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a compound also obtained by the direct action of bromine on ethylene mercaptan. It forms insoluble crystals, decomposing at 151-154° with carbonisation. Its isomeride, diethylidene tetrasulphide,

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is prepared by the oxidation of thialdine hydrochloride by iodine dissolved in potassium iodide. It forms an amorphous flocculent precipitate. V. H. V.

Action of Nitrous Acid on Ketones. By L. CLAISEN (Ber., 20, 252).-Nitrosoketones have hitherto only been obtained by indirect methods; the author now finds that they can be obtained directly by the action of free or nascent nitrous acid on the ketones. For instance, nitrosoacetone is obtained in considerable quantity by adding hydrochloric acid to a mixture of amyl nitrite and acetone, and heating on the water-bath. In like manner, when a well-cooled mixture of acetophenone and amyl nitrite is saturated with hydrogen chloride, a white crystalline mass separates which melts at 133-134°, and seems to be nitrosoacetophenone hydrochloride. Amyl nitrite reacts also with aldehydes, yielding products now under investigation.

A. J. G.

Derivative of Dimethylene Disulphone. By W. AUTENRIETH (Ber., 20, 373-376).-Duplosulphacetone, S2(: CMe2), (Wislicenus, Zeit. für Chem., 1869, 224), is prepared as follows:-50 grams of acetone (from bisulphite compound) are heated at 120-130° with 50 grams of phosphorus trisulphide for 6-8 hours, the product poured into water and steam-distilled. The oil is dried over calcium chloride and redistilled; it boils between 180° and 190°. It yields an additive compound with methyl iodide.

SOCMe, is obtained

SO

Tetramethyldimethylene disulphone, CMe2< by oxidising duplosulphacetone by means of potassium permanganate. It is extracted by ether. It crystallises from hot alcohol in slender, white needles melting at 220-225° with decomposition. It dissolves readily in alcohol, ether, and chloroform, sparingly in hot water. Concentrated sulphuric and nitric acids dissolve it unchanged. It is not changed when boiled with aqueous alkali; prolonged heating with concentrated alkali decomposes it completely. N. H. M.

y-Amidovaleric Acid. By J. TAFEL (Ber., 20, 249-251).—In a previous communication (Abstr., 1886, 1008) it was suggested that the substance C,H,NO, obtained by heating y-amidovaleric acid, was a .CHMe•NH oxymethylpyrrolidine having the formula.

CHMe N.

or

CH–CH,>CO CH,CH,COH; this hypothesis is now confirmed, as it is shown to yield a methylpyrrolidine on reduction; there is, however, as yet no evidence as to which of the two formulæ is correct.

CHMe CH2

Methylpyrrolidine, < CH2-CH2>NH, is obtained by adding sodium

to a boiling solution of oxymethylpyrrolidine in amyl alcohol as long as hydrogen is evolved. It is a colourless, mobile liquid, boils at 96-97° under a pressure of 737 mm. (mercurial column in vapour), but volatilises rapidly at the ordinary temperature, and has a penetrating, stupefying odour; the vapour quickly produces violent headache.

The use of Ladenburg's reduction method for the removal of oxygen seems to be generally applicable not only to the pyrroline but also to the pyridine and quinoline 'series, seeing that by it nonoxygenated bases have been prepared from oxylepidine, methylepidone, and carbostyril (Knorr and Klotz, this vol., p. 278).

A. J. G. Hydroxybutyric Acid in Diabetic Urine. By E. STADELMANN (Zeit. Biol., 32, 456-459).-The preparation of the salts of hydroxybutyric acid in a pure state from the urine of diabetic patients is a matter of some difficulty, as they become mixed with a dark-coloured sticky mass, which is probably composed of derivatives of diabetic sugar, and which is soluble in ether. It becomes black on evaporation.

According to Minskowski the preparation of the silver salt is that which presents least difficulties. The author finds that the zinc salt is prepared with greater ease. The sugar is best removed by means of fermentation (see Külz, this vol., p. 290), but this method is not without its drawbacks, as putrefactive decomposition is apt to occur simultaneously.

Putrefaction was prevented by adding salicylic acid to the extent of 0.2 per cent., and also by letting the fermentation take place in a cool cellar. At the end of a fortnight the urine showed no signs of putrefaction and all the sugar had disappeared from 55 litres, the quantity used. Another difficulty arises from the quantity of urea. which in these cases is very abundant in the urine. The method adopted for getting rid of it was as follows:-1 kilos. lime was added to the total quantity of urine, much ammonia came off, and after five hours the filtered liquid still showed a diminished but still a high percentage of urea; it was, therefore, evaporated down to 20 litres, when more ammonia was evolved, another kilo. of lime was added, and heat applied for 30 hours, at the end of which time no more ammonia was given off; the remaining quantity of urea was removed by mercuric nitrate. From the clear, greenish-yellow filtrate, the zinc salt of hydroxybutyric acid was then prepared and crystallised; the brown colour beforementioned was, however, still present; the crystals were therefore treated with absolute alcohol, in which they are but sparingly soluble, while the coloured mass dissolves easily. An advantage of this calcium hydroxide process is that by its means the sulphates and phosphates are also removed. The salicylic acid used in process is removed by washing the zinc salt with alcohol.

the

W. D. H.

B-Bromolevulinic Acid. By I. WOLFF (Ber., 20, 425–433).— In order to determine the constitution of the isomeric angelolactones produced by the distillation of levulinic acid, the reactions were studied of the bromolevulinic acid obtained both from a-angelo

lactone bromide and directly from levulinic acid. When treated with sodium carbonate, this bromo-acid yields acetoacrylic acid, so that its constitution is expressible by the formula COMe CHBr·CH, COOH, and the angelolactone from which it is derived by <CH: CMe -CH, CO– CMe>0. Acetoacrylic acid, CHAC: CH-COOH, forms glistening scales, melting at 125-125.5°, sparingly soluble in alcohol and chloroform; it combines with phenylhydrazine and also with bromine to form a-B-dibromolevulinic acid; this crystallises in needles melting at 107— 108°, and is readily soluble in alcohol, ether, and benzene. Simultaneously with acetoacrylic acid a hydroxylevulinic acid is formed, an oily liquid, which, when heated with ammonia, yields a base, C.H2N2, besides two subsidiary products not as yet investigated. This base, which is also obtained from bromolevulinic acid, is identical with the dimethyl ketone of Gutnecht and Treadwell; it crystallises from water as a hydrate, C,H,2N2,3H2O, in white lustrous needles, melting with loss of water at 74-77°, and when dried over desiccating substances is converted into brittle, lustrous prisms of the anhydrous base; this melts at 86° and boils at 190°; the hydrochloride, CH12N2,HCI + 2H2O, melts at 91°; the platinochloride crystallises in glistening needles. The methiodide, CH12N2,MeI + 2H2O, is a citron-yellow, crystalline substance. It seems that the dimethyl ketone contains four methyl-groups and may be represented by a formula C.Me,N2; in confirmation, the silver salt of a tetracarboxylic acid, C.(COOH),N2, has been obtained.

Bromolevulinic acid, when heated with aniline, yield a base, C2H22N2, which crystallises in silky needles melting at 107-108°, soluble in alcohol, ether, and chloroform.

In conclusion, it is remarked that the above-mentioned dimethyl ketone, or azo-ketone, the benzoimide of Erdmanu, the base, C29H20N2, obtained by Japp and Wilson (Trans., 1886, 825), and isoindole, can be represented as derived from a fundamental substance, CH,N2, which it is proposed to call pyrazine. The above substances will then be its tetra- and di-methyl-, tetra- and di-phenyl-derivatives respectively. V. H. V.

Composition and Constitution of Arabinosecarboxylic Acid and Arabinose. By H. KILIANI (Ber., 20, 282 and 339-346; compare this vol., p. 229).-When the lactone of arabinosecarboxylic acid is boiled with concentrated hydriodic acid (15 parts) and amorphous phosphorus, a product is obtained consisting chiefly of normal caprolactone and a small quantity of normal caproic acid. Arabinosecarboxylic acid is therefore pentahydroxycaproic acid, CH12O7, and not hexahydroxyheptylic acid, and has the same composition as gluconic and galactonic acids. When the lactone of arabinosecarboxylic acid is digested with nitric acid (sp. gr. 1-2) for 24 hours at 50°, the product diluted and evaporated, a viscous substance is obtained which when dissolved in a little warm water solidifies on cooling to a hard cake of crystals. This is redissolved, the oxalic acid present precipitated with lime, and the filtrate evaporated; it separates in long, colourless needles. This compound is a double

lactone of metasaccharic acid, and has the formula C.H ̧О ̧ + 2H2O: It differs from saccharic acid in having a neutral reaction. It is soluble in 8 parts of cold water, insoluble in ether, sparingly in alcohol. The calcium salt, CH,O,Ca + H2O, forms microscopic spheres. When the solution of the hydrogen potassium salt is exposed to air, it acquires an intense red colour. When the double lactone is reduced by means of hydriodic acid, a small quantity of an acid is formed which melts at about 200°; this when treated with sodium amalgam is converted into an acid, probably adipic acid. lactone has probably the constitution

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The

The above experiments show that arabinose has the formula CsH10Os, and not C,H2O, and the fact that it yields with hydrocyanic acid a compound containing a normal carbon-chain, shows further that it is an aldehyde of normal pentahydroxypentane :

OH CH2CH(OH)·CH(OH)·CH(OH)·CHO.

The formation of arabonic acid from arabinose is readily explained, being analogous to that of gluconic acid.

Small quantities of arabinosecarboxylic acid are best prepared by saturating the solution from which the amide has separated with dry hydrogen chloride, and, after 12 hours, evaporating with baryta-water; the barium is then precipitated by sulphuric acid, the hydrochloric acid by silver oxide, and the solution evaporated to a syrup. During treatment with hydrochloric acid, the solution should be cooled with ice. The yield is 70 to 80 per cent. N. H. M.

Action of Nitric Acid on Bibasic Acids. By H. P. N. FRANCHIMONT (Rec. Trav. Chim., 5, 281–289).—In continuation of experiments on the action of nitric acid on substituted malonic acids (Abstr., 1886, 533), the author has more fully examined this reaction in the case of methylmalonic acid. The products obtained were carbonic anhydride, acetic acid, and trinitroethane, the last of which forms brilliant crystals, melting at 55°, sparingly soluble in water, volatile in the air, and volatilising rapidly in steam. Attempts were made to prepare trinitro- from bromo-dinitroethane, but without success. The trinitro-compound is also formed in small quantities in the reaction between nitric and isosuccinic acids. In the case of amylmalonic acid, no appreciable quantity of a nitro-derivative of a hydrocarbon was obtained, but only carbonic anhydride and hexylic acid. Thus the action of nitric acid on substituted malonic acids consists mainly in the production of a monobasic acid containing two atoms of carbon less than the original substance, and the evolution of 2 mols. of carbonic anhydride for each molecule of the substance employed.

V. H. V.

Isonitroso-compounds. By H. BERGREEN (Ber., 20, 531534). The author finds that ethyl isosuccinate, when treated with nitrous acid, yields ethyl isonitrosopropionate (Abstr., 1878, 659). Ethylic ethylmalonate and ethyl benzylmalonate, when similarly

treated, yield oily compounds, from which pure crystalline substances have not yet been obtained. W. P. W.

Action of Phosphoric Chloride on Ethyl Acetonedicarboxylate. By B. S. BURTON and H. v. PECHMANN (Ber., 20, 145 -149).-B-Chloroglutaconic acid, COOH-CH: CCI-CH, COOH, is obtained by gradually adding 50 grams of ethyl acetonedicarboxylate to 160 grams of phosphorus pentachloride, and then heating the whole on a water-bath. The product is poured into water, the oil extracted with ether, and the ethyl salt so obtained saponified by boiling for two or three hours with 20 to 25 times the amount of strong hydrochloric acid. The acid melts at 129° and becomes dark at 170°, is readily soluble in water, ether, and alcohol, less soluble in chloroform, from which it separates in groups of white needles; it is also soluble in boiling benzene. When reduced by zinc-dust and acetic acid, an acid melting at 132° (the m. p. of glutaconic acid) is formed; it decomposes at a higher temperature with evolution of gas. Chloroglutaconic acid is reduced by sodium amalgam to glutaric

acid.

Glutic acid, COOH-C C-CH, COOH, is formed when 5 grams (1 mol.) of the chlorinated acid dissolved in alcohol is gradually dropped into and shaken with a 5 per cent. alcoholic solution of potash containing rather more than the theoretical amount (3 mols.) of potash. The potash solution is previously heated at 50-60°. It is filtered, washed with alcohol, and dried. The united products of several preparations are treated with a large excess of dilute sulphuric acid and extracted with ether. The acid is purified by washing with warm benzene and crystallising from a mixture of ether and benzene. It forms groups of slender needles which melt at 145 · 146° with evolution of carbonic anhydride; it is readily soluble in water, alcohol, and ether, insoluble in chloroform and benzene. It decomposes when kept long. When a solution of the hydrogen potassium salt is heated, carbonic anhydride is evolved, and there is an odour of acetone. The lead salt forms a white precipitate; the barium and potassium salts crystallise in slender needles and in long, flat needles respectively; both contain water of crystallisation.

N. H. M.

Aconitic Acid. By W. HENTSCHEL (J. pr. Chem., 35, 205-206). -Aconitic acid is readily obtained when crystallised citric acid (2 parts) is heated with sulphuric acid (2 parts) and water (1 part) for 4-6 hours in a reflux apparatus; the yield amounts to 35-45 per cent. of the citric acid employed. Acetone is also formed in the reaction, and gas is evolved consisting of 2 vols. carbonic anhydride and 1 vol. carbonic oxide. W. P. W.

Reduction of Dihydroxytartaric Acid Diphenylhydrazine. By J. TAFEL (Ber., 20, 244-249).-Phenylhydrazineamidooxalacetic acid, COOH-CH(NH2)·C(: N2HPh) COOH, is obtained by the reduction of an alkaline solution of dihydroxy tartaric acid diphenylhydrazide by the addition of successive small quantities of sodium amalgam until the intense yellow solution is just decolorised; it could not be

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