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Acetoparatoluidine orthodiazopiperidide melts at 154°, and dissolves in alcohol and in ether. When hydrogen chloride is passed into the alcoholic solution, the diazochloride, NHAC.C,H,Me-N2Cl, is precipitated in a state of purity. In a dry state, the diazochloride is stable. It explodes when heated, and is decomposed by boiling with water or weak alcohol, yielding acetamidocresol. The diazopiperidide is decomposed by warm hydrochloric or hydrobromic acid, yielding orthochloro- or orthobromo-acetoparatoluidine and monochloro- or monobromotoluidine. W. C. W.

Hydrazines. By E. FISCHER (Annalen, 236, 198-199).-Phenylhydrazine distils without decomposition under 35 mm. pressure. It boils at 241-242° under a pressure of 750 mm. (column of mercury surrounded by vapour). At 22-7° the sp. gr. of the base is 1.097°, compared with water at 4°.

In the preparation of methylphenylhydrazine, the author finds that the reduction of the nitrosamine (Abstr., 1878, 312) may be carried out in aqueous instead of in alcoholic solution. The base boils at 131° under 35 mm. pressure, and at 227° under 745 mm.

W. C. W.

Phenylhydrazine-compounds. By C. Bülow (Annalen, 236, 194-197). Malic, tartaric, and mucic acids unite with phenylhydrazine at 130°, forming diphenylhydrazides. The malic compound, OH C2H (CO.N2H2Ph), melts at 218°, the tartaric compound, C2H2(OH)2(CO•N2H2Ph)2, melts at 226°, and the mucic compound at 238-240°. Phenylacetic phenylhydrazide, CH,Ph.CO.N2H,Ph, melts at 168-169°, and dissolves freely in alcohol and acetic acid. Ethyl oxalate phenylhydrazide crystallises in plates and melts at 119°. Benzil phenylhydrazine, COPh CPh:N,HPh, is formed by warming equal molecular weights of benzil and phenylhydrazine. It melts at 128-129°. W. C. W.

anhydro-compound,

Dicyanphenylhydrazine-compounds. By J. A. BLADIN (Ber., NCMe 19, 2598-2604). — The anhydro- compound, NPh<C(CN): N>, previously obtained by the action of acetic anhydride on dicyanphenylhydrazine (Abstr., 1885, 979) can be prepared by adding the calculated quantity of pyruvic acid to an alcoholic solution of the cyanocompound and warming gently. The author regards this compound as a derivative of the hypothetical triazole, NH<CH:N>; it will therefore be phenylmethylcyantriazole.

N.CH.

The salts of the corresponding phenylmethyltriazolecarboxylic acid, C2N,MePh⚫COOH, are described. The copper salt with 11⁄2 mols. H2O, is obtained in the form of microscopic needles; the silver salt with 1 mols. H2O does not crystallise well; and the lead salt with 2 mols. H2O forms small, white needles; all these salts are sparingly soluble, whilst those of barium and the alkalis are easily soluble in water. The ethyl salt, CN,MePh-COOEt, is a thick, bright-yellow oil, insoluble in water, but readily soluble in alcohol, ether and benzene. With hydro

chloric acid, a hydrochloride, C2N2MePh·COOH,HCl, is obtained in small, colourless tables, which are decomposed by water. The amide, which can be obtained by the action of hydrogen peroxide on dicyanphenylhydrazine, crystallises in small, colourless prisms, soluble in water and alcohol, less soluble in ether, and melting at 170°. The amidoxime is sparingly soluble in water, but more so in alcohol, and crystallises in colourless leaflets melting at 208-210°. Acids and alkalis, with the exception of ammonia, dissolve it, whilst with acetic anhydride a compound crystallising in needles and melting at 148° is obtained.

Phenylmethyltriazole, C2N,HMePh, obtained by heating the acid at 180°, is an oil which does not solidify at -15°. It forms a platinochloride, (C2N2HMePh)2,H,PtCl + H2O, which crystallises from alcohol in lemon-yellow tables melting at 122-124°; it is decomposed by water. To the compound CN,Ph-CN obtained by the action of nitrous acid on dicyanphenylhydrazine (Abstr., 1886, 146), the author gives the name phenylcyantetrazole, regarding it as a derivative of the CHÍNH hypothetical tetrazole, N< N

N>

W. P. W. Phenazine-derivatives. By A. BERNTHSEN and H. SCHWEITZER (Ber., 19, 2604-2607).-On diazotising Witt's toluylene-red, CHIN,HCI (Trans., 1879, 356), a compound, dimethamidomethylphenazine, NMe, C.H.C.H,Me, is obtained, which forms beautiful dark-red

N

N

needles or flat prisms having a greenish lustre. It dissolves in dilute acids with a violet, and in concentrated sulphuric acid with a reddish-brown coloration. Alcohol dissolves it to a red, and ether to a yellowish-red solution exhibiting golden-yellow fluorescence. It shows considerable analogy to eurhodine, and, like that base, sublimes without decomposition.

When, instead of nitrosodimethylaniline, 1:4 phenylenediamine acts on metatoluylenediamine in the presence of oxidising agents, a "simple" tolnylene-blue, and subsequently a "simple" toluylenered are produced. On diazotising, the latter yields methylphenazine; this class of dyes must therefore be regarded as derived from phenazine. The formation of toluylene-blue is represented by the equation NMe, C, H, NH2 + NÍ2·CH ̧Me•NH2

N

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4H

=

NMeC.HC.H2Me NH2. This, on further oxidation, yields

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19,

Constitution of the Safranines. By A. BERNTHSEN (Ber., 2690-2693; comp. preceding Abstract).-The fact that an indamine

is formed as an intermediate product in the preparation of phenosafranines makes it probable that the phenyl-group in the latter is combined with the same nitrogen-atom which connects the two other benzene nuclei. The constitution of leucophenosafranine (formed by oxidising equal mols. of paradiamidodiphenylamine and aniline) would thus be NPC,H,(NH,)>NH. CH(NH) NH. This reaction, and the form

ation of safranines by the oxidation of a paradiamine (1 mol.) with a monamine (2 mols.), explains why the para-position to the amidonitrogen cannot be taken up, and shows that 2 atoms of nitrogen are present in safranine as amido-groups.

The following constitutional formulæ are suggested for phenosafranine hydrochloride:

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The first formula is in accordance with the analogy of the dye with the thionine-group, and the fact that rosaniline yields a triazo-derivative, although its salts contain one imido- and two amido-groups. On the other hand, the presence of two intact amido-groups in the safranine dye, and the fact that toluylene-red can also be diazotised, are in favour of the second formula (comp. also Abstr., 1885, 1026). N. H. M.

Metanitromethylsalicylaldehyde and its Derivatives. By A. SCHNELL (Chem. Centr., 1886, 469-470).-All attempts to prepare a hydroxymethoxybenzaldehyde by the amidation and diazotation of the above compound (first prepared by Voswinckel, Abstr., 1882, 189) were unsuccessful. An amide was formed, but was so unstable

that it could not be isolated.

When metanitromethylsalicylaldehyde is heated with sodium acetate and acetic anhydride, metanitro-orthomethoxycinnamic acid,

NO2 CH2(OMe)·CH:CH·COOH [CH: OMe : NO2 = 1 : 2 : 5],

2

is formed. It melts at 238°, and when reduced with ammonia and ferrous sulphate yields metamido-orthomethoxycinnamic acid, which forms yellow needles melting at 189°. Sodium nitrite and concentrated hydrochloric acid convert this acid into orthomethoxycinnamic acid diazochloride, CH,(OMe) (C3H3O2)·N: NCI, which is very unstable. The corresponding nitrate is much more stable; it explodes at 151152°. When either of these salts is heated with water, metahydroxyorthomethoxycinnamic acid is formed, and yields yellow crystals melting at 179-180°. When this acid is fused with potash, it is almost completely decomposed; when methylated, it yields methyl metorthodimethoxycinnamate (dimethylgentisate), a thick, red-brown oil, which yields the acid on saponification. The acid melts at 143°: Tiemann and Müller (Abstr., 1882, 53) give the melting point as 76°. This

acid when oxidised with alkaline permanganate yields dimethylgentisaldehyde.

These results prove the nitro-group to be present in the metaposition. L. T. T.

New Chlorine-derivatives of Acetophenone. By H. GAUTIER (Compt. rend., 103, 812-814).-Trichloracetophenone, COPh CCI,.— 60 grams of trichloracetic chloride is mixed with 100 grams of benzene, heated to the boiling point of the latter, and aluminium chloride added in small quantities. After treatment with water, the dried product is fractionated under reduced pressure, and the portion boiling at 135-155° under a pressure of 25 mm. is re-fractionated. About 20 to 25 grams of trichloracetophenone is thus obtained as a colourless liquid with a pungent odour and extremely burning taste. It remains liquid at -21°, and boils without decomposition at 145° under a pressure of 25 mm., and with slight decomposition at 249° under atmospheric pressure; sp. gr. at 16° = 1·427. It is very slowly oxidised by alkaline potassium permanganate, yielding benzoic acid; when subjected to prolonged boiling with water, or when treated with very dilute alcoholic potash, the product is likewise benzoic acid.

Dichloracetophenone, COPh CHCl2, is obtained in the same manner from 50 grams of dichloracetic chloride and 100 grams of benzene; the yield being about 20 grams. It is a colourless liquid, with an odour and taste resembling those of the tri-derivative. It boils unchanged at 143° under a pressure of 25 mm., and with slight decomposition at 247-248° under atmospheric pressure; sp. gr. at 15° = 1.338. It is as difficult to oxidise as the tri-derivative, and is not sensibly affected by boiling water. When subjected to prolonged treatment with an alcoholic solution of potassium acetate, the whole of the chlorine is removed with formation of potassium chloride and a product which has not yet been examined.

These derivatives afford further illustration of the stability of chlorine in combination with the carbonyl-group. It is attacked with difficulty by reagents which readily remove the chlorine from the side-chains of benzene hydrocarbons, whilst energetic reagents act on the ketonic group, and give rise to simpler substitution derivatives of benzene. C. H. B.

Action of Sulphuric Acid on Aromatic Ketones. By K. KREKELER (Ber., 19, 2623-2628; comp. Abstr., 1886, 538).-Benzylmethylketonesulphonic acid, SO,HCH, CH, COMe, is prepared by heating benzyl methyl ketone with sulphuric acid on a water-bath. Acetophenonesulphonic acid, SO,H.C.H, COMe, is obtained by gradually adding pyrosulphuric acid (4 grams) to acetophenone (1 gram) kept well cooled; the intensely red liquid is then heated for half an hour on a water-bath. The lead salt dissolves very readily in water. The sulphonic acid reacts with phenylhydrazine, and yields the compound N2HPh: CM ̧·CH ̧ SO,H(N2HPh); this crystallises in lustrous plates, readily soluble in alcohol.

Isobutyrothienonesulphonic acid, CHMe, CO-C,SH, SO,H, is obtained

VOL. LII.

by acting on the thienone with pyrosulphuric acid in the cold. The lead and barium salts are very readily soluble in water, and can be crystallised from dilute alcohol. The phenylhydrazine-derivative, N2HPh: CPr C1SH2 SO2H (N2HPh), crystallises in lustrous plates, readily soluble in alcohol, very sparingly in cold water.

N. H. M.

Plöchl's Phenylglycidic Acid. By E. ERLENMEYER, Jun. (Ber., 19, 2576-2577). The phenylglycidic acid prepared by Plöchl's method (Abstr., 1884, 604) yields well characterised hydroxylamineand phenylhydrazine-derivatives, and also gives the LaubenheimerVictor Meyer thiophen reaction. From these facts, the author draws CHPh.CH COOH the conclusion that the formula Plöchl cannot be sustained, and advances the view that the compound is probably phenylpyruvic acid. W. P. W.

suggested by

Para- and Ortho-nitrophenyloxyacrylic Acid. By A. LIPP (Ber., 19, 2643–2650).—Paranitrophenyloxyacrylic acid, first obtained by Erlenmeyer, is readily prepared by heating paranitrophenyla-chlorolactic acid with alkalis; it crystallises in glistening leaflets, which melt at 186-188° with complete decomposition; when heated with sulphuric acid it yields paranitrophenylglyceric acid, which crystallises from water in small interlaced leaflets, melting at 167168°. In order to determine whether the constitution of this acid is NO2 CHCH CH.COOH

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that of a glycide, or of a ẞ-hydroxy-acid, its reaction with hydrochloric acid was studied; nitrophenyl-ß-chlorolactic acid was formed, thus confirming the former view. This B-lactic acid resembles the corresponding a-acid in appearance and behaviour towards solvents; it forms small, glistening crystals which melt at 167-168°. When boiled with water, it is completely decomposed into hydrochloric acid, carbonic anhydride, and a red resin; its barium salt when heated yields paranitrophenethylaldehyde and carbonic anhydride. Since the paranitrophenyl-- and -B-chlorolactic acids yield the same nitrophenylacrylic acid, which in its turn is reconverted into the ß-lactic acid, the constitution of the oxyacrylic acid is analogous to that of glycidic acid, according to the formula written above.

The orthonitrophenylacrylic acid, obtained by Baeyer, behaves like the above in combining directly with hydrochloric and hydrobromic acids; its constitution therefore is analogous. V. H. V.

Amido-acids. By R. STEPHAN (Chem. Centr., 1886, 470-471). -Tiemann, Friedländer, and Priest (Abstr., 1882, 50 and 56) have shown that the cyanhydrins of aromatic aldehydes form an easy source for the preparation of substituted amido-acids. The author finds that the same holds good in the case of aldehydes of the fatty series.

Acetaldehyde cyanhydrin, when heated on the water-bath with aniline, yields a-anilidopropionitrile, NHPh·CHMe CN, melting at 92°.

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