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The concluding portion of the paper is devoted to a criticism of the hypothesis put forward by Erlenmeyer to explain the isomerism of the bromocinnamic acids (Abstr., 1886, 945), which is rejected by the authors in favour of their theory of alloisomerism (ibid., 687).

W. P. W.

Derivatives of Phenylmethacrylic Acid and of Phenylisobutyric Acid. By L. EDELEANO (Ber., 20, 616-622).-The author finds that the yields of phenylmethacrylic acid prepared by Conrad and Bischof's method (Annalen, 204, 188) is only slightly lessened if, instead of using sealed tubes, the materials are heated at 125-130° for 30 hours in a flask with a cooling tube attached. Phenylmethacrylamide, CHPh: CMe CONH2, crystallises in prismatic scales, melts at 128°, and is sparingly soluble in ether and cold alcohol, soluble in hot water.

Phenylisobutyramide crystallises in needles, melts at 109°, and is readily soluble in alcohol and ether, soluble in hot water. When treated with bromine and aqueous potash, it is converted into phenylisopropylamine, CH2Ph CMeH NH2, a colourless, strongly refractive liquid boiling at 203°; its platinochloride crystallises in matted needles, and is sparingly soluble in water.

Methyl phenylmethacrylate is obtained when phenylmethacrylic acid is dissolved in an equal weight of methyl alcohol and the solution saturated with hydrogen chloride. It crystallises in long needles, melts at 39°, boils at 254°, and is soluble in all ordinary solvents. Two nitro-derivatives are formed when the methyl salt is treated with five times its weight of fuming nitric acid (sp. gr. = 152), and can be separated by crystallisation from alcohol. The less soluble compound is methyl paranitrophenylmethylacrylate; it crystallises in rectangular scales, and melts at 115°. Paranitrophenylmethacrylic acid,

NO2CH,CH: CMe.COOH,

crystallises in rhombs, melts at 208°, and is soluble in hot alcohol and acetic acid, very sparingly soluble in all ordinary solvents in the cold. Its silver salt, CH,NO.Ag, crystallises in slender, white needles and is soluble in hot water. The more soluble compound is obtained by evaporation of the alcohol as a liquid, which solidifies in a freezing mixture and yields orthonitrophenylmethacrylic acid when saponified. This is a feebly coloured powder, melts at 164-165°, and is readily soluble in alcohol and ether, sparingly soluble in benzene and light petroleum.

When phenylmethacrylic acid is nitrated, dinitrophenylpropylene, C2H2(NO2)2CH: CHMe, is obtained together with other nitration products. It crystallises in pale-yellow needles, melts at 118°, and is soluble in alcohol. W. P. W.

Preparation of Ethyl Benzoylacetate. By L. CLAISEN and O. LOWMAN (Ber., 20, 651-654).-Ethyl benzoylacetate is prepared by heating 140 grams of sodium methoxide with 300 grams of ethyl benzoate in a water-bath until the mixture becomes solid. It is then mixed with 350 grams of ethyl acetate and heated for 15 hours cn a water-bath in a reflux apparatus; 150 grams of glacial acetic acid are

added, and then water; the oil thus separated is washed with aqueous soda, dried over potash, and distilled in a partial vacuum (20 mm.). The yield of pure salt is 33 per cent. of the weight of ethyl benzoate. Ethyl acetoacetate, unchanged ethyl benzoate, and dihydrobenzoylacetic acid are also obtained. Almost the same yield is obtained when the reaction is allowed to take place at the ordinary temperature.

The authors think it probable that in the formation of ethyl acetoacetate and benzoylacetate, the compounds CMe(OEt), ONa and CPh(OEt), ONa respectively are first formed and that these then react with ethyl acetate, yielding the acetoacetate or benzoylacetate and 2 mols. of ethyl alcohol. N. H. M.

Oak-tannin. By C. BÖTTINGER (Ber., 20, 761-766).-This was obtained by treating the syrupy commercial "oak wood-extract" with about 20 times its volume of water, filtering off the insoluble substance, evaporating the solution to dryness, and treating the powdered residue with acetic anhydride. The tannin was thereby converted into an acetyl-compound which was soluble in excess of the anhydride. When the acetic solution is poured into water, the acetylderivative C1H-Ac,O, is precipitated as a heavy greyish-white powder. When exposed to the air, it gradually loses its acetyl as acetic acid. The acetyl-compound is soluble in ethyl acetate, chloroform, glacial acetic acid, ethyl acetoacetate, &c., insoluble in water and cold alcohol. Boiling alcohol eliminates the acetyl-groups and then dissolves the tannin. Cold concentrated sulphuric acid acts like boiling alcohol. The free tannin is converted into an anhydride by inorganic acids. The anhydride, when heated with ethyl iodide and alcoholic potash, yields an ethyl salt which decomposes when heated. The best means of obtaining the free tannin from the aceto-derivative is to heat the latter with water at 135° in closed tubes. The tannin thus obtained when dried in the desiccator has the composition C15H12O9 + 2H2O. It loses 1 mol. H2O at 100° and the second at 135°. The author has obtained from the aceto-compound two bromoderivatives, C15H10BrAcO, and C1H,Br,AcO,.

The author believes this oak-tannin to be a methyl salt of digallic acid. L. T. T.

Etherification of Opianic Acid. By C. LIEBERMANN and S. KLEEMANN (Ber., 20, 881-882).-Opianic acid is characterised by its ready susceptibility to etherification; this property may be utilised for its purification, as the ethereal salts formed are decomposed when boiled with water. The methyl salt melts at 102°, the ethyl salt at 92°, and the propyl salt at 103°. Possibly the above property is dependent on the constitution of opianic acid as an ortho-aldehydic acid. V. H. V.

Reduction of Nitro-cpianic Acid. By S. KLEEMANN (Ber., 20 875-881).-Nitro-opianic acid, when treated with concentrated. sodium methoxide, is converted into a nitroso-acid, crystallising in long, golden-green needles which melt at 175-176° and decompose.

at 200°. It is sparingly soluble in water, more readily in alcohol, and is distinguished from the nitro-acid in that it does not react with phenylhydrazine under the same conditions. Its silver salt crystallises in colourless needles, sparingly soluble in cold, readily in hot water. When reduced with stannous chloride, the nitroso- is converted into an amido-acid, which is crystalline, but owing to decomposition is not of definite melting point; its solution gives a green coloration with ferric chloride. Its hydrochloride, when heated with acetic anhydride and sodium acetate, yields a compound, C2H2N2O11, derived from the condensation of 1 mol. of the amido-acid and 1 of the anhydride with elimination of 1 mol. of water. It forms ill-defined crystals, insoluble in water, sparingly soluble in alcohol, and melts at 232--233° with decomposition. On reduction with zinc-dust and ammonia, the nitrosoacid yields an azo-acid,

[blocks in formation]

24

?>C2H(OMe)2COOH,

not obtainable in a definite crystalline form; it melts with decomposition at 245o, and dissolves in alkalis with a yellow, and in concentrated sulphuric acid with a purple coloration. Its silver salt is a yellowish-brown, flocculent precipitate: its ethyl salt crystallises in small, yellow needles melting at 101°, insoluble in water, soluble in alcohol and benzene.

Meconineacetic acid (this vol., p. 47) dissolves in ammonia to form a yellow liquid, which is decolorised when boiled with zinc-dust. The acid is insoluble in water, but dissolves in alcohol with partial decomposition. V. H. V.

y-Meconine. By O. SALOMON (Ber., 20, 883-889). As it is to be supposed that meconine stands to hemipinimide in a relation analogous to that of phthalide to phthalimide, it should be possible to convert hemipinimide into the former, but experiments showed that instead of meconine, a compound isomeric with it, called provisionally y-meconine, is produced.

With

On hydrogenation with tin and hydrochloric acid, hemipinimide yields hemipinimidine, C10H1O,N, analogous to phthalimidine; this crystallises in leaflets melting at 181°, soluble in benzene. nitrous acid, it yields a nitroso-derivative, CHINO, NO, crystallising in silky needles which melt at 156° with decomposition, sparingly soluble in cold, more readily in hot water. On treatment with dilute soda, this compound yields -meconine or dimethoxyphthalide,

CO.

:

C&H2(OMe) 2< CHO [OMe : CH, CO: OMe = 1:2:3:6], a formula which may explain the isomerism of this compound with meconine, which contains the CH, and CO groupings in the reverse positions. -Meconine crystallises in long, colourless needles which melt at 123-124°, soluble in benzene, alcohol, and ether. With fuming nitric acid, it yields a nitro-derivative, CH,O,NO2, crystallising in yellow needles which melt at 166°; on further treatment with nitric acid, oxalic acid is produced. On reduction, an amido-derivative is formed, a yellowish substance melting at 165°, and distinguished

VOL. LII.

29

from amido-meconine (m.p. 171°) by its melting point, the difference in solubility in benzene, and the more marked basic properties of the former. Bromo-y-meconine is a white flocculent precipitate, which melts at 141–142°, and is soluble in benzene, insoluble in petroleum. The isomeric meconines are also distinguished by their behaviour towards oxydising agents; thus with manganese dioxide and sulphuric acid meconine yields opianic acid almost in quantitative proportions, whilst y-meconine is, for the most part, unaltered. With nitric acid (sp. gr. 1.14), y-meconine yields, besides the nitro-derivative, nitrohemipinic acid; but meconine, under the same conditions, yields nitromeconine. It is further shown that hemipinic anhydride when hydrogenised yields -meconine. V. H. V.

=

Action of Potassium Cyanide on Meconine. By W. BOWMAN (Ber., 20, 890--891).-Another method of distinguishing the two isomeric meconines described in the preceding Abstract is their behaviour with potassium cyanide; y-meconine remains unaltered while meconine is converted into normethylmeconine, first isolated by Matthiessen and Foster. The change is probably to be explained by the alkaline nature of the potassium cyanide which, at the high temperature, effects the removal of the methyl-group. V. H. V.

Orthotolylphthalimide. By M. KUHARA (Amer. Chem. J., 9, 51— 58; comp. Abstr., 1881, 1039).-According to v. Gerichten, phthalyl .CCI2 chloride is either C.H.<COO or a mixture of this substance with the normal chloride. By treating phthalyl chloride with ammonia, a substance isomeric with phthalimide was on one occasion obtained, but its preparation could not be repeated (loc. cit.). By substituting orthotoluidine, a similar result is obtained, only one substance being produced, and hence it is probable that phthalyl chloride is not a mixture of two substances. The substance produced is—

Orthotolylphthalimide, CH(CO), NCHMe, melting at 182°, and identical with Froelich's phthalorthotoluide, obtained from phthalic anhydride and orthotoluidine.

Orthotolylphthalamic acid, COOH-C,H,CO-NH.C,H,Me, is obtained by boiling the imide with ammonia, and acidifying; it crystallises in needles. The two lead salts and silver salts, as well as the normal barium salt, are described.

Methyl-derivatives of Orthotolylphthalamic Acid.-The above acid. was treated with sodium in presence of xylene and then with methyl iodide, and finally with water in the presence of the excess of sodium used; the methylated compound was thus saponified, and yielded phthalic acid and dimethylorthotoluidine, which is formed most probably from the decomposition of the methiodide of sodium methylorthotolylphthalamate, COONa C, H, CO NMe,(C,H,)I. Neither this compound nor sodium methylorthotolylphthalamate,

COONa C.H, CO•NMeC.H,,

could be properly purified, as they do not crystallise readily.

The existence of the salts described is held to be in favour of the symmetrical formula for phthalyl chloride.

H. B.

Syntheses of the Ethyl Salts of Ketonic Acids. By W. WISLICENUS (Ber., 20, 589-595).—An almost theoretical yield of ethyl oxalacetate (this vol., p. 234) can be obtained by employing twice the weight of sodium indicated by theory, inasmuch as one-half of the metal enters into combination to form sodium ethoxide. When ethyl acetate (2 mols.) is slowly added to a solution of ethyl oxalate (1 mol.) in ether to which sodium wire (4 atoms) has been added, and the well-cooled product is treated with water, the aqueous layer yields ethyl ketipate (this vol., p. 362) on acidification.

Ethyl phenyloxalacetate, COOEt CHPh-CO-COOEt, is prepared by dissolving 10 grams of ethyl oxalate in 40 grams of ether, adding 32 grams of sodium wire, and then gradually adding 12 grams of ethyl phenylacetate; the product is decomposed by dilute sulphuric acid, and the compound extracted from the ethereal layer by means of aqueous soda. It is a very viscous oil, decomposes on distillation, is insoluble in water, readily soluble in alkalis, ether, and alcohol. The alcoholic solution gives an intense red coloration with ferric chloride. When boiled with 10 per cent. sulphuric acid, it decomposes with evolution of carbonic anhydride and formation of phenylpyruvic acid.

Phenylpyruvic acid, CH,PhCO.COOH, crystallises in lustrous scales, melts at 153° with a feeble evolution of gas, and is readily soluble in ether and alcohol, soluble in hot chloroform and benzene, sparingly soluble in hot water, and insoluble in cold water and light petroleum. The alcoholic solution gives a dark-green coloration with ferric chloride. The phenylhydrazide crystallises in small, yellowish needles, melts at 160-161° with evolution of gas, and is insoluble in water and light petroleum, sparingly soluble in ether, soluble in alcohol, chloroform, and benzene. It is probably identical with the phenylhydrazide of Plöchl's phenylglycidic acid (this vol., p. 142).

Ethyl phthalate is not attacked by sodium at 100°, but when ethyl acetate is gradually added a reaction occurs, resulting in the formation of an acid of the composition C,H6O2. This crystallises in small, lustrous, yellow needles, melts at 130-132°, and is soluble in alcohol, ether, and benzene. Its salts have generally an intense yellow coloration, the iron salt is dark-red. When treated with nitrons acid, it yields a yellow nitroso-derivative; the phenylhydrazide, C,HO(N2HPh), crystallises in microscopic needles, melts at 162-163° with decomposition, and is readily soluble in alcohol, ether, and benzene. When the acid is boiled with water, an acid of the composition C8H10O3 is obtained in microscopic scales; this is insoluble in all solvents, melts at 206-208° with complete decomposition, and yields salts showing an intense coloration; thus the salts of the alkaline metals are intensely violet, the silver salt is dark-red, the zinc salt intensely violet-blue, and the copper salt deep-blue. W. P. W.

Synthesis of Ethyl Trimesate. By A. PIUTTI (Ber., 20, 537— 539).-Ethyl sodacetate does not react with formic acid either in the cold or on heating, and when treated with ethyl formate yields only sodium ethoxide, carbonic oxide, and ethyl acetoacetate. If, however, a mixture of ethyl acetate and ethyl formate in equimolecular pro

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