that in addition to this reaction a second also occurs in which a portion of the thymol reacts with thymoquinoneoxime to form amidothymol and thymoquinone (compare Sutkowski, Abstr., 1887, 41). W. P. W.

Formation of Secondary Aromatic Amines. By A. PICTET (Ber., 20, 3422-3424).—Ethylacetanilide is prepared by adding 75 grams of finely-powdered acetanilide to a cold solution of 31 grams of caustic potash in 300 grams of 95 per cent. alcohol; after a short time the flask containing the mixture is fitted with a reflux condenser, 65 grams of ethyl bromide is added, and the whole slightly warmed on a water-bath. When the reaction becomes less violent, the mixture is heated for one to two hours, allowed to become cool, and filtered. The advantages of this method over Hepp's (Ber., 10, 327) are that it does not involve the use of large amounts of sodium, and that the product is more easily purified. The yield of ethylaniline (41 per cent. of the theoretical) is, however, not so good as that obtained by Hepp's method. In the case of formanilide, the yield is almost theoretical.

N. H. M.

Action of Sulphur on Dimethylaniline and Methylaniline. By R. MÖHLAU and C. W. KROHN (Ber., 21, 59-67).-When dimethylaniline is boiled with sulphur for 12 hours and distilled, an oil boiling at 210-345° is obtained. When this is treated with hydrochloric acid, it is separated into an oil of indifferent character which soon solidifies, and a mixture of several basic compounds. From the latter, Hofmann's methenylamidophenyl mercaptan (Abstr., 1887, 823, 1039), aniline, and methylaniline were separated. The indifferent

crystalline substance has the formula C,H,NS. (?NCH-S SCN),

\CH2-S/

melts at 88-89°, and boils above 360°. When boiled with sulphur, it is converted into methenylamidophenyl mercaptan, and seems therefore to be the primary product. When treated with nitric acid, the compound C.H,NS2 is changed into the base C,H,NS, probably CHCH. N<

C&HS

By the action of sulphur on methylaniline, the same compounds are obtained. The authors think that at first a decomposition of 2 mols. of methylaniline into dimethylaniline and aniline must have taken place, the dimethylaniline so formed then reacting with sulphur as described above. J. W. L.

Action of Thiocarbonyl Chloride on Secondary Amines. By O. BILLETER and A. STROHL (Ber., 21, 102-110).-Propylphenylthiocarbamine chloride, CSCI-NP Pr, crystallises from light petroleum in thick, colourless prisms melting at 36°. It is more stable in damp air than the corresponding methyl and ethyl compounds. Dipropylthiocarbanilide, CS(NPhPr)2, forms colourless plates melting at 103.5°. Methylpropylthiocarbanilide, NPhMe CS-NPhPr, prepared either from methyl chloride and propylaniline or from propyl chlorie and methylaniline, forms colourless prisms melting at 56.5°.

Ethylpropylthiocarbanilide, NPhPr-CS NPhEt, is prepared like the last-named compound and melts at 66·3°. All these derivatives dissolve easily in concentrated acetic, hydrochloric, and sulphuric acids without change, whereas by warming with concentrated sulphuric acid or heating at 150° with hydrochloric acid the secondary base is readily eliminated.

Alcohols and phenols, the corresponding sulphur compounds, and also their metallic salts, react readily with the thiocarbamine chlorides already described, with formation of the corresponding thioand dithio-carbamic acids. Of this series, the following were prepared:-Ethyl ethylphenylthiocarbamate, NEtPh·CS OEt, prepared by the action of ethyl phenylcarbamine chloride on sodium ethoxide in ethereal solution, distils at 1436° under a pressure of 12 mm. Sp. gr. 1066 at 15°. It solidifies by prolonged cooling to a colourless, crystalline mass which melts at 18°. Phenyl ethylphenylthiocarbamate, NEtPh CS OPh, forms colourless needles and melts at 69.2°. Phenyl ethylphenyldithiocarbamate, NPhEt CSSPh, crystallises in compact, colourless needles, and melts at 1278°. Ethyl ethylphenyldithiocarbamate melts at 66-4°. A trisubstituted thiocarbamide is formed by the action of ethyl phenylthiocarbamine chloride, aniline, &c., and can be isolated by stopping the reaction after the mass first solidifies. It is decomposed if the reaction proceeds too far into thiocarbanilide and aniline hydrochloride. A small quantity of a dithiobiuret is also formed. The dithiobiurets are readily obtained by the further action of thiocarbamine chloride on the tertiary carbamides first formed.

Dimethyltriphenyldithiobiuret, C2S2N ̧Ph2Me2, prepared from methylphenylthiocarbamine chloride and methylthiocarbanilide, forms yellow needles melting at 202-5°. It is sparingly soluble in alcohol and ether, readily so in chloroform.

3

Diethyltriphenyldithiobiuret, C2S2N,Ph,Et2, prepared from ethylphenylthiocarbamine chloride and ethylthiocarbanilide, crystallises in lemon-yellow needles melting at 158°. It is more readily soluble than the methyl compound.

Methylethyltriphenyldithiobiuret, (a), NEtPh.C(NPh) S.CS⚫NMePh, prepared from methylphenylcarbamine chloride and ethylthiocarbanilide, forms small, pale yellow needles melting at 157.5°. It is soluble in chloroform, sparingly soluble in alcohol and ether. (b.) NMe Ph C(NPh) S.CS-NEtPh, prepared from ethylphenylcarbamine chloride and methylthiocarbanilide, forms small, light-yellow needles like those of the (a) compound, and melts at 156.5°.

Dipropyltriphenyldithiobiuret, C2S2N,Pr2Ph3, prepared from propylphenylcarbamine chloride and propylthiocarbanilide, forms shining, yellow needles melting at 153-7°. It is soluble in chloroform.

Methylpropyltriphenyldithiobiuret, C2S2N,MePrPh (a), prepared from methylphenylcarbamine chloride and propylthiocarbanilide, crystallises in shining yellow pyramids, melting point 110°; (b) prepared from propylphenylcarbamine chloride and methylthiocarbanilide, forms yellow pyramids similar to the (a)-derivative, and melts

at 111°.

Ethylpropyltriphenyldithiobiuret, C2S2N,EtPrPh,, (a) prepared from ethylphenylthiocarbamine chloride and propylthiocarbanilide, crystal

lises in pale yellow needles melting at 165.8°. Very sparingly soluble in alcohol; (b) prepared from propylphenylthiocarbamine chloride and ethyl thiocarbanilide, crystallises in yellow needles melting at 165°.

Propylthiocarbanilide, CSN,H.Pr.Ph2, prepared from propylaniline and phenyl isothiocyanate, consists of colourless, shining needles which melt at 104-3°. It is readily soluble in alcohol, and is decomposed by hydrochloric acid into its components. J. W. L.

Constitution of Mixed Azo-compounds. By V. MEYER (Ber., 21, 11—18).—The author had independently arrived at views on the constitution of the mixed azo-compounds identical with those brought forward by Japp and Klingemann (Proc., 1887, 140).

Compounds of Phenylhydrazine with Ketone Alcohols. By H. LAUBMANN (Annalen, 243, 244-248).-Benzoylcarbinolphenylhydrazone, N,HPh: CPh.CH, OH, crystallises in needles, melts at 112°, and dissolves freely in alcohol and ether. It is converted into an amorphous product, probably hydroxyphenylindole, by the action of zinc chloride at 150°. The hydrazone is converted into the osazone, N2HPh:CPh CH: N2HPh, by treatment with phenylhydrazine and sodium acetate in alcoholic solution. The osazone melts at 152° and is soluble in ether, benzene, and in hot alcohol.

The osazone of acetol is identical with the product v. Pechmann (Abstr., 1887, 1103) obtained by the action of phenylhydrazine on nitrosoacetone. W. C. W.

Action of Phenylhydrazine on Dioximes. By M. POLONOWSKY (Ber., 21, 182-184).-When glyoxime in alcoholic solution is treated with an equimolecular proportion of phenylhydrazine, an additive

CH(NOH).

compound, CH(NOH)>NH, NHPh, is obtained. This crystallises

from alcohol in white scales, melts at 110°, and is readily soluble in alcohol, less so in ether, and insoluble in water. Concentrated aqueous soda dissolves it, and the solution when heated yields phenylhydrazine; a like decomposition is also produced by concentrated sulphuric acid.

Under similar conditions diphenylglyoxime yields an additive compound, C20H20N,O2, which crystallises in needles, melts at 149-150°, and closely resembles the preceding derivative in its properties.

B-Naphthaquinonedioxime, in like manner, forms an additive compound, C16H16N,O2. This crystallises from alcohol in tufts of long needles, begins to fuse at 105°, and melts at 138°. W. P. W.

Aldines and Amidoacetophenone. By E. BRAUN and V. MEYER (Ber., 21, 19-21).-When isonitrosoacetophenone is reduced in hydrochloric acid solution, it is completely transformed into the hydrochloride of an amidoacetophenone, COPh·CH2 NH2. This salt crystallises from water in large, hard, colourless crystals, and is very stable; it can be recrystallised from hot water, and forms a crystalline platinochloride. The freshly precipitated base redissolves in acids,

but when purified by washing or recrystallising from alcohol, it becomes orange-coloured, and completely loses its basic properties, being converted into a coloured crystalline substance, which resembles isoindole very closely, and with which it is probably identical. A ketine, N/CPh: CPN, is readily obtained from the monoxime \CPh•CPh/

of benzil.

F. S. K.

Formation of Phenylhydrazile Acids from the Anhydrides of Bibasic Acids. By R. ANSCHÜTZ (Ber., 21, 88-89).-By the action of phenylhydrazine on the chloroform or ethereal solutions of the bibasic anhydrides, the corresponding phenylhydrazile acids are obtained. The following anhydrides react in this way: maleïc, succinic, citraconic, itaconic, camphoric, phthalic, diphenylmaleïc, phthalic, diphenylmaleïc, and diphenylsuccinic (compare Hötte, Abstr., 1887, 669). J. W. L.

Formation of Orthosulphaminecarboxylic Acids. By C. FAHLBERG and R. LIST (Ber., 21, 242-248).—The products of the oxidation of orthotoluenesulphonamide under different conditions were examined, and the results show that when the oxidation is carried on in alkaline solutions by potassium ferricyanide (Abstr., 1886, 804), by potassium manganate, and by potassium permanganate, orthosulphaminebenzoic acid is formed; that when it is carried on in neutral solutions by permanganate, benzoic sulphinide is the chief product, a small quantity of orthosulphaminebenzoic acid being also formed, probably by the action of the alkali produced by the decomposition of the permanganate, since the yield was much diminished by adding acid from time to time to neutralise the alkali formed; and that when it is carried on by permanganate in solutions rendered acid either by hydrochloric acid, or by a current of carbonic anhydride, orthosulphobenzoic acid and potassium nitrate are formed. Benzoic sulphinide is to be regarded as the primary product of the oxidation, since on evaporation with hydrochloric acid it is converted into orthosulphobenzoic acid and ammonia, and on evaporation with potassium hydroxide into orthosulphaminebenzoic acid. Ammonia, alkaline carbonates, and the oxides of the alkaline earths cannot be employed for this purpose; moreover, in the case of barium oxide, the barium salt of the sulphinide is obtained (compare this vol., p. 282).

:

Orthoparadisulphaminebenzoic acid, [COOH: SO2NH, SO,NH2 = 1:24], is obtained either by oxidising orthoparatoluenedisulphonamide with alkaline potassium manganate, or by evaporating sulphaminebenzoic sulphinide with potassium hydroxide. It crystallises in slender, satiny, microscopic needles, melts at 182-183°, is completely decomposed at 250-260°, and is very soluble in water and alcohol, sparingly soluble in ether. The salts of the alkalis and alkaline earths are readily soluble, and those of the metals are sparingly soluble in water. The barium salt, with 5 mols. H2O, erystallises in large, colourless, monoclinic prisms, the copper salt, with 2 mols. H2O, in bright-blue, silky needles, and the silver salt in anhydrous, white needles. The ethyl salt is identical with that pre

pared from disulphaminebenzoic acid (Abstr., 1881, 816). For purposes of comparison, the corresponding salts of disulphaminebenzoic sulphinide were prepared; the barium salt, with 34 mols. H2O, crystallises in granular aggregates of needles, and the copper salt, with 4 mols. H2O, in blue, microscopic needles; the silver salt is anhydrous and indistinctly crystalline. W. P. W.

Derivatives of Phenyldibromisobutyric Acid. By A. KÖRner (Ber., 21, 276-277).-When a-methylcinnamic acid (m. p. 78°) dissolved in carbon bisulphide is treated with bromine, phenyl dibromisobutyric acid, CHPhBr-CMeBr-COOH, melting at 137°, is obtained. This, when warmed with alcoholic potash, yields bromophenylcrotonic acid, CPhBr: CMe-COOH, which crystallises from water in matted needles, and melts at 124°. If phenyldibromisobutyric acid is boiled with water, phenylbrom hydroxyisobutyric acid is formed, melting at 148°. In both cases, the yield of the acid is small, the chief product being phenylbromopropylene, C,H,Br; this is a colourless liquid, of pleasant odour, and boils at 226° with decomposition. When treated with alcoholic potash, it is converted into phenylallylene, CPh: CMe; this is a pale-yellow liquid of unpleasant odour, boils at 185°, and yields with bromine a liquid dibromide, which boils at 250-255° with the evolution of much hydrogen bromide, and a solid tetrabromide, which crystallises in lustrous plates and melts at 75°. On treatment with an aqueous solution of mercuric chloride, phenylallylene forms a white, amorphous compound,

2C,H,3Hg0,3HgCl2,

which when heated with hydrochloric acid yields not phenylallylene but phenyl ethyl ketone, COEt Ph. W. P. W.

Parisobutylorthohydroxybenzoic Acid. By L. v. DOBRZYCKI (J. pr. Chem. [2], 36, 389-400).-Anhydrous sodium isobutylphenoxide was prepared by adding the exactly equivalent quantity of isobutylphenol (Liebmann, Abstr., 1882, 171) to alcoholic sodium ethoxide, evaporating off the alcohol, and drying the phenoxide at 140 -150° in a stream of hydrogen. The dry phenoxide was then treated, under pressure, with carbonic anhydride, which was rapidly absorbed with evolution of much heat, sodium isobutylphenyl carbonate being formed. When this substance was heated for some time at 130— 160° it yielded sodium parisobutylorthohydroxybenzoate. The free acid, C ̧H, CH(OH) COOH, is soluble in boiling water, volatile in steam, and crystallises in long, thin, glistening, white needles. It dissolves readily in alcohol, ether, and chloroform. The aqueous solution gives an intense violet coloration with ferric chloride. The metallic salts are not well characterised. The methyl salt yields large, colourless prisms, melts at 54°, and boils at 266°. It is easily soluble in alcohol and ether. Cold soda converts it into a white mass probably of the formula C,H,C,H,(ON) COOMe. The ethyl salt is a colourless aromatic liquid boiling at 276°. The phenyl salt was prepared by heating the acid with phenol at 130°, and adding the requi site quantity of phosphoric chloride in small quantities. It forms