benzoic acid. Besides this acid, its a-amide, Ph-CO-CONH2, and the so-called y-amide, (C,H,NO2)2, are produced, as well as the compound C16H12N2O3 previously described (loc. cit.). The latter compound is probably somewhat analogous in formation and constitution to the nitrile described in the Abstract, p. 483. It is very stable towards acids, alkalis, and reducing and oxidising agents, and is now being investigated. The phenylglyoxylic acid is probably formed from the a-amide, and not from the compound C16H12N2O3. L. T. T.

Methyl Salt of Methyldibromoparacoumaric Acid. By A. VALENTINI (Gazzetta, 16, 424-425). The methyl salt of paramethoxycoumaric acid, OMе·CH ̧·C2H2·COOMe, crystallises in laminæ melting at 89°; when dissolved in chloroform it readily takes up a molecule of bromine to form a compound, OMe C,H,CHBr·CHBr·COOMe, which may be regarded as a dibromo-derivative of methylhydroparacoumaric acid. This substance melts at 118°, and forms minute white crystals. V. H. V.

Oxidation of a- and ß-Hydropiperic Acids. By C. REGEL (Ber., 20, 414-425).-By the oxidation of the a-acid in alkaline solution by very dilute potassium permanganate, hydroxypiperohydrolactone, CH2<>CH, CH, CHCH CH(OH).CH2 -CO, and small quantities

of piperonal, piperonylic acid, and oxalic acid are produced. This lactone crystallises in long, glistening, colourless needles, soluble in water, ether, and chloroform, insoluble in light petroleum. It melts at 104.5°. Bromine acts on it readily, hydrogen bromide being evolved and a bromo-derivative formed; this crystallises in needles. When the lactone is dissolved in a small quantity of warm concentrated potash, and the product cooled in a freezing mixture and treated with a very slight excess of sulphuric acid, B--dihydroxypiperohydronic acid, CH,<0>C2H2• CH2•CH(OH)·CH(OH)·CH ̧·COOH, separates. This acid forms minute white crystals melting at 123°, at the same time giving off water and re-forming the lactone. When an aqueous solution of the acid is boiled, it is partially converted into the lactone, but, on the other hand, an aqueous solution of the lactone is by long-continued boiling partially converted into the acid. The addition of a few drops of hydrochloric or sulphuric acid facilitates the conversion of the acid into the lactone, and even determines it in the cold. The barium salt is soluble in water, the silver salt sparingly so.

When B-hydropiperic acid is similarly treated with permanganate, it yields, besides piperonal and oxalic acid, methylenehydrocaffeic (piperopropionic) acid, CH2: O2: C2H, CH2 CH2 COOH (Lorenz, Abstr., 1881, 49), and a-ẞ-dihydroxypiperohydronic acid,

CH2O2 CH3CH2·CH2·CH(OH)·CH(OH)·COOH.

The latter is easily soluble in alcohol and boiling water, sparingly so in benzene, carbon bisulphide, chloroform, light petroleum, and cold water. It crystallises in colourless, concentrically grouped

needles, and melts at 165°. Its calcium salt (+ H2O) and silver salt are sparingly soluble. It does not form a lactone.

The oxidation of the hydropiperic acids appears to take place by the addition of oxygen and the elements of water to the two doublylinked carbon-atoms. The non-formation of a lactone and the production of methylenecaffeic acid from the B-acid leaves little doubt that the formula for B-hydropiperic acid is

CH2O2: CH, CH2·CH2·CH: CH.COOH,

and of the dihydroxy-acid that given above. The formation of a lactone from the a-acid proves that one of the doubly-linked carbonatoms must be in the y-position to the carboxyl-group, but whether the second occupies the B- or d-position is still uncertain. The author believes the former probably to be the case when the formula CH2O2: CH, CH2 CH: CH·CH, COOH, given by Fittig to a-hydropiperic acid, would be the correct one, and those of its derivatives would be those given above. L. T. T.

Action of Bibasic Acids on Thiocarbimides. By F. MOINÈ (Chem. Centr., 1887, 39-40).-When equal molecules of phthalic acid and allylthiocarbimide are heated together at 145°, allylphthalimide is formed; when treated with bromine in carbon bisulphide. solution, it yields the dibromide melting at 108-109°.

.CO.

Allylsuccinimide, CH<C>N.CH, is obtained by heating together equivalent amounts of succinic acid and allylthiocarbimide. It is a mobile, colourless, not unpleasant smelling oil, boiling at 244-245°; sp. gr. 1.1543 at 0°, 1·1432 at 12°, 1·1112 at 50°, and 1.0677 at 100°, compared with water at 4°. It is easily soluble in water, alcohol, and ether, has a neutral reaction, is decomposed on boiling, and gives a semi-solid compound with bromine.

.CO.

Phenylsuccinimide, CH.CO>NPh, is obtained by heating succinic acid and phenylthiocarbimide at 140°; it melts at 253-255°. There is also formed a little succinanilide, C2H(CONHPh),. Malonic acid and phenylthiocarbimide yield malondianilide (Abstr., 1884, 729).

.CO.

Allylcamphorimide, C.H.<CONCH,, is formed when camphoric acid is heated with allylthiocarbimide. It forms colourless plates, and melts at 48-49°. It is almost insoluble in water, soluble in alcohol and ether.

When the anhydrides of phthalic and camphoric acids are heated with allylthiocarbimide, the corresponding imides are formed, together with the above compounds. G. H. M.

Action of Phenylhydrazine on Lactones. By W. WISLICENUS (Ber., 20, 401-403).-V. Meyer and Münchmeyer have shown (Abstr., 1886, 883) that phthalide reacts with phenylhydrazine to form a nitrogenous compound. The author has investigated this reaction, and finds the compound formed to be a simple additive pro

VOL. LII.

2 k

12

duct, CHN2O2, and not a substance, CH2N2O, formed by the elimination of water (loc. cit.). The compound CHN2O2 crystallises in minute, glistening needles, easily soluble in boiling alcohol, insoluble in water and benzene. It melts at 173-174° with partial decomposition into its constituents. It is very unstable towards dilute acids and alkalis, thus differing from the hydrazine condensation products of the aldehydes and ketones. It dissolves to a colourless solution in strong sulphuric acid, but the addition of a trace of an oxidising agent such as ferric chloride produces a reddish-violet coloration. Bulow has observed a similar reaction with the acid hydrazides, and the author considers that the constitution of the compound is probably OH CH, C,H ̧·CO·N2H2Ph.

2

Valerolactone reacts with phenylhydrazine in an exactly similar manner, producing a compound which crystallises in small flat needles. It seems to have the formula C1H6N2O2, and the melting point 76-79°, but the author has not yet succeeded in obtaining it in a pure state. It is soluble in alcohol, benzene, chloroform, and water, insoluble in ether. L. T. T.

Nitrobenzyl-derivatives of Ethyl Malonate. By E. LELLMANN and C. SCHLEICH (Ber., 20, 434-442).—In the reaction between paranitrobenzyl chloride and ethyl sodiomalonate there are formed simultaneously ethyl mono- and di-nitrobenzylmalonate, of which the latter, C(CH2 C&H, NO2);(COOEt)2, crystallises in silky needles melting at 170°, sparingly soluble in alcohol, chloroform, and benzene; the former, CH(CH2 C&H, NO2) (COOEt)2, crystallises in golden-green prisms. On treatment with alkali, the di-derivative is unaltered, whilst the mono-derivative is converted into paranitrobenzylmalonic acid, NO2 CH, CH2CH(COOH)2, a light yellow powder, which carbonises at 240° without fusion. An ammoniacal solution of this acid gives precipitates with solutions of salts of the heavy metals. The above di-derivative when reduced gives an amido-derivative, C(CHCH, NH2)2(COOEt)2, a hard crystalline mass, the platinochloride of which crystallises in leaflets, the sulphate and the oxalate in scales. In a similar manner ethyl nitrobenzylethylmalonate, CEt (CH2 CH, NO2) (COOEt)2, is produced from paranitrobenzylic chloride and sodium ethylmalonate; this crystallises in colourless needles, melts at 52°, and is soluble in alcohol, ether, and benzene. On treatment with potash and subsequent acidification, this compound is converted into paranitrobenzylethylacetic acid,

NO2 CH, CH, CHET COOH,

a sparingly soluble substance, carbonising at 300° without fusion. Similarly from ethyl sodiomalonate and orthonitrobenzylic chloride the corresponding ortho-compound, C(CH2 CH4 NO2)2(COOEt)2, is produced, which forms golden crystals melting at 97°, soluble in alcohol and ether. Ethyl orthonitrobenzylethylmalonate was not obtained in a definite state; on hydrogenation, the impure product is converted into ethyl B-ethylhydrocarbostyril-ẞ-carbonate,

which crystallises in colourless silky needles melting at 114°. Similar experiments on the reduction of ethyl orthodinitrobenzylmalonate led to indefinite results. V. H. V.

Synthesis of the Ethereal Salts of Trimesic Acid. By A. PIUITI (Ber., 20, 537-539; Chem. Centr., 1887, 36-37).-Ethyl trimesate, CH3(COOEt),, is formed when 16 grams of sodium are added to 72 grams (1 mol.) of ethyl formate and 86 grams (1 mol.) of ethyl acetate in the cold and the mixture then heated, but by acting on a mixture of ethyl acetate and formic acid with sodium, ethyl formylacetate is not formed but only ethyl acetoacetate. The author considers that the ethereal salt of trimesic acid is formed by the condensation of three molecules of ethyl formylacetate with elimination of three molecules of water. When sodium acts on a mixture of methyl formate with ethyl acetate or of ethyl formate with methyl acetate in molecular proportions, a mixture of methyl and ethyl trimesates is formed in each case. The reaction takes place much more readily when a mixture of the two radicles is used than when one radicle only is present.

Methyl trimesate, C,H,(COOMe), crystallises from dilute alcohol in small needles and melts at 143°.

When ethyl formate is added to a solution of sodium in ethyl acetate, it is decomposed into alcoholate and carbonic anhydride.

G. H. M.

The Six Isomeric Toluenedisulphonic Acids. By P. KLASON (Ber., 20, 350-357).-Toluenedisulphonic acid, [Me: (SO,H)2 = 1:26], was prepared by Komatzki (Abstr., 1884, 70). The constitution ascribed to it by the author is shown by the fact that it is formed from parabromotoluene (hence neither sulphonic group can have the para-position), and by its non-identity with the three acids which are shown to have a sulphonic group in the meta-position. Tolueneorthometadisulphonic acid, [Me: (SOH), = 1: 2: 3] (this 1:23] vol., p. 264), was obtained by Limpricht and Richter (Abstr., 1885, 1233) from paratoluidine, and by the author (loc. cit.) from toluenemetasulphonic acid.

Tolueneorthometadisulphonic acid [1:2:5] was first obtained by Håkansson (Ber., 5, 1088), who named it B-toluenedisulphonic acid. It was prepared by the author (loc. cit.) by heating toluenemonosulphonic acid with fuming sulphuric acid at 180°. When orthotoluidine is heated with sulphuric acid, orthotoluidinemetasulphonic acid [1: 2: 5] (Nevile and Winther, Trans., 1882, 421) is formed. Orthotoluidinemetasulphonic acid was converted into the diazo-compound, and the latter, after being carefully dried (it explodes easily), gradually added to a warm alcoholic solution of potassium sulphide. The product is diluted with water and treated with lead acetate, filtered and treated with ammoniacal solution of lead acetate; the precipitate is washed and decomposed by hydrogen sulphide. The impure orthothiocresolmetasulphonic acid [1: 2: 5] is oxidised by potassium permanganate, the tolueneorthometadisulphonic acid thus formed treated with phosphoric chloride, and the acid chloride converted into the corresponding acid by heating it with water at 140°.

The acid thus obtained is identical with B-toluenedisulphonic acid, and has the constitution [1: 2: 5].

Tolueneorthoparadisulphonic acid [1: 2: 4] is the a-toluenedisulphonic acid prepared by Blomstrand (Ber., 4, 717); it was also prepared by Senhofer (Annalen, 164, 129), who described it as 7-toluenedisulphonic acid, supposing it to be different from the a-acid, and by Håkansson (loc. cit.). It is formed both from tolueneparasulphonic acid (Fahlberg, Abstr., 1879, 804) and from tolueneorthosulphonic acid (Klason and Berg, Abstr., 1880, 889), and has, therefore, the constitution given by the author.

Toluenemetadisulphonic acid [1: 3: 5] was prepared by Limpricht and Hasse (Ber., 18, 2177). Orthotoluidinemetasulphonic acid was converted into orthotoluidinedisulphonic acid, which has the constitution [1:23:5] (Nevile and Winther, loc. cit.). This was converted by means of the diazo-compound into the iodotoluenedisulphonic acid, from which the iodine was eliminated by boiling with strong hydrochloric acid.

Toluenemetaparadisulphonic acid [134] is prepared in the following manner:-Paratoluidinemetasulphonic acid is converted into a toluidinedisulphonic acid. The latter is converted into the diazocompound, which is converted successively into parathiocresolmetasulphonic acid and toluenedisulphonic acid. The potassium salt of the acid is treated with phosphoric chloride, and the chloride, after being recrystallised from chloroform several times, is converted into the acid by heating it with water at 140°. Like all toluenedisulphonic acids, it is extremely soluble in water. The potassium salt (with 1 mol. H2O) crystallises in needles and is readily soluble; the barium salt (with 2 mols. H2O) forms lustrous prisms soluble in 666 parts of cold water. The chloride, CH(SOCl)2, melts at 111°, and dissolves readily in chloroform, less in ether. The amide melts at 235-239° with slight decomposition; it dissolves readily in water and alcohol. Dithiocresolsulphonic acid, S(C,H, SO2OH)2, was obtained in small quantity; the chloride melts at 192°, and is very sparingly soluble in all solvents except glacial acetic acid. N. H. M.

Diphenylhydroxyethylamine. By H. GOLDSCHMIDT and N. POLONOWSKA (Ber., 20, 492-495).-When benzoïnoxime is reduced with sodium amalgam and acetic acid (compare this vol., p. 249), diphenylhydroxyethylamine, OH CHPh.CHPh NH2, is obtained; it crystallises in small, white, transparent needles, melts at 161°, and is insoluble in water, sparingly soluble in ether and cold alcohol. The hydrochloride, CHINO,HCl, crystallises in long needles, melts at 210 with decomposition, and is readily soluble in water; the platinochloride, (CHNO)2,H,PtCl + 2H2O, forms microscopic, golden-yellow scales; the acetate crystallises in prisms showing a vitreous lustre and melts at 156°. By the action of acetic anhydride on the base, a diacetyl-derivative is obtained; it is a white crystalline powder, melts at 159°, and is soluble in benzene. Diphenylhydroxyethylamine, when heated with methyl iodide, yields a tertiary base, OH CHPh CHPh NMe; this crystallises in long, white needles, melts at. 108-110° and forms a platinochloride, (C16H19ÑO)2,H2PtCl + H2O. W. P. W.