at 186°, give the same violet-blue, pine-wood reaction, the same nitroso-product and the same amidophenylindole melting at 174. Phenylacetaldehydephenylhydrazone, CH,Ph CH:N,PhH, is obtained by mixing phenylhydrazine with phenylacetaldehyde, and warming the mixture; it crystallises from light petroleum in almost colourless forms, melting at 58°, and readily soluble in alcohol, ether, and benzene.

2'-Phenylindole is produced by heating the preceding compound with zinc chloride for 5 to 10 minutes at 180-185°; it crystallises from hot alcohol or benzene in thin leaves melting at 180°. This compound resembles methylketole in all its reactions, except in its behaviour towards nitrous acid.

Nitroso-2-phenylindole, [Ph: NO = 2′ : 3′] (Möhlau, Abstr., 1883, 342; Fischer, Abstr., 1886, 805), is best obtained by saturating a glacial acetic acid solution of the indole with a very concentrated solution of sodium nitrite. On heating quickly, it becomes darker coloured about 250°, and melts, not quite constantly, at about 258°, with decomposition. It is readily soluble in potash or soda, and is reprecipitated on addition of hydrochloric acid. It does not give Liebermann's reaction, but on reduction yields an amido-base, which has the closest resemblance to amidomethylketole (Wagner, this vol., p. 284).

Amido-2-phenylindole, [ÑH2 = 3′], is produced when the nitrosocompound is reduced with zinc and hydrochloric acid; it crystallises from hot benzene in thin, colourless, shining scales, which melt at 174°, and are almost insoluble in water, but dissolve readily in alcohol, ether, benzene, and dilute acids. It reduces Fehling's solu tion on boiling, and colours pine-wood orange. When in a moist condition, it is converted into a violet dye by oxidising agents, even by the oxygen of the air.

Benzylidene-2-phenylindole, CHPh(C1H1N)2, is formed by heating the indole with benzaldehyde; it crystallises from hot acetone in slender, shining needles, which melt at 262-263°, and are very sparingly soluble in alcohol.

Hydro-2-phenylindole, C1HN, is obtained by boiling the indole with zinc and hydrochloric acid; it separates from light petroleum in almost colourless crystals, which melt at 46°, are readily soluble in dilute mineral acids, and colour pine-wood orange. Nitrous acid converts it into a nitrosamine.

F. S. K.

Metaditolyl. By E. STOLLE (Ber., 21, 1096-1099).—Metaditolyl, MеCH,CH,Mе, can be prepared by the action of nitrous acid and alcohol on orthotolidine, by heating orthodicresol with zinc-dust, or by the reduction of dichloroditolyl. It is a yellowish oil, boiling at 289°; its sp. gr. = 0.9993 at 16° (water at 4° = 1).

Dichloroditolyl, CH,MeC1-C,H,MeCl, is obtained from orthotolidine by Sandmeyer's method; the intermediate copper compound, C12H,Me2N,Cl2, CuCl, is a dark, yellowish-brown powder. Dichloroditolyl crystallises from alcohol in white, shining leaves, melting at 51°. On oxidation with chromic acid, it yields chlorotoluylic acid, melting at 205°. When heated with phosphorous pentachloride, a

compound, CHCl, is formed, which on oxidation with dilute nitric acid yields dichlorodiphenylmeta carboxylic acid,

:

COOH-C,H,Cl.C,H,C1·COOH [(COOH), : Cl2 = 3: 3' 4: 4′]. This acid is readily soluble in hot, sparingly in cold water, and melts at 267-268°.

Di-iododitolyl, CH,MeI CH3Mel, obtained by Sandmeyer's method, crystallises in yellow needles melting at 99-100°. F. S. K.

Aldines. By E. BRAUN and V. MEYER (Ber., 21, 1269–1282; compare this vol., p. 366).-Tetraphenylaldine* (Polonowska, this vol., p. 485) is prepared by gradually adding 5 per cent. sodium amalgam to a solution of benziloxime in aqueous soda. The product is filtered, washed with water, dried over sulphuric acid, and then rubbed with cold alcohol; it is again filtered, well washed with alcohol, dissolved in chloroform, and precipitated with alcohol. Finally it is dissolved in much boiling alcohol, from which it separates in slender, matted needles, melting at 245-246°. It is sparingly soluble, except in chloroform. Sulphuric acid dissolves it without change, yielding an intensely orange-coloured solution. It is not a base. The tetranitro-derivative, C28H16N6Os, melts at 130°—140°, dissolves in chloroform and benzene, and is insoluble in ether, alcohol, and light petroleum.

An attempt was made to prepare diphenylaldine by reducing isonitroso-acetophenone with stannous chloride and hydrochloric acid. Eso-amidoacetophenone hydrochloride, COPh CH, NH, HCl, is formed. This salt separates from its aqueous solution in crystals melting at 183-184°. The platinochloride crystallises in long, slender, yellow needles melting at 200°. The aurochloride crystallises from water containing alcohol in slender, gold-coloured needles. The sulphate forms long crystals. The free base could not be isolated, as it decomposes when dried with formation of the compound C6H1N2O. This crystallises from alcohol in stellate groups of slender needles, melting at 118-119°; it is readily soluble in hydrochloric acid. When eso-amidoacetophenone hydrochloride is treated with ammonia, instead of soda, iso-indole (diphenylaldine), CH12N2, is obtained (compare Wolff, Ber., 20, 432). The above compound was prepared by the action of alcoholic ammonia on bromacetophenone (Städel and Kleinschmidt, Abstr., 659), and the two preparations compared.

14

Eso-amidoacetophenone is also formed by the action of ammonia on bromacetophenone.

When isonitrosomethyl ethyl ketone is reduced with stannous chloride and hydrochloric acid, a hydrochloride of a base is obtained not identical with tetramethylaldine; aldines of the fatty series are, therefore, not directly formed when isonitroso-ketones are reduced in acid solution. N. H. M.

Both the authors and Polonowska seem to have overlooked the fact that this substance is identical with the compound described as ditolaneazotide and as tetraphenylazine by Japp and Wilson (Trans., 1886, 827), and by Japp and Burton (Trans., 1886, 843, and 1887, 101).—Ed.

Substitution in Benzoïn and in Analogues of Desoxybenzoïn and Benzyl Cyanide. By V. PÄPCKE (Ber., 21, 1331-1343).Benzylated derivatives are obtained when the three tolyl cyanides are respectively treated with sodium ethoxide and benzyl chloride, hence the substitution of methyl in the phenyl-group in benzyl cyanide does not interfere with the displacement of one of the hydrogenatoms of the methylene-group by an alkyl-radicle. Benzylated metatolyl cyanide, CH,Me CH(C,H,) CN, is an oil which, after long standing, crystallises in rectangular tables, melts at 53°, and boils at 350-360° with slight decomposition. On treatment with aqueous alkalis, it yields benzylated metatoluylacetic acid, which separates from all solvents as an oil slowly solidifying to a crystalline mass which melts at 79-80°. Benzylated orthotolyl cyanide is an oil, and boils at 340-350° with slight decomposition; the corresponding acid forms large crystals and melts at 95.5°. Benzylated paratolyl cyanide crystallises from alcohol in long, white needles, melts at 79°, and is insoluble in water, but soluble in alcohol; the corresponding acid crystallises from alcohol in small aggregates, melts at 105°, and is soluble in ether. It was not found possible to substitute a second benzyl-radicle for the remaining hydrogen-atom of the methylenegroup in any one of these cyanides.

Benzoïn yields benzil only when acted on by sodium ethoxide, but forms a sodium-compound when its solution in benzene is treated with sodium; this derivative, however, contains more sodium than is required for the formula CHPhBz-ONa. Acetylbenzoïn also, which melts at 83° and not at 75° (Zinin, Annalen, 104, 120), does not react when treated with sodium ethoxide, but decomposes into its constituents, acetic acid and benzoin. Lastly, benzoin isobutyl ether, which can be prepared by heating benzoïn (10 grams), sodium (2 grams), alcohol (20 grams), and isobutyl bromide (20 grams) at 150° for four hours, and is an oil boiling at 240-245° under 110 mm. pressure, does not form a benzylated derivative when treated with sodium ethoxide and benzyl chloride; from this it follows that it is not possible to effect a substitution of an alkyl-radicle for the hydrogenatom of the methylene-group in benzoïn and its ethers.

Diphenyl benzyl ketone, C,H,Ph CO-CH,Ph, is prepared by dissolving phenylacetic chloride and diphenyl in molecular proportion in carbon bisulphide, treating the mixture with aluminium chloride in the cold, and finally heating at 100° in a reflux apparatus to complete the reaction. It crystallises from acetic acid and alcohol in lustrous scales, melts at 150°, and is insoluble in water, sparingly soluble in ether and cold alcohol. The benzylated ketone, C,H,Ph·CŎ·CHPh·C2H,, is obtained by the action of sodium ethoxide and benzyl chloride; it crystallises in long, white needles, melts at 158°, is sparingly soluble in alcohol, and when heated for five hours at 160° with hydroxylamine hydrochloride is converted into the oxime, C2H22:N OH, which crystallises in slender needles, and melts at 175°. On treatment with thiocarbonyl chloride, diphenyl benzyl ketone is converted into the compound C,H,Ph-CO-CPh:CS (compare this vol., p 484); this has an intense yellow colour, melts at 320°, is insoluble in alcohol and ether, very sparingly soluble in chloroform, and dissolves in concen3 a

VOL. LIV.

trated sulphuric acid with a green colour, which soon changes through violet to red, owing to the absorption of moisture.

Naphthyl benzyl ketone, CH, CO-CH,Ph, obtained in like manner from naphthalene, yields the corresponding alkyl-derivatives when treated with sodium ethoxide and ethyl bromide, isobutyl bromide, and benzyl chloride respectively. The products are oils, which cannot be crystallised, and do not yield crystalline oximes.

9

Fluoryl benzyl ketone, C1H, CO-CH,Ph, obtained under like conditions from fluorene, crystallises in small, white tables, melts at 156°, and is sparingly soluble in alcohol and ether; the yield amounted to 5 per cent. only of the weight of fluorene employed. When treated with sodium ethoxide and benzyl chloride, it yields a benzylated-derivative, C1H CO-CHPh C,H,, which crystallises from alcohol in slender, matted needles, melts at 149-150°, and is insoluble in ether, very sparingly soluble in hot alcohol. Fluoryl benzyl ketone reacts with thiocarbonyl chloride forming an orange-yellow powder, insoluble in alcohol and ether, but readily soluble in chloroform and benzene; although it could not be purified sufficiently for analysis, it probably has the composition CH, CO-CPh:CS, since it gives an intense colour reaction with concentrated sulphuric acid.

Acenaphthyl benzyl ketone, C12H, CO-CH2Ph, formed in like manner from acenaphthene, crystallises in pale-yellow scales, melts at 114°, and is readily soluble in hot alcohol; the yield amounted to 30 per cent. of the weight of acenaphthene employed. On treatment with sodium ethoxide and benzyl chloride, it is converted into the benzylated derivative, C12H, CO-CHPh C,H,, which crystallises from alcohol in pale-yellow needles, and melts at 104°. In none of these ketones was it found possible to substitute an alkyl-radicle for the second hydrogen-atom of the methylene-group. W. P. W.

Negative Nature of Organic Radicles and the Question of the Existence of true Nitroso-compounds. By V. MEYER (Ber., 21, 1291–1295).-The great analogy existing between ethyl malonate and acetoacetate on the one hand, and desoxybenzoïn and benzyl cyanide on the other was previously mentioned. The two latter compounds differ from the former in not yielding sodium compounds which can be isolated. Homologues of benzyl cyanide can be obtained by heating the cyanide with alkyl chlorides and solid potash. In like manner, derivatives of desoxybenzoïn can be prepared by using aqueous alcoholic potash. Desoxybenzoin and benzyl cyanide are converted by nitrous acid into the isonitroso-derivatives,

COPh CPh:N OH and CPh.C(N.OH).CN.

Methyldesoxybenzoïn, however, does not yield the nitroso-compound, COPh CMcPh NO, but benzoic acid and acetophenoneoxime.

When diphenylacetonitrile is treated with amyl nitrite and sodium ethoxide the polymeride described by Anschütz and Romig (Abstr., 1886, 1033) is formed. It is probable that the nitroso-compounds (such as contain the group NO in direct combination with carbon) cannot exist; the pseudonitroles, the only class of compounds of which the nitroso-nature is generally undisputed, may be considered as nitrates

of the acetoximes, a view supported by Scholl's experiments (this vol., p. 443); thus, the formula of propylpseudonitrole would be CMe2:N•O•NO2. (Compare this vol., p. 147.) N. H. M. Examination of

Negative Nature of Organic Radicles. Desoxybenzoin. By V. MEYER and L. OELKERS (Ber., 21, 12951306). Desoxybenzoin is prepared as follows:-20 grams of benzoïn, 60 grams of 75 per cent. alcohol, and 10 grams of granulated zinc are heated in a water-bath, treated with 20 grams of 80 per cent. alcohol saturated with hydrogen chloride, and the whole boiled for 2 to 3 hours. 10 grams of alcohol containing hydrochloric acid is then added, the liquid reduced to half its bulk by evaporation, and poured off from the unchanged zinc. The desoxybenzoin is precipitated by hot water, the water poured off (on cooling more desoxybenzoïn separates) and the desoxybenzoïn made to solidify by cold water. It is pressed between filter-paper, distilled and then crystallised several times from alcohol. It melts at 60° and boils at 320-322° (corr.). The yield of pure substance is 60 per cent. of the weight of the benzoïn used.

The introduction of alkyl-groups into desoxybenzoïn is carried out in the following manner :-A weighed amount of sodium is treated. with absolute alcohol, the calculated amount of finely powdered desoxybenzoin added, and the whole heated for two minutes on a waterbath. When cold, the alkyl-derivative is added and the mixture heated on a water-bath for 15 minutes.

Methyldesoxybenzoin, COPh.CH Me Ph, crystallises from alcohol, which dissolves it readily in long, slender needles, which melt at 53°, and boil at 317·5-318.5° (corr.). The oxime, CHPhMe CPh:N·OH, crystallises in long, prismatic needles, melting at 120°. Desoxybenzoïn oxime crystallises similarly and melts at 98°.

Ethyldesoxybenzoin, CÓPh-CHEtPh, crystallises in long, slender needles, melts at 58° and boils at 323-324° (corr.). The hydroxylaminederivative crystallises from alcohol in needles melting at 129-130°. Isobutyldesoxybenzoin, CH, CHPh·COPh, prepared from isobutyl bromide, crystallises in short needles rather less soluble than the methyl and ethyl compounds; it melts at 78° and boils at 329-5-330-5 (corr.) The hydroxylamine compound crystallises in prisms melting at 118°.

Benzyldesoxybenzoin, CH,Ph.CH Ph-CÓPh (from benzyl chloride) crystallises in short, slender needles melting at 120°. It is very sparingly soluble in cold alcohol. The oxime crystallises from dilute alcohol in needles of a silvery lustre melting at 208°.

Attempts to introduce two alkyl-groups into desoxybenzoïn and to introduce a second alkyl-group into the derivatives described above gave negative results.

When a slow stream of nitrous acid is passed through sodium desoxybenzoïn, benzil monoxime is found. (Wittenberg and Meyer, Abstr., 1883, 803.) The compound is most readily obtained by Claisen's method (Abstr., 1887, 575), by adding 1 gram of desoxybenzoïn and 0.6 gram of amyl nitrite to a well-cooled solution of 0.12 gram of sodium in 3 to 4 grams of absolute alcohol; after two days the product is poured into water, shaken with ether, acidified