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Paranitrochlorazobenzene, NO2 C&H, N2°C,H,Cl [4:1:4], is prepared by treating parachlorazobenzene with fuming nitric acid. It forms slender, pale-yellow needles, melts at 132.5°, and is insoluble in water, sparingly soluble in cold alcohol and ether, readily soluble in acetic acid.

Parachlorazobenzenesulphonic acid, SO2H·CH, N2 CH‚Cl, [4:1:4], is obtained by heating parachlorazobenzene with 10 per cent. fuming sulphuric acid at 60-70° for some time. It crystallises in brown needles, melts at 148°, and is very soluble in water and alcohol. The sodium and barium salts are described. The chloride, C12HN2CI SO2CI, melts at 130°, and crystallises in glistening, red prisms, soluble in alcohol and ether; boiling with water converts it into the acid. The amide forms brownish-yellow prisms, melts at 211°, and is insoluble in water, sparingly soluble in ether and cold alcohol. W. P. W.

Cyanazobenzene and Parazobenzenecarboxylic Acid. By E. MENTHA and K. HEUMANN (Ber., 19, 3022-3025).-Paracyanazobenzene, C13H,N3, is prepared by slowly adding a solution of diazobenzene chloride (from 40 grams of amido-azobenzene hydrochloride) to a solution of copper sulphate (100 grams) and potassium cyanide (90 per cent., 112 grams) in 600 c.c. of water at 90°. When cold, it is filtered, well washed, and dried; it is then sublimed and recrystallised from benzene, from which it separates in short brown needles. It melts at 100-101°, is insoluble in water, readily soluble in warm alcohol, ether, and benzene.

Parazobenzenecarboxylic acid, NPh: N-C2H ̧·COOH, is obtained by boiling the above nitrile in the pure state for three hours with concentrated aqueous potash. It crystallises from alcohol in long, lustrous, brown prisms, soluble in ether and warm benzene. When heated above 210°, it becomes dark, and decomposes at a higher temperature. When heated with lime, a sublimate is obtained which melts at 170-171°, and is probably azophenylene. The potassium salt crystallises in brownish-yellow needles soluble in water and in alcohol; the barium salt forms needles sparingly soluble in water, rather readily soluble in alcohol. Several other salts were prepared.

N. H. M.

Chloroparazotoluene. By E. MENTHA (Ber., 19, 3026).—Chloroparazotoluene, C1H3N2Cl, is prepared by treating 4.5 grams of amidoparazotoluene (obtained by Nölting and Witt's method, Abstr., 1884, 742) with 200 c.c. of water and 150 c.c. of strong hydrochloric acid, and adding a solution of 5 grams of cuprous chloride in 45 c.c. of hydrochloric acid. It is then heated to 90°, and a solution of 2.5 grams of sodium nitrite in 25 c.c. of water gradually added. The product is filtered, treated with hydrochloric acid and with soda solution, and ultimately crystallised from alcohol. It forms brown plates which melt at 97°, dissolves readily in ether, alcohol, and benzene, and closely resembles parachlorazobenzene (compare Abstr., 1886, 874). N. H. M.

Reduction of Aldoximes and Acetoximes. By H. GOLDSCHMIDT (Ber., 19, 3232-3234).—Carvylamine, CH1N, is obtained by reducing carvoxime in alcoholic solution with sodium amalgam in presence of acetic acid.

Benzylamine can be conveniently prepared by gradually adding 160 grams of 2 per cent. sodium amalgam to a solution of 5 grams of benzaldoxime in 20 c.c. of alcohol at 50-60°; the solution must be kept acid by addition of acetic acid. It is poured into water, saturated with ether, made alkaline, and again extracted with ether. The ethereal extract is dried, and treated with hydrogen chloride; benzylamine hydrochloride then separates as a white precipitate. Benzhydrylamine and isobutylamine were prepared in a similar manner from benzophenoxime and isobutylaldoxime respectively.

N. H. M.

Pyrogenic Formation of Phenazine. By A. BERNTHSEN (Ber., 19, 3256-3258).-The author succeeded in isolating phenazine from the product obtained by passing aniline through a red-hot tube (Abstr., 1886, 471). The product was repeatedly exhausted with moderately dilute hot hydrochloric acid, the brown solution precipitated with ammonia, extracted with ether, and the ethereal solution shaken several times with dilute hydrochloric acid. In this way, the stronger bases were dissolved, but not the phenazine. The ether was distilled off, the residue extracted with hot dilute hydrochloric acid, filtered when cold, and precipitated with ammonia. It was then sublimed, and the lustrous, yellow needles identified as phenazine. This pyrogenic formation of phenazine corresponds with that of anthracene from toluene.

N. H. M.

Safranine Dyes. By R. NIETZKI (Ber., 19, 3017-3022).-Previous experiments (Abstr., 1883, 731) made it probable that safranine contains two amido-groups, and that the third nitrogen-atom is tertiary or quaternary.

When phenosafranine, CH1N4, is boiled with alcohol, sulphuric acid, and sodium nitrite, the compound C8H13N3 is formed. This is a dye of a bluer shade than safranine, from which it is also distinguished by the absence of fluorescence of its alcoholic solution and in its behaviour towards strong sulphuric acid :-safranine dissolves with a green colour, which changes to blue and red on addition of water; the new compound dissolves, yielding a yellowish-brown solution, which when diluted becomes first green and then red. The monacetylderivative is violet, and yields crystalline, yellow salts.

The second amido-group in safranine can be removed only with difficulty, and in strongly acid solution. A reddish-violet base was obtained, which yields brownish-yellow salts. It shows the same reactions as the acetyl-derivatives of safranine.

The two constitutional formulæ for safranine lately proposed by Bernthsen (this vol., p. 139) are shown by the author to be incorrect. With the one, the existence of the two isomeric diethylsafranines obtained by the author (loc. cit.) cannot be accounted for; the other formula permits the existence of the two isomerides, but only one of

the latter could be diazotised. It has been shown that both the diethylsafranines very readily yield diazo-compounds. N. H. M.

Constitution of the Safranines. By O. N. WITT (Ber., 19, 3121-3124).-The author criticises the constitution assigned to the phenosafranines by Andresen (Abstr., 1885, 1026) and by Bernthsen (this vol., p. 139), and suggests the following:

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Constitution of Safranine. By R. NIETZKI (Ber., 19, 3163– 3166).—The author supports the correctness of the formulæ suggested by Witt (see preceding Abstract). O. Lehmann has examined crystallographically the nitrates of the two dimethylsafranines previously described by the author, and the non-identity of which has been lately called in question by Bernthsen (this vol., p. 139). Lehmann declares the two compounds to be undoubtedly different.

The author has carried out the idea mentioned in his last paper on this subject, and tested the safranine-forming power of the six isomeric xylidines, CH,Me2 NH2, and of the three isomeric compounds (CH,Me, NH2) cumidine, mesidine, and isocumidine when heated with paradiamidodiphenylamine. The results-taking NH2 as always occupying the position 1-may be expressed as follows:The xylidines 1:3:4 and 1:24 gave safranine; 1:2:5, 1:26, and 1:3:5 gave no safranine; and 1:2:3 gave only traces, which were probably due to traces of the 1: 3: 4 compound present as impurity in the xylidine used. Ordinary cumidine, [12:45], gave a safranine, whilst mesidine, [1: 2: 4: 6], and isocumidine, [1: 3: 4 : 5], gave none. It is therefore clear that the position of the methyl-groups in the monamine plays a determining part in the formation or non-formation of safranines.

The author considers that Witt's formula is much more in harmony with the above and other facts known about safranine than is either Andresen's or Bernthsen's formula. L. T. T.

Paranitroformanilide. By T. B. OSBORN and W. G. MIXTER (Amer. Chem. J., 8, 346-347). This substance, NO, CH, NH·COH, was prepared by adding formanilide to fuming nitric acid, sp. gr. 1·53, in a freezing mixture, and pouring the product into cold water; it was washed with water and ether, then crystallised from alcohol. It

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melts at 187° or 194°, according as it has been crystallised from alcohol
or from hot water. When boiled with caustic potash, it yields para-
nitraniline. Attempts to obtain azo-compounds by its reduction were
H. B.

Orthazoparabromacetanilide. By C. H. MATTHIESSEN and W. G. MIXTER (Amer. Chem. J., 8, 347-349).-Parabromacetanilide was converted into orthonitroparabromacetanilide and then treated in warm alcoholic solution with zinc and strong aqueous ammonia for half an hour. The red precipitate was washed with water, dilute acid, and alcohol. During the reduction, a portion of the bromine is displaced with formation of azoacetanilide, which is only removed by heating with concentrated hydrochloric acid at 100°. The product thus purified is orthazoparabromacetanilide, N2(CH3Br•NHAc)2. It is a pale red substance melting at 280-282°, and is acted on by potash with great difficulty. H. B. Halogen-derivatives of Oxanilide. By J. O. DYER and W. G. MIXTER (Amer. Chem. J., 8, 349-357).-Tetrachloroxanilide,

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is obtained by passing chlorine into an acetic acid solution of oxanilide. It separates in slender, white fibres melting at about 255°, and is difficult to obtain quite pure. On decomposition, it yields metadichloraniline, melting at 63°.

Paradibromoxanilide, C2O,(NH.C,H,Br)2, is obtained by adding bromine in excess to a boiling acetic acid solution of oxanilide. It melts above 300°. Treated with alcoholic potash, it yields parabromaniline.

Paradiiodoxanilide is prepared by the action of iodine and strong nitric acid; crystallised from aniline it is quite white. It decomposes before melting. Treated with potash it yields paraiodaniline.

Boiling alcoholic potash converts oxanilide into oxanilic acid, and then into oxalic acid and aniline. The substituted oxanilides behave similarly, Metadichloroxanilic acid, CH3Cl2 NH CO-COOH, is formed along with metadichloraniline by the hydrolysis of the tetrachloroxanilide. It dissolves in 808 parts of water at 25° and melts at 122°; the potassium salt crystallises from hot water in fine fibres.

Parabromoxanilic acid, C,H,Br·NH·CO·COOH, is readily soluble in hot water, and in 515 parts of water at 25°; it melts at 198°. The potassium salt is anhydrous, and forms tabular, monoclinic crystals; the calcium, barium, and silver salts are also anhydrous, and sparingly soluble in water. Paraiodoxanilic acid, CHI·ÑH·CO.COOH, melts with decomposition at 197-200°, and dissolves in 1385 parts of water at 25°; the potassium salt is anhydrous. H. B.

Action of Concentrated Sulphuric Acid on Aromatic Ketones. By A. CLAUS (Ber., 19, 2879-2881).-In this paper, preliminary experiments are described on the decomposition of aromatic ketones by fuming sulphuric acid. The reaction consists in the decomposition of the ketone and formation of a carboxylic acid and a sulphonic acid: thus mesityl phenyl ketone yields mesitylsulphonic and benzoic acids. It is proposed to carry on a series of investiga

tions to determine in the case of mixed ketones containing a simple and a replaced phenyl-group, whether in all cases the former remains combined with the carbonyl grouping and the latter yields the sulphonic acid, as also to investigate the changes produced in the case of a ketone containing the substituted phenyl groupings of differing degrees of complexity. At a low temperature, a sulphonic acid of the ketone is formed; thus barium salts of mesitylphenylketonemonosulphonic and para-xylylphenylketonedisulphonic acids are described. V. H. V.

Aromatic Ketones. By O. PAMPEL and G. SCHMIDT (Ber., 19, 2896-2899).-Phenyl ethyl ketone (propiophenone), COEtPh, is conveniently prepared by Friedel and Crafts' aluminium chloride reaction. Its acetoxime- and phenylhydrazine-compounds are colourless oils; with bromine, it yields a monobromo-derivative as a dark oil, which gives an anilide, COPh C2H, NHPh, separating in yellow, glistening crystals melting at 38°; its acetyl-derivative crystallises in colourless needles melting at 103°.

Naphthyl methyl ketone, CHCOMe, prepared by aid of the aluminium chloride reaction, is a pale-yellow oil boiling at 296-299°. Its acetoxime- and phenylhydrazine-derivatives are crystalline compounds melting at 101° and 146° respectively. Its anilide,


separates in golden-red crystals melting at 130°; its thiocyanate crystallises in micaceous crystals. V. H. V.

Benzene-derivatives of High Molecular Weight. By F. KRAFFT (Ber., 19, 2982-2988).-Pentadecyl phenyl ketone, C15H31 COPh, is obtained by gradually adding aluminium chloride (14 parts) to a cooled solution of palmitic chloride (1 part) in benzene (2 parts) and afterwards gently warming; the product is poured into water, excess of benzene removed by distillation, and by fractional distillation under 15 mm. pressure the ketone is approximately separated from the regenerated palmitic acid, the last traces of which are removed from an alcoholic solution of the distillate by precipitation as barium palmitate. The ketone crystallises in large, glistening laminæ, melts at 59°, boils at 250-5-251° under 15 mm. pressure, and is very sparingly soluble in cold alcohol, soluble in ether and hot alcohol. On oxidation with chromic acid, it yields benzoic and pentadecylic acids.

Hexadecylbenzene, CH,Ph, is prepared by the action of sodium on a mixture of cetyl iodide and iodobenzene. It crystallises in glistening tables, which subsequently become opaque, melts at 27°, and boils at 230° under 15 mm. pressure. When dissolved in fuming sulphuric acid, hexadecylbenzene yields a monosulphonic acid, and by fusing its sparingly soluble sodium salt with potassium hydroxide at 250°, hexadecylphenol, CH3CH, OH, is obtained. This is a colourless, odourless and tasteless compound, melting at 77.5°, and boiling at 260-261° under 16 mm. pressure. Hexadecylnitrobenzene is a crystalline powder, melts at 35-36°, and when reduced yields hexadecylamidobenzene, which melts at 53°, and distils without decomposition at 254-255° under 14 mm. pressure;


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