bable that free diazobenzene is first formed in the oxidation of the hydrazine. N. H. M. Isonitrosovaleric Acid and y-Valeroximidolactone. By P. RISCHBIETH (Ber., 20, 2669-2673).-Isonitrosovaleric acid (Abstr., 1883, 1129) can readily be obtained by dissolving hydroxylamine hydrochloride (50 grams) and levulinic acid (83 grams) in a small quantity of water and adding a concentrated aqueous solution of sodium carbonate (38 grams); a separation of the acid immediately occurs, and this is purified by recrystallisation from water. The yield amounts to 90 per cent. of that theoretically possible. When treated with hydrogen chloride, the acid melts and absorbs the gas, and on warming the product, a sudden reaction occurs with the evolution of nitrogen, and production of a black residue. On oxidation with dilute nitric acid, a large volume of gas is evolved, and acetic and succinic acids are formed; the residue is, moreover, found to be free from nitrogen. If the acid (6 grams) is heated with sulphuric acid (10 grams) in a vacuum at 150°, succinic acid sublimes, and nitrogen is evolved; when, however, a much larger proportion of sulphuric acid (36 grams) is employed, and the heating is continued for 6 to 12 hours at 100° at the ordinary pressure, the elements of a molecule of water are withdrawn from the molecule of isonitrosovaleric acid, and the "inner anhydride," y-valeroximidolactone, together with succinic acid, results. N -0 y-Valeroximidolactone, CMe<CH, CH2>CO, crystallises from ether and water in long, white prisms; it melts at 69-70° when slowly heated, and at a somewhat higher temperature when the heating is rapid, and boils at 232° without decomposition. When heated with aqueous alkalis, it yields the corresponding salts of isonitrosovaleric acid, but dilute sulphuric acid, hydrogen chloride, fuming hydrochloric acid, and ammonia are without action on it at 100°. On distillation with nitric acid (sp. gr. = 14), a distillate is obtained which contains in addition to unaltered lactone at least two distinct crystalline compounds; these have not yet been further examined. W. P. W. New Source of Capric Acid. By A. BUISINE and P. BUISINE (Compt. rend., 105, 614-617).-Capric acid does not exist as such in suint, but an aqueous solution of suint undergoes fermentation under the influence of microbes, and the quantity of fatty acids and especially of capric acid is greatly increased, the proportion of the latter rising to 5 per cent. The capric acid is separated by distillation, saponification, and subsequent fractionation, and is finally crystallised from boiling water. It forms a crystalline, buttery mass, with an odour of rancid butter, melts at 31°, is soluble in alcohol and ether, and is slightly soluble in boiling water, from which it crystallises in white needles. The barium salt is soluble in alcohol. C. H. B. Linoleic Acid. By L. M. NORTON and H. A. RICHARDSON (Ber., 20, 2735—2736).—When endeavouring to dry linoleic acid at 100° in a current of hydrogen, the authors found that a continued loss of weight occurred even after 28 hours, although no change in composition took place. Linoleic acid can be distilled without any appearance of decomposition at 290° under 89 mm. pressure, and a colourless product is obtained amounting to about three-fourths of the acid taken. This consists of an acid, C20H6O2, which cannot again be distilled in a vacuum without decomposition; its sp. gr. is 0·9108 at 15°, and its vapour-density = 153. Under similar conditions, ricinoleic acid yields an acid agreeing in composition with that just described. W. P. W. Butanedicarboxylic Acid. By R. OTTO and A. RÖSSING (Ber., 20, 2736-2747). By the reduction of dimethylmaleïc acids, two butanedicarboxylic acids are obtained, the one, melting at 193-194°, which has been shown to be symmetrical dimethylsuccinic acid, the other, ethylmethylmalonic acid, melting at 118-120°. In this paper, the anhydrides of these acids are more particularly studied. The former on dry distillation yields an anhydride melting at 87°, previously described by Bischoff and Rach; but this substance on rehydration and crystallisation from the aqueous solution yields not only the original or symmetrical dimethylsuccinic acid, but also the abovementioned isomeric ethylmethylmalonic acid. On the other hand, the symmetrical dimethylsuccinic acid, when treated with excess of acetic chloride, yields an anhydride isomeric with the above, which crystallises in rhombic tables melting at 38°; this on rehydration yields the original acid only. Again the butanedicarboxylic or ethylmethylmalonic acid, melting at 121°, remains unaltered on dry distillation, but when treated with acetic chloride it yields an anhydride of the same melting point, 86-87°, and crystalline form as the former of the anhydrides mentioned above, but which, however, differs from it in yielding on rehydration the original acid only. V. H. V. Distillation of Citric Acid with Glycerol. By P. DE CLERMONT and P. CHAUTARD (Compt. rend., 105, 520-523).-500 grams of crystallised citric acid mixed with 750 grams of ordinary glycerol of 28° are distilled in a glass retort of 3 litres capacity, and the product redistilled. The first fraction consists of about 250 grams of water containing a small quantity of acraldehyde, &c.; some crystals also separate in the colder part of the apparatus. The mass then swells up, and the temperature must be reduced, but it is afterwards gradually raised until the distillation is complete. The distillate during this second stage consists of 650 to 700 grams of liquid. The total products of the decomposition are 950 grams of liquid, 30 grams of a bulky, carbonaceous residue, carbonic oxide and carbonic anhydride, and vapours of acetone and acraldehyde. In addition to water containing small quantities of acraldehyde, the only products in the distillate are unaltered glycerol and pyruvine or the pyruvic ether of -O glycide, MeCO.COO.CH, CHCH2>, which is also obtained by the distillation of glycerol with tartaric acid or glyceric acid. Probably the pyruvine is a product of the reaction between glycerol and glyceric acid, the latter being formed as an intermediate product. The pyruvine thus obtained crystallises in large, prismatic needles, or tables, which melt at 82° and boil at 241° under a pressure of 764 mm. C. H. B. Double Lactone of Metasaccharic Acid. By H. KILIANI (Ber., 20, 2710—2716).—The oxidation product of the lactone of arabinosecarboxylic acid (Abstr., 1887, 465) dissolves readily in aqueous ammonia, and from the solution the diamide of metasaccharic acid, C&H12O6N2, separates as a white powder, consisting of microscopic, tabular, monoclinic crystals, which become yellow at 170° and melt at 189-190° with complete decomposition. The compound has a neutral reaction, and when heated at 100° with potassium hydroxide yields the potassium salt of metasaccharic acid as a colourless syrup; this becomes crystalline on stirring, and in aqueous solution does not reduce Fehling's solution. On treatment with a cold solution of phenylhydrazine hydrochloride (1 part) and sodium acetate (1·5 part), in water (10 parts), the oxidation product yields the monophenylhydrazide of the lactone of metasaccharic acid, C12HON2; this crystallises in colourless, microscopic scales with mol. H2O, dissolves readily in hot water and alcohol, and when rapidly heated becomes yellow at 185°, and melts at 190-192° with decomposition. If the mixture with phenylhydrazine (which, to obtain the preceding compound is allowed to remain for 20 minutes for the crystallisation to take place) is at once poured into boiling water, the diphenylhydrazide of metasaccharic acid, C18H22O6N4, separates after 10 to 15 minutes in yellowish-white, microscopic scales, which become yellow at 210°, melt at 212-213° with decomposition, and are very sparingly soluble in boiling water and alcohol. The solution in concentrated sulphuric acid is coloured red or bluish-violet by ferric chloride. When the oxidation product (12 grams) is dissolved in water (300 grams), treated with 3 per cent. sodium amalgam (200 grams), and dilute sulphuric acid added gradually so that the solution never becomes alkaline, allowed to remain five days with a further 200 grams of sodium amalgam, then treated with sulphuric acid and alcohol to free the product from sodium sulphate, and the mother-liquor evaporated, a syrup is obtained which still reduces alkaline copper solution, and from which mannite (2 grams) crystallises on standing over sulphuric acid. The strongly acid mother-liquor seems to consist of the lactone of a bibasic acid (? metasaccharic acid), a strongly acid syrup having similar properties being also obtained by continued heating of the oxidation product with water, or by repeated evaporation of its aqueous solution. The oxidation product of the lactone of arabinose-carboxylic acid dissolves in 18, not 8, parts of cold water (compare loc. cit.), and readily reduces alkaline copper solution. The aqueous solutions of its potassium and sodium salts, even in the absence of free alkali, become coloured intensely red on heating, or when allowed to evaporate spontaneously (Ber., 20, 343). The author, however, concludes, from the preceding experiments, that the oxidation product is not the lactone of a ketonaldehydic acid, but is a double lactone of metaCH(OH)-CH•O CO COO–CHCH(OH) - Си-си(ону saccharic acid, or ·O·CO- which, on account of its peculiar constitution is very labile, and on treatment with alkalis even at the ordinary temperature undergoes molecular change, or perhaps reduction to an aldehyde-compound yielding mannite by the action of nascent hydrogen. W. P. W. Thiohydantoïn. By R. ANDREASCH (Monatsh., 8, 407-424).— Loven has recently shown (Abstr., 1885, 241) that a methylene-group situated between a carbonyl-group and a sulphur-atom possesses similar properties to the methylene-group in ethyl malonate and acetoacetate. With the object of ascertaining whether this is the case in hydantoin, the author has prepared the disilver-derivative, and from that the dimethyl-compound. It Disilverthiohydantoin, Ag2C ̧N¿H2SO, was obtained by adding a warm aqueous solution of thiohydantoin to ammoniacal silver nitrate. forms a white, granular substance, sparingly soluble in nitric acid, insoluble in ammonia. It blackens when exposed to light. When treated with methyl iodide, the silver compound yields B-dimethylthiohydantoin, NH:C<NHCO> This substance is easily soluble in S.CMe2 water, sparingly in cold alcohol, crystallises in hexagonal scales, melts at 114, and decomposes at a slightly higher temperature. When oxidised in hydrochloric solution by barium chlorate, carbonic anhydride and mercaptan are evolved, and the residue is found to contain carbamide, and a mixture of barium salts which cannot be separated, but one of which seems to be barium methylsulphonate. When heated with barium hydroxide, the hydantoin yields cyanamide and some sulphur compounds which could not be isolated. With the aim of determining the constitution of the above compound, the author attempted to prepare the two isomeric dimethylhydantoïns in other ways. a-Dimethylthiohydantoin, S.CH2- may be prepared by heating together dimethylthiocarbamide and chloracetic acid in aqueous solution. It is easily soluble in water, alcohol, ether, and carbon bisulphide, crystallises in long, thin, colourless prisms, melts at 71°, and boils at a rather higher temperature. It volatilises slowly at ordinary temperatures. It has an odour somewhat resembling that of nicotine. When heated with aqueous alkalis, it yields thioglycollic acid. The isonitroso-derivative, C,H,N,SO, yields yellowish scales melting at 220°. Imidocarbaminethioisobutyric anhydride, CN2H,SO, was prepared by heating together thiocarbamide and z-bromisobutyric acid. It crystallises in plates, is easily soluble in alcohol and boiling water, sparingly in cold water, and melts at 242°. When oxidised with nitric acid, this substance yields carbamide and sulphoisobutyric acid, SO,H·C,H,COOH, which forms a barium salt, BaC,H,SO, + 4H,O, crystallising in needles, easily soluble in water, insoluble in alcohol. The sodium salt, Na,C ̧H ̧SO, + H2O, forms glistening needles easily soluble in water, insoluble in alcohol. The same sulpho-acid is obtained by the action of chlorosulphonic acid on isobutyric acid. The action of ammonium sulphite on a-bromisobutyric acid produces, however, an isomeric sulpho-acid, yielding an easily soluble barium salt, BaCH2SO, + 2H2O, crystallising in needles. S.CHEt. It is thus clear that this imido-anhydride is not identical with the B-dimethylthiohydantoin, as the author had anticipated. As it was possible that in the formation of the imido-anhydride a transformation from the iso to the normal butyric series had occurred, the author prepared imidocarbaminethiobutyric anhydride, NH: C<NH-CO by the action of a-bromobutyric acid on thiocarbamide. This crystallises in short, thick needles, easily soluble in boiling water, and melts at 200°. It is not identical with the compound obtained from isobutyric acid. The constitution of the latter is therefore still doubtful, but its formation may perhaps be due to the action of thiocarbamide on the methacrylic acid formed by the elimination of hydrogen bromide from the bromisobutyric acid, CH,: CMe-COOH + CS (NH2), = CHMe<CON>C: NH + H2O. >C:NH + H,O. The consitution of the B-compound would then be correctly expressed by the formula given above. Thiohydantoin when treated with benzaldehyde yields amidinethiocinnamic (benzylidenethiohydantoïc) acid, NH: C(NH,)(COOH): CHPh; this forms white, microscopic needles, insoluble in water, soluble in alcohol. Similar acids seem to be produced with other aldehydes. Several salts of thiohydantoïn are described. The sulphate, (C,H,N2SO)2, H2SO4, forms plates soluble in water; the nitrate, flat needles or prisms; the oxalate, C‚Í‚Ñ2SO,C2H2O, + H2O, prisms; the picrate yellow, microscopic needles. Thiohydantoin is best prepared as follows: 50 grams of thiocarbamide is dissolved in litre water, and 62 grams of chloracetic acid dissolved in 50 c.c. of water added. The whole is heated at 80-90° until reaction has ceased, and when cold it is gradually neutralised with soda, care being taken never to let the solution become alkaline. L. T. T. Orthothioxen and Orthothiophendicarboxylic Acid. By W. GRÜNEWALD (Ber., 20, 2585-2587).-Orthothioxen (Paal, Abstr., 1887, 1101) is prepared by distilling an intimate mixture of 10 grams of B-methyllevulinic acid and 17 grams of phosphorus trisulphide in a capacious retort. 250 grams of methyllevulinic acid yielded 150 grams of pure product. It is a colourless, strongly refractive oil, having an odour of petroleum; it boils at 136-137° (corr.). Sp. gr. at 21° 0.9938. When treated with 1 per cent. solution of potassium permanganate, a monocarboxylic acid only is formed; this melts at 134.5°. = |