Sulphamineterephthalic acid, CH3(COOH)2 SO2NH2, was extracted by dissolving the purified barium salt in hydrochloric acid and treating with ether; if, however, the salt is heated with hydrochloric acid, it is converted into hydrogen barium sulphoterephthalate,

Sulphamineterephthalic acid crystallises easily from hot water, and does not fuse at 310°. The monopotassium salt,

COOH C,H,(SO2NH2)·COOK + H2O,

is sparingly soluble in cold water.

The barium salt (+H2O) when formed by boiling the acid with barium carbonate, dissolves easily, but once separated in the solid condition, it is difficult to redissolve; it forms nodular masses without any well-defined crystalline structure.

.CO

For the sake of comparison, terephthalic sulphinide and its barium salt were prepared; the acid potassium salt has been previously described. Terephthalic sulphinide, COOH-CH,<SO2>NH, is easily soluble in hot water, and fuses at 297-299°; it gives a precipitate with silver nitrate almost insoluble in dilute nitric acid; sulphamineterephthalic acid does not give a similar reaction. The barium salt with 3H2O forms scales very sparingly soluble in water. H. B.

Conversion of B-Naphthaquinone into Indonaphthenederivatives. By T. ZINCKE (Ber., 20, 1265-1272).-In a former paper, Zincke has shown that dichloro-B-naphthaquinone is converted by alkalis into an acid, C10H.Cl2O3, which may be regarded as a dichloro-derivative of phenyleneacetyleneglycollic acid,

(this vol., p. 54). On oxidation, the acid is converted into a ketone, CH>CO, an analogue of diphenylene ketone. These compounds can also be considered as derivatives of indonaphthene, the former as a dichlorohydroxyindonaphthenecarboxylic acid, the latter as a dichloroindonaphthene ketone. The ketone crystallises in yellow, glistening needles, melting at 89-90°, resembling quinone not only in odour, but also in its reactions in that it combines with hydroxylamine and the amines. The hydroxylamine-derivative or oxime,

CHC:NOH,
C2Cl2

crystallises in needles melting at 120°, the methylamine-derivative in dark-red needles melting at 195°, and the dimethylamine-derivative in quadratic tablets melting at 140°. These amine-derivatives are decomposed by acids or alkalis with regeneration of the amine and formation of phenylenechlorohydroxyacetylene ketone, C,H,CIO.OH,

which crystallises in leaflets melting at 114°; it is soluble in alkalis with a red coloration, and is converted by phosphoric chloride into a compound, crystallising in leaflets, and differing from the original ketone. It readily takes up chlorine and bromine, yielding colourless, crystalline compounds which no longer possess a quinone character. V. H. V.

-CO

Synthesis of Indonaphthene-derivatives. By W. ROSER (Ber., 20, 1273-1274).-This paper is a preliminary communication with regard to the synthesis of indonaphthene-derivatives from those of cinnamic acid. Thus, dibromocinnamic acid when heated with concentrated sulphuric acid yields phenylenedibromoacetylene ketone or dibromoketoindonaphthene,C,HC,Br, crystallising in orange yellow needles melting at 123°. With hydroxylamine, it forms an oxime crystallising in needles melting at 195', and with aniline an anilide melting at 170°. The ketone combines directly with bromine to form a tetrabromo-additive product, which may be regarded as a derivative of hydrindonaphthene; this compound crystallises in prisms melting at 124°. V. H. V.

Nitrosamines. By O. FISCHER and E. HEPP (Ber., 20, 1247— 1253).—In a former paper (this vol., p. 244), it has been shown that the nitrosamines derived from aromatic amines are converted by alcoholic hydrogen chloride into paranitroso-derivatives corresponding with paranitrosodimethylaniline. Thus, from phenyl-a-naphthylnitrosamine a paranitroso-product, C16H12N2O, is obtained, which crystallises in leaflets or needles melting at 150°, and soluble in concentrated sulphuric acid with brown coloration. Similarly from paranitroso-adinaphthylamine, a compound, C20H1N2O, is obtained, crystallising in brownish-red needles melting at 169°, and from ß-naphthylethylnitrosamine a base, C12H10N2, which crystallises from methyl alcohol in short prisms containing 1 mol. MeOH, melting at 75°. The hydrochloride crystallises in colourless needles, and the platinochloride in yellow needles containing 3 mols. H2O, the picrate in yellow needles. This substance probably belongs to the anhydro-bases, and its constitution is that of an ethenyl-3-3-naphthalenediamine.

The base obtained from tetrahydroquinolinenitrosamine separates in greenish-yellow flocks, melting at 134°.

It has been observed that the above paranitroso-derivatives dissolve readily in dilute alkalis, and are again reprecipitated on passing in carbonic anhydride. The sodium salt of paranitrosomethylaniline separates in yellow needles of the composition C,H,N2O + NaOH, but the formation of such a salt is not in accordance with the formula proposed for those substances by Baeyer and Caro. V. H. V.

Azonium Bases. By O. N. WITT (Ber., 20, 1183-1186).— Phenylorthonaphthylene-diamine (this vol., p. 590) is prepared by mixing a solution of 10 grams of sulphobenzene-azo-B-naphthylphenylamine in 100 c.c. of alcohol and 10 c.c. of glacial acetic acid, with a solution of 12 grams of stannous chloride dissolved in 20 c.c. of glacial acetic acid. After a short time, pure hydrochloric acid is added until the

red colour of the solution has entirely disappeared. The hydrochloride of the diamine separates in white needles; these are collected and washed with alcohol and ether, and dried at 110°. The base is obtained by treating the alcoholic solution with potash. It forms transparent, flat prisms, which melt at 136-137, and gradually redden when exposed to air. When dry, it can be heated at 110° without decomposition, but in presence of water it rapidly becomes red. Phenylnaphthophenanthrazonium nitrate, CH19N3O3, is formed when a solution of equal parts of phenanthraquinome and the diamine in glacial acetic acid is boiled for a short time; alcohol and nitric acid (sp. gr. 13) are added to the cooled product. It separates after a day in long needles, which are crystallised several times from alcohol; it melts at 110°. The crystals are dichroic. It is almost insoluble in water, but more soluble in alcohol, with a yellowish-red colour. The alcoholic solution when treated with boiling water dyes cotton and wool a salmon colour. The other salts of the base are much more soluble; the platinochloride is a red precipitate. The free base is soluble in ether; the solution is yellow; it has the constitution N.C10H

and is therefore the analogue of the hypothetical NPh(OH) phenylphenazonium hydroxide, of which the author considers saffranine to be the asymmetrical diamido-derivative (Ber., 19, 3121).

N. H. M.

Azo-derivatives of Phenyl-p-naphthylamine. By T. ZINCKE and A. T. LAWSON (Ber., 20, 1167-1176).-Benzene-uzo-B-naphthylphenylamine is obtained by converting 20 grams of aniline into diazobenzene chloride, diluting the liquid with an equal weight of alcohol, and adding it to a warm solution of 47 grams of phenyl-pnaphthylamine in 900 to 1000 c.c. of alcohol. The azo-compound separates in a crystalline form, and after being filtered, washed, and extracted with alcohol, is pure enough for most purposes. It crystallises from hot acetic acid in small lustrous needles of an intense red colour and dark metallic lustre, and melts at 141-142° (not 128— 129°; Henriques, Abstr., 1885, 168). When boiled with glacial acetic acid (5-6 parts) and hydrochloric acid (1-1 part), it is converted into naphthaphenazine, CoH&N CH, and aniline. This reaction supports the view that the azo-derivatives of B-naphthylamine are hydrazimides; the constitution of benzeneazo-B-naphthylphenylNPhamine would therefore be CoHe<N(NHP) Bromine acts on

2

the compound dissolved in warm glacial acetic acid with formation of phenyl-B-naphthylamine tetrabromide, melting at 202-203°; the latter is identical with the compound obtained by Streiff (Annalen, 209, 158).

10

Amido-B-naphthylphenylamine, NH2°C10H, NHPh, is obtained by reducing the azo-compound with stannous chloride. The hydrochloride forms long, colourless, lustrous needles, very sparingly soluble in water, more soluble in alcohol; it becomes violet when

exposed to air. The sulphate resembles the hydrochloride.

The

free base crystallises from alcohol in wide needles or plates, which melt at 138-140°, and readily become violet.

Diphenylnaphthaleneazammonium hydroxide, C1HNPh2 OH, is prepared by dissolving the azo-derivative of B-phenylnaphthylamine in hot glacial acetic acid (10 parts), heating almost to boiling, and gradually adding to it a hot concentrated solution of potassium dichromate until the solution acquires a brownish-red colour. It is then boiled for a few minutes and diluted with an equal volume of hot water; on cooling, the chromate of the base separates in yellow needles. The free base was only obtained in solution; it shows a green fluorescence, precipitates metallic salts, and liberates ammonia. The chloride, C22H16N3Cl, crystallises in well-formed lustrous prisms readily soluble in alcohol, less soluble in water. The platinochloride, (C22H16N3C1)2PtCl, forms a crystalline, reddish precipitate sparingly soluble in water; the sulphate and nitrate form lustrous prisms and long, flat, lustrous needles respectively. The picrate crystallises in small needles of an intense yellow colour; it melts at 243°, and is very sparingly soluble in water. N. H. M.

2

Orthamidoazo- and Hydrazimido.compounds. By T. ZINCKE and A. T. LAWSON (Ber., 20, 1176-1183).- When a solution of orthodiazoazotoluene (prepared by treating a solution of 5 grams of orthamidoazotoluene in 50 grams of alcohol and 5 grams of strong hydrochloric acid with 1.6 gram of sodium nitrite dissolved in 5 parts of water) is mixed with an alcoholic solution of 3 grams of a-naphthol, and treated with concentrated aqueous soda, a deep red precipitate consisting of the sodium salt of the compound C2H, N2 C2H, N2C10H2OH is formed. The latter is obtained by decomposing the sodium salt with acetic acid; it crystallises from aniline in brownish-red needles melting at 210°, is sparingly soluble in neutral solvents, but dissolves in dilute alcoholic soda with violet-red coloration. When reduced with stannous chloride in alcoholic solution it yields tolueneazimidotoluene, CH, NC,H,, melting at 126°, and amido-a-naphthol hydrochloride together with a small quantity of a substance, probably orthotoluylenediamine.

Orthodiazoazotoluene reacts with B-naphthol with formation of a compound isomeric with that described above. In the case of B-naphthol, the free diazo-compound, and not the sodium salt, separates on the addition of soda. It may be crystallised from chloroform or benzene, when it is obtained in long, deep red prisms of an intense green metallic lustre. It melts at 177°, dissolves readily in chloroform, benzene, and xylene, sparingly in alcohol, acetone, and light petroleum. Alcoholic soda dissolves it only slightly. When reduced, it is converted into the azimide, CH, NC, H, and the hydrochlorides of B-amidonaphthol and para- and ortho-toluidine.

Orthodiazoazotoluene reacts readily with B-naphthylamine with formation of the compound C,H¬·N2°C2H ̧•N2°C10H NH2. This crystallises from hot alcohol in deep red, lustrous plates melting at 201-203°; it is readily soluble in chloroform and benzene. When reduced,

it behaves like the naphthol - derivatives, yielding the azimide CH, NC,H,, and probably also orthonaphthylenediamine; when boiled with hydrochloric acid in alcoholic solution, the azimide is also formed.

The diazo-compounds of paramidoazotoluene are prepared in a manner similar to those of the ortho-compound.

Paradiazoazotoluene nitrate crystallises in slender, brownish-yellow needles, rather readily soluble in water and alcohol; the perbromide forms a yellow, crystalline precipitate which changes to slender, violet needles, melting at 96°.

Paradiazoazoimide is obtained by treating the perbromide with an excess of alcoholic ammonia in long, slender, slightly yellow plates melting at 58-60°; it can be crystallised from alcohol, but decomposes when heated or when in contact with sulphuric acid.

When the diazo-salts are reduced with zinc-dust and glacial acetic acid or with stannous chloride, orthotoluidine and orthometatoluenediamine are formed; when sodium sulphite is used, sodium diazoazotoluene sulphonate, CH, N, CH, N2SO,Na, is obtained; this is a reddish crystalline precipitate, readily soluble in alcohol, sparingly

in water.

The diazo-salts combine readily with the naphthols; the B-naphtholderivative forms deep red needles melting at 186°; it is readily soluble in hot alcohol and benzene. When reduced with stannous chloride, it yields B-amidonaphthol, orthotoluidine, and orthometatoluylenediamine.

The diazo-salts of paramidoazotoluene, as well as the perbromide, correspond, therefore, only partially with the compounds of orthamidoazotoluene which yield hydrides when reduced. N. H. M.

Naphtholcarboxylic Acids. By R. NIETZKI and A. L. GUIterMANN (Ber., 20, 1274-1277).-The naphtholcarboxylic acids are readily decomposed into carbonic anhydride and the corresponding naphthol; in this respect, the ẞ-acid is more unstable than the a-acid. On adding diazobenzene chloride to a solution of a-naphtholcarboxylic acid in dilute alkali, a crystalline precipitate is obtained, but analyses show that it is not homogeneous. On hydrogenation, however, there was obtained an amidonaphtholcarboxylic acid, OH C10H (NH2) COOH, as a colourless, crystalline powder, decomposing at 230° with evolution of carbonic anhydride. The amidonaphthol obtained from it on oxidation yielded a-naphthaquinone, and thus its constitution was that of a 1 : 4-derivative. Then since the a-naphtholcarboxylic acid is obtained by Kolbe's process from a-naphthol, and in that in the reaction only 1:2- and 1: 4-derivatives are formed, and as the introduced amido-group takes up the second 4-position in the naphtholcarboxylic acid, the OH and COOH groupings are probably in the 1: 2 positions respectively. V. H. V.

B-Naphthylaminesulphonic Acid. By F. BAYER and C. DUISBERG (Ber., 20, 1426-1432).—B-Naphthylamine-d-sulphonic acid, NH2 CH SO3H, is prepared by the action of much sulphuric acid on B-naphthylamine at 150" for 1 hour. The hot solution is poured at