Ethyl chlorocarbonate and thiocarbamide react to form a compound, NH, CS NH COOEt, HCl, which melts at 117°. Chloracetone and thiocarbamide yield a substance of the formula

NH, CS NH CH2 COME, HCI,

melting at 126°. Similar reactions are being investigated.

A. J. G.

Substituted Biurets. By B. KÜHN and E. HENSCHEL (Ber., 21, 504-506).-Triphenylbiuret is formed when diphenylcarbamide is dissolved in an excess of hot phenyl cyanate, and the whole heated for half to one hour at 150°; at a higher temperature, it decomposes into diphenylcarbamide and phenyl cyanate. Diphenylbiuret prepared from monophenylcarbamide melts at 208-210°.

Phenylparaditolylbiuret, CH2N3O2, melts at 140°.

Phenylbenzylparatolylbiuret, C22H21N3O2, crystallises from dilute alcohol in microscopic needles melting at 95-104°. Paratritolylbiuret, C23H23N3O2, melts at 155-156°.

Orthoparaditolylbiuret, C16H1N3O1, is prepared from paratolylcarbamide and paratolyl cyanate, and crystallises from dilute alcohol in white needles which melt between 216° and 224°.

Diphenylparatolylbiuret, C2H1N3O2, melts at 214-216°.

N. H. M.

Derivatives of Ortho-xylene. By H. STRASSMANN (Ber., 21, 576 -581).-Ortho-xylylphthalimide, CH,Me CH2 N:C,H,O2, is obtained by heating ortho-xylyl bromide and potassium phthalimide at 200° for half an hour; the product crystallises from alcohol in white, hexagonal forms, melting at 148-149°; the yield is 76 per cent. of the theoretical amount.

Ortho-xylylphthalamic acid, COOH·C2H, CO·NH·C,H,, is produced when the preceding compound is boiled with soda; it melts at 156°, and crystallises from alcohol in needles.

Ortho-xylylamine hydrochloride is formed when xylylphthalimide is heated in sealed tubes with hydrochloric acid; the product crystallises from alcohol in transparent needles, and when treated with alkalis yields ortho-xylylamine, CH,Me·CH2 NH2, which is a colourless liquid boiling at 202°. The platinochloride, (CHN)2,H,PtCl, crystallises in yellow needles, the sulphate in prisms, readily soluble in water, and the picrate, C.H,N, CH,N,O,, in long, yellow needles, which decompose above 170° without melting.

2

Ortho-xylylthiocarbamide, NH, CS NH C,H,, is obtained by dissolving equivalent weights of ortho-xylylamine hydrochloride and potassium thiocyanate, and heating the residue obtained on evaporation at 140° for some time. It crystallises from water in white needles, melting at 167°, and turning red on exposure to the air.

Ortho-xylylcarbamide, NH, CO NH-C,H,, is prepared in a similar manner from the sulphate of the base and potassium cyanate; it crystallises from alcohol in radiating moss-like forms, melting at 172 -173°.

Ortho-xylylacetamide, C.H, NHAc, is formed when the hydrochloride

University of

is heated with sodium acetate and acetic anhydride; it crystallises from alcohol in needles melting at 69°.

Ortho-xylylthiocarbimide, CSN C,H,, is produced when an ethereal solution of the base is mixed with carbon bisulphide, and then distilled with mercuric chloride; it is an oil, boiling at 256°, and smelling strongly of radishes.

Ortho-xylylenediphthalimide, CH(CH2•N.C ̧H ̧O2)2, is obtained in almost theoretical quantities by gradually heating an intimate mixture of xylylene bromide and potassium phthalimide to 200°; it crystallises from acetic acid in slender, white needles melting at 253°. Ortho-xylylenediamine hydrochloride is formed when the preceding compound is heated with hydrochloric acid at 200° for two hours; when treated with potash, it yields the free base.

Ortho-xylylenediamine, CH(CH, NH2)2, is a strongly alkaline liquid with an ammoniacal smell, and attracts carbonic acid from the air; it gives a yellowish-red precipitate with ferric chloride, and yields the salt, C,HN,Au2Cls, in yellow plates, when precipitated with auric chloride. The picrate, CH,(CH2•NH2,C2H2N,O,)2, crystallises in yellow needles, which decompose above 170° without melting.

Orthodiacetylxylylenediamine, CH, (NHAc)2, crystallises in tufts of needles and melts at 146°. Orthodibenzoylxylylenediamine,

CH, (NHBz)2,

obtained by heating the hydrochloride with benzoic chloride at 200°, crystallises in needles melting at 168°.

Chloro-xylylenephthalimide, CH,Cl•C2H ̧•CH2•N:C ̧H,O2, is prepared by heating xylylene chloride (1 mol.) with potassium phthalimide 1 mol.); it crystallises from alcohol in prisms, melting at 140°, and when heated with hydrochloric acid yields chloro-xylylamine hydrochloride, CH2C1·CH ̧·CH2·NH2,HC). F. S. K.

By B. LEDERMANN

Tetrabenzylphosphonium - compounds. (Ber., 21, 405-409).-Tetrabenzylphosphonium iodide, P(C,H;),I, is prepared by heating phosphonium iodide (1 mol.) and benzyl alcohol (3 mols.) in sealed tubes at 100° for six to eight hours; it crystallises well, melts at 191°, and is sparingly soluble in water, more readily in chloroform, ether, and alcohol. The chloride, P(C,H,).Cl, prepared by digesting the iodide with silver chloride, forms white crystals. The sulphate, (PC2H28) SO, also forms white crystals. The platinochloride, (PC28H28)2PtCle, is obtained as a yellow, crystalline precipitate. The nitrate and bromide both form white crystals. The picrate forms yellow crystals. The mercurochloride, P(C,H1),HgCl, + H2O, and stannochloride (PC2H28),SnCle, are insoluble. The hydroxide could not be formed, as moist silver oxide is without action on the haloïd salts, and the sulphate, when treated with barium hydroxide, yields tribenzylphosphine oxide. When tetrabenzylphosphonium iodide is boiled for some time with strong alkalis, tribenzylphosphine oxide and toluene are formed.

The oxygen in tribenzylphosphine oxide is so firmly combined that it is not displaced by treatment with phosphoric chloride or potassium

hydrosulphide. Experiments made with a view to isolate tribenzylphosphine were unsuccessful. A. J. G.

Conversion of Ketones and Aldehydes into Acids and Acid Amides by Means of Ammonium Sulphide. By C. WILLGERODT (Ber., 21, 534-536).-The compounds formed by the action of ammonium sulphide on methyl aromatic ketones are not ketone-imides (Abstr., 1887, 1046) but acid amides, accompanied with the ammonium salts of the corresponding acids. Phenyl methyl ketone yielded phenylacetamide and phenylacetic acid; paratolyl methyl ketone, paratoly lacetamide (m. p. 185°), and paratolylacetic acid (m. p. 92°), &c.

Aromatic ethyl and propyl ketones react similarly with ammonium sulphide. In the case of paratolyl ethyl ketone, the reaction takes place at 250°. From a-naphthyl ethyl ketone and a-naphthyl propyl ketone, the compounds CHINO and CHNO, melting respectively at 140° (uncorr.) and at 160°, were obtained.

When benzil is heated with ammonium sulphide at 270°, benzoic acid and a compound melting at 241° are formed. Enanthaldehyde and ammonium sulphide when heated at 300° yield oenanthylamide, inelting at 95°; benzaldehyde reacts much more readily, and yields more benzoic acid than benzamide. N. H. M.

Perkin's Reaction. By H. W. SALOMONSON (Rec. Trav. Chim., 6, 23-30).-Benzaldehyde, ethyl succinate, and acetic anhydride were heated together at 125°, 140°, 180°, and 200' for six hours, but no reaction took place. Nitrobenzaldehyde and sodium succinate were heated together under various conditions but without the presence of acetic anhydride; no reaction took place. Meta- or para-nitrobenzaldehyde heated at 180-200° with sodium succinate and glacial acetic acid yields a small quantity of nitrocinnamic acid, but no nitrophenylparaconic acid.

It follows that ethyl succinate cannot be substituted for sodium succinate, or acetic acid for acetic anhydride, and it would seem that the reaction depends on the simultaneous presence of a sodium salt and an anhydride. Perkin showed that even at 100° sodium succinate is decomposed by acetic anhydride, with formation of sodium acetate and succinic anhydride, but the author finds that this reaction takes place only to a very limited extent, and there is little doubt that a condition of equilibrium is established between sodium succinate, acetic anhydride, sodium acetate and succinic anhydride. When one of these substances is removed by the action of the aldehyde, a further quantity of the same substance is formed, which is again removed by the aldehyde, and so on.

The assumption that the action takes place between the sodium salt and the aldehyde will not explain why acetic acid cannot be substituted for acetic anhydride, or ethyl succinate for sodium succinate, but these facts are explained at once, if it is assumed that the action takes place between the aldehyde and succinic anhydride. The acetic anhydride liberates a small quantity of succinic anhydride from the sodium salt with formation of sodium acetate, and as fast as the

succinic anhydride reacts with the aldehyde, a fresh quantity is liberated in the nascent state until decomposition is complete. The advantage gained by using acetic anhydride in place of the anhydride corresponding with the sodium salt is due to the fact that in the latter case the anhydride is in the free state from the beginning, and is not liberated in the nascent condition during the reaction. Acetic anhydride and ethyl succinate do not interact, and the avidity of the aldehyde for the ethyl succinate is not sufficient to produce direct action.

Sodium propionate and the sodium salts of bibasic acids of the paraffin series react directly with benzaldehyde.

Perkin's reaction is strictly analogous to the aldol reaction of Wurtz. C. H. B.

Phenylsalicylic Acid and Diphenyleneketone Oxide. By C. GRAEBE (Ber., 21, 501—504).—Phenylsalicylic acid, OPh CH, COOH, is prepared by adding the calculated amount of sodium in small pieces to phenyl salicylate, heated at 280-300°: when cold, the product is treated with alcohol, extracted with water, filtered, and precipitated with hydrochloric acid. The precipitate is redissolved in sodium carbonate, precipitated and crystallised from dilute alcohol, from which it separates in plates melting at 113°. It is readily soluble in alcohol and ether, and distils at 355° with slight decomposition into diphenylene-a-ketone oxide. The silver salt is sparingly soluble. The methyl salt is insoluble in alkalis. When the acid is heated with 10 parts of sulphuric acid, it is converted almost quantitatively into diphenyleneketone oxide; the constitution of the latter CO. compound is therefore CH,<C>CH ̧.

N. H. M.

Paramethoxyphenylacrylic Acid. By A. EINHORN and J. P. GRABFIELD (Annalen, 243, 362-378).- Paramethoxyphenylacryl methyl ketone, OMe CH, CH.CH.COMe, is prepared by agitating a mixture of anisaldehyde, acetone, and a solution of sodium hydroxide. The compound melts at 73°, and dissolves freely in ether, alcohol, benzene, and acetic acid. It is converted into paramethoxyphenylacrylic acid (described by Perkin, this Journal, 1877, i, 408) by treatment with sodium hypochlorite. When the methyl ketone is poured into a mixture of sulphuric and nitric acids at 0°, a nitroderivative, OMe C&H3(NO2)·CH:CH·COMe, and other products are formed; this is soluble in water, alcohol, ether, ethyl acetate, and benzene, yields metanitroanisic acid on oxidation with potassium permanganate, and can also be prepared by agitating a mixture of metanitroparamethoxybenzaldehyde and acetone with an aqueous solution of sodium hydroxide.

By the nitration of paramethoxyphenylacrylic acid, metanitroparamethoxyphenylacrylic acid and metanitroparamethoxyphenylethylene are formed. The latter, OMe C,H3(NO2) CH:CH2, forms rhombic crystals and melts at 89o. It is volatile in a current of steam, and is soluble in the ordinary solvents. It unites directly with two atoms of bromine forming a crystalline dibromide melting at 78—79°.

Dinitroparamethoxyphenylethylene can be separated from the mononitro-product by its insolubility in chloroform. The dinitro-compound melts at 162-163°, and is deposited from alcohol in needles. It forms an additive compound with bromine. Metanitroparamethoxybenzaldehyde crystallises in yellow prisms, and melts at 83.5°. It is soluble in the usual solvents, and forms a compound with phenylhydrazine, melting at 130.5°. It is converted by Perkin's reaction into metanitroparamethoxycinnamic acid. This melts at 140°, and dissolves in ether, hot water, and alcohol. The methyl salt melts at 125°. Nitromethoxycinnamic acid does not form an additive compound with hydrobromic acid, but by the action of an ethereal solution of hydrogen bromide on the acid at 90°, ethyl bromide and ethyl nitromethoxyphenylacrylate are produced. The ethyl salt melts at 100°. At 100°, an acetic acid solution of hydrogen bromide converts nitromethoxyphenylacrylic acid into metanitroparahydroxyphenylacrylic acid; this crystallises in needles, melts at 198°, does not unite with hydrogen bromide, but unites with bromine (in ethereal solution) to form a dibromide. Nitromethoxycinnamic acid readily absorbs bromine forming metanitroparamethoxyphenyldibromopropionic acid, OME CH3(NO2) CHBr CH Br-COOH, which melts at 178°, and is decomposed by a cold solution of potassium hydroxide, losing 1 mol. HBr and yielding nitromethoxyphenylbromacrylic acid. Alcoholic potassium hydroxide removes 2 mols. HBr, and converts the dibromide into metanitroparamethoxyphenylpropiolic acid. W. C. W.

Compounds of Aldehydes, Ketones, and Ketonic Acids with Thioglycollic Acid. By J. BONGARTZ (Ber., 21, 478-487).—Ethylidenedithioglycollic acid, CHMe(S·CH2 COOH)2, is formed when acetaldehyde is mixed with thioglycollic acid; the product when kept in a vacuum crystallises to a white mass, which can be recrystallised from chloroform. It melts at 107-108°.

Benzylidenedithioglycollic acid, CHPh(S-CH, COOH)2, crystallises from hot water (20 to 30 parts) in well-formed needles, melting at 123-124°.

Orthonitrobenzylidenedithioglycollic acid,

NO2 C&H CH(S.CH, COOH)2,

crystallises from hot chloroform in colourless crystals which gradually become yellow when exposed to light, and melt at 122-123°. The meta-compound crystallises from 10 per cent. acetic acid in needles, melting at 129-130°. The para-derivative crystallises from dilute acetic acid in lustrous, yellowish needles, melting at 161-162°. Orthohydroxybenzylidenedithioglycollic acid,

OH.C.H, CH(S⚫CH COOH)2,

is prepared by treating a mixture of salicylaldehyde and thioglycollic acid with zinc chloride; it is readily soluble in hot water, alcobol, and ether, insoluble in benzene, light petroleum, and chloroform, and melts at 147-148°.

Cinnamaldehydedithioglycollic acid, CHPh: CH CH(S·CH2 COOH)2, crystallises from hot water in white plates, melting at 142-143°,