and then extracted with ether. The yield is 07 gram of pure isonitroso-compound.

Desoxybenzoinacetic acid, CO Ph CHPh CH2 COOH, is prepared by adding 4 grams of ethyl chloracetate to 5 grams of desoxybenzoïn, 07 gram of sodium, and 7 grams of alcohol. It dissolves readily in aqueous potash, less in soda, and crystallises from alcohol in small tabular crystals melting at 156°. The silver salt was prepared. (Compare Knovenagel, p. 706.)

N. H. M.

Negative Nature of Organic Radicles. By R. RATTNER (Ber., 21, 1316-1322).-Dibenzylacetoxime, OH N:C(CH)2, forms yellowish crystals melting at 119.5°.

Dibenzyl dibenzyl ketone, CO(CHPh C,H,)2, obtained by the action of benzyl chloride on dibenzyl ketone in presence of sodium, forms lustrous crystals melting at 121.5°. It is insoluble in water, readily soluble in ether, chloroform, and carbon bisulphide.

Methyl diphenylacetate, CHPh, COO Me, crystallises from alcohol in plates melting at 59-60°. This salt and also methyl methylmandelate were treated with sodium ethoxide and isobutyl bromide, but with negative results.

Dibenzyl paraphenyl-ne diacetonitrile, C,H,[CH(C,H,)CN], is prepared in a manner similar to dibenzyl dibenzyl ketone. This when boiled with concentrated aqueous potash yields potassium paraphenylenedibenzyldiacetate. The free acid is obtained as a resin, and is purified by alternately boiling with calcium carbonate and precipitating with acid four or five times. It is a microcrystalline powder which melts at 251° and is insoluble in water, readily soluble in alcohol, ether, and chloroform. The barium and silver salts are described.

2

In the preparation of the nitrile an amorphous compound of the empirical formula C1HN2 is obtained. It is possibly formed by the condensation of 3 mols. of the cyanide with elimination of 2 mols. of hydrogen cyanide. It is insoluble in the usual solvents, soluble in hot phenol, and is very indifferent towards reagents.

Methyl phenylbenzoylacetate, CO Ph CHPh COOMe, is prepared by dissolving sodium in absolute alcohol, heating the product (after evaporating off the alcohol) at 200° in a stream of hydrogen; desoxybenzoin dissolved in ether is added and heated at 200 until white fumes appear in the flask. The product is treated with ether and an excess of methyl chlorocarbonate, and heated on a water-bath. On adding water, an oil is obtained which is extracted with ether and dried over sulphuric acid. It cannot be otherwise purified, as when distilled it decomposes into stilbene, benzoic acid, and carbonic anhydride. If ethyl chlorocarbonate is used, stilbene is formed at once in large quantities. N. H. M.

Substitution in Organic Compounds containing Negative Radicles. By W. SCHNEIDEWIND (Ber., 21, 1323-1330).-V. Meyer has shown that one atom of hydrogen in the methylene-group present in benzyl cyanide and desoxybenzoin can be displaced by an alkylgroup when either compound is treated with sodium ethoxide and an

alkyl iodide (this vol., p. 147). This reaction has been extended by the author to compounds containing in their formulæ two methylene- or methenyl-groups united together and each united with a negative radicle, and it is found that the nitrile of cinnamic acid, the nitrile of phenylpropionic acid, ethyl succinate, ethyl levulinate, benzalacetophenone, benzylacetophenone, and the nitrile of dibenzylacetic acid do not yield benzylated derivatives when respectively heated with the calculated quantities of sodium ethoxide and benzyl chloride at 103° until all alkaline reaction has disappeared.

Benzylacetophenone, COPh.CH, CH,Ph, could not be obtained by the action of aluminium chloride on a mixture of phenylpropionic chloride and benzene, but is formed by boiling benzalacetophenone in acetic acid solution with zinc-dust for 3 to 4 hours. It crystallises from alcohol in lustrous scales, melts at 72-73°, boils at above 360° without decomposition, and is insoluble in water, readily soluble in alcohol and ether. When oxidised with potassium permanganate, it yields carbonic anhydride and benzoic acid. The oxime crystallises in slender needles, melts at 87°, and is insoluble in water, readily soluble in alcohol and ether. The phenylhydrazone is an oil. The isonitroso-derivative, COPh.C(N.OH).CH2Ph, prepared by adding amyl nitrite (2 mols.) and then the ketone to sodium (2 at.) dissolved in 20 times its weight of alcohol, crystallises from ether in beautiful, pale-yellow forms, melts at 125-126°, and is readily soluble in alcohol and ether. Inasmuch as only one isonitroso-group could be introduced into the molecule of this compound, an attempt was made to prepare the di-isonitroso-derivative of the isomeric dibenzyl ketone but without success, since the product, which was formed in small quantity and crystallised in needles melting at 107-108°, contained too high a percentage of nitrogen.

The nitrile of dibenzylacetic acid, CH,Ph-CH(CN).CH,Ph, is prepared by heating dibenzylacetamide and phosphorus pentachloride in molecular proportion dissolved in phosphorus oxychloride at 100° until evolution of hydrogen chloride ceases. It crystallises in white scales, or, by slow evaporation of its solutions, in tables, melts at 89-91°, and is insoluble in water, readily soluble in alcohol and ether. Dibenzylacetamide crystallises in white needles, melts at 128129°, and is readily soluble in alcohol and ether, sparingly soluble in hot water.

Benzylcarbamine, CH,Ph NC, is obtained by heating pure benzyl iodide dissolved in toluene with twice its weight of silver cyanide in a reflux apparatus for 3 to 4 hours. The product has the odour of the carbamines, boils chiefly at 220-221°, the thermometer afterwards gradually rising to 231°, and is a mixture of the carbamine with some benzyl cyanide. On treatment with sodium ethoxide and benzyl chloride, it yields benzylated phenylacetic acid (derived from the benzyl cyanide) and benzylamine only, hence the hydrogen of the methylene-group in benzylcarbamine unlike that in benzyl cyanide, is not displaceable by an alkyl-group under these conditions.

W. P. W. Negative Nature of Organic Radicles. By E. KNOEVENAGEL (Ber., 21, 1344—1354).—In the first portion of the paper, the author

gives the details of the experiments in which acetonitrile, isobutyronitrile, the nitrile of mandelic acid, diphenylmethane, triphenylmethane, fluorene, and the nitro-derivatives of these hydrocarbons were respectively treated with sodium ethoxide and benzyl chloride with negative results (compare this vol., p. 147).

Phenylbenzylsulphone, CH,Ph SC2Ph, is readily obtained by treating sodium benzenesulphinate dissolved in dilute alcohol with benzyl chloride. It is crystalline, melts at 148°, and is insoluble in water, sparingly soluble in ether and cold benzene, and dissolves in 60 parts of cold or 7 parts of boiling alcohol. It does not react with sodium ethoxide and benzyl chloride.

Desylacetic acid (desoxybenzoïnacetic acid, compare Meyer and Oelkers, p. 703), COPh CHPh⚫CH, COOH, is best prepared by adding desoxybenzoin (1 mol.) to a solution of sodium (1 mol.) in 10 times its weight of alcohol, treating the product with acetic bromide (1 mol.) and heating it for 10 to 15 minutes on a water-bath. The product is then boiled for two hours in a reflux apparatus with 10 to 15 per cent. aqueous potash, diluted with water, shaken with ether to remove unaltered desoxybenzoin, aud the acid finally precipitated by addition of hydrochloric acid to the aqueous solution. The copper, silver, zinc, lead, calcium, and barium salts were prepared. B-Desylpropionic acid, COPh-CHPh CH, CH, COOH, is formed in like manner from desoxybenzoïn, sodium ethoxide, and ethyl ẞ-iodopropionate. It crystallises from alcohol in slender, white, seemingly quadratic needles, melts at 136°, and is insoluble in water, readily soluble in ether and hot alcohol. The silver, copper, zinc, barium and calcium salts are described. The methyl salt, C16H15O.COOMe, crystallises in colourless needles, melts at 63-64°, and is readily soluble in alcohol and ether, insoluble in water; the ethyl salt, C16H15O COOEt, crystallises in small, pale-yellow needles, melts at 33-34°, and is readily soluble in alcohol and ether. Hydroxylamine and phenylhydrazine react with the acid, yielding products which however could not be obtained in a state suitable for analysis.

a-Desylpropionic acid, COPh.CH Ph·CHMe COOH, is obtained under like conditions from desoxybenzoin, sodium ethoxide, and a-bromopropionic acid. It crystallises from alcohol in slender, colourless needles, melts at 213-215°, and is less soluble in alcohol and ether than the B-acid. The silver, copper, zinc, culcium and barium salts were prepared.

W. P. W.

Bidesyls. By E. KNOEVENAGEL (Ber., 21, 1355-1361).-Bidesyl, COPh CHPh CHPh COPh, is obtained, together with a small quantity of desylmalonic acid, by the action of sodium desoxybenzoïn (1 mol.) on ethyl bromomalonate (1 mol.) in alcoholic solution. It is also formed, together with isobidesyl, by heating desoxybenzoïn (1 mol.) with sodium (2 at. prop.) dissolved in 10 times its weight of alcohol, and adding to the cooled product an ethereal solution of iodine (mol.), and both compounds are formed when a mixture of desoxybenzoïn (1 mol.) and sodium ethoxide (1 mol.) in alcoholic solution is treated with desyl bromide (1 mol.). It crystallises from benzene in needles, melts at 254-255°, and is insoluble in water, ether, alcohol,

acids, and alkalis. When heated with hydroxylamine hydrochloride in alcoholic solution at 160°, it yields a compound which does not contain nitrogen; this crystallises from alcohol in lustrous forms, and melts at 171-172°.

Isobidesyl crystallises in colourless prisms, melts at 160-161°, and is readily soluble in hot alcohol and benzene, sparingly soluble in ether and light petroleum. Like bidesyl, it is optically inactive, and both compounds when heated under like conditions boil almost simultaneously at about 340°. When boiled with hydroxylamine hydrochloride (3 to 4 mols.) and aqueous potash (2 mols.) on a water-bath in a reflux apparatus for four hours, isobidesyl is converted into a compound, CH7N3O4, which melts between 110-120°, and is extremely soluble in cold alcohol, ether, and benzene, but insoluble in light petroleum. The research is being continued.

Desyl bromide, CHPhBr·COPh, can be obtained in almost quantitative yield by treating desoxybenzoïn with bromine by Staedel and Kleinschmidt's method for the preparation of bromacetophenone from acetophenone (Abstr., 1880, 659). It melts at 54-55°.

Ethyl bromomalonate, COOEt CHBr COOEt, is prepared by adding bromine (1 mol.) to ethyl malonate (1 mol.), distilling, and collecting the fraction boiling at 230-236°. W. P. W.

Diphthalylic Acid. By P. JUILLARD (Chem. Centr., 1887, 11431145; Arch. sci. phys. nat. [3], 17, 502-535, and 18, 24—62).— Diphthalylic acid, C2O2(CH, COOH)2, is formed in good quantity by oxidising diphthallyl with potassic permanganate, or with potassic hypobromite or hypochlorite; it melts at 272°. The ethyl salt melts at 154. If the acid is heated at about 110° with 40 per cent. caustic alkali, hydroxydiphenylmethanetricarboxylic acid,

OH C(C,H,COOH)2COOH,

is formed, which, however, exists only in combination with bases; when liberated by the action of an acid, it is converted into the lactone. By heating the solution, phthalidecarboxylic acid is formed. With strong bases it deports itself as a tribasic acid, with ammonia and barium hydrate as a bibasic acid. The ethyl salt melts at 108°. Phosphorus and hydriodic acid reduce it to diphenylmethanetricarboxylic acid, CH(CHCOOH), COOH, which crystallises with 1 mol. H2O. At about 200° it melts, and at 250° is transformed into a beautiful, red substance melting at 260°. If diphthalylic acid is heated with 50 to 55 per cent. potash at 125-130°, hydroxydiphenylmethanedicarboxylic acid, OH CH(CH,COOH)2, is formed, which is transformed into the lactone on being liberated. The latter, CO< >CH.C.H.COOH, melts at 205°. With potash and soda it acts as a bibasic acid, with ammonia as a monobasic acid only. The methyl salt melts at 154-155°, the ethyl salt at 99.5°. Alcoholic ammonia reacts with the ethereal salt with formation of an amide, CH,O, CONH2, melting at 158-160°. With nitrosulphuric acid, a dinitro-acid is formed, melting at 270-280°. By oxidation with alkaline potassic permanganate, benzophenonedicarboxylic acid is formed, whilst chromic

acid in glacial acetic acid oxidises phenylpthalidecarboxylic acid to a C&H

dilactone, <><>, which is also formed by heating benzophenonedicarboxylic acid either in the dry state or in solution. The salts of barium, copper, and silver, as well as the methyl and ethyl salts were prepared. It reacts with phenylhydrazine without loss of water. The hydroxylamine-derivative,

melts at 213-215°. The dilactone is extremely stable, and is only transformed into the acid when boiled with alkali. With fuming sulphuric acid it forms a sulphonic acid, which on fusion with potash gives alizarin. Aqueous and also alcoholic ammonia react with the dilactone, the former with production of an imide melting at 251-252°, the latter with production of a diimide which melts at 284-285°. Phenylphthalide mono- and di-carboxylic acids, and also the dilactone, are reduced by hydriodic acid and phosphorus at 170-180° with formation of diphenylmethanedicarboxylic acid,

CH,(C,H,COOH),

melting at 254-255°. If the temperature of the reaction with the dilactone is allowed to rise to 210-220°, anthranolcarboxylic acid is formed; this melts at 252-253°. J. W. L.

Derivatives of Orthotolidine. By P. L. HOBBS (Ber., 21, 1065— 1068). Diacetylorthotolidine, CHNO2, crystallises from hot acetic acid in slightly-coloured needles which melt above 310°, and are only sparingly soluble in ordinary solvents. Dibenzoylorthotolidine, C28H2N2O2, crystallises from hot acetic acid in snow-white ncedles melting at 259°; it is insoluble in ordinary solvents. The condensation-product of orthotolidine and phthalic anhydride, CH20 N2O, crystallises from benzene in dark-brown needles melting at 307°. The urethane, CH2N2O4, crystallises from alcohol in large, pale-red needles melting at 187°. The formyl-derivative, C16H16N2O2, forms microscopic needles which melt at 254°; on distillation, a compound is obtained which melts at 121°, and has the properties of an amidine. Tolyldithiocarbimide, C16H12N2S2, crystallises from benzene in large, transparent plates melting at 157°.

Orthodicresol, CHO2, crystallises from water in slightly-coloured, large, broad needles melting at 157°.

18

Benzoylorthodicresol, C2H2O, crystallises from glacial acetic acid in long needles melting at 185°. The acetyl-derivative, CiH1O4, forms long needles melting at 131°. The ethyl-derivative melts at 156°. The propyl-derivative crystallises from alcohol in snow-white leaves. The amyl-derivative crystallises from amyl alcohol in thick needles or prisms, which are readily soluble in alcohol and ether, and melt at 69. (Compare Gerber, this vol., p. 484.) F. S. K.

Action of Chlorine on Phenols. By T. ZINCKE (Ber., 21, 1027— 1048). Ketochloride is the generic name given to the ketone-like products obtained by the action of chlorine on phenols.