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with picric acid, and yields a dibromo-derivative which has the composition C18H16 Br2 or C1H1Br2. When oxidised with chromic acid and acetic acid, it yields yellowish or white needles, which melt at 325° and sublime completely without decomposition at a higher temperature. The composition of this product agrees more nearly with the formula C18H3O2 than C8H1O2. With bromine, a mixture of a mono- and dibromo-derivative is obtained. Most probably the hydrocarbon is an isomeride of tetramethylanthracene, although it differs markedly from it and the other methylanthracenes.

C. H. B.

Decomposition of Mixed Ethers by Heat and Nitric Acid. By G. ERRERA (Gazzetta, 17, 193-209).-In former investigations it has been shown that when the mixed ethers containing a paraffinoïd and aromatic grouping are heated with nitric acid, they yield the corresponding aromatic aldehyde or its nitro-derivative, and the nitrate of the paraffin. Also Liebig, Cannizzaro, and others have shown that when heated, the ethers decompose into an aldehyde and hydrocarbon. In this paper, the reactions are studied in the case of benzyl isobutyl ether and benzyl isoamyl ether, and halogen-derivatives of benzyl ethyl ether. When benzyl isobutyl ether is heated with concentrated nitric acid, it forms benzaldehyde and isobutyl nitrate, whilst benzyl isoamyl ether yields the same aldehyde and isoamyl nitrate.

Considerable difficulty was experienced in the preparation of parabromobenzyl chloride, whether by the bromination of benzylic chloride or the chlorination of benzylic bromide; the product was invariably a mixture nearly in molecular proportion of parabromobenzylic chloride and bromide. This mixture, however, serves for the preparation of parabromohenzyl ethyl ether, CH,BrCH2OEt, which is a colourless liquid of fruity odour boiling at 243°, but with appreciable decomposition into parabromobenzaldehyde and ethane; this change is instantaneous at the temperature of boiling sulphur. The bromobenzyl ethyl ether is converted into parabromobenzaldehyde by the action of nitric acid.

Parachlorobenzyl ethyl ether, CH,CI-CH2OEt, from parachlorobenzylic bromide, is a liquid of properties similar to those of the bromo-compounds; it boils at 225-227°, and is decomposed at a higher temperature into the corresponding aldehyde and ethane; it also yields the same aldehyde when treated with nitric acid.

V. H. V. Isonitroso-derivatives. By H. v. PECHMANN (Ber., 20, 2539— 2544). When pure benzaldoxime is shaken with 10 times its volume of a 30 per cent. solution of sodium hydrogen sulphite, a crystalline compound is obtained, which after removal of the mother-liquor and washing with alcohol and ether, crystallises from water in small, white needles of the composition SO,Na CHPh·NH·SO,Na + 3H2O compound is insoluble in alcohol but very soluble in water; its aqueous solution is decomposed on boiling. When heated with dilute acids or alkaline carbonates, or when treated with alkalis in the cold, it decomposes quantitatively into benzaldehyde, sodium sulphate, and ammonium hydrogen sulphite.


Acetoxime dissolves in a solution of sodium hydrogen sulphite with

development of heat, and yields a clear liquid from which, on addition of alcohol and some acetic acid, a crystalline compound slowly separates. Dilute acids decompose this compound into acetone, sodium sulphate, and ammonium hydrogen sulphite.

With sodium hydrogen sulphite, under similar conditions, nitrosoacetone forms a compound which most probably has the composition. SO,Na CMe(OH)·CH(SO,Na) NH-SO,Na + 3H2O. This separates from dilute alcohol as a powder consisting of colourless needles, and is extremely soluble in water but insoluble in alcohol. When heated with dilute acids, it is decomposed into methylglyoxal, sodium sulphate, sodium hydrogen sulphite, and ammonium hydrogen sulphite. The methylglyoxal was recognised by subjecting the product to steam distillation and treating the distillate firstly with phenylhydrazine acetate, when the phenylhydrazide, N2HPh: ČH CMe: N2HPh, which crystallises in slender, yellow needles melting at 145°, was obtained; and secondly with toluylenediamine, when methyltoluquinoxaline, identical with that described by Hinsberg (Abstr., 1886, 561), was formed. These derivatives are also formed by the action of these reagents on nitrosoacetone, but their formation in the absence of this compound may be regarded as affording evidence of the presence of methylglyoxal W. P. W.

Unsymmetrical Secondary Hydrazines. By B. PHILIPS (Ber., 20, 2485-2488).-Sodium phenylhydrazine suspended in benzene is treated with an alkyl bromide, and the mixture after the lapse of some hours is heated on a water-bath to complete the reaction. The product, after filtration from the sodium bromide, is purified by saturating the benzene solution with hydrogen chloride and filtering from the insoluble hydrochlorides; the benzene is then removed by distillation, the residue dissolved in ether, the solution again distilled, and the base obtained by precipitating the aqueous solution of the hydrochloride with an alkali. The secondary hydrazines when freshly distilled are colourless liquids which become brown in the air, dissolve to clear solutions in concentrated hydrochloric acid, and show all the characteristic properties of Fischer's methyl- and ethyl-phenylhydrazine.

a-Isopropylphenylhydrazine, NPrPh-NH2, boils at 185° under 172 mm. and at 233° under the ordinary pressure; the hydrochloride crystallises well from benzene and melts at 135°. The tetrazone forms colourless crystals and melts at 85°, the thiosemicarbazide, NPPh NH CS NHPh, crystallises from alcohol in large, well formed crystals and melts at 116°, and the acetyl-derivative, NPrPh-NHAC, melts at 97°.

a-Isobutylphenylhydrazine, CH, NPh-NH2, boils at 193-195° under 179 mm., and at 240-245° under the ordinary pressure, in the latter case with partial decomposition and formation of small quantities of ammonia. The hydrogen sulphate forms nacreous scales.


-Isoamylphenylhydrazine, C,H'N Ph NH2, boils at 210° under 57 mm., and at 260° under the ordinary pressure.

a-Benzylphenylhydrazine (Abstr., 1886, 1025) is a thick, colourless liquid which cannot be distilled without decomposition in a partial vacuum, and when cooled in open vessels gradually solidifies to a

crystalline mass; this melts at 21° and seems to contain 1 mol. H2O. The anhydrous base does not solidify in dry air. The acetyl-derivative melts at 121°, and the tetrazone at 109°. When treated with benzaldehyde, benzylidenebenzylphenylhydrazine, CH, NPh⋅N: CHPh, is obtained; this crystallises in needles, melts at 109°, and is readily soluble in alcohol, ether, and benzene. This base could not be prepared by the direct action of benzyl chloride on benzylidenephenylhydrazine; if, however, the sodium compound of the base, obtained by the addition of finely divided sodium to benzylidenephenylhydrazine in benzene solution, is treated with benzyl chloride, a compound is obtained which shows all the properties of benzylidenebenzylphenylhydrazine. The author regards this result as affording experimental evidence in favour of the formula NHPh-N: CHPh for benzylidenephenylhydrazine. W. P. W.

Azophenines and Indulines. By O. FISCHER and E. HEPP (Ber., 20, 2479-2484).-Azophenine can be obtained by heating nitrosomethylaniline and nitrosoethylaniline with aniline hydrochloride (1 part) and aniline (4 to 5 parts) at 80°. The best method of preparation, however, consists in digesting paranitrosodiphenylamine (1 part) with aniline hydrochloride (1 part) and aniline (5 parts) at 100° for 8 to 10 hours; the product, which contains induline and paramidodiphenylamine (m. p. 66-67°), is washed with water and alcohol, and crystallised from toluene: the yield amounts to 15 part of pure azophenine. The azophenine of paratoluidine can also be prepared from nitrosodiphenylamine and paratoluidine, and is identical with Kimich's compound (this Journal, 1876, i, 268).


Chlorazophenine, C36H28CIN5, is obtained from parachloronitrosodiphenylamine by a similar method; it melts at 230°, and closely resembles azophenine in its properties, but is somewhat more soluble in benzene and toluene. Tetrabromazophenine, C6H25 Br.Ns, results from the action of nitrosodiphenylamine (1 part) on parabromaniline (4 parts) and parabromaniline hydrochloride (1 part) at 100°; it melts at 243°. If metahydroxynitrosodiphenylamine is substituted for nitrosodiphenylamine in the preparation of azophenine, hydroxyazophenine is obtained. Dibromonitrosophenol also yields & brominated azophenine when heated at 90° with aniline and aniline hydrochloride. From these results, it is evident that nitrosodiphenylamine enters in some way into the molecule of azophenine, and that the views advanced by Witt with regard to the constitution of this compound (this vol., p. 821) must be abandoned in favour of those originally put forward by Kimich. If paranitrosodiphenylamine be repreNHPh

sented as a quinoneoxime-derivative of the formula C.H.<

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the authors regard the formation of azophenine as analogous to that of quinone-anilide, and attribute to azophenine the formula

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[N:NHPh:N:NHPh 1:2:4:6]. This view may be considered as being confirmed in the following way :-Azophenine when heated with alcoholic ammonium sulphide and toluene at 130-140° for some hours is converted into dihydrazophenine, CHaNs; this crystallises in white needles, melts at 173-174°, and is soluble in alcohol, readily soluble in chloroform and toluene, and insoluble in hydrochloric acid. Moreover, if azophenine is digested with alcohol and concentrated sulphuric acid at 100° in a reflux apparatus, it is converted into a compound, C24H,N3O2, which crystallises from aniline in silver-grey scales, red by reflected light, dissolves in concentrated sulphuric acid with a magenta colour, and yields with tin and hydrochloric acid, a colourless crystalline reduction compound; aniline and a blue dye are also produced in this reaction.

When nitrosodiphenylamine, aniline, and aniline hydrochloride in alcoholic solution are heated at 120°, two indulines are formed, one of which yields a hydrochloride readily soluble, and the second a hydrochloride sparingly soluble in hot alcohol. The latter is identical with the blue-shade induline obtained from azobenzene and aniline hydrochloride, and is formed in larger proportion by heating at 135 -140°, whilst pure azophenine heated with aniline and aniline hydrochloride at 140° is almost wholly converted into it. W. P. W.

Action of Heat on Triethylbenzylphosphonium Salts. By N. COLLIE (Phil. Mag., 24, 27-37).-A continuation of the author's researches on the decomposition of phosphonium salts by heat (Proc., 1886, 164). Triethylbenzylphosphonium chloride, prepared by treating triethylphosphine with excess of benzyl chloride, first fuses when heated, and eventually decomposes without charring into ethylene and diethylbenzylphosphine. Triethylbenzylphosphonium bromide decomposes with charring into hydrogen bromide, triethylphosphonium and diethylbenzylphosphonium bromides, acetylene, and other hydrocarbons. Triethylbenzylphosphonium hydroxide gives triethylphosphine oxide and toluene. The hydrogen carbonate when heated decomposes into toluene, carbonic anhydride, and triethylphosphine oxide. The normal carbonate could not be obtained, thus showing the decrease in alkalinity produced by introducing the benzyl-group, the tetrethyl compound forming a normal compound, whilst the tetrabenzyl compound will not fix carbonic anhydride at all. Triethylbenzylphosphonium sulphate decomposes into triethylphosphine oxide, dibenzyl, and sulphurous anhydride, whilst the acetate decomposes partly into triethylphosphonium oxide and methyl benzyl ketone, partly into triethylphosphine and benzyl acetate. The oxalate gave triethylphosphonium oxide, toluene, carbonic anhydride, and carbonic oxide. It is supposed that water took part in this reaction, as no triethylphosphine was produced. These experiments show that when triethylbenzylphosphonium oxy-salts are heated, the benzyl-group is invariably separated from the phosphorus. In the cases of the chloride and bromide, the ethyl-group separates as ethylene. H. K. T.

Action of Bromine on Bromanilic and Chloranilic Acids. By S. LEVY and K. JEDLICKA (Ber., 20, 2318-2321).-Experiments

made by the authors confirm the result obtained by Hantzsch and Schniter (this vol., p. 925), showing that the product of the reaction between bromine and bromanilic acid is perbromacetone (Stenhouse, Annalen, Suppl. 8, 17). Phenylhydrazine acts on perbromacetone so vigorously that ether has to be used as a diluent; the products of the reaction are phenylhydrazine hydrobromide and bromobenzene. Bromine acts on chloranilic acid with formation of the compound C&BraCl, OH (Stenhouse, loc. cit.). When 10 grams of the latter is treated with 8 grams of barium hydroxide and 500 c.c. of water and heated to boiling, chlorodibromomethane (6 grams) and barium carbonate, bromide, and chloride are formed. When dry ammonia is passed through a solution of the compound C,Br, Cl, OH in anhydrous ether, chlorodibromomethane and dibromochloracetamide are formed.

The mother liquor obtained in the action of bromine on chloranilic and bromanilic acids contained, besides oxalic acid, chlorodibromomethane and bromoform respectively. N. H. M.

Galloflavin. By R. BOHN and C. GRAEBE (Ber., 20, 2327-2331). -Galloflavin, CHO, (?), is obtained by dissolving 50 grams of gallic acid in 875 c.c. of alcohol and 1 litre of water, cooling to -5° to +5°, and adding 135 c.c. of 28 per cent. aqueous potash. Air is passed through for five hours. The potassium salt which separates is dissolved in hot water (at 90°), and treated with acid with exclusion of air. Galloflavin separates in greenish-yellow, crystalline plates. When heated, it carbonises without melting. It dissolves sparingly in water, alcohol, and ether; alkalis and alkaline carbonates dissolve it with yellow colour; sulphuric acid dissolves it unchanged. The potassium salt, C13H,O,K,, is a greenish-yellow, crystalline substance, very sparingly soluble in cold water, insoluble in alcohol; when boiled with water, free galloflavin is formed. Galloflavin yields coloured insoluble salts with the oxides of aluminium and chromium. The acetylderivative, C3H2O,Ac., crystallises from benzene in white needles melting at 230°; it dissolves readily in glacial acetic acid and in chlo. roform, but is insoluble in alkaline carbonates. When galloflavin is heated with chloracetic chloride at 100-110° for 15 hours, the compound CH2O,(CH2CI-CO), is formed. This crystallises in white. needles, soluble in ethyl acetate and acetic acid, very sparingly soluble in alcohol, ether, chloroform and benzene; it melts at 210-212°.

N. H. M.

Ethyl Parabromobenzoate and Parabromobenzoic Acid. By G. ERRERA (Gazzetta, 17, 209-213)-According to the results. described previously (p. 1103), ethyl parabromobenzyl ether is obtained by the action of alcoholic potash on parabromobenzyl chloride or bromide.

In a recent paper, Elbs (this vol., p. 151) has stated that ethyl parabromobenzoate is formed in the above reaction, together with parabromobenzyl alcohol and parabromobenzoic acid as subsidiary products; the view is supported by the formation of parabromobenzoic acid by the prolonged action of boiling alcoholic potash on the supposed ethereal salt.

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