Oil from the Seeds of Curcas Purganus (formerly Jatropha Curcas). By F. M. HORN (Zeit. anal. Chem., 27, 163–165).—This oil, formerly employed as a purgative under the names Oleum ricini majoris, Oleum infernale, is at the present time much used for burning and for soap making, also for adulterating olive oil, and seemingly for making Turkey-red oil. It begins to crystallise at 9°, and is completely solid at 0°. At 15° its sp. gr. is 0.9192. It differs from castor oil in its very sparing solubility in alcohol. It appears to saponify readily in the cold, but in reality forms only acid soaps; for complete saponification heat is required, and solid potash acts better than solution.

It gives for Hehner's number, 879; for Reichert's, 0·65; for Köttstorfer's, 2305; and for Hübl's, 127.

M. J. S.

Constitution of Ethyl Sodacetoacetate and Ethyl Sodacetomalonate. By A. MICHAEL (Amer. Chem. J., 10, 158-160).-Ethyl acetylmalonate has been prepared by Ehrlich, Conrad, and Guthzeit, from ethyl sodacetoacetate and ethyl chlorocarbonate, and lately by Lange from acetic chloride and ethyl sodiomalonate. But the acetates prepared by these two methods are not identical; the one being insoluble in strong cold alkaline solutions, the other being very readily soluble in any alkali, and boiling also 5° lower; moreover, in the latter process, ethyl diacetylmalonate is formed at the same time.

From these data it is concluded that whilst ethyl acetoacetate is correctly represented by the formula CH, CO-CH, COOEt, the corresponding sodium compound is CH, C(ONa):CH COOEt, and the substance obtained from it by the action of ethyl chlorocarbonate is CH, C(O.COOEt):CH COOEt. This certainly explains why the substance has no distinct acid properties like the real ethyl acetylmalonate, CH, CO-CH(COOEt)2.

Further, Conrad and Guthzeit have prepared ethyl methenyltricarboxylate by the action of ethyl chlorocarbonate on ethyl sodiomalonate, and ascribe to it the constitution CH(COOEt), and yet it is at once decomposed by alkalis and has no acid properties. The ethyl sodiomalonate used by these authors was first prepared in the solid state; but if ethyl chlorocarbonate is at once added to the product of the action of sodium on ethyl malonate, then a substance is obtained which has acid properties, forms a very stable sodium salt, and is doubtless expressed by the above formula, whilst the compound of Conrad and Guthzeit is OEt∙C(O·COOEt):CH COOEt. This and the above constitutional formula for ethyl sodacetoacetate is explained on the assumption that sodium acting on ethyl malonate or ethyl acetoacetate forms at first sodium salts expressed by the usual formulæ, COOEt.CHNa CO OEt and CH, CO-CHNa-ČOOEt, but that owing to the affinity of sodium for oxygen, these are converted by heat, &c., into OEt-C(ONa):CH COOEt and

CH, C(ONa):CH·COOEt.

The action of sodium on isatin is probably similar.

H. B.

By A.

Acetoacetic Acid and Ethyl Succinosuccinate. HANTZSCH and F. HERRMANN (Ber., 21, 1084-1085).-A reply to the article by Geuther (this vol., p. 579).

Condensation Products of Urethane and Ethyl Acetoacetate. By J. MEISTER (Annalen, 244, 233-253).—A condensation product of the composition C,H,NO, is prepared by heating at 140° in sealed tubes a mixture of urethane (10 grams), ethyl acetoacetate (20 grams), ether (10 grams), and a small quantity of ammonium chloride. It is easily decomposed by acids: thus with strong hydrochloric acid it yields ammonia, acetone, ethyl chloride, and carbonic anhydride.

As this substance is also formed by the action of ethyl chlorocarbonate on ethyl paramidoacetoacetate, it may be regarded as ethyl B-amidocrotonate, in which an atom of hydrogen is displaced by the group COOEt. Its constitution is represented by the formula COOEt NH CMe:CH COOEt. It is not attacked by aqueous solutions of the alkalis, but is saponified by alcoholic potash, yielding an oily liquid of the composition C12HNÓ6.

A tribromo-derivative, soluble in alcohol and in ether, is obtained by the action of bromine on the condensation product suspended in water, but a corresponding trichloro-derivative could not be obtained.

At 160°, alcoholic ammonia acts on the condensation product, and crystals of the composition of B-uramidocrotonamide, containing 1 mol. of alcohol, are deposited. The crystals melt at 131°, and are soluble in hot alcohol. The same compound is formed by the action of alcoholic ammonia on ethyl ẞ-uramidocrotonate. A corresponding anilide could not be prepared. The amide is decomposed by water, yielding urea, ammonia, acetone, alcohol, and carbonic anhydride. A strong boiling aqueous solution of potassium hydroxide decomposes the amide, yielding an oily liquid of the composition C1H2N2O4. W. C. W.

20

Antimony Potassium Oxalate. By P. KAY (Chem. News, 57, 193-194). Two samples of this substance were found to correspond respectively with the formule K,Sb2(C2O1) + 3H2O and K,Sb(C2O4)3 + 2H2O. The antimony was estimated either by mixing the solution with tartaric acid, neutralising with sodium carbonate, adding potassium carbonate, then bleaching powder, and titrating the excess of the latter with sodium arsenite; or by direct titration with potassium hydroxide, using phenolphthaleïn as indicator. The potassium was estimated by converting into carbonate and titrating. The oxalic acid was determined in the usual way. D. A. L.

Derivatives of Ethylmalonic Acid. By M. FREUND and B. B. GOLDSMITH (Ber., 21, 1245-1247).-Ethylmalonamide,

CHEt(CONH2)2,

is obtained by acting on diethyl ethylmalonate with concentrated ammonia. It crystallises from alcohol, and melts at 207-208°.

Ethylmalonanilide, CHEt(CONHPh)2, produced by heating diethyl ethylmalonate or ethylmalonamide with aniline, crystallises from

alcohol in needles melting at 213-215°. It is insoluble in water, but dissolves readily in alcohol and glacial acetic acid.

Phenylethylmalinamide, NH, CO CHE CO NHPh, obtained by heating 1 mol. of the amide with 1 mol. of aniline, crystallises from water or alcohol, and melts at 182°.

Ethylmalonanilic acid, COOH CHEt CO·NHPh, is obtained by boiling the preceding compound with an excess of lime. It is soluble in alcohol, crystallises from water, and melts at 150° with evolution of carbonic anhydride. F. S. K.

Action of Ethyl Oxalate on Acetone. By L. CLAISEN and N. STYLOS (Ber., 21, 1141-1143; compare Abstr., 1887, 917).-A very characteristic bluish-violet colour is formed when ethyl acetopyruvate is boiled with acetic acid and some sodium acetate. Copper acetopyruvate, (CHO) Cu, crystallises in small, bright-green needles. When the ethyl salt is boiled with phenylhydrazine in acetic acid solution, and the product treated with water, a thick oil is obtained which, after saponification with alcoholic soda, yields a white crystalline precipitate of a methylphenylpyrazolecarboxylic acid, C10H,N2 COOH, on treatment with hydrochloric acid. The acid melts at 96°, but seems to contain either water or alcohol of crystallisation, since the melting point gradually rises to 134-136° by prolonged drying at 80-90°. At 200-210°, the acid loses carbonic anhydride, and is converted into a methylphenylpyrazole probably identical with that prepared from acetoacetaldehyde (this vol., p. 671), and isomeric with that obtained by Knorr (Annalen, 238, 202); it has a sp. gr. 1·085 at 15°, solidifies in a freezing mixture, and boils at 256-257° without decomposition.

Oxalyldiacetone, CH2Ac-CO.CO.CH,Ac, is obtained by adding to a well-cooled mixture of anhydrous ether and sodium ethoxide (2 mols.) free from alcohol, first acetone (2 mols.), and then ethyl oxalate (1 mol.), and allowing the product to remain for two days; the resulting yellow salt is then dissolved in water, and decomposed by the addition of acetic acid. It crystallises in white prisms, melts at 120-121°, is soluble in alcohol, ether, and chloroform, sparingly soluble in light petroleum and cold water, and gives a dark brownishred coloration with alcoholic ferric chloride. W. P. W.

Derivatives of Saccharic and Mucic Acids. (Bull. Soc. Chim., 48, 719-723).-Tetracetylmucic acid,

CH.(OAc),(COOH)2 + 2H2O,

By MAQUENNE

is obtained by boiling mucic acid with acetic anhydride (2 parts) in presence of zinc chloride, until it is dissolved. The product is precipitated with water, washed, and crystallised from alcohol. It forms colourless, efflorescent needles, melting at 266° (corr.), sparingly soluble in water, readily soluble in hot alcohol; its reaction is strongly acid, but it does not form salts.

The lactone of diacetylsaccharic acid, C10H100s, is prepared by adding strong sulphuric acid, drop by drop, to a mixture of hydrogen potassium saccharate and acetic anhydride (2 parts). The product is

precipitated by water and washed until no longer acid. It melts at 188° (corr.) without decomposition, and is sparingly soluble. It seems to be identical with the compound prepared by Baltzer by the action of acetic chloride on saccharic acid (Annalen, 149, 241).

Saccharic acid diphenylhydrazide, CHNO, (Kiliani, this vol., p. 46) is obtained by heating an aqueous solution of saccharic acid, phenylhydrazine hydrochloride (each 8 grams), and sodium acetate (12 grams), on a water-bath for two hours. It is slightly yellow, melts at 210° with evolution of gas, is insoluble in water, alcohol, and ether, soluble in hot alcoholic potash. The diphenylhydrazide of mucic acid (Bülow, Abstr., 1887, 138) was prepared in a similar manner.

N. H. M.

Synthesis of Aspartic Acid. By A. PIUTTI (Chem. Centr., 1888, 68-69, from Rendi. Acc. Linc. [4], 3, 300—303).-Ethyl sodoxalacetate was prepared by treating 25 grams of ethyl oxalate and 15 grams of ethyl acetate dissolved in four times their weight of absolute ether, with 4 grams of sodium in small pieces. From this compound, the oxime was prepared by dissolving molecular proportions of the above compound and hydroxylamine hydrochloride in water, and gently warming. If the oily oxime which separates after a time is dissolved in ether, and the ether evaporated, a colourless oil is left, which soon appears blue or green by reflected, and violet by transmitted light. If a watery solution of this oxime is reduced with sodium amalgam, aspartic acid is formed.

The aspartic acid agrees in its properties with Dessaigne's acid and Piutti's inactive acid. The reduction of the oxime in watery, alcoholic and acetic acid solutions gives rise to highly coloured products, and small quantities of mono- and di-ethyl aspartates. Reduction of a watery solution of the oxime with ammonia also gives a good yield of acid. J. P. L.

Furfuran-derivatives. By W. MARCKWALD (Ber., 21, 1398— 1404). The ethyl salt of the bibasic acid, CH ̧O(COOЕt)2, obtained by treating furfuracrylic acid in alcoholic solution with hydrogen chloride (this vol., p. 135), and now termed ethyl propiononedicarboxylate, forms an oxime, OH-N:C,H,(COOEt)2, which crystallises in long, slender, white needles, melting at 38°. It is sparingly soluble in water and light petroleum; readily soluble in most other solvents, and in cold hydrochloric acid and alkalis. The phenylhydrazone of propiononedicarboxylic acid, N2HPh:C,H,(COOH)2, crystallises from alcohol in pale-yellow, microscopic crystals, melts at 1145°, and is insoluble in water, benzene, light petroleum, and chloroform, soluble in ether, and readily soluble in alcohol, acetone, and acetic acid. On heating with excess of hydriodic acid (sp. gr. = 1·7) and the theoretical quantity of amorphous phosphorus at 200-220° for many hours, the acid is converted into normal pimelic acid, hence it has the formula CO(CH2 CH2 COOH)2. The author regards its formation from furfuracrylic acid by the splitting of the furfuran "ring" as an additional argument in favour of the view that furfuraldehyde has CH:C(COH). the formula <CHICH->0, and not that ascribed to it by Baeyer.

Ethyl hydrogen propiononedicarboxylate, COOH-C,H,O-COOEt, is formed by boiling the ethyl salt with the calculated quantity of alcoholic potash. It crystallises in white needles, melts at 67-68°, and is insoluble in light petroleum, soluble in water, readily soluble in alcohol, ether, benzene, chloroform, and carbon bisulphide. The silver salt, C9H130,Ag, decomposes very readily. The phenylhydrazone, CHO N2HPh, forms pale-yellow, microscopic crystals, melts at 112°, and is insoluble in water and light petroleum, readily soluble in ether, hot alcohol, benzene, and acetic acid.

On digestion with alcoholic ammonia, either for some hours at 100° or for a short time at 150°, ethyl propiononedicarboxylate is converted into a compound, C-H6O2N2, which is probably symmetrical imidopimelimide. It crystallises from hot water in long, thick prisms, from alcohol in long, compact, white needles, begins to sublime rapidly at 250-260° without decomposition, melts at 292°, is sparingly soluble in the ordinary solvents, and decomposes when boiled with hydrochloric acid or alkalis into ammonia and propiononedicarboxylic acid. Ethyl furfuracrylate, C,H,O-CH:CH-COOEt, is prepared by heating furfuropropionic acid with an equal weight of alcohol and one-fourth its weight of sulphuric acid for four hours at 100°. It is a colourless oil of pleasant odour and bitter taste, boils at 228-230° without decomposition, and is insoluble in water but miscible with alcohol and ether. W. P. W.

Furfuralmalonic Acid. By W. MARCKWALD (Ber., 21, 10801083).-Diethyl furfural malonate, C,H,O.CH.C(COOEt)2, is obtained. by heating a mixture of furfuraldehyde and ethyl malonate with acetic anhydride; the product is a slightly yellow, thick oil, with an ethereal odour and sharp bitter taste. It is insoluble in water, but mixes with alcohol and other solvents in all proportions.

Furfuralmalonic acid, C,H,O-CH:C(COOH)2, obtained by hydrolysing the ethyl salt, crystallises from ether, alcohol, or glacial acetic acid in compact prisms, which melt at 187° with decomposition, are readily soluble in water, but insoluble in benzene, light petroleum, and chloroform. When heated above its melting point, carbonic anhydride is evolved, and furfuracrylic acid is obtained. The salts are mostly readily soluble.

Monethyl furfuralmalonate, CH2O·CH(COOH)·COOEt, is formed by gently heating the diethyl salt for a short time with an excess of potash; it crystallises from benzene in large, thick, transparent, slightly yellow, rhombic prisms, melting at 102.5°. It is very sparingly soluble in cold, more readily in hot water, dissolves tolerably readily in benzene and chloroform, but is insoluble in light petroleum. When distilled, it yields carbonic anhydride and ethyl furfuracrylate. The alkaline salts are readily, those of the alkaline earths and the heavy metals only sparingly, soluble.

Furfuralmalonamide, C,H,O-CH:C(COONH2)2, is obtained by the action of concentrated ammonia on diethyl furfuralmalonate. It is tolerably readily soluble in hot water and boiling alcohol, from which it crystallises in white needles, melting at 180° with decomposition; it dissolves very readily in glacial acetic acid, but is insoluble in ether,