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vol., p. 498). It may be prepared in a pure state as follows:-Purree is mixed with water, and digested with hydrochloric acid, the excess of which is removed by filtering, and washing the precipitate with water; the euxanthic acid which is insoluble in water is dissolved in hot alcohol, and on cooling separates in yellow needles; it is purified by repeated recrystallisation. Spiegel's method of decomposing this acid into euxanthone and glycuronic acid by weak sulphuric acid not giving good results, it was found better to mix it with water and subject it to a temperature of 120-125° in a Papin's digester for some hours. On cooling, yellow needles of euxanthone form, and are filtered off. The filtrate is twice more subjected to the same process. The acid filtrate is then concentrated to a thin syrup by means of an air-pump. Large brown crystals of glycuronic anhydride separate; they are obtained colourless by recrystallisation. Free glycuronic acid is easily obtained by the action of sulphuric acid on the barium salt. The anhydride may also be obtained from this by heating its aqueous solution; the crystals belong to the monoclinic system, and have a sweetish, somewhat bitter, taste. The lead and barium salts were described by Schmiedeberg and Meyer. The potassium salt crystallises in colourless, strongly refracting needles with four prismatic faces, having the composition C,H,O,K. The sodium salt is as easily obtained, and crystallises in fine needles arranged in a dendritic or radial manner. Attempts to crystallise the zinc, cadmium, copper, calcium, and silver salts failed. By mixing solutions of glycuronic anhydride with phenylhydrazine hydrochloride and sodium acetate, according to Fischer's method (Abstr., 1885, 53), brown drops form and sink to the bottom of the vessel, where they form a sticky, black mass; this is a compound of glycuronic acid with phenylhydrazine, but a similar product in a form available for analysis may be obtained by using a solution of potassium glycuronate instead of the anhydride. Yellow needles are then formed, of neutral reaction, melting point 114-115°, and composition C2H48N10010. They reduce Fehling's solution on the application of heat. Attempts to obtain a benzoyl compound by Baumann's method (this vol., p. 228) failed.

The specific rotation of the anhydride is [a] = +19-25; Külz gives 194 (this vol., p. 498). Difference of temperature, however, probably accounts for the discrepancy, the present determinations being made at 18°, those of Külz at 21°. Experiments moreover showed that the specific rotation rises with the temperature of the solution.

Glycuronic acid reduces copper and bismuth salts in warm alkaline solutions; comparing its reducing power with that of dextrose, 1 part of the latter corresponds with 0.989 of glycuronic anhydride.

By the action of bromine, it yields saccharic acid. By the action of sodium amalgam, gluconic acid is obtained. By the action of mineral acids, lævulinic acid is not obtained but an acid containing two atoms of hydrogen less (CHO). W. D. H.

Thiënethylamine. By H. GOLDSCHMIDT and W. SCHULTHESS (Ber., 20, 1700-1701). As the method of preparation of amines from the

oximes has been shown to be applicable to the furfuran-derivatives, it is here applied to thiophen-compounds. Thus, acetothiënoxime is converted on hydrogenation into thienethylamine, C,SH, CHMe NH2. This reaction is best effected in a freezing mixture. The resultant compound is a colourless liquid, boiling at 185-187°; it absorbs carbonic anhydride from the air, is decomposed on evaporation with hydrochloric acid; with acetic acid, it yields an acetate, C,H,SN OAc, crystallising in colourless, very soluble needles. Its benzoylderivative forms glistening, white needles melting at 95°, and gives the indophenine reaction.

V. H. V.

Constitution of Benzene. By A. CLAUS (Ber., 20, 1422-1426). -The author considers that the introduction of three pairs of quinone-oxygen atoms in benzene (Nietzki and Kehrmann, this vol., p. 473), can only be simply explained by his diagonal formula for benzene, and discusses the point raised against the diagonal formula, that it does not show a difference between ortho- and para-positions. The benzene formula lately suggested by J. Thomsen (Ber., 19, 2944) is criticised, and R. Meyer's octahedral formula (Ber., 15, 1825) referred to. N. H. M.

Aromatic Nitriles: Action of Sodium and Alcohol on a-Naphthonitrile, Benzonitrile, and Tolunitrile. By E. BAMBERGER and W. LODTER (Ber., 20, 1702, and 1703-1710).—On hydrogenation of the aromatic nitriles two classes of substances are formed, namely, the corresponding hydrocarbon, or more generally its dihydro-derivative, thus: CoH CN + 2H2 C10H10 + HCN, and the primary amine; and in part its tetrahydro-derivative, thus: CH.CN +4H2 = C10H11 CH2 NH2. CH•CH,NH,

Dihydronaphthalene, C10H10, formed as in the above reaction, is a strongly refractive oil, boiling at 211° under 713 mm. pressure, and solidifying at low temperatures in large, glistening tables which melt at 15.5°. It readily takes up bromine to form a dibromide, C10H10Br2, which crystallises in colourless prisms of the monoclinic system, melting at 73·5-74°, and is readily converted into naphthalene with evolution of hydrobromic acid.

Tetrahydronaphthobenzylamine, C10H11 CH2 NH2, also obtained in the above reaction, is a colourless, strongly refractive, viscid oil, of peculiar ammoniacal odour, boiling at 269-270° under 722 mm. pressure. It is monobasic, and shows a remarkable affinity for carbonic anhydride. Its hydrochloride crystallises in needles; its platinochloride is a paleyellow, crystalline precipitate. On hydrogenation of benzonitrile, benzene, and benzylamine are obtained, and from paratolunitrile, a methylbenzylamine, C.H.Me CH, NH, [Me: CH,NH2 = 1 : 4], colourless oil, resembling trimethylamine in odour, and absorbing carbonic anhydride. Its hydrochloride crystallises in flat needles, melting at 234.5-235°; and the platinochloride in four-sided tables, sparingly soluble in water.

V. H. V.


Constitution of Quinone-derivatives. By A. HANTZSCH (Ber., 20, 1303-1308).-When the sodium salt of quinonedihydroxydicarboxylate is treated with hydrobromic acid until carbonic

anhydride ceases to be evolved, and bromine is added to the product, paradibromodihydroxyquinone, C.Bra(OH)2O2, is formed. This is shown by its physical properties and crystallographic measurements, as also of its sodium and potassium salts, to be identical with bromanilic acid. The rest of the paper is occupied by speculations on the constitution of bromanilic acid; it is suggested that it may be a paradibromotetraketohexamethylene. V. H. V.

Isomeric Chloro- and Bromo-thymoquinones. By K. SCHNITER (Ber., 20, 1316-1319).—In the mono-substituted thymoquinones, the positions 3 and 6 are not identical in function, so that according to theory two mono-derivatives are possible. It is remarkable, however, that on addition of the halogen acid to thymoquinone and subsequent oxidation, the same chlorobromothymoquinone is formed whether the chlorine be introduced first and then bromine, or conversely, a result only to be explained by the substitution of different hydrogen atoms by the halogen in the two cases.

a-Chlorothymoquinol, prepared by adding thymoquinone to concentrated hydrochloric acid, crystallises in silky needles melting at 70°, soluble in alcohol and ether.

a-Chlorothymoquinone, prepared by oxidising the above with ferric chloride, was not obtained in a crystalline form.

B-Bromothymoquinol forms colourless needles melting at 53°; it is converted by oxidation into the quinone, which crystallises in yellow leaflets melting at 45°.

a-Chloro-B-bromothymoquinol, obtained either from the above a-chloro-derivative and hydrobromic acid, or from the B-bromo-derivative and hydrochloric acid, crystallises in needles melting at 63°; when oxidised it yields the corresponding quinone, crystallising in golden leaflets, and melting at 87°.

B-Chlorothymoquinone, formed from the B-bromo-derivative by substitution, was not obtained in a well-defined condition. The B-chloroa-bromo-thymoquinone melts at 78°, and the corresponding quinol V. H. V.

at 56°.

Substitution of the Amido- by the Nitro-group in Aromatic Compounds. By T. SANDMEYER (Ber., 20, 1495-1497).-Nitrobenzene is prepared from aniline in the following way :-50 grams of crystallised copper sulphate and 15 grams of grape-sugar are dissolved in 100 c.c. of boiling water and at once treated with a cold solution of 20 grams of soda in 60 c.c. of water. The whole solidifies

and then becomes quite liquid; it is quickly cooled and neutralised with acetic acid. 9 grams of aniline, 50 c.c. of water, and 20 grams of nitric acid (sp. gr. 14), are mixed, and gradually treated (being kept cool) with a solution of 15 grams of sodium nitrite in 50 c.c. of water; the whole is then added in portions to the solution first prepared contained in a two-litre flask. After two hours, it is distilled, the distillate treated with caustic soda and the nitrobenzene separated. The yield is 5 grams of almost pure nitro


Parabromonitrobenzene is prepared in a manner similar to bromo

benzene from 17 grams of parabromaniline, the amount of nitric acid, &c., being the same as given above; 3 grams of pure product were obtained.

B-Nitronaphthalene is obtained by dissolving 7 grams of B-naphthylamine in a boiling mixture of 15 grams of nitric acid and 250 c.c. of water, cooling quickly, and adding 12 grams of sodium nitrite in 40 c.c. of water. After being treated with the cuprous oxide mixture, it is left for 20 minutes, and treated with alcohol; it is then kept cool for some hours and distilled. The yield of pure B-nitronaphthalene isgram. N. H. M.

Conversion of the Higher Homologues of Phenyl into Amines. By R. LLOYD (Ber., 20, 1254-1262).-Merz and Weith have succeeded in converting phenol into aniline and diphenylamine by heating it with ammonium-zinc chloride; the conversion is more complete the higher the molecular weight of the phenol. In this paper, the examination of amines obtained from isobutyl- and isoamylphenols, thymol and carvacrol is described. Thus isobutylphenol yields mono- and di-isobutylphenylamine. Isobutylphenylamine, NH2 CH, CH, is a brown oil, boiling at 230-231°, its acetyl-derivative crystallises in leaflets, melting at 170°. Diisobutylphenylamine, NH(CH ̧•C‚Â ̧)2, boils at 305-315°; it gives at first a violet, then a blackish-blue coloration with nitric acid; its platinochloride crystallises in yellow needles, and its acetyl-derivative in glistening leaflets, melting at 75°, sparingly soluble in water, soluble in alcohol and benzene.

Similarly isoamyphenol yields mono- and di-isoamylphenylamine. Isoamylphenylamine, NH, CH, CH, boils at 259-262°. Diisoamylphenylamine, NH(CH, CH)2, is a thick oil, boiling at 319-321°; its platinochloride forms golden-yellow crystals, and its acetyl-derivative glistening leaflets, melting at 81°.

From thymol were obtained thymylamine, NH, C10H13, and dithymylamine, NH(C10H13)2; the latter is an oil of aromatic odour, boiling at 340-345°; its acetyl-derivative crystallises in leaflets, melting at 78°; the former has been investigated by Widman. Of the bases formed from carvacrol, carvacrylamine, C10H13NH,, is a colourless oil, boiling at 241--242°, and solidifying at -16°; its platinochloride crystallises in prisms, its acetyl-derivative crystallises in white tablets melting at 115°, and the benzoyl-derivative in rhombic crystals melting at 102°. Dicarvacrylamine is a colourless oil boiling at 344-348°, its hydrochloride forms a white and the platinochloride a yellow precipitate; the acetyl-derivative crystallises in scales melting at 78°. In each case numbers are given showing the relative proportions of the primary and secondary base formed according as ammoniacal solutions of zinc ammonium chloride or bromide were used; the bromide gave a better yield than the chloride. The most satisfactory results were obtained in the case of carvacrol. V. H. V.


By C. L. JACKSON and J. F. WING (Amer. Chem. J., 9, 78-81).-This base has been prepared by

Schotten, but not fully described. Dimethylbenzylamine is prepared by the action of benzyl chloride on dimethylamine; the product in aqueous solution is treated with ether, which extracts the substance in question, but leaves dissolved in the water the excess of dimethylamine and also dibenzyldimethylammonium chloride. It boils at 183-184°; its chloride and nitrate are deliquescent; the following three crystalline salts were analysed: (NMe C,H7)2, H2PtCl, (NMe2 C,H,)2,H,Fe(CN)e, and (NMe2 C,H,,HCl)2, ZnCl2.

Dimethyldibenzylammonium chloride, NMe,(C,H,),Cl, prepared as above described, is, after purification, a white crystalline solid, soluble in water and in chloroform; when it separates from aqueous solution it is obtained as an oil, which, however, soon solidifies. Its platinochloride crystallises easily. H. B.

Action of Ethylenediamine on Catechol. By V. MERZ and C. Ris (Ber., 20, 1190-1197). — Ethyleneorthophenylenediamine, CH NH<C2H>NH, is obtained by heating 3 grams of catechol with 3.2 grams of dried ethylenediamine hydrate at 200° to 210° for 15 hours. The product is treated with cold water, washed with water, and dried over sulphuric acid; it is then distilled in an atmosphere of hydrogen. It crystallises from ether in white, lustrous plates, melts at 965-97°, and boils at 287.5-288-5°. It dissolves readily in hot water, warm ether, and in cold alcohol, benzene, and chloroform. When the aqueous solution is heated with ferric chloride, it acquires a blue colour when dilute, violet when more concentrated; on adding hydrochloric acid, the blue colour changes to green or greenish-yellow, and then slowly (on heating quickly) to brown and red. The oxalate crystallises in colourless needles, sparingly soluble in alcohol, more soluble in water; it melts at 184° with decomposition. The picrate forms a yellow crystalline precipitate, readily soluble in alcohol; it melts just above 120°, with decomposition. When the diamine is oxidised with about five times its weight of potassium ferricyanide, and the product extracted with ether, quinoxaline is obtained. The yield is 644 per cent. of the theoretical. The quinoxaline melts at 27.5°, and distils at 225-226° (comp. Hinsberg, Annalen, 237, 333).

Quinoxaline can be reconverted into ethylene orthophenylenediamine by gradually treating the boiling alcoholic solution with sodium; the yield is about 40 per cent. of the weight of the quinoxaline. Other substances are formed in the reaction.

N. H. M.

Nitrophenols and Phenylhydrazine. By A. BARR (Ber., 20, 1497-1500).—When orthonitrophenol is warmed with phenylhydrazine in presence of xylene as diluent for 1 hours, orthamidophenol is obtained (comp. Merz and Ris, Ber., 19, 1754); benzene, ammonia, and nitrogen are formed in the reaction.

Paranitrophenol reacts in like manner with phenylhydrazine; a-dinitrophenol and phenylhydrazine yield benzene and ammonium dinitrophenol. N. H. M.

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