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it has stronger basic properties than methylpseudocarbostyril, and yields a sparingly soluble hydrochloride; the platinochloride,

(C12H1NO2)2,H,PtCl。,

crystallises in long pyramids. The y-ethoxy-compound crystallises from water in slender, white needles which melt at 87.5°. When heated with hydrochloric acid at 120°, both alkoxy-derivatives yield. a compound, C,NH,MeO2, which crystallises in white needles melting at 259-260°; it is soluble in the usual solvents, and in caustic alkalis, from which it is precipitated by carbonic anhydride. COCH, It has the constitution CH,C(OH): CH >, or C.HNMe.CO NMe CO When treated with nitrous acid, a sparingly soluble nitroso-derivative, C10H NO, NO, is formed. This crystallises from acetic acid in red needles which decompose at about 188°, dissolve in alkaline carbonates with green coloration, and yield methylpseudoisatin when heated with hydrochloric acid at 120°. Stannous chloride reduces it to B-4-dihydroxymethylpseudocarbostyril; this crystallises from alcohol in sparingly soluble needles which decompose at 210°. When a drop of soda is added to the alcoholic solution, a greenish-blue precipitate is formed which gradually dissolves with yellow colour; on adding ferric chloride, it acquires an emerald-green colour, which changes to reddish-yellow on warming, and it then contains a pseudoquinisatin, -CO-COCH<NMeCO. The latter is very readily soluble in the usual solvents, dissolves in alkalis with yellow coloration, and melts at about 120-122°. N. H. M.

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and its Deri

a-Metanitrophenylparamethoxyquinoline vatives. By W. v. MILLER and F. KINKELIN (Ber., 20, 1919-1927). -a-Metanitrophenylparamethoxyquinoline, C,NH,(OMe) CH, NO2 [CH, NO2: OMe 2': 4'], was prepared by treating a mixure of metanitrocinnamaldehyde and paranisidine with hydrochloric acid. It crystallises in glistening yellowish needles, melts at 130°, and is soluble in benzene, sparingly so in ether. Its salts are decomposed by water and their alcoholic solutions are not fluorescent. The chloride and platinochloride crystallise in needles. When the nitro-compound is reduced with stannous chloride, it yields a-metamidophenylparamethoxyquinoline, which crystallises in colourless iridescent needles, melts at 127°, and is soluble in ether and benzene, sparingly so in alcohol and boiling water. It forms three series of salts, acid, normal, and basic. The sulphate, CHN2O,H2SO, + 2H2O, crystallises in concentrically grouped yellow needles; the hydrochloride, C16H1N,O,2HCl + H2O in yellow prisms, and the platinochloride, C16H1N2O, H2PtCl + H2O, in thin, glistening prisms. a-Metamidophenylparamethoxyhydroquinoline is obtained from the amido-derivative by the action of tin and hydrochloric acid. It forms crystals melting at 87°. The hydrochloride forms compact plates; the platinochloride a brown, amorphous precipitate.

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a-Metahydroxyphenylparamethoxyquinoline is obtained by diazotising It crystallises in scales, is soluble in alcohol, melts

the amido-base.

The hydrochloride and

at 188°, and forms compounds with alkalis. sulphate form yellow crystals, and the acid solutions are not fluorescent. When a dilute sulphuric solution is treated with chlorine-water, the precipitate formed redissolved by the addition of soda, and ammonia added immediately, this base shows the green coloration hitherto considered characteristic of quinine, and this coloration becomes more marked on further dilution with water. The amido-base does not show this reaction, the nitro-base but very slightly. a-Metahydroxyphenylparamethoxyhydroquinoline is formed from the hydroxybase by the action of tin and hydrochloric acid. It crystallises in plates melting at 110-111°, and is easily soluble in alcohol and ether. The hydrochloride forms small plates, and gives an intense green coloration with ferric chloride. The sulphate and sodium-derivative are both crystalline.

Its

The a- and B-paramethoxydiquinolyline, CN,H,,O, were obtained by Skraup's reaction by heating the amido-base with glycerol, strong sulphuric acid, and nitro-phenol. The a-base is soluble in alcohol (but much less so than the B-base), ether, and benzene, sparingly in boiling water; it melts at 151°, but cannot be distilled without decomposition. Its ethereal solution shows blue fluorescence. salts are yellow; the methiodide is a yellow, crystalline powder. The B-base is easily soluble in benzene and alcohol, sparingly so in ether, and the two latter solutions show blue fluorescence. Its melting point is not definite. The hydrochloride and platinochloride are crystalline. These bases only show the green colour reaction, mentioned above, to a very slight extent. L. T. T.

Oxidation-products of Diquinoline [2': 2']. By H. WEIDEL and J. WILHELM (Monatsh. Chem., 8, 197-200; compare Abstr., 1886, 949 and 950).—In a former paper (Abstr., 1886, 950), the authors considered that all the evidence pointed to the constitutional formula of cyclothraustic acid being C,NH, C(OH): NCH COOH. They find, however, that when a mixture of anthranilic acid and quinaldine is heated, a substance is obtained which agrees in all respects with cyclothraustic acid, the constitution of which must therefore be C,NH, CO NH CH, COOH, and consequently that of pyridanthrilic acid, C.NH,(COOH)CONH CHCOOH. G. H. M.

Bases in Galician Petroleum. By F. X. BANDROWSKI (Monatsh. Chem., 8, 224-226).-The author has isolated a very small quantity of a base or series of bases from Galician petroleum. The substance gives all the reactions for and seems to belongs to the group of alkaloïds. G. H. M.

Occurrence of Alkaloïd-like Bases in Paraffin Oil. By A. WELLER (Ber., 20, 2097-2099).-The so-called yellow oil of sp. gr. 0.850-0.860, obtained in the manufacture of Saxon petroleum, contains small quantities of basic substances, which can be separated by shaking with dilute sulphuric acid, precipitating with aqueous soda, and extracting with ether. A partial purification is then effected by redissolving and reprecipitating several times, and finally the dark

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brown product is subjected to steam-distillation to remove the nonvolatile fluorescent impurities. The bases are thus obtained as a colourless oil, which is free from oxygen and sulphur, has an intensely unpleasant odour, and a sp. gr. 0.98-0.99, does not solidify at -11°, and is readily soluble in alcohol, ether, and chloroform, very sparingly soluble in water. Bromine and methyl iodide react with the mixture of bases, and form non-crystalline products, and treatment with concentrated aqueous potash causes the evolution of strongly alkaline but ammonia-free vapours. A separation of the bases cannot be effected by repeated fractional distillation, since the product obtained after many distillations boils, like the oil, between 220° and 260°, without the thermometer remaining constant at any one point. The most characteristic salt described is the oxalate, which crystallises in scales, and is soluble in alcohol, chloroform, benzene, and light petroleum, sparingly soluble in ether and water.

W. P. W. Normal Quinine Hydrochloride. By A. CLERMONT (J. Pharm. [5], 15, 15).—A solution of the normal hydrochloride CH2N2O4,2HCI

is easily obtained, either by mixing equivalent solutions of normal quinine sulphate and barium chloride, or by adding an equivalent of hydrochloric acid to a solution of basic quinine hydrochloride. The solution obtained by either process, when completely evaporated below 100°, yields the normal hydrochloride. This salt dissolves easily in its own weight of water at the ordinary temperature, and appears to be suitable for hypodermic injections, as its solation is not caustic. Below 5°, it becomes a mass of crystals, which again liquefy at 15°.

J. T.

Amorphous Cocaïne. By R. STOCKMAN (Pharm. J. Trans. [3], 17, 861). From the properties and reactions of amorphous cocaïne, it is concluded that the substance really consists of ordinary crystalline cocaïne retained in the amorphous state by hygrine, the liquid alkaloïd which is also present in cocaïne leaves.

R. R.

Emetine. By H. KUNZ (Arch. Pharm. [3], 25, 461-479).— Ipecacuanha powder was extracted with ether until all soluble matter was removed. The dried powder was then treated with strong alcohol, and the tincture thus obtained freed from spirit by distillation. The dry residue was freed from tannic acid by the addition of 10 to 13 per cent. of ferric chloride in concentrated solution, and the addition of sodium carbonate to strong alkaline reaction, too much liquid being carefully avoided. The sodium carbonate sets free emetine, but not the tannic acid, and the former can be extracted by boiling with light petroleum. The author, however, finds it best to dry the mass on the water-bath, powder finely, and extract with hot alcohol. On distilling off the alcohol, the resulting impure emetine is dissolved in dilute sulphuric acid, fractionally precipitated by ammonia, and these precipitates are now dissolved in boiling light petroleum. From the saturated petroleum solution, the emetine separates

spontaneously on cooling or on passing a current of air, in the form of a snow-white amorphous powder. 10 kilos. of root gave 80 grams of pure emetine. The powder again dissolved in sulphuric acid, precipitated by ammonia, and taken up with light petroleum as above, gives a perfectly white, amorphous powder, highly electric, and quickly becoming yellow to brown in the light, soluble in alcohol to a wineyellow solution. It is very sparingly soluble in cold water, but somewhat more soluble on heating. Light petroleum and ether dissolve only traces in the cold, but take up a large quantity when boiling. Methyl alcohol, chloroform, and benzene are also good solvents of emetine. The base has a decided alkaline reaction with litmus-paper. It fuses to a colourless liquid, which gradually passes through yellow to brown. The melting point appears to vary with the molecular condition and the state of dryness of the sample, from 65° to 74°. The formula seems to be CH40N2O5. Emetine platinochloride, CH4N2O5, H2PtCle, is a whitish-yellow powder, unchanged in sunlight. Emetine appears to be, like quinine, a diatomic diamine. The chromate,

C30H0N2O5,H2Cr2O7,

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was also prepared. Emetine is insoluble in soda and potash, ammonia, and the corresponding carbonates. A methiodide, CHMeN2OI, is readily formed, even in the cold.

Methylemetonium hydroxide, C30H40MeN2O, OH, is obtained by treating the iodide with silver oxide; it is strongly alkaline. Various salts of this base are described by the author. He further shows that emetine, like quinine, is probably a quinoline-derivative, and that the Radix ipecacuanha contains bilineurin or choline. J. T.

Alkaloïds of Gelsemium Root. By F. A. THOMPSON (Pharm. J. Trans. [3], 17, 805-808).—The author has isolated a second alkaloïd, gelseminine, from the root of Gelsemium sempervirens.

Analyses of gelsemine and several of its salts point to the formula CH69NO12 (Gerrad considered it to be CH2NO). It is tribasic. The following salts were analysed :-Hydrochloride, CH6N4O12,3HC1; aurochloride, C54HNO12,3HAuCl; platinochloride,

2C54H6N4O12,3H2PtCl.

The nitrate and sulphate are also described, as are further several colour reactions for the alkaloïd.

Gelseminine could not be obtained in a state fit for analysis. It is a dark-brown resinous mass, permanent in air, sparingly soluble in water and light petroleum, readily so in alcohol, ether, and chloroform. It has strongly marked basic properties, but only amorphous salts have been obtained. Its reactions are described in detail.

A. J. G.

Asiminine. By J. U. LLOYD (Arch. Pharm. [3], 25, 503).-The alkaloïd is obtained from the seed of Asimina triloba (Papaveracea) by extraction with alcohol, concentrating, and, to separate the fatty oil, diluting with water, acidifying with acetic acid, shaking well, and filtering after 24 hours. Ammonia is added to the filtrate until only a slight precipitate results, and the still moist precipitate is shaken

with ether. The residue from evaporation of the ethereal extract is taken up with a little alcohol, and a slight excess of hydrochloric acid is added. With a concentrated solution, the whole mass becomes crystalline, whilst a dilute solution requires concentration. The hydrochloride thus obtained can be purified by recrystallisation from hot alcohol. The pure alkaloid can be obtained by solution in water, precipitation by ammonia, and drying. It is white, amorphous, tasteless, and odourless; insoluble in water, easily soluble in alcohol and ether, less soluble in chloroform and benzene. Excepting the acetate and nitrate, its salts are easily crystallised. The hydrochloride is slightly soluble in water, the other salts are easily soluble, and have a bitter taste. Minute quantities give with nitric acid a carmine-red coloration, which quickly becomes purple-red, and can easily be mistaken for morphine. With sulphuric acid, asiminine effervesces and dissolves with a yellowish-green colour, gradually passing through yellowish-red to dark red. Hydrochloric acid after warming, and the addition of some sulphuric acid, produces a purple-red colour in the liquid.

J. T.

Cholic Acid. By F. MYLIUS (Ber., 20, 1968-1989; compare this vol., p. 606).—Cholic acid is readily purified by recrystallisation from alcohol. The results of several analyses of the acid and of the silver salt point to the formula CHOs (compare Latschinoff, this vol., p. 682). It readily forms stable compounds with alcohols. The compound C2H4005 + MeOH forms colourless tetrahedra; compounds with propyl and ethylene alcohols were also prepared. No double compound with acetone could be obtained. Cholamide (Hüfner, Abstr., 1879, 949) crystallises from water with 3 mols. H2O; it melts at 130-140°, solidifies at 180°, and melts then at 228° without decomposition or loss of weight; when it is recrystallised from alcohol, it again has the low melting point. When cholic acid is heated, it appears to yield a mixture of different anhydrides. Phenylmercaptandehydrocholic acid, C3H4OS2, is obtained by passing hydrogen chloride through a solution of dehydrocholic acid in phenyl mercaptan, and crystallises from alcohol in lustrous needles melting at 220°. It has acid properties; the sodium salt forms hair-like needles. Phenylmercaptan-phenylhydrazine-dehydrocholic acid,

COOH C23H33 (N2HPh)2(SPH)2,

melts at 210-220°; it is almost insoluble in alcohol and glacial acetic acid.

Bilianic acid is prepared by adding 20 grams of cholic acid (free from alcohol) to a mixture of 60 grams of sulphuric acid, 160 c.c. of water, and 40 grams of potassium dichromate. It is purified by means of the potassium salt. It has the formula CHO. The silver salt, CHOAg3, was analysed. The hydroxylamine compound, CHNO, crystallises in lustrous plates soluble in dilute alcohol; the phenylhydrazine-derivative, CHNO, is sparingly soluble.

When crude bilianic acid is boiled with baryta-water, the barium salt of isobilianic acid is formed; the latter is readily soluble in cold, almost insoluble in hot water.

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