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the platinochloride and crystallised from alcohol. The yield of pure pyrrolidine is small. The author hopes to obtain phenyleneethylenimine from phthalimide by means of this reaction.

N. H. M.

Pyridine-derivatives from Metanitrobenzaldehyde. By R. LEPETIT (Ber., 20, 2397-2400).—In a previous communication (this vol., p. 845), the author has described the formation of lutidine-derivatives by the action of ammonia and ethyl acetoacetate on the isomeric nitrobenzaldehydes. In the present paper, further compounds derived from metanitrobenzaldehyde are described.

Ethyl metahydroxyphenyllutidinedicarboxylate,

OH CH, CNMe2(COOEt)2,

obtained from the corresponding amido-ether (loc. cit.) by means of the diazo-reaction, crystallises in white needles, soluble in benzene, and melting at 174°. The same amido-compound yields well-defined colouring matters with amines, phenols, and naphthols. Ethyl dimethylamidobenzeneazophenyllutidinedicarboxylate,

NMe CH, N2 C2H, C2NMe2(COOEt)2,

crystallises in flat, red needles, soluble in alcohol, and melting at 167°. Ethyl B-naphtholazophenyllutidinedicarboxylate,

OH C10H N2 CH, C2NMe2(COOEt)2,

2

forms small, silky, scarlet needles, soluble in acetic acid, and melting at 152°. Metamidophenyllutidinedicarboxylic acid,

[blocks in formation]

obtained by the hydrolysis of its ethereal salt, forms small, white needles, sparingly soluble in alcohol and water, and melting with decomposition at 238°. The salts are soluble. With amines and phenols, the acid forms dyes similar to those obtained from its ethereal salt. On distillation, its calcium salt yields metamidophenyllutidine,

NH, CHỌC NH, Me.

This is crystalline, dissolves in benzene, and melts at 110°. Its yellow picrate forms minute crystals, and its mercurochloride glistening needles decomposing at 160°. By means of the diazo-reaction, it yields metahydroxyphenyllutidine, OH C,H,C,NH,Me2, which forms white crystals, soluble in ether and melting at 191°. It is basic in character, and yields well-characterised platino- and mercuro-chlorides. Amidophenyllutidine when treated with nitrobenzene, glycerol, and sulphuric acid, yields lutidyl-quinolyl, C,NH,Me C,NH. This base forms colourless, rhombic crystals, melting at 107-109°. Its hydrochloride, nitrate, and auro- and platino-chlorides are all crystalline.

L. T. T. Pyrimidines. By A. PINNER (Ber., 20, 2361-2365).-Referring to his last paper on this subject (Abstr., 1886, 45), the author states that the formula C1N2H,Br there given for a bromo-derivative is incorrect. The correct formula is C1N2H,BrO, and the compound is CPh: N phenylmethylhydroxybromopyrimidine, N<

VOL. LII.

CMe CBr

>C.OH.

4 b

A concentrated aqueous solution of dimethylhydroxypyrimidine, when treated with bromine, yields dimethylhydroxybromopyrimidine CMe N >COH,HBr. This crystallises in colour

hydrobromide, NCMe CBr

less needles, moderately soluble in water. Ethylmethylhydroxybromopyrimidine crystallises in long, colourless needles, sparingly soluble in water and melting at 194-195°. The formation of a potassium-derivative (which crystallises in needles with 1 mol. H2O) shows the continued presence of a hydroxyl-group.

Phenylmethychloropyrimidine, CN2H,Cl (Abstr., 1885, 158), yields with ammonia phenylmethylamidopyrimidine, CuNH, NH2, which crystallises in prisms or scales and melts at 130°. Its chloride and platinochloride are crystalline.

When phenylmethylhydroxypyrimidine is treated with a mixture of strong sulphuric and nitric acids, it yields a compound which is probably a nitro-nitroso-derivative, CN2H2O(NO2) NO. It crystallises in needles and melts at 238-243°. When reduced with hydriodic acid, it yields diamidophenylmethylhydroxypyrimidine, which crystallises in needles and melts with decomposition at 230-240°. It is soluble in soda solution. The hydrochloride, hydriodide, and platinochloride are crystalline. L. T. T.

Derivatives of Pyrazole. By L. BALBIANO (Gazzetta, 17, 176— 182). Wislicenus has recently shown that phenylhydrazine and phthalide combine directly to form the hydrazide of a hydroxymethylbenzoic acid. In the present paper, the reaction between phenylhydrazine and compounds of the type of ethylene oxide is studied epichlorhydrin being selected as a suitable substance. When phenylhydrazine and epichlorhydrin are heated in presence of benzene, to moderate the action, phenylhydrazine hydrochloride at first separates; the crude product is then heated in an oil-bath to 140° to remove the benzene, and the residue is distilled, when a yellow oil passes over. This substance is shown by its reactions to be a phenylpyrazole, C,H,PhN,; it is insoluble in water, soluble in alcohol and ether, as also in fuming hydrochloric acid. Its platinochloride crystallises in yellowish-red prismatic needles, and its ethiodide, C,H,N,EtI, in small white prisms melting at 116-117°, soluble in water, sparingly soluble in alcohol.

The formation of a phenylpyrazole in the above reaction is explained thus : C,H,OC1 + 2PhN,H = C HON,H,Ph + PhN,H,HC =NH,Ph + NHỌC1 + H,O + CH.N,Ph.

It would appear from this reaction that in the pyrazole the two atoms of nitrogen are combined to all three atoms of carbon, and thus it differs from the pyrazole obtained by Knorr, in which the nitrogen-atoms are combined with only two carbon-atoms; further investigation is required, however, to settle this point.

V. H. V.

Action of Carbamide on Cyanhydrins. By A. PINNER and J. LIFSCHÜTZ (Ber., 20, 2351-2358).-When the cyanhydrins of aldehydes are heated with carbamides, derivatives of carbamide of the general formula CN CHR NH·CONH, are formed. Attempts to

CHR⚫NH.
N.CO.

obtain the corresponding acids by hydrolysis of these compounds with alkalis yielded only uncertain results, but when the saponification was carried out with dilute acids, anhydrides of the correspondCHR NH ing acids were obtained of the general formula CO<NH.CO This class of compounds, to which the authors give the name metapyrazolones, pass easily into isomeric compounds of the formula. OH.CN CHR-N >COH or OH·C< >, to which the authors ascribe the name metapyrazoles, as they differ from Knorr's pyrazoles mainly by having the two nitrogen-atoms separated by a COgroup. Phenylcrotononitrilecarbamide, CHPh CH-CH(CN) NH-CONH2, formed from cinnamaldehyde cyanhydrin and carbamide, crystallises in needles easily soluble in boiling alcohol, very sparingly in boiling water. It melts with decomposition at 160°. Alkalis convert it into a mixture of acid compounds. When boiled with dilute hydrochloric acid, it yields styrylmetapyrazolone, CHPh: CH CH<NH.CO crystallises in glistening, white scales easily soluble in alcohol, sparingly in boiling water. This melts at 171-172°, but if retained at this temperature resolidifies after a time to the isomeric compound styrylmetapyrazole, which melts at 194-195°. The same conversion seems to be brought about by dissolving the pyrazolone in boiling water containing a little alkali. The pyrazole obtained by fusion forms small needles which, even after repeated recrystallisation, melt at 194-195°; that by heating with water forms flat needles melting at 190°, but in other respects they are similar, and are both easily soluble in acids and alkalis. The authors cannot at present determine whether these two substances are identical or isomeric.

CH-CH-CO-NH

which

Phenylacetonitrilecarbamide, CN CHPh⚫NH.CONH2, prepared from benzaldehyde cyanhydrin, forms long prisms easily soluble in alcool and boiling water and melting with decomposition at 170°. With acids, it yields a compound, C,H,N,O2, which crystallises in quadratic scales, is easily soluble in alcohol and boiling water, and melts at 181-182°. Neither heating nor the action of alkalis converts it into an isomeride, and it is therefore probably phenylmetapyrazole. It is easily soluble in alkalis and in acids.

Isobutyronitrilecarbamide, CH, CH(CN) NH·CONH2, from isovaleraldehyde cyanhydrin and carbamide, is an oil soluble in alcohol and ether, insoluble in water. With hydrochloric acid, it yields isoC(OH):

butylmetapyrazole, CH, CH<NH-CON, which forms small, white needles, soluble in alcohol and boiling water and melting at 209-210°. The isomeric pyrazolone does not appear to be formed. Besides the above oil, a small quantity of imidoisocapronitrile (Erlenmeyer, Abstr., 1882, 191), NH(CH10 CN)2, is obtained. Its hydrochloride forms silky needles soluble in alcohol, insoluble in ether..

Similar compounds appear to be obtainable from acetaldehyde cyanhydrin, and are now under investigation.

L. T. T.

Sparteïne. By F. AHRENS (Ber., 20, 2218-2222).-Dihydrosparteine, CH2N2, is prepared by reducing sparteïne dissolved in strong hydrochloric acid with a slight excess of tin. The hydrochloride obtained by decomposing the stannochloride with hydrogen sulphide is treated with potassium nitrite and the nitroso-compound extracted with benzene; it is then decomposed by hydrochloric acid, the hydrochloride treated with potash and steam-distilled. It is a thick, colourless oil, which boils at 281-284°. The platinochloride crystallises well, and becomes black at 239°. The picrate forms matted needles which melt at 123-125° and decompose at 215°. The mercurochloride crystallises in long needles; the hydrochloride and sulphate were also prepared.

When sparteïne is added to a solution of hydrogen peroxide, it dissolves with evolution of gas. The product of the reaction is an almost colourless base, C15H2N2O2; this could not be obtained crystalline and distils with difficulty with steam; it dissolves readily in water and alcohol, sparingly in benzene and chloroform, and is insoluble in ether. The platinochloride, C15H26N2O2, H2PtCle, becomes black at 235°; the aurochloride crystallises in densely matted needles melting at 143-146°; the aqueous solution decomposes quickly when warmed, with separation of gold. The sulphate forms a thick syrup; the hydriodide separates from its solution in colourless, feathery crystals melting at 121-122°; the picrate and mercurochloride were also prepared.

N. H. M.

Reactions of Creatinine. By G. COLASANTI (Gazzetta, 17, 129133). The most delicate test for creatinine in the presence of other reducing agents is that proposed by Weyl, which consists in adding to the liquid to be examined a few drops of sodium nitroprusside and a dilute solution of sodium hydroxide, which gives a yellow coloration. On adding acetic acid and warming an emerald-green colour is produced at first, which changes after some time to blue, a reaction peculiar to creatinine according to Salkowski, and to acetone contained in urine according to Nobel. This reaction is due to the formation of a sodium ferrocyanide derived from the decomposition of the nitroprusside and its subsequent conversion into Prussian blue. In the paper it is shown that other organic and inorganic acids can be substituted for acetic acid, and that the creatinine reaction can be obtained even after ammoniacal fermentation has proceeded for some time. The same reaction is also obtained even after the urine has been preserved for 30 months in sterilised vessels. V. H. V.

Acetylhydrocotarnineacetic Acid. By W. BOWMAN (Ber., 20, 2431-2433). Acetic anhydride combines directly with cotarnine to form acetylhydrocotarnineacetic acid, CiH19NOs; this substance crystallises in pale-yellow needles melting at 201°, sparingly soluble in water, soluble in alcohol and benzene. Its silver and mercury salts are white, the copper a blue precipitate; the ethyl salt crystallises in delicate needles melting at 113°. The acid is decomposed when boiled with dilute hydrochloric acid, forming a hydrochloride of a compound, C1HNO

V. H. V.

By

Identity of Cadaverine with Pentamethylenediamine. A. LADENBURG (Ber., 20, 2216-2217).-When a solution of pentamethylenediamine hydrochloride (1 mol.) is mixed with a solution of mercuric chloride (4 mols.), a mercurochloride with 3 mols. HgCl, is formed (this vol., p. 126); if a greater excess of mercuric chloride is employed, the compound C,H1N2,2HC1,4HgCl, is obtained. The identity of pentamethylenediamine with cadaverine is therefore established. (Compare also this vol., p. 742.) N. H. M.

11

Hydrastine and its Derivatives. By M. FREUND and W. WILL (Ber., 20, 2400-2406).—This is a continuation of the author's previous work (this vol., p. 383). Hydrastinine when treated with an aqueous solution of potash yields hydrohydrastinine and hydroxyhydrastinine, CHNO. The reaction appears to take place according to the equation 2CHNO2+ H2O = CH1NO2+ CH1NO. Hydroxyhydrastinine is a feeble base, crystallises in needles, melts at 97-98, and distils above 350°. It is easily soluble in alcohol, chloroform, ethyl acetate, benzene, &c. The hydrochloride is crystalline, melts at 138°, and is decomposed into acid and the free base by water and by alcohol. The platinochloride, (CHNO,HCI), PtCl1, forms yellow needles melting at 160°; the aurochloride,

(CHNOз, HCl)2, AuCl3,

a reddish-brown mass melting at 100°.

Nitrohydroxyhydrastinine, CHNO3 NO2, formed by dissolving the base in dilute nitric acid, yields crystals which are soluble in alcohol and acetic acid, and melt at 271°. It is insoluble in hydrochloric aeid, sodium carbonate, or ammonia.

Several fresh salts of hydrohydrastine are described. The hydroehloride, CHNO2, HCl, forms white crystals melting at 273-274°; the platinochloride, (CH3NO2)2,H,PtCl, yellow scales melting at 216°, the dichromate, (C1Ì ̧ÑO2),H2Cг2O,, red scales which explode at 150°. The hydrobromide previously described melts at 272°. The hydriodide melts at 232°, the ethiodide crystallises in needles melting at 206-207°. Hydrastinine dichromate has the formula

(CH1NO2)2H2Cr2O1,

and not that previously given.

L. T. T.

Synthesis of Pilocarpine. By HARDY and CALM ELS (Compt. rend., 105, 68-71). The synthesis of pilocarpine was effected by converting B-pyridine-a-lactic acid into pilocarpidine, which was then transformed into pilocarpine by oxidation.

One gram B-pyridine-a-lactic acid was mixed with 100 grams of carbon bisulphide and 10 grams of phosphorus bromide and distilled to dryness. The residue was extracted with water, the solution neutralised with baryta, the excess of baryta removed by means of carbonic anhydride, and the solution evaporated to dryness at a temperature not exceeding 60°. The residue thus obtained was purified by repeated treatment with alcohol, and then mixed with hydrobromic acid and auric chloride, when crimson plates of the normal aurobromide of B-pyridine-a-bromopropionic acid are obtained. The gold is removed by means of hydrogen sulphide, and the free acid is heated in

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