When heated much above its boiling point, it is decomposed, yielding carbon oxychloride. It also closely resembles carbon oxychloride in its reactions. With dimethylaniline and benzaldehyde, it yields a green, with dimethylaniline a violet colour-base. With sodium acetate it yields acetic anhydride. Methyl alcohol acts on it to form a liquid boiling at 163–164°, probably impure OMe COO CC13.

When the chlorination is stopped at an earlier stage, a compound, C1HClO4, may be obtained. This is a liquid boiling at 108-109°, and having a very irritating odour. Its sp. gr. is 14786 at 14° and 1-4741 at 27°, compared with water at the same temperatures. When heated strongly, it decomposes. With water, it yields carbonic anhydride, carbonic oxide, formaldehyde, and hydrochloric acid. With methyl and ethyl alcohol, it yields methylated derivatives which have not yet been isolated. The compound described by Cahours as perchlormethyl chloroformate has probably a more complicated constitution. L. T. T.

Derivatives of Isopropylformamide. By M. SPICA (Gazzetta, 17, 168-171).-Isopropyl chlorocarbonate, prepared by the action of carbonyl chloride on isopropyl alcohol, is a colourless oil boiling at 94-96°; sp. gr. at 4° 1.144; it has an irritating odour, is insoluble in water, but soluble in alcohol and ether.

=

With a-naphthylamine, it yields isopropyl formonaphthylamide, PrO CO NH C10H, together with a-naphthylamine hydrochloride, of which the former is soluble, the latter insoluble in alcohol. The formonaphthylamide crystallises in long needles melting at 78-79°, of pungent, aromatic taste, soluble in ether and chloroform.

From 6-naphthylamine the corresponding B-derivative is obtained; it melts at 70°, and resembles the above compound in crystalline form and appearance. V. H. V.

Derivatives of Isopropyl Chlorocarbonate. By M. SPICA and G. DE VARDA (Gazzetta, 17, 165-168).-On passing a current of ammonia into isopropyl chlorocarbonate, isopropylformamide is produced together with ammonium chloride; the former is separated from the latter by its solubility in alcohol. The formamide, PrO-CONH, thus obtained crystallises in white, slightly deliquescent needles, melting at 36-37°, soluble in most menstrua.

Similarly from aniline and isopropyl chlorocarbonate, the corresponding phenyl-derivative is obtained together with aniline hydrochloride; the two substances are separated by fractional crystallisation from aqueous alcohol. The phenylformamide, PrO CONHPh, crystallises in prismatic needles melting at 42-43°, soluble in alcohol and ether, insoluble in cold water. V. H. V.

Preparation of Valeric Acid. By E. DUCLAUX (Compt. rend., 105, 171-173).-The oxidation of amyl alcohol by potassium permanganate should be effected in presence of an excess of alcohol, otherwise the valeric acid first formed is converted into acetic acid, and this is further oxidised to carbonic anhydride and water. It is likewise necessary to keep the liquid cool. Some acetic acid is always

produced, but this is readily removed by taking advantage of the fact that when a dilute solution of the two acids is distilled, almost the whole of the valeric acid is found in the first quarter of the distillate, whilst the acetic acid remains in the retort. This property of valeric acid seems to be independent of its optical properties. C. H. B.

Isomerism in the Crotonic Acid Series. By A. MICHAEL and G. M. BROWNE (J. pr. Chem. [2], 36, 174—176).-The authors have not succeeded in obtaining a good yield of a-B-dichlorobutyric acid by passing a current of chlorine through a solution of crotonic acid in carbon bisulphide (compare this vol., p. 655), since the greater part of the crotonic acid is not attacked under these conditions. If, however, the solution, cooled in a freezing mixture, is saturated with chlorine, allowed to remain three days, again saturated with the gas, and finally allowed to remain for three days more, a good yield of the dichlorobutyric acid is obtained. On treatment of an alcoholic solution of the acid (1 mol.) with alcoholic potash (2 mols.) in small portions at a time, a-chlor-allocrotonic acid is formed; this crystallises in needles which melt at 67°, and are soluble in water and light petroleum. The potassium salt crystallises from water in white, thin tables, from alcohol in slender needles; the sodium salt forms small, prismatic needles; the barium salt forms slender needles; the lead salt forms octahedral crystals, and the copper salt crystallises in greenish-blue, concentrically-grouped prisms. Although anticipated by Wislicenus (loc. cit.) in the publication of this work, the authors reserve to themselves the right of continuing the research.

W. P. W.

Ethyl Acetocyanacetate. By A. HALLER and A. HELD (Compt. rend., 105, 115-117).-23 grams of ethyl cyanacetate is dissolved in its own weight of absolute alcohol and mixed with a solution of 46 grams of sodium in 60 grams of absolute alcohol; 8 grams of acetic chloride dissolved in 20 grams of ether is then added, and the liquid is heated until the alkaline reaction disappears. The product is evaporated on a water-bath, the residue taken up with water, and treated with ether to remove ethyl cyanacetate. The aqueous solution is then acidified with sulphuric acid, and the ethyl acetocyanacetate is extracted with ether. It is purified by fractionation in a vacuum. The reaction is represented by the equation 2CN.CHNa COOEt + AcCl = NaCl + CN·CH2COŎEt + CN CNaAc-COOEt.

This reaction affords positive proof of the accuracy of the constitution generally assigned to this compound.

Three methods of preparing ethyl acetocyanacetate are now known, and the product is the same in all three cases.

C. H. B.

Thio-derivatives of Ethyl Carbonate. By P. KLASON (Ber., 20, 2384-2385).—When ethyl alcohol is treated with thiophosgene the principal reaction takes place according to the equation EtOH + CSCI, = HCl + EtCl + COS, but at the same time some ethyl chlorothiocarbonate, CSCI-OEt, is formed. This is a colourless oil of very irritating odour, and boils at 136°. Ammonia converts it into xanthogenamide. When sodium ethoxide is substituted for alcohol in

the above reaction, the action follows the equation OEtNa + CSCI2 OEt CS ONa+ 2NaCl + Et2O. With ethyl hydrosulphide, thiophosgene yields ethyl chloroperthiocarbonate, CSCI-SEt. It is a yellow oil of irritating odour resembling garlic. In a vacuum, it distils at 100°. Its density at 16° is 11408. With sodium thioethylate, thiophosgene forms ethyl perthiocarbonate, CS(SEt)2, which is a yellow oil boiling at 240°. L. T. T.

20,

Acids from Acetone-chloroform. By C. WILLGERODT (Ber., 2445-2449).-Three acids are derived from acetone-chloroform, namely, acetonic acid, acetonaloxyisobutyric acid, and acetoxyisobutyric acid. To obtain these oxyisobutyric acids, acetone-chloroform is heated directly with water or aqueous solutions of the alkalis; for the preparation of acetonoxyisobutyric acid, 2 mols. of chloroform and 3 mols. of acetone are condensed with 8 mols. of potash; and for acetonoxybutyric acid 1 mol. acetone-chloroform and 1 mol. acetone are required.

Acetonaloxybutyric acid has been described by the author (Abstr., 1883, 177), and more recently by Engel; its barium salt can be obtained in a crystalline form by slow evaporation in a vacuum; the zinc salt crystallises in aggregates with I mol. H2O, and the calcium salt in small pyramids with 13 mol. H2O.

Acetonoxyisobutyric acid, C,HO4, crystallises with 1 mol. H2O in the monoclinic system: a b c = 1·719:1:0·609; B 109° 80'. Observed faces, coPco, coP, Foo. When kept, it slowly effloresces.

V. H. V.

Constituents of Rape-seed Oil. By C. L. REIMER and W. WILL (Ber., 20, 2385-2390).-The authors find that this oil contains the glycerides of erucic, behenic, and rapic acids. The behenic acid is only present in small quantities. The oil was saponified, and the erucic and rapic acids separated by means of their zinc salts, zinc erucate being very sparingly soluble in boiling ether, zinc rapate easily so. The latter salt was recrystallised from alcohol, and then melted at 78°. Rapic acid, C18H3O3, is an oil. Its composition seems to point to its being a hydroxyoleic acid, and an isomeride of ricinoleic acid, but unlike this acid, it does not yield sebacylic acid when fused with potash. Under these circumstances it yields stearic acid, and a second crystalline acid, which has not yet been isolated. Barium, calcium, magnesium, and silver rapates form flocculent precipitates; the sodium salt is soluble in water and boiling alcohol.

Goldschmiedt has shown that the oil from black mustard seed contains the glycerides of erucic and behenic acids and of another liquid acid, and it is probable that this oil is identical with rape-seed oil.

Trierucin, C3H5(C2H21O2)3, was obtained by heating dierucin (this vol., p. 233) and erucic acid together at 300°. It is crystalline, melts at 31, and is soluble in ether and benzene, sparingly so in alcohol. When warmed with nitric acid and sodium nitrite, it is converted into the isomeric tribrassidin. L. T. T.

Preparation of Ethyl Cyanomalonate and Ethyl Benzoylcyanacetate. By A. HALLER (Compt. rend., 105, 169—171).—Ethyl

cyanomalonate.-22 grams of ethyl cyanacetate is dissolved in its own volume of absolute alcohol and mixed with a solution of 4.6 grams of sodium in 60 grams of absolute alcohol, and about 6 grams of ethyl chlorocarbonate. A rapid action takes place, and the liquid is heated until it is no longer alkaline. The alcohol is then distilled off, the residue dissolved in water, the unaltered ethyl cyanacetate is removed, and the liquid allowed to evaporate spontaneously. It yields slender needles of the composition CN-CNa(COOEt)2, and when the aqueous solution of this compound is acidified with sulphuric acid, ethyl cyanomalonate is liberated and can be extracted with ether.

Ethyl benzoyleyanacetate is obtained in a similar manner, 1 mol. proportion of benzoic chloride being used for each molecular proportion of ethyl cyanacetate taken.

The action of ethyl iodide on the silver-derivative of ethyl cyanacetate yields a liquid which has an odour of carbylamine, and is in all probability ethyl ethylisocyanacetate.

C. H. B.

Action of Ammonia on Ethyl Bromosuccinate. By G. KOERNER and A. MENOZZI (Gazzetta, 17, 171-176).-Although asparagine is justly regarded as amidosuccinamic acid, yet hitherto it has not been obtained from succinic acid by any direct method of synthesis. With this view, the authors investigated the action of ammonia on ethyl bromosuccinate under various conditions. It is found that both alcoholic and aqueous ammonia in the cold yield fumaramide; if, however, the mixture is heated at 105-110°, a substance isomeric with fumaramide is obtained, which yields barium aspartate when heated with barium hydrate. This compound is pro.CONH bably an imide of aspartic acid, NH, CH<CH, CO

as when heated with aqueous ammonia in a sealed tube it takes up a molecule of water, and is thereby converted into asparagine. This synthetical asparagine resembles the natural substance in crystallising with 1 mol. H2O, but differs from it in being optically inactive. The crystals are holohedral, with hemihedric faces. V. H. V.

Ethyl Succinimidoacetate and Camphorimidoacetate. By A. HALLER and G. ARTH (Compt. rend., 105, 280-283).—Succinimide (1 mol.) is dissolved in absolute alcohol, and mixed with sodium ethoxide (1 mol.) and ethyl monochloracetate (1 mol.), and the mixture heated until the alkaline reaction disappears. The alcohol is then driven off, the residue allowed to crystallise and the product purified by repeated crystallisation from ether. Ethyl succinimidoacetate, CH,CO,

CH, CON.CH, COOEt, is thus obtained in slender needles, very soluble in water, alcohol, and ether. They melt at 66.5°, and remain superfused at the ordinary temperature.

.CO.

Ethyl camphorimidoacetate, CH1<C>N-CH2-COOEt, is obtained in a similar manner, and crystallises from alcohol in large transparent crystals, which melt at 86°, and are soluble in ether.

When ethyl succinimidoacetate dissolved in absolute alcohol is

mixed with an equivalent quantity of metallic sodium also dissolved in alcohol, a gelatinous mass is precipitated, which, after being dried in a vacuum, is very hygroscopic, and dissolves completely in water. The percentage of sodium agrees fairly well with the formula CH, CO N.CHNA COOEt, hence it would seem that the presence -CH, CO

of the two CO-groups confers acidic functions on the CH-group, although they are separated by the nitrogen-atom. C. H. B.

Action of Carbamide on the Chloralcyanhydrins. By A. PINNER and J. LIFSCHÜTZ (Ber., 20, 2345-2351). When equal weights of chloralcyanhydrin, CC1, CH(OH) CN, and carbamide are heated together at 90° and lastly at 110°, trichlorethylidenediureïde, CCI CH(NH.CO.NH2)2, is formed. This crystallises in white needles, insoluble in the usual solvents, and decomposes at a high temperature without previous fusion. Biuret and cyanuric acid are also formed, but are probably secondary products due to the action of the liberated hydrogen chloride on carbamide.

When butyrochloral-cyanhydrin and carbamide are heated together at 100-105, and finally at 120°, two compounds, C,H,Cl,N,Ö, and CH,CIN2O2, are formed. The former crystallises in small needles, easily soluble in alcohol, sparingly in water; when heated strongly, it is decomposed without previous fusion. It is probably butyrochloralbiuret, CHCIMe CCl2 CH: (N2H2C2O2) NH. The second compound is chlorocrotonylcarbamide, CHMe: CCI.CO.NH.CO.NH. It appears to be dimorphic, crystallising sometimes in rhombic plates, melting at 224-225°, easily soluble in alcohol, sparingly in water, and sometimes in flat prisms easily soluble in water; the latter melt at 194, but the re-solidified mass when again heated melts at 209°. When heated above 224°, both modifications of this carbamide evolve hydrochloric acid and yield ethylidenemetapyrazolome, CHMe:C<NHCO CONH, This substance crystallises in pale grey

needles easily soluble in boiling water. decomposes without previous fusion.

When strongly heated it

Besides these compounds, a small quantity of an easily soluble substance crystallising in rhombic prisms was formed. This has not yet been obtained in a pure state.

L. T. T.

By

Behaviour of Furfuraldehyde in the Animal Organism. M. JAFFE and R. COHN (Ber., 20, 2311-2317).-Furfuraldehyde was given to dogs in daily amounts of 5 to 6 grams without producing any appearance of poisoning. In the case of rabbits, the action was much more marked. In the urine of the animals experimented on, the following compounds were found :-Pyromucic acid, pyromykuric acid, and a glycocine compound of furfuracrylic acid.

Pyromykuric acid (glycocine pyromucate), C,H,NO,, separates from the ethereal extract of the urine in crystalline crusts; it crystallises from water in colourless, transparent prisms, resembling hippuric acid, and melts at 165°. The barium salt, (C,H,NO,),Ba + 14H2O, is precipitated by alcohol from its concentrated aqueous solution in plates