Page images

soluble in cold, but readily in hot water; its silver salt is a voluminous, flocculent precipitate. With reducing agents, it yields picoline and picolinic acid.

Chlorohydroxypicolinic acid, OH-C,NH2CI-COOH, formed simultaneously with the above, crystallises in clusters of needles, melts above 315°, is sparingly soluble in cold, readily in hot water, alcohol, and ether. Like the above acid, it does not combine with mineral acids. These acids are not identical with those obtained by Ost (Abstr., 1883, 794). With phosphoric chloride, nicotinic acid yields an oil containing chlorine, and this, when boiled with sulphuric acid, is converted into chlorhydroxy- and dichloro-nicotinic acids, together with trichloropyridine. The first of these acids crystallises in monoclinic prisms and needles, melting at 302°, sparingly soluble in cold, readily in hot water and alcohol. The aqueous solution gives with silver nitrate a white, flocculent precipitate, soluble in ammonia, and with ferric chloride a dirty red precipitate, Its barium salt crystallises in transparent rhombic prisms.

Trichloropyridine, C,NHCl, crystallises in colourless needles, melting at 64°, insoluble in water, soluble in alcohol, ether and benzene.

Dichloronicotinic acid crystallises in small, white, grouped needles, melting at 138°; its ethyl salt forms colourless needles, melting at 50°, sparingly soluble in water, but soluble in alcohol, ether, and chloroform. V. H. V.

Bromoquinoline. By A. CLAUS and F. COLLISCHONN (Ber., 19, 2763-2769).—It was previously mentioned (this vol., p. 60) that when quinolinepropiobromide dibromide is heated, the hydrobromide of a new monobromoquinoline is formed. The bromo-compound is heated at 170° for some time, and then at 190°; a crystalline residue is thus obtained without carbonisation. The bromoquinoline is separated from the quinoline that may be present by distilling with steam: the hydrobromide of the bromo-compound is decomposed, the free base going over with the steam, whilst the quinoline salt remains bebind. It is a slightly yellow oil, having an odour resembling that of quinoline; it boils at 273-274° (uncorr.). The hydrobromide forms characteristic envelope-shaped crystals, which dissolve sparingly in cold water with partial decomposition, more readily in alcohol, and is almost insoluble in chloroform. When carefully heated at about 190°, it sublimes without having melted.. The hydrochloride sublimes readily without melting. The platinochloride, (C,NH,Br), H2PtCle, crystallises from dilute hydrochloric acid in slender, orange-coloured needles. nitrate and sulphate melt respectively at 180° and 182-183° (uncorr.). The dichromate crystallises in flat, short prisms, which melt at 144145° with decomposition. The compound (C,NHBr), AgNO, melts at 172-173°, and detonates at a high temperature with evolution of red vapour. The same bromoquinoline is obtained when an ethereal solution of bromine is added to a solution of quinoline in ordinary ether (containing alcohol); a yellow precipitate is formed. The latter crystallises from chloroform in lustrous, garnet-coloured crystals, melting at 88° (uncorr.). Analysis points to the formula C,NH,.HBr, Br2. When exposed to air it gives off bromine. The hydrochloride,


C,H,,HCl, Br, forms small, orange-coloured crystals melting at 100105°. When the bydrobromide of the quinoline dibromide is heated at 180°, it is converted with evolution of hydrobromic acid into bromoquinoline hydrobromide.

When bromoquinoline is oxidised with potassium permanganate, Friedländer and Ostermayer's oxalylanthranilic acid (Abstr., 1882, 732), melting at 210° (not 200°), and bromopyridinedicarboxylic acid, C,NH,Br(COOH)2, are obtained. The latter forms yellowish crystals, readily soluble in water, alcohol, ether, &c.; it melts at 165° with evolution of carbonic anhydride and formation of bromonicotinic acid, melting at 183° (uncorr.).

The bromoquinoline described above is identical with that obtained by La Coste (Abstr., 1881, 741) by brominating quinoline hydrochloride. N. H. M.


Synthetical Experiments with Ethyl Acetoacetate. L. KNORR (Annalen, 236, 69–115).-The action of ethyl acetoacetate on aniline at different temperatures has already been investigated by the author (Abstr., 1884, 334). The anilide of acetoacetic acid, previously described as B-phenylamido-a-crotonic acid, melts at 85° and decomposes on distillation, yielding symmetrical diphenylcarbamide. On the addition of bromine to a solution of the anilide in chloroform, an unstable additive product is formed, which decomposes when the mixture is warmed, yielding the anilide of monobromacetoacetic acid, COMe CHBr CO NHPh. This substance crystallises in plates, and melts at 138° with decomposition. Isonitrosoacetoacetic anilide, COMe C(NOH) CO NHPh, crystallises in prisms, and is freely soluble in alcohol, ether, acetic acid, and light petroleum. It melts at 99-100°. On reduction with zinc and acetic acid, a crystalline compound, melting between 212° and 215°, is obtained. The formation of hydroxylepidine (y-methylcarbostyril),

[blocks in formation]

by the action of dehydrating agents on acetoacetic anhydride, has been already described (Abstr., 1884, 334 and 1198), and this substance has been described under the names of hydroxymethylquinoline and hydroxyquinaldine. On distillation with zinc-dust, it is converted into y-lepidine, and it yields chlorolepidine when treated with phosphoric chloride (Abstr., 1885, 274). Chlorolepidine, C,NH,MeCl [Me: Cl2': 4'], melts at 59° and boils at 296° (corr.); it yields 7-methylquinoline when reduced with hydriodic acid, and also when decomposed by water at 200°.

Methoxylepidine, C,NH,Me-OMe, formed by the action of potassium methoxide on chlorolepidine, is an oily liquid boiling at 275–276°. It forms a crystalline platinochloride. Ethoxylepidine melts at 51° and boils at 250° under 342 mm pressure. Chlorolepidine reacts with aniline, forming phenyllepidinamine, a crystalline compound melting at 129-130°. The platinochloride melts at 235°.

CMe: CH.

Methyllepidone or dimethylpseudocarbostyril, CH<NMeCO>, has already been described by the author as dimethylpseudoquinoxyl

(Abstr., 1885, 274). It can be prepared by the action of methyl iodide on hydroxylepidine, by the condensation of methylaniline and ethyl acetoacetate, and also by heating methoxylepidine at 280°. Methyllepidone melts at 130-132°, and sublimes without decomposition. It boils at 290° under 250 mm. pressure. It is a strong base, forming salts which are not decomposed by water. The platinochloride, (CH1NO)2,H2PtCl + 3H2O, decomposes at 214-215°. Nascent hydrogen converts methyllepidone into a sparingly soluble crystalline compound, which melts at 258°. With bromine-water, methyllepidone forms bromomethyllepidine, C1HNOBг. This compound crystallises in needles and melts at 172°. It is insoluble in water and alkalis, but dissolves in dilute acids and forms a crystalline platinochloride. On the addition of brominé to a solution of methyllepidone in chloroform, a dibromo-additive product appears to be formed. It is decomposed by warm water, forming monobromomethyllepidone.

The properties of methyllepidone, methoxylepidine, and lepidine are seen in the following table :


[blocks in formation]

Metaquinolinecarboxylic Acid. By Z. H. SKRAUP and P. BRUNNER (Monatsh. Chem., 7, 519–520).-It is here shown that the seventh quinolinecarboxylic or the metaquinoline benzocarboxylic acid, recently obtained by Tortelli from a-amidophthalic acid by means of the glycerol reaction, is also formed in small quantities, together with its isomeride, from meta-amidobenzoic acid, by means of the same reaction. In previous experiments, its formation was overlooked (Abstr., 1882, 71). V. H. V.

Synthesis of Active Conine. By A. LADENBURG (Ber., 19, 2578 -2583). Further experiments on a larger scale, and with pure materials, have confirmed the author's previous results (Abstr., 1886, 478). a-Allylpyridine boils at 1875-1925°, and is a strongly refracting liquid of sp. gr. 0.9595 at 0°, sparingly soluble in water, and having a distinct conyrine-like odour. The platinochloride, (C,H,CH,N)2,H,PtCle, melts at 185-186°, and crystallises in needles sparingly soluble in water. The aurochloride melts at 135-136°; the mercuriochloride and cadmio-iodide are also described. By the action of sodium on an alcoholic solution at the boiling point, a-allyl

pyridine is reduced almost quantitatively to a-propylpiperidine. This base has a sp. gr. 08626 at 0°, and boils at 166-167°; its hydrochloride crystallises in white, silky needles, melting at 203-205°. In smell, solubility, specific gravity, and physiological action, a-propylpiperidine resembles conine, and not only are the platinochlorides, aurochlorides, and cadmio-iodides similar, but when a-propylpiperidine is converted into conyrine by Hofmann's method, a blue fluorescence is obtained just as with conine. This fluorescence is due to an accompanying product, for if the fluorescent base after separation from unaltered conine be converted into the platinochloride, the conyrine regenerated from it is no longer fluorescent. Conyrine platinochloride from conine crystallises in monoclinic forms: a b c = 1-06141: 1-5374; B = 87° 8'; and the crystals from the synthetical base give practically the same values on measurement.


-Propylpiperidine, however, in addition to the lower melting point of its hydrochloride, is optically inactive, and must be regarded as a physical isomeride of conine. To effect a separation into two optically active bases, a sterilised nutritive solution containing 0.5 per cent. of the tartrate was seeded with Penicillium glaucum, but without result. The active base, however, was obtained by introducing a crystal of the salt into a very concentrated solution of a-propylpiperidine hydrogen tartrate; a slow separation of crystals took place, which yielded a dextrorotatory base, whose specific rotation was [a] = 13° 87', compared with [a]D = 13° 79' for conine. The hydrochloride of the synthetical active base melts at 217.5°, that of conine at 217-5-218-5°.

From the mother-liquor, a lavorotatory base was obtained, but it contained a large proportion of the dextrorotatory modification, which could not be further separated by the crystallisation method. However, on converting this lavorotatory mixture into the cadmioiodide, it was found that after crystallisation, the crystallised salt yielded a base which was less lævorotatory than before, whilst from the mother-liquor a base was obtained, which in a 50 per cent. alcoholic solution gave a rotation of -3° 30′ in a decimetre tube, compared with 3° 10' for conine under the same conditions. W. P. W.

Reduction of Nicotine. By A. LIEBRECHT (Ber., 19, 2587-2598). -The author gives reasons for regarding nicotine as a ßß.hexahydrodipyridyl, in which one of the pyridine nuclei has taken up two, and the other four atoms of hydrogen. The author not having succeeded in obtaining dipyridyl by the oxidation of nicotine, has examined the complete reduction product obtained from its solution in absolute alcohol by the action of sodium (comp. Abstr., 1886, 161). Dipiperidyl, CH20N2, is a colourless, oily liquid, solidifying at a low temperature, and having an odour like that of piperidine. It has a sp. gr. = 0·9561 at 4°, is lævorotatory, boils at 250-252° without decomposition, and is volatile to some extent with steam. In water, alcohol, and ether, it is readily soluble, and on exposure to light or the air it turns slowly yellow. Contrary to expectation, dipiperidyl acts only as a feeble poison. Dipiperidyl is a bi-acid base: its simple salts are very soluble and do not readily crystallise, although some

of the double salts crystallise well. The hydrochloride is very deliquescent; the periodide, CoH20N2,2HI,212, crystallises in brown needles, which lose iodine on drying in the air. The platinochloride, CieH20N2, H2PtCl, forms small, red prisms, which on rapid crystallisation, separate either singly or in staurolite-like groups: it melts at 202-203°. The aurochloride, CH20N2,2HAuCl, crystallises in yellow lamina, melting at 131-132°, and is sparingly soluble in water. A mercuriochloride, CH2N2,2HC1,5HgCl2, crystallises in small sparingly soluble tables. Carbon bisulphide combines with dipiperidyl, forming a yellow salt, easily soluble in water and alcohol, less soluble in benzene and insoluble in ether. It readily becomes resinified, and when its alcoholic solution is boiled with mercuric chloride, the odour of allylthiocarbimide is evolved.

Diacetodipiperidyl, CN,HAC2, is prepared by heating the base with acetic anhydride at 170° for six hours. It is a yellow, oily liquid, boiling at 400-410° with slight decomposition, and does not solidify in a freezing mixture.

The action of methyl iodide results in the formation of the hydriodides of two bases, dimethyl- and trimethyl-dipiperidyl, of which the former is readily soluble, whilst the latter is insoluble in water.

Dimethyldipiperidyl, CN2H1Me, is an oil boiling at 230-332°, soluble in water in all proportions, and slightly volatile with steam. Its salts, with the exception of the mercuriochloride,

[blocks in formation]

are readily soluble, and can scarcely be crystallised; the platinichloride, CHIME2N2, H2PtCl, forms small dark red crystals.

Trimethyldipiperidyl, C10H1Me,N2, is obtained as a yellow oil of repulsive odour resembling that of methylamine, boiling at 205212; it is insoluble in water, and is not volatile with steam. The salts are very easily soluble and seem to be uncrystallisable, the platinochloride, C10H17Me N2, H2PtCl, is insoluble in alcohol and ether. The action of methyl iodide does not appear to yield a higher methylated base than trimethyldipiperidyl. W. P. W.

Sparteine. By E. BAMBERGER (Annalen, 235, 368-376).— Sparteine was discovered by Stenhouse (this Journal, 1851, 213), and its compounds were afterwards investigated by Mills (this Journal, 1862, 1). The author has re-examined these bodies, and his results in many cases differ from the observations of Mills. Sparteine boils at 311-311.5°, under a pressure of 723 mm. The sulphate, C15H2N2, H2SO, forms large, transparent prisms, which are very soluble in water. The hydriodide, CH2N, HI, forms glistening, foursided plates, which probably belong to the rhombic system. It is freely soluble in alcohol and in hot water. When aqueous hydriodic acid acts on sparteine, a resinous mass is formed, from which the dihydriodide can be obtained in silky needles, by boiling the alcoholic solution with animal charcoal.


The compound C1HN2EtI2, which Mills obtained by the action of ethyl iodide and alcohol on sparteine at 100°, is decomposed by

« PreviousContinue »