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is converted by hydrogen sulphide into paratoluenesulphonic acid (in small amount), tolyl hydrogen sulphide, toluenesulphinic acid, ethyl hydrogen sulphide, sulphur, and a thick oil, probably consisting of toluene polysulphides. No ethyl tolyl sulphide is formed in the reaction. N. H. M.

Manufacture of a-Naphthylamine. By O. N. WITT (Ding. polyt. J., 265, 225-230).—An important feature in the success attending the manufacture of naphthylamine is the purity of the naphthalene employed. The nitration is effected in cast-iron cylinders fitted with stirrers and cooling jacket. The charge consists of 250 kilos. of naphthalene, 200 kilos. of nitric acid of 40° Baumé, 200 kilos. of sulphuric acid of 66° Baumé, and 600 kilos. of the waste acid from a previous nitration, the latter being used as diluent. The nitration is performed at 45-50°, the temperature being regulated by the rate at which the naphthalene is added and the flow of cold water through the cooling jacket. The reaction is completed in about 12 hours. The contents of the apparatus are then transferred to wooden vats lined with lead and allowed to cool. The waste acid is run off and the nitronaphthalene boiled out with water until free from acid. It is then reduced in apparatus similar in construction to those employed in the manufacture of aniline. For this purpose, 600 kilos. of airdried nitronaphthalene are added gradually to a mixture of 800 kilos. of iron borings and 40 kilos. of hydrochloric acid, the temperature being regulated by the introduction of the nitro-product, so that it is about 50. When all the nitronaphthalene has been put in, the operation is continued for 6-8 hours, the temperature being kept at 50°. At the end of the reduction, milk of lime is stirred into the mass, and the contents are transferred to shallow iron trays and distilled in retorts constructed to carry several tiers of trays. The distillation is assisted by the introduction of superheated steam. A black oil is obtained which solidifies on cooling. The crude product is purified by rectification in wrought-iron stills which are heated directly by the fire. Naphthylamine comes over as an almost colourless oil, which is poured into moulds to solidify, when it forms crystalline cakes which are light grey or nearly white.

The author is of opinion that the reduction of nitronaphthalene is effected essentially by ferrous chloride, which during the reaction is converted into a basic chloride, possibly Fe,CLO, according to the following equation:-24FeCl + 4C10H, NO2+ 4H,O= 12Fe,CIO + 4C10H, NH. The basic compound is then attacked by the excess of iron, and reduced to ferrous chloride with formation of ferrosoferric oxide, thus: 12Fe,CLO + 9Fe 3Fe,0, + 24FeCl2. The ferrous chloride then acts on a further portion of nitronaphthalene.

As commercial naphthylamine is frequently supposed to contain small quantities of the beta-compound, the author has made a series of experiments, the results of which showed that no trace of ẞ-naphthylamine is formed. The author has, however, detected the presence of a base in crude naphthylamine, which judging from its properties seems to be paranaphthylenediamine.

D. B.

Action of Bromine on Anthranol. By F. GOLDMANN (Ber., 20, 2436—2437).—When two molecular proportions of bromine are added to one proportion of anthranol dissolved in carbon bisulphide, anthraquinone dibromide, CHCBC.H., separates in large, rhombic crystals, decomposed by acetic acid with formation of anthraquinone. If, however, one proportion of bromine is used, bromanthranol, CH(OH)>C.H., is produced, which crystallises in small, transparent tables melting at 148-151°, soluble in carbon bisulphide and chloroform. V. H. V.


By W.

Erythrolhydroxyanthraquinonecarboxylic Acid. BIRUKOFF (Ber., 20, 2438-2439).-Methylerythrohydroxyanthraquinone, when heated with concentrated sulphuric acid, yields a carboxylic acid by oxidation of the methyl-group, with evolution of sulphurous anhydride. The acid, CH,Os, crystallises in citron-yellow needles melting at 236-238° with decomposition; it is readily soluble in water and ammonia, thus differing from the methyl compound; its barium and calcium salts are sparingly soluble. When heated above 270, it is decomposed into carbonic anhydride and erythrohydroxyanthraquinone. V. H. V.

Derivatives of Dianthryl. By A. GIMBEL (Ber., 20, 2433–2435). Dinitrodianthryl, C8H8(NO2)2, obtained by the direct nitration of dianthryl, crystallises in pale-yellow needles melting at 337° with decomposition. When oxidised with chromic acid, it yields anthraquinone, a result which proves that the nitro-groups displace the hydrogen-atoms combined with the central carbon-atoms. On reduction, the nitro-compound is converted into the corresponding amidoderivative, C2s H16(NH4)2, which crystallises in glistening, yellow leaflets melting at 307-309° with decomposition. Its acetyl-derivative, C29H16(NHAC)2, crystallises in yellow leaflets, sparingly soluble in alcohol and benzene; the picrate forms brown leaflets decomposed completely by ammonia into acid and base. V. H. V.

Azines of Chrysoquinone. By C. LIEBERMANN and O. N. WITT (Ber., 20, 2442-2444).—As an extension of the applicability of the azine-reaction of the diketones, the formation and properties of the azine-derivatives of chrysoquinone are described.

Chrysotoluazine, C25H16N2, prepared from chrysoquinone and orthotoluenediamine, crystallises in yellow, glistening needles; the corresponding naphthyl-derivative, C28H16N2, is a yellow, minutely crystalline powder. The formation of these compounds confirms the analogy of chrysoquinone with phenanthraquinone. Picequinone did not yield satisfactory results, but only a large quantity of a tarry matter; in this respect it resembles B-naphthaquinone. V. H. V.

Derivatives of Camphor. By L. BALBIANO (Gazzetta, 17, 155-164). As V. Meyer has recently raised the question as to whether the phenylhydrazine reaction can be considered to be charac

teristic of ketonic and aldehydic compounds only, the constitution and reactions of camphyldiphenylhydrazine are here discussed. This compound, when decomposed by hydrochloric acid, yields aniline and ammonia in considerable quantities, together with phenylhydrazine and a rather indefinite resinous substance; the latter is considered to be a nitrile as, when boiled with alkali, it yields ammonia and acid compounds, and gives a basic substance, C6H2N3, on hydrogenation. This base forms a hydrochloride melting at 155-157°, and crystallising in delicate needles, very soluble in water. Its solution reduces the salts of the heavy metals and Fehling's solution. The compound is probably a camphylamine in which one of the bydrogen-atoms is displaced by the phenylhydrazine residue. V. H. V.

Racemic Camphol and its Derivatives. By A. HALLER (Compt. rend., 105, 66-68).-The author has prepared and examined camphol, camphor, monobromocamphor, and camphoric acid, inactive by compensation. The last three compounds were obtained in two ways, namely, by mixing dextrogyrate and lævogyrate compounds in equivalent proportions, and by oxidising racemic camphol to camphor, part of which was then used for the preparation of a monobromocamphor, and part for the preparation of camphoric acid. The product of bromination in the latter case is a buttery mass very difficult to purify. No variations in the mode of preparation gave a better product. Similar difficulties have been experienced with other racemic compounds. The melting points of the products are as follows::

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The melting points of the corresponding optically active compounds are camphol, 208-210°; camphor, 177-178°; monobromcamphor, 76°; camphoric acid, 187°.

The racemic compounds obtained by the two methods are identical, but there is considerable difference between the melting points of the racemic compounds and the corresponding active substances. Their solubilities are likewise different; racemic monobromocamphor is more soluble in alcohol than the active derivative, whilst racemic camphoric acid is less soluble than the active modifications. C. H. B.

Inactive Borneols yielding Active Camphors. By A. HALLER (Compt. rend., 105, 227-230).-The author confirms Montgolfier's earlier results.

Montgolfier has shown that when camphol is heated with sodium, the rotatory power increases. It seemed probable that the camphol obtained by the action of the sodium on camphor is a mixture of equivalent quantities of the dextrogyrate and lævogyrate modifications, but that the sodium acts on the unstable modification, and converts it into the more stable form. This supposition is confirmed by the

following results. 100 grams of camphor was dissolved in 250 grams of toluene, and mixed with 5 grams of sodium (one-third the theoretical quantity). The mixture was heated, and when the action began the lamp was removed. The liquid was then saturated with carbonic anhydride, agitated with water, and the aqueous solution. removed and allowed to remain for several days, when the borneol separates out and can be purified by the usual methods. This experiment was repeated with both dextrogyrate and lævogyrate camphors, and the melting points and rotatory powers of the products were as follows:

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It is evident that when camphor is converted into borneol and back, its rotatory power does not alter. It would seem that by whatever process camphor is hydrogenised, the product is never a single substance, but always an unstable mixture. C. H. B.

Alkannin. By C. LIEBERMANN and M. RÖMER (Ber., 20, 24282431). Although alkannin, the colouring matter of the alkanna root, was described more than 70 years ago, and has frequently been investigated, yet at present little is known as regards its constitution. Carnelutti and Nasini (Abstr., 1881, 53) ascribe to it a formula CHO, and state that of the hydrogen-atoms two may be displaced. by acetyl. As the tinctorial properties of alkannin resemble those of quinalizarin, and their absorption spectra are similar, the authors prepared considerable quantities of the dye; the process used is fully described. The results of analysis pointed to a formula either identical with that of Carnelutti and Nasini or to C16H12O4. When alkannin is passed over hot zinc-dust, methylanthracene is formed. (m. p. 175-177°), a result which points to the constitution of alkannin as a derivative of methylanthracene, probably the dihydroquinone or its dihydride. V. H. V.

Ruberythric Acid. By C. LIEBERMANN and O. BERGAMI (Ber., 20, 2241-2247).-Ruberythric acid, CarH2O14, is obtained by extracting powdered madder root with absolute alcohol (9 litres of alcohol to 1 kilo. of root). The yield was 0.1 per cent. of the weight of root. It is identical with Schunck's rubianic acid, and has all the properties ascribed to it by Rochleder. It forms lemon-coloured needles of a silky lustre, which melt at 258-260°. The octacetyl-derivative, CH20AcsO6, crystallises in bright yellow needles melting at 230°; it

dissolves readily in glacial acetic acid, sparingly in alcohol, and is insoluble in water. The acetyl compound was decomposed, and the alizarin, sugar, and acetic acid determined. The following two constitutional formulæ are suggested for ruberythric acid, preference being given to the second :

C1H[O.C2H2O(OH).], and OH·C11H2O2·Õ·С12H14O3(OH),.


The authors intend preparing the ethyl salt of the acid, which, assuming the correctness of the second formula, should decompose into the acid ether of alizarin and sugar. N. H. M.

Action of Acetone on Pyrroline. By M. DENNSTEDT and J. ZIMMERMANN (Ber., 20, 2449-2459).-One of the products of the condensation of acetone with pyrroline by hydrochloric acid (compare this vol., p. 598) is a crystalline substance, to which the authors attribute the formula C1H1N2, as obtained thus:-2C,H ̧O + 2C,H ̧N = C1H1N2 + 2H2O. To this same compound, Baeyer assigned the formula C1H26O2, and considered that hydrogen was evolved in the course of the reaction, a view not confirmed by investigations described in this paper. The substance crystallises either in pale-yellow or colourless crystals belonging to the tetragonal system: axial ratio a: c = 1 : 0·8343; observed faces, coP, P, 2P, 5P. As regards its constitution, it is pointed out that the imide-group of pyrroline is attacked in the reaction, inasmuch as no acetyl- or potassium-derivative is obtainable; with silver nitrate, it gives a compound which crystallises in needles, and is not a substitution but an additive product, (C14H18N2)2, AgNO,.

16 22

In like manner, methyl ethyl ketone yields a compound 3CH2N2 + 5H2O, which forms glistening crystals melting at 142° when anhydrous; so also diethyl ketone yields a compound, C1, H26N2, melting at 208-210°. Both substances form crystalline combinations with silver nitrate.

On fractionation of the crude product of the condensation of acetone with pyrroline, an oil is obtained boiling at 275-285°, and of the composition CH3N; this is shown to be a derivative of pyrroline in that it gives the pinewood reaction, and a yellow precipitate with mercuric chloride. Potassium also dissolves in it with evolution of hydrogen. To it is ascribed the following constitutional formula: C C

CMe; probably several molecules of the reacting

substances take part in its formation.

V. H. V.

Formation of Pyrrolidine. By A. LADENBURG (Ber., 20, 2215— 2216).—A solution of succinimide in absolute alcohol is warmed on a water-bath and gradually treated with a large excess of sodium. The product is diluted with water and distilled so long as the distillate is alkaline; the latter is made slightly acid, distilled until free from alcohol, and evaporated to a small bulk. The solution is precipitated with bismuth potassium iodide, and the precipitate washed and distilled with soda; the free base thus obtained is then converted into

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