Derivatives of Orthotolidine. By A. GERBER (Ber., 21, 746 — 750).-Diacetylorthotolidine, CH2(NHAC), obtained by heating tolidine with glacial acetic acid in a reflux apparatus, forms lustrous, white needles, melts at 314°, sublimes at a still higher temperature with partial decomposition, and only dissolves readily in phenol.

Tetracetylorthotolidine, C1H12(NAc)2, is prepared by heating the diacetyl compound with acetic anhydride at 160-170° for about six hours; it forms snow-white, lustrous needles, melts at 211°, and is very readily soluble in the ordinary solvents. When heated with concentrated hydrochloric acid, it is reconverted into the diacetyl compound.

Dinitrodiacetylorthotolidide, CH12 (NHAc)2(NO2)2, forms nearly white crystals, decomposes without previons fusion at 320°. When saponified, it yields dinitro-orthotolidine [Me: (NH2)2: (NO2)2 = 3:34:45: 5']; this forms shimmering, garnet-red needles, melts at 266-267°, explodes at a few degrees higher, and when reduced with zinc-dust, is converted into a ditoluylenediamine which yields an azine with phenanthraquinone, and therefore must have the amido-groups in the ortho-position.

Orthodicresol, CH(OH)2, is prepared by diazotising orthotolidine and boiling the product with dilute sulphuric acid. It forms a white, crystalline powder, melts at 160-161°, and is sparingly soluble in boiling water, readily in alcohol, ether, acetic acid, and in boiling benzene hydrocarbons. A dinitro-derivative is prepared by boiling the diazotised product with nitric acid; it crystallises in goldenyellow needles, melts at 272-273°, sublimes with partial decomposition, is insoluble in water, alcohol, and ether, and dissolves in hot alkalis to form salts which crystallise in stellate groups; the potassium and sodium salts are reddish-violet, the ammonium salt orange-red. A. J. G. Thio-derivatives of Desoxybenzoïn and its Analogues. By V. MEYER (Ber., 21, 353-355).-The compound obtained by Bergreen by the action of thiocarbonyl chloride on sodium ethoxide and desoxybenzoïn (this vol., p. 446) possesses much interest, since, in addition to its remarkable properties, it affords the first instance of the displacement of both hydrogen-atoms of the methylene group in desoxybenzoiïn by a radicle containing carbon (compare this vol., p. 147). The compound has a fiery, golden-yellow colour, and in appearance resembles the most beautiful yellow organic dyes. Concentrated sulphuric acid dissolves it, forming a deep violet-coloured solution from which water precipitates the compound unchanged. When heated with pyrosulphuric acid, it is converted into a yellow sulphonic acid, which yields a sparingly soluble barium salt and readily soluble alkaline salts. The substance itself, however, is too sparingly soluble to admit of its employment as a dye, whilst the sulphonic acid is almost destitute of tinctorial properties. It is improbable that the compound has the composition expressed by the formula CO Ph CPh:CS, since this would in no way correspond with its properties, which differ in so marked a manner from those of the thioderivatives of ethyl malonate and ethyl acetoacetate prepared under like conditions by Bergreen (loc. cit.); on the contrary, the author

regards it as a polymeride, and proposes to determine its molecular weight by Raoult's method: in the meantime, it is suggested that it is either a derivative of a six-carbon "ring or a thiophen-derivative formed by a condensation analogous to that occurring in the formation of thiazoles (this vol., p. 256).

The ketones, CH2Ph·CO C2H,Me and CH2Ph.CO.C,SH,, form corresponding compounds when treated with thiocarbonyl chloride and, under like conditions, the phenylated desoxybenzoïn,

CH,Ph•CO CH Ph

also yields a yellow compound which, however, dissolves in sulphuric acid with a green colour. These compounds are extremely stable; the thiophen-derivative for example, when heated with fuming nitric acid is converted into a yellow nitro-derivative, which gives no colour reaction with sulphuric acid.

Methyldesoxybenzoïn, COPh-CHMe Ph, and its homologues do not react with thiocarbonyl chloride, and hence this reagent affords a ready means of discriminating between primary and secondary derivatives of desoxybenzoin.

Thiocarbonyl chloride cannot be employed to distinguish between primary and secondary benzyl cyanides. Benzyl cyanide, however, reacts with a mixture of sodium ethoxide (14 parts of sodium in 20 parts of alcohol) and benzaldehyde forming the nitrile of phenylcinnamic acid, CHPh:CPh CN, which melts at 88°, whilst the nitrile of hydratropic acid, CHMePh CN, does not form a condensation compound under similar conditions. This method can not only be used qualitatively, but may also be employed to separate benzyl cyanide from a mixture of the two compounds. W. P. W.

Oximes of Benzil. By N. POLONOWSKA (Ber., 21, 488-491).When benzilmonoxime in alcoholic solution is reduced with 2 per cent. sodium amalgam in presence of acetic acid, diphenylhydroxyethylamine is obtained. No tetraphenylaldine is formed, as when the reduction is effected by means of tin and hydrochloric acid (Braun and Meyer, this vol., p. 367). When benzildioxime is reduced with sodium amalgam, tetraphenylaldine (loc. cit.) is obtained; ammonia is formed in the reaction. The yield of tetraphenylaldine is small.

N. H. M.

Intramolecular Change in Benzildioxime. By E. GÜNTHER (Ber., 21, 516-518).-When benzildioxime is heated with a solution of hydrogen chloride in glacial acetic acid aud acetic anhydride, a diacetyl-compound is formed which, when saponified, yields Goldschmidt's isobenzildioxime, melting at 206° (Abstr., 1884, 62).

The compound (m. p. 121-122°) obtained by the action of phosphorus pentachloride on benzildioxime (Beckmann, Abstr., 1887, 826) is a dichloride, NCI:CPh CPh:NCI; two other nitrogenous compounds melting at 146° and 95° respectively, are also formed in the reaction. The chloride could not be obtained from isobenzildioxime.

N. H. M. Hydrodiphthallactonic Acid and Hydrodiphthalyl. By E. HASSELBACH (Annalen, 243, 249-272).-Wislicenus (Abstr., 1885,

VOL. LIV.

2 k

57) has shown that diphthalyl, hydrodiphthalyl, and hydrodiphthallactonic acid are formed by the action of acetic acid and zinc-dust on phthalic anhydride, also that hydrodiphthallactonic acid,

is converted into hydroxydiphthalylic acid,

COOH CH,CH2·CH(OH)·C2H ̧COOH,

by boiling with potash.

Silver hydroxydiphthalylate decomposes at 225° in a vacuum, yielding water, phthalic anhydride, and other products. The ethyl salt is a thick liquid which slowly crystallises. Hydrodiphthallactonic acid is converted into stilbenediorthocarboxylic acid,

COOH-CH,CH: CH.C.H, COOH,

by the action of potassium cyanide at 215°. This acid when reduced with hydriodic acid forms dibenzyldiorthocarboxylic acid. Stilbene diorthocarboxylic acid begins to melt at 250°, and is converted at this temperature into hydrodiphthallactonic acid. The ethyl salt forms small needles and melts at 79-80°.

Hydrodiphthallyl (m. p. 250°) dissolves in alkalis, yielding salts of dihydroxybenzyldiorthocarboxylic acid, CHO. The free acid has not been isolated; on the addition of acetic acid to its salts, an acid is deposited having the composition C16H12Os; this acid is converted into hydrodiphthallyl at 190° or by heating with acetic anhydride. The precipitate which is formed when hydrochloric acid is added to a solution of hydrodiphthallyl in alkalis is not a definite chemical compound, but a mixture consisting chiefly of hydrodiphthalyl. Hydrodiphthallactonic acid is not the sole product of the reduction of diphthalyl with zinc and potassium hydroxide; hydrodiphthalyl is always formed in small quantities. Hydrodiphthalyl is partly converted into hydrodiphthallactonic acid by reduction with zinc-dust in alkaline solutions. W. C. W.

10

Derivatives of a-Naphthol. By O. N. WITT (Ber., 21, 321— 325). In addition to a-naphtholsulphonic acid, a-hydroxynaphthyl methyl ketone, OH C10H COMe, is obtained on sulphonating a-naphthol in acetic acid solution, and is also formed by heating equal weights of a-naphthol and acetic acid with zinc chloride as in Nencki and Sieber's method of preparing analogous compounds (Abstr., 1881, 591, 811). It crystallises from benzene in six-sided prisms, from alcohol in needles, melts at 103°, has a pale-green colour, and is insoluble in water. Sulphuric acid dissolves it with a red, alkalis with a pure yellow colour. The alkaline salts crystallise in long, citron-yellow needles, and are decomposed by carbonic anhydride. In alkaline solution, it yields an intense reddish-brown colour with orthonitrobenzaldehyde, but does not form an indophenol on treatment with paradiamines either in the presence of air or of oxidising agents. A comparison of the azo-colours obtained from the ketone with the corresponding a-naphthol-derivatives shows that the shade of colour is invariably more yellow in the case of the former. The crime

crystallises from dilute alcohol in long, pale-yellow needles, and melts at 168-170° with decomposition. When heated with 12 per cent. alcoholic ammonia at 180-200°, the ketone is converted into the ketimide, OH C10H CMe:NH, which crystallises from alcohol in long, golden-yellow needles, melts at 203° with decomposition, and is decomposed into its constituents on treatment with acids or alkalis. B-Naphthol, when heated with acetic acid and zinc chloride, does not form a compound corresponding with a-hydroxynaphthyl methyl ketone. W. P. W.

Action of Carbon Bisulphide on Benzene-azo-p-Naphthol. By P. JACOBSON (Ber., 21, 414-422).—By the action of carbon bisulphide on benzene-azo-B-naphthol, phenyl thiocarbimide, sulphur, thiocarbamidonaphthol, and carbanilamidonaphthol are formed. This reaction shows that under certain conditions benzene-azo-ß-naphthol is capable of reacting as though it were a true azo-compound, for its explanation is difficult on the hydrazide formulæ proposed by Liebermann (Abstr., 1884, 610) and by Zincke and Lawson (Ber., 20, 2903), although at the same time the insolubility in alkalis precludes the substance being regarded as an azo-compound.

Thiocarbamidonaphthol, CH<>CSH, is obtained, together with the products mentioned above, by heating benzene-azo-B-naphthol with five times its weight of carbon bisulphide for 8 to 12 hours at 250°; it is separated from the other products by means of its insolubility in carbon bisulphide and its solubility in alkalis. It crystallises in long, colourless needles, melts at 248-249°, and is sparingly soluble in benzene, readily soluble in hot acetic acid, and very readily soluble in cold alcohol. When heated for some hours at 150-180° with hydrochloric acid, it yields amido-ß-naphthol. From the latter, it can be re-formed by heating with carbon bisulphide. When boiled with aniline, hydrogen sulphide is evolved and carbanilamidonaphtbol formed. By the action of an alcoholic solution of iodine, it is converted into the corresponding bisulphide,

this crystallises in tufts of microscopic needles, is readily soluble in hot benzene and acetic acid, nearly insoluble in hot alcohol.

Carbanilamidonaphthol, CH<>C-NHPh, the main product of the reaction, forms small colourless needles, melts at 167-168°, and is very readily soluble in cold alcohol, sparingly soluble in boiling hydrochloric acid, and insoluble in alkalis. The acetate crystallises in lustrous, flat needles and melts at 120-130°. The picrate melts at 209-210°. When heated with hydrochloric acid for four hours at 180-190°, it is resolved into amidonaphthol, carbonic anhydride, and aniline. A. J. G.

Substitution of the Acetyl-group for the Amido-group by Aid of the Diazo-reaction. Ry R. MELDOLA (Ber., 21, 601).— The compounds formed by the action of nitrous acid on meta- and para

nitrobenzene-azo-B-naphthylamine are readily decomposed by glacial acetic acid with formation of the acetyl-derivatives of the corresponding B-naphthol-compounds. For instance, if nitrobenzene-azo-B-naphthyl. amine is dissolved in hot (not boiling) acetic acid and the necessary amount of sodium nitrite added, metanitrobenzene-azoacetyl-B-naphthol soon separates; it crystallises in hair-like, red needles, and melts at 161-162°; when heated for hour with alcoholic potash, metanitrobenzene-azo-ẞ-naphthol is readily obtained.

This method gives a means of displacing the amido-group by the acetyl-group, and will probably be of general applicability for the synthesis of phenol-derivatives containing different acid radicles. A. J. G. Nitro-derivatives of Phenyl-p-Naphthylamine. By E. HEIM (Ber., 21, 589-594).-Dinitrophenyl-B-naphthylamine,

CH;•NH-CH(NO,) [NH:(NO) = 1:2:4],

is formed by the action of bromodinitrobenzene (m. p. 72°) on an alcoholic soltuion of B-naphthylamine. It crystallises in crimson prisms, melts at 169.5°, is soluble in acetic acid, acetone, hot benzene, and ether, very sparingly soluble in alcohol, and insoluble in water. The reduction-products obtained by the action of iron and acetic acid, and of stannous chloride and hydrochloric acid, could not be isolated.

Nitramidophenyl-B-naphthylamine, [NH: NH, NO, 1: 2: 4], is prepared by reducing the dinitro-compound with ammonium sulphide; it is dimorphous, crystallising in brown needles of cantharidine lustre, or in small, crimson prisms, it melts at 195°; and is very readily soluble in ether, acetic acid, acetone, and chloroform, moderately soluble in alcohol, benzene, and its homologues, insoluble in light petroleum. The acetyl-derivative forms lustrous, orange-red needles, which melt below 200° with decomposition.

∙CH3(NO2). Nitrophenylethenylamido-B-naphthylamine, CH-N< CMeN is prepared by heating nitramidophenyl-B-naphthylamine with ten times its weight of acetic anhydride for seven hours in a reflux apparatus; it forms pale-yellow, lustrous needles, melts at 162°, is readily soluble in alcohol and ether, still more so in benzene, toluene, acetone, and chloroform, and dissolves in acids. The formation of this anhydro-base leaves no doubt that in nitramidophenyl-3-naphthylamine, the amido- and imido-groups are relatively in the ortho-position. Nitrazoimid phenyl-B-naphthylamine, CH, NCH3(NO2) obtained by the action of nitrous acid on the nitramido-compound; it crystallises in delicate, white needles, melts at 203-204°, is sparingly soluble in alcohol, readily in ether, acetic acid, benzene, chloroform, and acetone, and is indifferent to reagents. A. J. G.

N

=

is

Ketonaphthol (Aceto-a-Naphthol). By H. ERDMANN (Ber., 21, 635-636).-Ketonaphthol, CH&AcOH [OH: Ac 1: 3], was ob 1:3], tained by the author in 1886, by the distillation of benzallevulinic acid; it melts at 167°, is rather sparingly soluble in benzene in the