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portions is treated with sodium, hydrogen and carbonic oxide are evolved and ethyl trimesate is obtained. The yield amounts to 6 to 7 per cent. on the ethyl formate used; at the same time ethyl acetoacetate is also formed in some quantity. When mixtures in equimolecular proportions of methyl formate and ethyl acetate, and of ethyl formate and methyl acetate are respectively treated with sodium, a mixture of ethyl and methyl trimesate is obtained in both cases; this melts at 105-110° after one crystallisation from alcohol.

Methyl trimesate crystallises in small, silky needles melting at 143°, and a mixture of it and ethyl trimesate in equal proportions melts at 105-110°. W. P. W.

Rosindole. By E. FISCHER and P. WAGNER (Ber., 20, 815-818). -Methylketole when heated with benzoic chloride in presence of zinc chloride yields, in addition to a benzoyl-derivative, the hydrochloride of a base, C25H20N2. This salt, which may be completely separated from its aqueous solution by the addition of sodium chloride, forms green iridescent crystals, resembling in appearance rosaniline hydrochloride; on adding an alkali, the free base is obtained in reddish-yellow, prismatic crystals, which change colour at 250° and fuse completely at 270°. With acids, it forms salts which are soluble in water and alcohol, and dye silks and wools of a red colour; it appears also to form unstable salts with alkalis, readily decomposed by water. When the alcoholic solution of the base is treated with zinc-dust and ammonia, it is decolorised with formation of benzylidenemethylketole, a change analogous to the formation of leucaniline from rosaniline. From the similarity in colour, dyeing properties, and chemical reactions of the above base with those of rosaniline, it is proposed to call it dimethylrosindole; it is probably the anhydride of a carbinol, CPh(C,H,N)2'OH.

Benzoylmethylketole crystallises in glistening leaflets, melting at 82°, and is moderately soluble in ether and alcohol, sparingly soluble in water. V. H. V.

Methylation of Indole-derivatives. By E. FISCHER and A. STECHE (Ber., 20, 818--820).-When methylketole is heated with methyl alcohol and iodide, it yields the hydriodide of a basic compound, CHEN, crystallising in prisms, and from which the base itself is obtained as a colourless oil boiling at 243°. This compound is not an indole-derivative in that it gives neither the pine-wood reaction nor the red picrate; also it is unaltered by nitrous acid, and differs from the indoles by its strongly basic character. It is probably a dimethyldihydroquinoline, containing a methyl-group attached to the nitrogen, and another in the quinoline residue; but of this view no proof is given. Of its salts, the sulphate crystallises in leaflets soluble in alcohol, and the picrate in golden-yellow leaflets; the hydrochloride forms a compound with ferric chloride.

In like manner, dimethylindole yields a base, C12H15N, boiling at 244°, and dimethyl-6-naphthindole yields a compound, CH15N, probably a methyldihydronaphthaquinoline, which crystallises in colourless leaflets, melts at 115°, and is readily soluble in mineral acids forming crystalline salts.

V. H. V.

Derivatives of Diphenyl. By P. ADAM (Compt. rend., 104, 691-693).-Diphenyl-diphenyl ketone, CO(CH,Ph), is obtained in almost theoretical quantity, when a mixture of diphenyl, 15 parts, carbon bisulphide, 20 parts, and carbonyl chloride, 10 parts. is added to 15 parts of aluminium chloride. There is an immediate evolution of hydrogen chloride, and towards the end of the reaction the flask is placed in tepid water. The carbon bisulphide is distilled off, and the residue washed with dilute alkali, then with pure water, dried, and recrystallised from boiling benzene or acetone. Diphenyldiphenyl ketone forms white needles which melt at 229°, and are somewhat soluble in acetone, benzene, and chloroform, but almost insoluble in benzene and light petroleum. It is reduced with great difficulty. When dissolved in a mixture of alcohol and benzene, and treated with a large quantity of sodium amalgam, it yields diphenylbenzhydrol, CH(CH,Ph), OH, which crystallises readily, melts at 151°, and is very soluble in alcohol.

The action of carbonyl chloride on diphenyl in presence of aluminium chloride, with the aid of heat, but without carbon bisulphide, also produces the ketone, but the yield is smaller. The use of carbon bisulphide has advantages in the case of acid chlorides, but not with haloïd derivatives of hydrocarbons.

Acetic chloride acts readily on diphenyl in presence of aluminium chloride, whether carbon bisulphide is present or not. The product is diphenyl methyl ketone, or diphenylacetyl, CH, Ph.COMe; this forms white, flexible, nacreous crystals, readily soluble in alcohol or acetone; it melts at 121°, and boils at 325-327°.


C. H. B.


Condensation of Diphenic and Orthodiphenylcarboxylic Acids. By C. GRAEBE and C. AUBIN (Ber., 20, 845—848).—Anschütz has shown that diphenic acid yields an anhydride with acetic chloride or acetic anhydride, but Mensching and Graebe, by the action of concentrated sulphuric acid, obtained a substance of the same position, but of higher (7°) melting point. In this paper, these experiments are repeated; in the latter case, diphenyleneketonecarboxylic acid, CHCH, COOH, is produced, which crystallises in needles melting at 227°; its salts are also crystalline; the ethyl salt crystallises in needles melting at 103°, and the methyl salt at 132°. The acid combines with hydroxylamine to form a colourless acetoxime, and with phenylhydrazine it yields a condensation product. The potassium salt is reconverted into the salt of diphenic acid by fusion with alkali. On vaporisation, the acid is decomposed into carbonic anhydride and diphenylene ketone. In like manner, orthodiphenylcarboxylic acid is converted into diphenylene ketone by heating with concentrated sulphuric acid. The diphenic anhydride, isomeric with the above acid, crystallises in pyramidal needles melting at 217°, and sparingly soluble in alcohol and ether. When boiled with solutions of alkalis, it is converted into the potassium salt of diphenic acid.

V. H. V.

Formula of Diphenic Acid. By C. GRAEBE (Ber., 20, 848-850). -In this paper, the question is discussed whether the diphenic acid

COOH.C.HC.H1.COOH [COOH : COOH = 1:1'] is isomeric or identical with the acid, [COOH: COOH = 1:6′]. If the two benzene nuclei were in the same plane, these two acids would be identical; but if they were situated in different planes, it is possible that the acids might be isomeric. At present, the evidence is insufficient to decide the question. V. H. V.

Preparation of B-Nitronaphthalene. By E. LELLMANN (Ber., 20, 891-893).—The following method has been found to be the most practicable for the preparation of B-nitronaphthalene; the mixture of the ortho- and para-nitroacetonaphthalide is boiled with a 14 per cent. potash solution in presence of alcohol, and the mixture of the orthoaceto-compound and para-nitronaphthalene is treated with ethyl nitrite, when the diazo-amido-derivative of para-nitronaphthylamine separates as a brown precipitate. This is filtered off, and the orthonitroacetonaphthalide crystallises out, and, after purification, is best decomposed by an alcoholic solution of hydrogen chloride. The orthonitronaphthylamine thus obtained serves for the preparation of the nitronaphthalene. V. H. V.


B-a-Azonaphthalene. By R. NIETZKI and J. GÖTTIG (Ber., 20, 612-613).-B-a-Amidoazonaphthalene, CH, N2 CH, NH2, is prepared by diazotising B-naphthylamine (1 mol.), adding a-naphthylamine hydrochloride (1 mol.), and subsequently precipitating the base with soda; it crystallises in yellowish-brown needles, melts at 152°, and is soluble in alcohol. Its solution in concentrated sulphuric acid has a violet coloration.

B-a-Azonaphthalene, CH, N2 C1,H,, is obtained by adding 3 parts of sulphuric acid to a solution of 1 part of B-a-amidoazonaphthalene dissolved in 50 parts of alcohol, diazotising, boiling the whole for some time, and afterwards precipitating with water. It crystallises in darkbrown scales with steel-blue iridescence, melts at 136°, and is more soluble in alcohol, acetic acid, &c., than the corresponding a-a-derivative (Abstr., 1886, 245). It dissolves in sulphuric acid yielding a violet solution. W. P. W.


New Method of Preparing Azines. By O. N. WITT (Ber., 20, 571-577).—When diazobenzenesulphonic acid (1 mol.) is gradually added to phenyl-ß-naphthylamine (1 mol.) dissolved in acetic acid at 50°, and the mixture afterwards treated with potassium carbonate, iridescent, blood-red needles of sulphobenzeneazophenyl-B-naphthylamine, NHPh CoH N2·C,H ̧·SO2H [N2 NHPh= 1:2], are obtained. These dissolve readily in water, and the solution, even when dilute, solidifies in the cold to a transparent, red jelly. Concentrated sulphuric acid produces a cherry-red colour; whilst stannous chloride in acid solution decolorises the compound with formation of phenylorthonaphthylenediamine. Sulphobenzeneazophenyl-B-naphthylamine is the lowest member of a series of beautiful, ponceau-red dyes, which have great tinctorial power, but are extremely sensitive to light; sunlight rapidly producing the same change that is brought about when the dyes are boiled with dilute mineral acids.


Naphthaphenazine, [1 : 2] C.H.C,H. [1:2].—Sulphobenzeneazophenyl-ẞ-naphthylamine, when boiled with dilute sulphuric acid, decomposes quantitatively into sulphuric acid and naphthaphenazine. This crystallises in lustrous, citron-yellow needles or prisms, melts at 142.5°, sublimes at about 200° in long, flat needles, and boils above 360° with slight decomposition. It is readily soluble in hot benzene, very sparingly in alcohol and ether, and dissolves in concentrated sulphuric acid with a brownish-red colour. With mineral acids, naphthaphenazine forms crystalline salts which are decomposed by water, and show a peculiar dimorphism. The two sulphates are respectively obtained in cinnabar-red tufts of needles or garnet-red, compact, twinned prisms; the nitrates are very sparingly soluble, one forms orange-yellow and the other brick-red aggregates of needles; the hydrochloride obtained by dissolving the azine in hydrochloric acid forms long, reddish-yellow needles, and when heated at 150° is converted into the second form, which crystallises in needles; the two forms of each salt are convertible into one another. Stannous chloride reduces the azine to the corresponding hydro-compound, crystallising in violet needles. Naphthaphenazine can also be obtained by the action of B-naphthaquinone (1 mol.) on orthophenylenediamine (1 mol.) in 50 per cent. acetic acid at 0°, and by oxidising a mixture of orthophenylenediamine and B-naphthol in equimolecular proportions with potassium ferricyanide in alkaline solution.

W. P. W.

Constitution of the Isomeric Tolunaphthazines. By O. N. WITT (Ber., 20, 577-581).-Inasmuch as naphthaphenazine (comp. preceding Abstract) is a 1: 2-derivative of naphthalene, the tolunaphthazine (m. p. = 179.8°) obtained by the simultaneous oxidation of B-naphthcl and orthotoluylenediamine (Trans., 1886, 404), must have a similar constitution. Hinsberg's tolunaphthazine (m. p. = 139— 142°), from its method of preparation (Abstr., 1885, 909), must also be a 1 : 2-cerivative of naphthalene, and to assign to each its constitutional formula (in other words to determine the position of the methyl-group in the benzene nucleus) sulphobenzeneazoparatolyl-ßnaphthylamine was prepared from paratolyl-ß-naphthylamine and diazobenzenesulphonic acid, and afterwards decomposed by boiling with dilute sulphuric acid (comp. preceding Abstract). The tolunaphthazine so obtained, however, crystallises from benzene in needles and prisms, and from alcohol, in which it is very sparingly soluble, in lustrous, citron-yellow scales; it melts at 169°, and forms well-crystallised salts. The solution in sulphuric acid is dark cherry-red in colour, and the sulphate crystallises in long, orange-yellow, lustrous needles. The same tolunaphthazine can be prepared from woolblack," a dye obtained by the action of diazobenzenedisulphonic acid on paratolyl-p-naphthylamine, by boiling it with dilute sulphuric acid. The author finds that when equal weights of the tolunaphthazines melting at 19° and 179.8° respectively, are mixed and crystallised from alcohol, compound melting at 139-142°, and undistinguishable


from Hinsberg's modification, is obtained. The following are the con stitutional formulæ assigned to the isomeric tolunaphthazines :

[blocks in formation]

Paratolyl-B-naphthylamine, obtained by heating paratoluidine hydrochloride with B-naphthol for eight hours at 200°, crystallises in snowwhite scales, melts at 104°, and is soluble in alcohol, benzene, ether and acetic acid, the solutions showing a beautiful violet-blue florW. P. W.


Acenaphthene. By C. GRAEBE (Ber., 20, 657-659).-In oxidising acenaphthene to naphthalic acid, a compound of the formula C2H1O2 is formed. The latter sublimes when heated (at 269°) in red needles which melt at 260°. It is sparingly soluble.

When acenaphthene, dissolved in glacial acetic acid, is oxidised with chromic acid, a compound is obtained which crystallises in reddish-yellow needles melting at 230°. Analyses of the compound after prolonged treatment with sodium carbonate solution, point to the


formula CoH Co ; when oxidised, it is converted into naphthalic


N. H. M.

Derivatives of Acenaphthene. By F. QUINCKE (Ber., 20, 609 -611).-Nitracenaphthene, C12H, NO2, is obtained when fuming nitric acid is added to a solution of acenaphthene in acetic acid. It crystallises in yellow, matted needles, melts at 102°, and is soluble in alcohol, ether, light petroleum, acetic acid, and hot water. When it is reduced with tin and hydrochloric acid amidoacenaphthene, C12H, NH2, is formed. This is a white, asbestos-like compound, melts at 96°, is volatile with steam, and yields a crystalline hydrochloride.

V. P. W.

Dimethylanthragallol. By W. BIRUKOFF (Ber., 20, 870873).-Dimethylanthragallol, CH,Mе2O.(OH2) [Me2 : (OH), = 1:3: 1'2': 3′], is obtained, in like manner to the trimethyl-derivative, by heating metaxylic and gallic acids with concentrated sulphuric acid; it crystallises in golden-red needles; it resembles aithragallol as regards its solubility in alkalis and its absorption-spectrun. On distillation over zinc-dust, it yields a dimethylanthracene, melting at about 220°, and yielding on oxidation a quinone crystallsing in white needles melting at 112°. These compounds are isomeric, therefore, with those which Gresly obtained melting at 202° and 180° respectively. V. H. V.

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