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by warming thioparatoluidine with excess of benzoic chloride as long as hydrochloric acid is evolved. It crystallises from alcohol in snowwhite, brilliant needles, easily soluble in alcohol, benzene, and ether, and melts at 186°.

Hydroxythiotoluene, S(C,H,MeOH)2, is obtained by boiling diazothioparatoluidine hydrochloride with water, saturating the solution. with sodium chloride, dissolving the precipitated substance in alkali, and again precipitating with dilute sulphuric acid. It can also be obtained by dissolving the crude product in benzene and fractionally precipitating with light petroleum. It forms a brown powder, soluble in alcohol, ether, and benzene; it melts at 135°.

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Thioparatolylthiocarbamide, SC.H,Me NH>CS, is obtained by treating an alcoholic solution of thioparatoluidine with excess of carbon bisulphide. Hydrogen sulphide is evolved and, after some time, colourless crystals mixed with crystals of sulphur separate. The latter are removed by means of carbon bisulphide. The substance is insoluble in all ordinary solvents, but dissolves in strong nitric and sulphuric acids. It melts at 234-235°. Another very stable substance is formed at the same time; it melts at 231°. Attempts to prepare thioparatolylsulphocarbanil from it were unsuccessful.

The picrate of thioparatoluidine, C1H16N2S,2C6H2(NO2)3OH, is obtained in aggregates of fine needles by evaporating alcoholic solutions of thioparatoluidine and picric acid. It crystallises from benzene in stellate needles with brilliant lustre, and melts at 179°. When quickly heated, it explodes.

Dithioparatolyldicarbamide, SC, H, NH-CO-NH-C,HS, is ob-CHỂNH CO NHÁC,H. tained as a yellow, amorphous powder, together with thioparatoluidine hydrochloride, by passing carbonyl chloride (1 mol.) into a solution of thioparatoluidine (2 mols.) in benzene. By solution in alcohol and reprecipitation, it forms a whitish, amorphous powder which is decomposed at 130°. It is only slightly soluble in ether and in cold alcohol, but easily in hot. It is not acted on by concentrated hydrochloric acid, but is soluble in strong nitric and sulphuric acids.

G. H. M. Secondary and Tertiary Quinones. By R. NIETZKI and F. KEHRMANN (Ber., 20, 322-328).—When sodium rhodizonate (Abstr., 1885, 1127) is dissolved in dilute hydrochloric acid and treated with CO.C(OH): C.N

an orthotoluylenediamine salt, the compouĊO-C(OH): CNCH

is obtained. It is a gelatinous substance, sparingly soluble in water, readily in alcohol. Alkali solutions dissolve it with a fine violet colour. When oxidised with dilute nitric acid, it is converted into a derivative of triquinoyl, diquinoyltolazine,

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This forms yellow needles, almost insoluble in cold water, ether, and

TOL. LII.

2 i

alcohol, readily soluble in warm glacial acetic acid.

When the compound C3H6N2O, is warmed with an excess of an orthotoluylenediamine salt, benzotritolazine, Cε(N2: C,H6)з, is obtained. This is a yellow, crystalline substance, very readily soluble in alcohol and in chloroform; it crystallises from the latter in long needles (with 1 mol. CHCl3). It has feeble basic properties.

When sodium rhodizonate, dissolved in water, is treated with an excess of a salt of orthotoluylenediamine and sodium acetate, a compound is obtained containing three toluylenediamine-groups; when oxidised, it is converted into the triazine, C27H1N6, already described. The above experiments show that triquinoyl contains six quinone oxygen-atoms. It is probable that the hydroxyl-groups in rhodizonic acid have the para-position. This view being accepted, the fact that adjacent oxygen-atoms react like an orthoquinone-group and are independent of para-oxygen, forms an important support for the ketonic formulae of quinones. N. H. M.

Preparation of Dimethylaniline on a Large Scale. By P. SCHOOP (Chem. Zeit., 11, 253-254).-The author describes the preparation of dimethylaniline from aniline, wood spirit, and hydrochloric acid. It is important to use pure materials, therefore the aniline is tested by quantitative fractional distillation, by its sp. gr., and by its solubility in hydrochloric acid; the wood spirit must be free from acetone and ethyl alcohol, and is tested by the iodoform test. The materials are mixed in the proportions of 93 parts of aniline, of which 18 are saturated with hydrochloric acid, and 75 parts of methyl alcohol. The excess of methyl alcohol and the comparatively small quantity of hydrochloric acid tend to produce a purer oil. With more hydrochloric acid, the reaction takes place at a lower temperature, but there is danger of the formation of toluidine. The mixture is heated in a closed vessel, the temperature (from 270-230°) and pressure (of which a table is given in the paper) being carefully regulated; a fall of pressure with a constant temperature (230°) indicates the completion of the operation. The product consists of an oily and watery portion which are separated; the latter is then treated with soda and the oil which separates is removed, the alkaline water being finally distilled and the oil from this collected in a separate receiver. Each of these three lots of oil is rectified by itself, the product obtained from the first lot being the best and that from the third the worst. Many modes of testing the purity of the product are given; it is especially important to have a pure substance for the preparation of green dyes. D. A. L.

Ortho- and Para-chlorodimethylaniline. By T. HEIDlberg (Ber., 20, 149-151).-Orthochlorodimethylaniline, CH,CI-NMe2, is obtained by Staedel's method, which consists in heating the hydrobromide of the chloraniline with rather more than 2 mols. of methyl alcohol at 145°. It is a clear, colourless liquid boiling at 206-207°. The hydrochloride forms white, hygroscopic needles; the platinochloride crystallises in lustrous yellow prisms. Nitrosorthochlorodimethyl

aniline crystallises from alcohol in yellow needles. Parachlorodimethylaniline was prepared by Sandmeyer's method:

50 grams of amidomethylaniline was dissolved in 82 grams of hydrochloric acid; 300 c.c. of water is added and then a solution of 26 grams of sodium nitrite in 60 c.c. of water. The whole is added to a boiling solution of 10 per cent. cuprous chloride solution. It crystallises in large, lustrous, flat needles, soluble in alcohol, ether, and benzene, insoluble in water; it melts at 230-231°. The hydrochloride is a syrup which crystallises with difficulty; the ferrocyanide forms microscopic prisms. The platinochloride, (C,H,CI-NMe:)2, H2PtCle, crystallises in gold-coloured prisms. Nitrosoparachlorodimethylaniline crystallises in splendid, orange-yellow needles melting at 56°; it is soluble in alcohol, ether, and benzene, &c. Like the ortho-compound it is a very feeble base. N. H. M.

Carvole-derivatives. By H. GOLDSCHMIDT and E. KISSER (Ber., 20, 486-492).-Carvylamine (this vol., p. 249), a primary amine, is a colourless liquid, and yields a benzoyl-derivative which crystallises in white needles melting at 169°. The hydrochloride, C10H1N,HCl, crystallises from absolute alcohol in small, white, silky needles, and melts at about 180° with decomposition; when heated with sodium nitrite, an oil, probably identical with Leuckart's carveol, is obtained (this vol., p. 376).

From carvole, by the action of dry hydrogen chloride, hydrochlorocarvole, CHOCI, is obtained; this decomposes on distillation with evolution of hydrogen chloride, and when treated with hydroxylamine yields hydrochlorocarvoxime (Abstr., 1885, 1058). The phenylhydrazine-derivative, C10H16C1: N2HPh, crystallises in small, white prisms, and melts at 137°. When a mixture of carvole and ethyl acetoacetate in equimolecular proportions is treated with hydrogen chloride, the product poured into water and afterwards extracted with ether, two compounds are obtained, one an oil, and the other a crystalline substance of the formula CH25C1O4, which forms lustrous, white, hard prisms, melts at 146°, and does not yield a derivative with acetic chloride.

The constitution of carvole is now represented by the formula CH.CO CPr<CH:CH>CHMe, and that of limonene by the formula

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Action of Aromatic Diamines on Sugars. By P. GRIESS and G. HARROW (Ber., 20, 281-282).-The diamidobenzenes and their carboxylic acids react with some sugars to form compounds analogous to those obtained by Fischer with phenylhydrazine and sugars. Those with the orthodiamine are especially interesting, as they are relatively easily prepared and show well-characterised physical properties.

If, for instance, concentrated aqueous solutions of orthophenylenediamine (1 part) and dextrose (2 parts) are mixed, a few drops of hydrochloric acid added, and the whole allowed to remain eight days in a moderately warm place, a feebly basic substance is formed. This crystallises in lustrous, white needles, which are moderately soluble in

=

hot water and alcohol; it also dissolves very readily in hydrochloric acid, and is reprecipitated unaltered from the solution by ammonia. It has a bitter taste, and reduces Fehling's solution. If in the above reaction the corresponding 7-diamidobenzoic acid [COOH: (NH2), : 12:3] is substituted for the diamine, a substance having the character of an amido-acid is obtained. It crystallises in lustrous, white plates, is very sparingly soluble even in boiling water or alcohol, does not reduce Fehling's solution to any marked extent, and behaves like sugars when heated in a tube. A very similar acid was prepared from maltose. A. J. G.

Action of Orthotoluylenediamine on Dextrose. By O. HINSBERG (Ber., 20, 495-497).—An almost quantitative yield of a condensation-compound, C19H30N2O10, is obtained when an alcoholic solution of orthotoluylenediamine (1 mol.) is heated with dextrose (2 mols.) on a water-bath. The compound crystallises from dilute alcohol in slender, white, silky needles, which become brown when heated at 100° in a capillary tube, and melt at about 160° with evolution of gas; it is readily soluble in water, sparingly soluble in alcohol and ether, and gives a red coloration with ferric chloride. A loss of about 4 per cent. in weight occurs if the compound is heated at 100°, and it then gives figures showing a slightly lower percentage of carbon. Diluté alkalis are without action on it, but mineral acids, on warming if dilute, reconvert it into orthotoluylenediamine and, probably, dextrose. The constitution of this compound is probably

CH.(N C6H12O5)2,

and its instability in the presence of acids raises the question whether the view that dextrose contains the aldehyde-group is correct. Other aromatic diamines yield compounds analogous to dextrose; no wellcrystallised compound can be obtained from orthotoluylenediamine and lactose. W. P. W.

NH

Tetramidobenzene and its Derivatives. By R. NIETZKI and E. HAGENBACH (Ber., 20, 328-338).-Diethenyltetramidobenzene, CH2(<>C2H2), is obtained by reducing diacetyldinitroparaphenylenediamine with hydrochloric acid and tin. It crystallises in long, colourless needles, sparingly soluble in cold water, readily in hot water and in alcohol. It melts at 210°. The platinochloride, C10H10N, H2PtCl + H2O, crystallises in long gold-coloured needles; the sulphate (with 1 mol. H,O) crystallises from hot water in colourless needles almost insoluble in alcohol. When the sulphate is dissolved in fuming nitric acid (5 parts), a mononitro-derivative, C10H,N,NO2+ H2O, is obtained; this forms orange-red needles melting at 276°. The platinochloride, CH,N,O2,H2PtCl + H2O, crystallises in long, gold-coloured needles.

NH.

Ethenylnitrotriamidobenzene, C2H,<>C,H,(NH2) NO2, is formed when diacetyldinitrophenylenediamine is heated with alcoholic ammonia.

at 150°. It melts at 295-300°. The hydrochloride and sulphate were prepared.

NH.

Ethenyltetramidobenzene, C2H<>CH.(NH2)2, is obtained by reducing the nitrotriamido-compound with stannons chloride and hydrochloric acid. It only exists in the form of its salts. The picrate crystallises in sparingly soluble yellow needles.

Diacetyldinitrometaphenylenediamine, CH2(NHAc)2(NO2)2, is obtained by treating diacetylmetaphenylenediamine with nitric acid (sp. gr. 1.533); it forms pale-yellow needles which melt at 228°. Dinitrometaphenylenediamine is prepared by heating the acetyl-derivative with dilute sulphuric acid. It is an orange-yellow substance, sparingly soluble in alcohol; it melts at about 300°.

Tetramidobenzene, CH2(NH2), [= 1:2:4: 5], is formed when freshly prepared dinitrometaphenylenediamine is added to a warm, strongly acid solution of stannons chloride containing an excess of metallic tin. The hydrochloride is very soluble in water, sparingly in hydrochloric acid. The dinitrate, CH2(NH2)1,2HNO3, forms small, green needles. All the salts absorb oxygen from the air, becoming blue-violet or brown. When the nitrate or hydrochloride is treated with sodium carbonate solution, the base is obtained in small, brown needles.

The constitution ascribed to tetramidobenzene is shown by the fact that the diethenyltetramidobenzene from metaphenylenediamine is not identical with that obtained from paraphenylenediamine, and that the nitrogen of the diethenyltetramidobenzene from paraphenylenediamine must be attached to adjacent carbon-atoms.

Diethenyltetramidobenzene, obtained by reducing dinitrodiacetylmetaphenylenediamine, melts above the range of the thermometer. The sulphate and platinochloride were prepared.

Tetramidobenzene reacts with phenanthraquinone, with formation of N

the compound CuH.<>C.H.(NH.). This is a feeble buse, and dis

N

solves in sulphuric acid with a greenish-blue colour which changes to violet and red when diluted. N. H. M.

Carbonylorthamidophenol and Thiocarborthamidophenol. By S. v. CHETMICKI (Ber., 20, 177-179).-When ethyl thiocarbamidophenol, C,H,NOS, is beated with strong hydrochloric acid at 156-160°, amidophenol, mercaptan, and carbonic anhydride are formed; the formation of mercaptan can only be explained on the supposition that the ethyl-group in the thiocarbamidophenol is combined with sulphur. Thiocarbamidophenol dissolved in hydrochloric acid, when oxidised with chloride of lime, yields a bisulphide, S.(C,H.<>>C)22 ; the same compound is also formed when the sodium salt of thiocarbamidophenol is treated with iodine solution. These results confirm the formula C.H.<>C.SH, ascribed by Kalckhoff to thiocarborthamidophenol.

N

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