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1:2:3], together with a quinone-derivative. The acid crystallises in long, colourless needles, which melt at 184°, and are at the same time converted into the anhydride. When heated with phenol and concentrated sulphuric acid, it yields a phthaleïn, dissolving in potash with violet coloration. The silver salt is a crystalline precipitate; the anhydride sublimes in colourless needles. This acid is not identical with the monochlorophthalic acids previously described.

The dibromonaphthalene, melting at 130°, yields on oxidation with chromic acid, under conditions similar to those used with the chloroderivative, a monobromophthalic acid, identical with that obtained by the author in the oxidation of monobromonaphthalene.

V. H. V.

Action of Bromine on Diamido-a-naphthol. By T. ZINCKE and C. GERLAND (Ber., 20, 1510-1516).-Bromamido-a-naphthaquinoneimide, NH¿C„H,Br<>, is formed when the zincochloride of diamidonaphthol (10 grams) is finely rubbed with glacial acetic acid and 5 to 6 c.c. of bromine added. It is washed with glacial acetic acid, stirred with strong ammonia, filtered and crystallised from alcohol. It forms orange-yellow needles which melt at 200-5°, and dissolves readily in hot alcohol and hot benzene; it is insoluble in water. The platinochloride, (CH,BrN2O)2,H,PtCls, crystallises in brown needles.

Bromamido-a-naphthaquinone, NH, CH,BrO2, is obtained by boiling the above imide with much water with repeated additions of sulphuric acid. It crystallises in intensely orange-coloured needles of a silky lustre, which melt at 205° and sublime without decomposition. When boiled with alkali it is converted into bromohydroxyquinone. The acetyl compound crystallises in sulphur-coloured plates melting at 136-137°.

Bromohydroxy-a-naphthaquinoneoximide, OH·CH,Br<NH


best prepared by boiling bromamido-z-naphthaquinoneimide with dilute aqueous soda, and adding alcohol from time to time. It is then allowed to settle, and the residue again boiled with soda. It forms deep, brownish-red, slender, lustrous needles, and melts at about 265°; it is sparingly soluble. It does not decompose carbonates. The sodium salt crystallises in red needles. The acetyl-compound forms hair-like, red needles melting at 270°. The oximide is identical with that formed by the action of ammonia on bromo-3-naphthaquinone.

Bromohydroxy-a-naphthaquinone (Diehl and Merz, Ber., 11, 1066) is formed when bromamidonaphthaquinone is boiled with dilute alkali, when bromohydroxynaphthaquinoneoximide is boiled with strong hydrochloric acid, and when bromo-ß-naphthaquinone is treated with alkali. N. H. M.

Derivatives of ß-Naphthylamine. By L. MASCHKE (Chem. Centr., 1886, 824).-B-Naphthylamine (6 mols.) when heated with acetic chloride (3 mols.) and phosphorous chloride (1 mol.) at 150° is converted into ethenyl-B-dinaphthylamidine, CoH, NH-CMe: N.CH, melting at 168°. The corresponding benzenyl-derivative, melting at

155°, is prepared in like manner. A mixture of B-naphthylamine (15 grams) and ethylene bromide (3 grams) heated at 150° yields B-ethylenedinaphthylamine, C,H,(CH,NH)2, which melts at 153°.

Dinitro-B-acetnaphthalide, C10H5(NO2), NAc, is obtained in two isomeric forms, melting at 185° and 235° respectively, by the action of fuming nitric acid on B-acetnaphthalide. These compounds resist the action of reducing agents.


Phthal-ß-naphthylimide, CH,N<CO>CH, melting at 218°, is obtained by heating together B-naphthylamine (1 mol.) and phthalic anhydride (1 mol.).

The a-derivative, melting at 182°, is obtained in like manner.

C. F. C. Substituted Naphthylenediamines. By J. ANNAHEIM (Ber., 20, 1371-1374).—The author has investigated the action of aniline, &c., on dihydroxynaphthalene.

When dihydroxynaphthalene and aniline are mixed together, some aniline hydrochloride or aqueous hydrochloric acid added, and the whole heated at 160°, diphenylnaphthylenediamine, CH(NHPh), is obtained. It forms small, glistening crystals soluble in ether, benzene, boiling alcohol, &c. It melts at 163-164° (uncorr.), easily enters into reaction, and when slightly warmed with zinc chloride gives a violet coloration, which disappears on the addition of water.

Paraditolylnaphthylenediamine, CH(NH-C,H)2, obtained in like. manner from paratoluidine, crystallises in small needles melting at 236-237° (uncorr.). It is almost insoluble in the ordinary solvents, but dissolves in boiling xylene and cumene. It reacts with zinc chloride in the same way as the phenyl-derivative.

L. T. T.

Amidonaphthyl Mercaptans. By A. W. HOFMANN (Ber., 20, 1798–1805).—Benzenylamido-a-naphthyl mercaptan, C1H<N>CPh, is prepared by heating 2 parts of naphthylbenzamide with 1 part of sulphur. The yield is only about 10 per cent. It crystallises in tufts of needles, melts at 100-101°; can be distilled without decomposition at high temperatures, is readily soluble in alcohol and acetic acid, and is practically destitute of basic properties.


Methenylamido-a-naphthyl mercaptan, CH<S>CH, prepared in like manner from a-naphthylformamide, is a colourless oil insoluble in water; it distils with steam. The platinochloride,

crystallises in needles.


When a-naphthylacetamide is heated with sulphur, hydrogen sulphide is evolved, ethenylamido-a-naphthyl mercaptan distils, whilst the residue consists mainly of the oxalyl-compound. The former resembles the methenyl-compound, but does rct distil so readily with steam; its platinochloride, (C12H,NS)2,H2PtCle, is more soluble, and crystallises in needles.


Oxalyldiamido-a-naphthyl mercaptan, CH<>C•c<N>C»H», crystallises in golden-yellow plates, which melt far above 300° with considerable carbonisation; it can be sublimed, but the greater part is always destroyed in the operation. It is scarcely soluble in the ordinary solvents, but can be dissolved in high-boiling petroleum, aniline, or best, nitrobenzene. When fused with potash it yields oxalic acid and amidonaphthyl mercaptan, NH, C10H, SH, but from the extreme readiness with which this is converted into the bisulphide it could only be obtained in an impure condition as a viscid oil. The bisulphide is a golden-yellow powder, insoluble in alcohol and ether. Benzenylamido-a-naphthyl mercaptan crystallises in interlaced needles melting at 107°. Its alcoholic solution shows a green fluorescence. The platinochloride, (C1HNS)2, H2PtCl, and aurochloride were prepared.

Oxalylamido-a-naphthyl mercaptan forms yellow, crystalline plates, and closely resembles the a-compound. Amido-B-naphthyl mercaptan also could only be obtained in admixture with the bisulphide.

A. J. G.

Naphthoic Acids. By Å. G. EKSTRAND (Ber., 20, 1353-1361). -The dinitro-a-naphthoic acid (m. p. 265°), previously described (this vol., p. 373, and Abstr., 1886, 948), when reduced with tin and hydrochloric acid yields, Aguiar's diamido-acid, obtained from the socalled B-dinitronaphthalene, which the author showed (Abstr., 1886, 155) to be the a-a-compound. This naphthoic acid must therefore have the constitution [NO, NO, COOH = 1: 1': 4].


a-Mononaphthoylhydroxamic acid, C1H, CO NH OH, is formed by the reaction of equal molecular proportions of hydroxylamine and a-naphthoic chloride. It crystallises in glistening scales, soluble in boiling water, almost insoluble in alcohol, and melts at 186-187°. It forms a potassium salt, but this decomposes very readily with formation of a-naphthylamine. When treated with B-naphthoic chloride the above acid yields a-a-dinaphthyl-carbamide. Together with the above mono-acid, a-a-dinaphthoylhydroxamic acid, OH·N (CO.C10H)2, is always formed. This crystallises in needles melting at 150°, and soluble in boiling alcohol. Its potassium salt crystallises in needles soluble in alcohol.

B-Mononaphthoylhydroxamic acid, prepared from B-naphthoic chloride, forms small, quadratic scales, easily soluble in alcohol, and melting at 168°. B-B-Dinaphthoylhydroxamic acid yields small needles melting at 171°. The potassium salts of both acids are crystalline. B-B-Dinaphthoylcarbamide crystallises in needles melting at 286°.

a-B-Dinaphthoylhydroxamic acid is obtained by heating the B-monoderivative with a-naphthoic chloride at 100°. It crystallises from boiling alcohol in needles melting at 160°. L. T. T.

Action of Sodium on Alcoholic B-Naphthonitrile. By E. BAMBERGER and O. BOEKMANN (Ber., 20, 1711-1712).-TetrahydroB-naphthobenzylamine, CHCH, NH2, is obtained by gradually adding 10 grams of sodium to a hot solution of 10 grams of B-naphthonitrile

in 100 grams of alcohol. It is a colourless liquid of odour closely resembling that of the a-compound (this vol., p. 719), boils at 270-2° (corr.) under 729 mm. pressure, and does not fluoresce when pure. It is a strong non-acid base, which absorbs carbonic anhydride from the air. The hydrochloride, CH16NCI, crystallises in tufts of needles and melts at 228-5-229°; the platinochloride, (C1HNCI),PtCl, forms small, lustrous, yellow needles; the sulphate crystallises in long, lustrous, thin prisms. The bye-products of the reaction are dihydronaphthalene, identical with that obtained from the a-compound (loc. cit.), ammonia, hydrogen cyanide, ß-naphthoic acid, and frequently B-naphthamide. Of these, the first alone occurs in any considerable quantity. A. J. G.

Trimethylnaphthalene. By L. MASCHKE (Chem. Centr., 1886, 824).-6-Naphthylamine was heated with methyl iodide and methyl alcohol at 100°, and the resulting ammonium iodide heated for some hours at 300-335°. From the resinous product, the hydrocarbon was isolated by distillation with steam. It boils at 275°, and yields a well defined picrate melting at 132-133°. C. F. C.

2:3 Dimethylanthraquinone. By K. ELBS and H. EURIch (Ber., 20, 1361-1363).-2: 3 Dimethylanthraquinone was obtained by heating F. Meyer's orthoxylenephthaloic acid,


(Abstr., 1882, 848). It is best crystallised from xylene, and melts at 183°. It resembles anthraquinone in properties. When heated with nitric acid (sp. gr. 11) at 210-220° it yields 2: 3 anthraqui nonedicarboxylic acid; this crystallises in yellow needles, is sparingly soluble in the usual solvents, and melts at 340°. It dissolves in ammonia to a red solution, which, however, cannot be evaporated without decomposition. Its salts all have a reddish colour. When treated with water it is converted into yellow needles of the anhydride which melt at 290°. The ammoniacal solution is reduced by zincdust to 23 anthracenedicarboxylic acid, which forms a crystalline powder melting at 345°. The quinone yields with ammonia and zinc-dust 2 3 dimethylanthracene melting at 246°. The picrate forms unstable, red needles.


L. T. T.

1:3 Dimethylanthraquinone. By K. ELBS and M. GÜNTHER (Ber., 20, 1364-1367).-This compound has already been briefly described by Elbs (Abstr., 1886, 557). When oxidised with dilute nitric acid it yields 1:3 anthraquinonedicarboxylic acid, which is sparingly soluble in the usual solvents, crystallises in needles, and is still solid at 330°. When reduced with zinc-dust in ammoniacal solution, this acid yields 1 : 3 anthracenedicarboxylic acid. is a crystalline powder, sparingly soluble in the usual solvents, and still solid at 330°. When the quinone is reduced with zinc-dust in ammoniacal solution no dimethylanthracene is formed, but a compound of the composition C16H12 is obtained; this is readily soluble in boiling alcohol, crystallises in scales, and melts at 85°. It


forms a compound with picric acid, crystallising in brownish-rod scales melting at 135°. Chromic acid in acetic solution reconverts it into the quinone. Its constitution is not yet definitely settled.

L. T. T. Derivatives of Camphor. By L. BALBIANO (Gazzetta, 17, 9599). When bromocamphor is heated with phenylhydrazine it yields camphyldiphenyldehydrazine, N2PhH2 C10H N2HPh.

Four monochlorocamphors have been described; it is here shown that one of the physically isomeric chlorocamphors obtained by Cazeneuve by the direct chlorination of camphor, is identical with that obtained by Schiff and Puliti by the decomposition of chlorocamphor-carboxylic acid. This compound, which melts at 92-92·5°, when heated with phenylhydrazine yields a camphyldiphenyldehydrazine, melting at 55-56°, and identical with that obtained from bromocamphor. The other physical isomeride, melting at 100-5°, but softening at 94.5°, yields under similar conditions the same phenylhydrazine-derivative. These experiments further confirm the view that camphor contains the ketonic group. V. H. V.

Isomeric Mononitro-camphors. By P. CAZENEUVE (Compt. rend., 104, 1522-1525).-600 grams of granulated zinc is treated with 1000 c.c. of a 10 per cent. solution of copper sulphate, and when the copper is deposited, the metal is washed and mixed with 1500 grams of alcohol of 93° and 300 grams of the chloronitrocamphors obtained by the action of fuming nitric acid on monochlorcamphor. The mixture is heated to boiling for five minutes, and the alcohol decanted off in order to stop the reaction. When the brown liquid has cooled, it is mixed with zinc-dust, filtered, concentrated to twothirds, mixed with a warm concentrated solution of 120 grams of sodium carbonate, heated with agitation, diluted with 2000 c.c. of water, boiled with animal charcoal, and filtered. The nitrocamphors are precipitated by adding hydrochloric acid, and the precipitate is treated with cold alcohol of 60°, which dissolves the B-nitrocamphor, but leaves the a-derivative undissolved.

The a-nitrocamphor is crystallised from boiling alcohol of 93°, and then from benzene. It forms large, rhombic prisms, insoluble in water but soluble in strong alcohol, and very soluble in benzene. It melts at 100-101°, and decomposes at 160°; it burns quietly on platinum foil, and does not detonate when rapidly heated. Its solution in benzene is lævogyrate, the rotatory power diminishing as the concentration increases. a- -Nitrocamphor reddens litmus and decomposes carbonates, forming well-defined salts. An alcoholic solution of the copper salt is maroon-coloured, of the ferrous salt garnet-red, of the ferric salt blood-red. The quinine salt crystallises readily with alcohol. a-Nitrocamphor forms ethereal salts. It is not affected by concentrated potash or soda, but when heated with water in sealed tubes it yields ammonia and nitric acid. With a mixture of sulphuric acid and fuming nitric acid it seems to form a dinitro-derivative, which is decomposed by water with evolution of nitric oxide and formation of camphoric anhydride.

B-Nitrocamphor crystallises with difficulty in microscopic, arborescent

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