteristic Reaction of Atropine and Daturine. Dr. D. Vitali. (L'Orosi, iii., 259.) The dry alkaloid is boiled for a few minutes with about ten times its quantity of nitric acid in a porcelain dish, and the heat then continued at a lower temperature until all free nitric acid is driven off. After cooling, a few drops of freshly prepared alcoholic solution of potash are allowed to run down the inner side of the dish. As soon as the alkaline solution touches the residue, a magnificent violet colour is developed, which

The

passes in a short time to wine-red and then to a muddy-red. test is said to be a most delicate one. Strychnine, under the same conditions, produces a red, and brucine a greenish colour.

Combinations of Morphine with Alkalies and Alkaline Earths. P. Chastaing. (Repert. de Pharm., June, 1881, 268.) Though morphine is a decided base, it exhibits in some instances the characters of an acid or a phenol. This is well seen from its combinations with lime, baryta, and potash, which the author has succeeded in producing. The two lime salts obtained and examined by him have compositions corresponding to the formulæ CaO, (C17 H19 NO3)2 + 4 H2 O, and Ca (C17 H18 N O3)2 + 2 H2O. The morphinate of baryta is represented by the formula Ba O (C17 H19 N O3)2 + 2 H, O, and the potash salt by K2 O (C17 H19 N O3) + 2 H2 O. The author gives K C17 H18 N O3 + H2 O as the probable formula of the true morphinate of potash, the existence of which he asserts though he has not yet been able to produce it.

2

Conversion of Morphine into Codeine. E. Grimaux. (Comptes Rendus, May 16th, 1881.) The colour-reaction of morphine with ferric chloride, and the solubility of this base in solutions of potash, lime, and baryta, are regarded by the author as indications of an approach to phenols in its cnaracters. If morphine, therefore, be considered a phenol, codeine, differing from it in its composition by CH, would appear to be its methylic ether, and likely, as such, to be obtainable from morphine. The author's experiments in this direction have proved successful. A solution of one molecular weight of morphine in alcohol containing one molecular weight of soda, when gently heated with one molecular weight of methyl iodide, yielded a small amount of codeine which, after purification, agreed in all its characters with codeine prepared from opium. Ethyl iodide, under the same conditions, yielded a new base, homologous with codeine, which may be regarded as the ethylic ether of morphine. A whole series of artificial bases may thus be prepared from morphine; and to these as a class he proposes to give the generic name of "codeines." Codoethyline" would then be the new base just mentioned, while codeine itself would figure in this series as "codomethyline."

66

Morphine Hydrochlorate. Dr. O. Hesse. (Liebig's Annalen, ccii., 151.) When allowed to crystallize slowly from methyl alcohol, this salt is obtained in an anhydrous condition, in the form of small crystalline grains, which are soluble in 51 parts of methyl alcohol, and also sparingly soluble in ethyl alcohol. When recrystallized from water it forms the ordinary hydrated salt.