displaces the H atom at 4 in a-cymenesulphonic acid, and at 6 in the B-acid. When bromocymenes are dissolved in sulphuric acid, the sulphonic group takes the position 4 in the a-compound, and 6 in the B-compound. The constitution of these compounds is shown in the following table : Bromotoluic acids, Me: COOH : Br Dibromocymene, Me: Pr: Br: Br B. a. .... 1:3:6 1:3:4 1:3:6 1:3:4 1:3:6 1:3:4 1:34:6 1:3:6:4 1:3:4:6 Bromoisophthalic acid, COOH: COOH: Br 1:3:6 1:3:4 W. C. W. Synthesis of Indole-derivatives. By E. FISCHER (Annalen, 236, 116-126).-Many of the results contained in this paper have already been published (Abstr., 1884, 52, 1180; and 1886, 835).-The fæcal odour of indole is most marked in skatole, and in the mono- and di-methyl compounds with the exception of those substances in which the methyl-group is united to the N-atom. The odour and volatility of the compounds is destroyed by the introduction of the phenylgroup. All indole-derivatives form crystalline picrates, and all the indoles with the exception of the carboxylic acids are reduced by zinc and hydrochloric acid to hydro-bases. The pine-wood reaction is not exhibited by the carboxylic acids, nor by those derivatives in which both the 2' and 3'* hydrogen-atoms are replaced by methyl, ethyl, &c. Nitrous acid converts indole and l' methylindole into nitrosocompounds. It forms complicated products with 2' methyl or phenyl indole, and converts 3' or 2', 3' substituted indoles into nitrosamines. The following is a list of indoles derived from the hydrazines. *Note.-In the notation of the indole series, 1, 2, 3, 4 refer to the positions in the benzene-ring, and 1', 2', 3' to the corresponding positions in the basic ring containing the nitrogen, where N 1', as shown in the annexed symbol: = Indoles from Phenylhydrazine. By E. FISCHER (Annalen, 236, 126-151). Most of the compounds mentioned in this paper have already been described by the author (Abstr., 1886, 805). 2', 3′ Dimethylindole, C,NH,Me, prepared from the phenylhydrazine compound of methyl ethyl ketone, melts at 106° and boils at 285°. The nitrosamine, C,NH,Me, NO [NO = 1'], melts at 61-62°, and decomposes at a higher temperature. 2' 3' Methylethylindole, C,NH,MeEt, prepared from the phenylhydrazine of methyl propyl ketone, is an oily liquid boiling at 291-293°. The picrate crystallises in dark red needles. Phenylhydrazinelevulinic acid, PhN2HCMe CH2 CH2COOH, melts at 108°, and at a higher temperature splits up into water and the anyhdride, CH12N2O. This substance crystallises in colourless plates. It melts at 106-107° and boils between 340° and 350° with partial decomposition. Ethyl phenylhydrazinelevulinate melts at 110°. Methylindoleacetic acid, prepared from this ethyl salt, melts between 1950 and 200°, and splits up into carbonic anhydride and 2, 3' dimethylindole. W. C. W. Indoles from Methylphenylhydrazine. By J. DEGEN (Annalen, 236, 151-164). The preparation of 1', 2' dimethylindole, 1, 2 methylphenylindole, and 1', 2', 3' dimethylindolecarboxylic acid from the compounds of methylphenylhydrazine with acetone, acetophenone, and ethyl acetoacetate, respectively, has already been described (Abstr., 1886, 805). Dimethylindolecarboxylic acid crystallises in six-sided plates. It melts at 185° with partial decomposition into carbonic anhydride and 1', 2' dimethylindole. 1', 2', 3′ Dimethylindoleacetic acid (loc. cit.) melts at 188° and decomposes at 200°, yielding 1', 2', 3' trimethylindole, an oily liquid which boils about 280° without decomposition. The picrate melts at 150°. Trimethylindole is obtained in a less pure state by the action of zinc chloride on the compound of methylphenylhydrazine with methyl ethyl ketone. 1', 3' Dimethylindole is obtained in an impure state by acting on propylidenemethylphenylhydrazine with zinc chloride. W. C. W. Indoles from Metahydrazinebenzoic Acid. By A. RODER (Annalen, 236, 164–173). — Metahydrazinebenzoic acid is con veniently prepared by adding the theoretical quantity of sodium nitrite to 100 grams of metamidobenzoic acid suspended in a mixture of 400 grams of water and 190 grams of strong hydrochloric acid. The liquid is poured into an ice-cold solution of sodium sulphite (4 mols. Na2SO, to 1 mol. amido-acid). As soon as the mixture turns yellow, strong hydrochloric acid is added to precipitate the hydrochloride of metahydrazinebenzoic acid. The free acid is obtained by adding sodium acetate to a solution of the hydrochloride. The acetone compound is formed when acetone and sodium acetate or potassium hydroxide are added to a solution of the hydrochloride. This substance forms colourless needles melting at 150°. It is freely soluble in alcohol and acetic acid, and is easily decomposed by warm mineral acids into acetone and hydrazinebenzoic acid. The ethylic salt CHN2O,Et, melts at 90-91° and dissolves freely in alcohol, ether and acetic acid. Hydrazinebenzopyruvic acid, C10H10N2O4 + H2O, melts at 206-208° with decomposition, and is freely soluble in ammonia and fixed alkalis. The barium and sodium salts are crystalline. The ethyl salt, CH,N2O,Et2, melts at 101-102°. It dissolves freely in alcohol, ether, and in warm benzene. By the action of zinc chloride on this compound, the ethyl salt of indoledicarboxylic acid is formed, together with indole and a small quantity of another substance. Monethyl indoledicarboxylate crystallises in needles and melts at 250° with decomposition. It is freely soluble in alcohol. The free acid melts at 250° with decomposition. It dissolves freely in hot alcohol and in acetic acid. It has the constitution [(COOH), = 4 : 2′ or 3:2′]. Hydrazinebenzoic acid unites with benzaldehyde, forming benzylidenehydrazinebenzoic acid. This acid crystallises in plates, melts at 170-172°, and is freely soluble in alcohol and acetic acid. Phenylglucosazonecarboxylic acid melts at 206-208° with decomposition. Metahydrazinebenzoic acid unites with phenyl isothiocyanate, forming diphenylthiosemicarbazidecarboxylic acid, CH13N3O2. This substance crystallises in colourless needles and melts at 204-205° with decomposition. W. C. W. Aluminium Chloride Reaction. By R. ANSCHÜTZ (Annalen, 235, 150-229 and 299-341). The experimental results of the author's research on the aluminium chloride reactions have already been published (Abstr., 1883, 807, 809, 1132; 1884, 326, 753, 754, 1034; 1885, 269, 768, 769). The following conclusions are deduced from these results. Dibenzyl and unsymmetrical diphenylethane (obtained by the action of aluminium chloride and benzene on the isomeric dibromethylenes) correspond with the dibromethylenes in constitution. The synthesis of anthracene from aluminium chloride, benzene, and acetylene tetrabromide, indicates that the mesocarbon-atoms in anthracene are probably linked together. The formation of dimethylanthracene from toluene, acetylene tetrabromide, and aluminium chloride, shows that the methyl-groups in dimethylanthracene, melting at 225°, are divided between the two benzene nuclei. Aluminium chloride not only removes but also transfers the side-chains of methyl and ethyl-benzenes from one molecule to another. Only the symmetrical tetraphenylethane is known. In many aluminium chloride reactions, theoretical yields are obtained when carbon bisulphide is used as a diluent. Symmetrical mesodimethylanthracene hydride is formed, together with ethylbenzene and unsymmetrical diphenylethane, by the action of benzene and aluminium chloride on ethylidene bromide or chloride, or on vinyl bromide. Ethyltoluene, unsymmetrical ditolylethane, and tetramethylanthracene hydride are formed by the action of aluminium chloride on ethylidene chloride and toluene. A new dimethylanthracene is formed by heating the tetramethylanthracene hydride with zinc-dust. W. C. W. Dehydrogenation by Means of Benzoic Peroxide. By E. LIPPMANN (Monatsh. Chem., 7, 521-528).-Benzoic peroxide can react as a dehydrogenising agent, removing two hydrogen-atoms from two molecules of an aromatic hydrocarbon. Thus from toluene a hydrocarbon, C1H12, is formed; the hydrocarbon boils at 258-262°, is strongly refractive, and of aromatic odour, sp. gr. 1.0032; it is isomeric with stilbene and diphenylethylene, and as, on oxidation, it yields benzoic acid only, its constitution is probably expressed by the formula CHCH2, that of a benzylidenetolylene. ·CH Similarly from xylene, a hydrocarbon, C16H16, is obtained as a refractive liquid, boiling at 260-270°, sp. gr. 998; as being isomeric with ditolylethylene and dimethylstillene, it is named dixylylene. V. H. V. Formation of Substituted Stilbenes. By K. ELBS (J. pr. Chem. [2], 34, 340-342).—On endeavouring to extend Strakosch's method of synthesis of stilbene-derivatives by the action of potash on benzylderivatives, the reaction with orthonitrobenzyl chloride was successful, but in the case of parabromobenzyl bromide the corresponding alcohol was obtained together with ethyl parabromobenzoate; the latter substance, the derivation of which in the above reaction is not satisfactorily explained, is a colourless viscid liquid, boiling at 236° under a pressure of 713 mm., of odour resembling pears, soluble in most menstrua with the exception of water, saponified only with difficulty. V. H. V. Substituted Stilbenes. By K. ELBS and F. Bauer (J. pr. Chem. [2], 34, 343-347).-Paradinitrostilbene is not altered by potassium permanganate; on oxidation with chromic acid in acetic acid solution, it is readily converted into paranitrobenzoic acid. With bromine, it forms paradinitrostilbene bromide, NO, CH¿CHBr·CHBr·CH ̧•NO2, a white, crystalline powder melting above 300°, but decomposing even at 110° with evolution of hydrobromic acid and the formation of paradinitrotolane; it is sparingly soluble in most menstrua. When an acetic acid solution of paradinitrostilbene bromide is boiled with potassium acetate, ethyl paradinitrohydrobenzoin acetate, NO, CH, CH(OAc)·CH(OAc) C.H, NO2, is formed; this crystallises in small, yellow crystals, melting at 340°, moderately soluble in alcohol, ether, and acetic acid. Paradinitrotolane, NO,C,H,CC-CH, NO2, obtained as described above, and best purified by sublimation, crystallises in needles melting at 288; it usually separates from solvents in the amorphous form. V. H. V. Euxanthone-group. By C. GRAEBE and A. FEER (Ber., 19, 2607-2614).-Spiegler (Abstr., 1884, 1182) ascribed to benzoCHOphenone oxide the constitution <CH.CO, as it reacts neither with hydroxylamine nor with phenylhydrazine. The authors suggest for this compound the constitution C.H-C-C.H.; this would account for the negative result with hydroxylamine, as well as for the fact that it yields dihydroxybenzophenone when fused with potash (Richter, Abstr., 1884, 324). Orthodihydroxybenzophenone (Richter, loc. cit.) boils at 330-334° with partial decomposition into water and benzophenone oxide. The potassium salt has the formula CO(CH, OK)2. The phenylhydrazine and hydroxylamine-compounds melt at 152° and 99° respectively. The methyl salt was found to melt at 104° (not 98°); it undergoes no change when heated with alcoholic potash at 150°; the hydroxylaminederivative melts at 188°. The ethyl salt crystallises from alcohol in colourless needles melting at 109°; the phenylhydrazine-compound melts at 114°. The acetyl-derivative melts at 96° (not 83°). When paracresol salicylate is subjected to the same treatment as the phenyl salt in the preparation of benzophenone oxide (Siefert, Abstr., 1885, CO. 1058), the compound CH1<>CH,Me is formed; this is very readily soluble in hot alcohol and melts at 105°. a-Naphthol salicylate yielded a-naphthophenone oxide, CH10O2; it melts at 155°, and dissolves very readily in hot toluene. The picrate is yellowish-red. B-Naphthophenone oxide crystallises in needles melting at 140°. When euxanthonic acid is fused with potash, it is converted into quinol; it has therefore the constitution : CH3(OH), CO-CH(OH)2 [CO: OH OH 6:14]. An ethyl salt was obtained which reacts with hydroxylamine. N. H. M. Preparation of Dinitronaphthylamine: Metanitrophenylazodimethylamidobenzene. By R. MELDOLA (Ber., 19, 2683— 2684).--Naphthylamine is boiled for several hours with acetic acid; the theoretical amount of nitric acid (sp. gr. 1·5) diluted with glacial acetic acid is then gradually added to the warm solution of the acetonaphthalide and the whole warmed until the reaction is finished. The product is then poured into cold water, filtered, and washed well with cold water. The precipitate whilst still moist, is mixed in small quantities with strong sulphuric acid and warmed; it is then poured into cold water, and the orange-red precipitate washed with water; it may be purified by recrystallisation from alcohol. The yield of crude substance is almost theoretical. |