product obtained by Stenhouse (this Journal, 1870, p. 8) by the action of chlorine in the presence of iodine on chloranilic acid is pentachlor acetone. When chloranilic acid is treated with potassium chlorate and hydrochloric acid, noteworthy quantities of oxalic acid are formed together with a neutral brownish-yellow liquid which distils with partial decomposition at 180-196°. The distillate is a yellow oil, and consists of two substances, one of which (the chief product) is liquid, and the other a crystalline solid; the latter can be separated by crystallisation in a freezing mixture, and forms beautiful, yellow scales. The liquid product is purified by addition of water, which converts it into the crystalline hydrate of symmetrical tetrachloracetone, CHCI, CO-CHCI, + 4H.O. This crystallises from water in colourless, long prisms, melts at 48-49°, loses its water of crystallisation on further heating, and boils at 179-181° at 725 mm. pressure. The coloured crystalline product is most probably symmetrical tetrachloracetyl, CHCI, CO-CO-CHCI. It crystallises from ether in large, yellow tables, melts at 83-84°, and boils at 201-203° with slight decomposition at 740 mm. pressure yielding a yellowish-green vapour. It has a pungent odour, is soluble in water, alcohol, and ether, and is turned brown on treatment with aqueous soda and ammonia. Ammoniacal silver solution is not reduced by it, and no trace of red colour can be detected when it is added to a magenta solution decolorised by sulphurous anhydride. Finally, when treated with phenylhydrazine, it yields a very characteristic phenylhydrazide, which crystallises in slender, orange-red, woolly needles, melts at 186° with decomposition, and is very sparingly soluble in alcohol. The research is being continued. W. P. W. Thiocarbonyl Chloride. By H. BERGREEN (Ber., 21, 337-352). -The decomposition of thiocarbonyl chloride by water, which takes place very slowly in the cold, is complete at the end of a few hours on boiling. The products of the reaction are carbonic anhydride, hydrogen sulphide, and hydrogen chloride. When dissolved in anhydrous ether free from alcohol, and saturated with carefully dried ammonia, thiocarbonyl chloride is converted into ammonium thiocyanate (compare Rathke, Annalen, 167, 195), ammonium chloride, and a third substance which, however, could not be identified owing to the small quantity obtained. The thiamidoformic chloride, CSC NH2, which might possibly be regarded as an intermediate product of this reaction, was not formed by heating the chloride with ammonium chloride at 200° for some hours; on the contrary, complete decomposition occurred with the formation of carbon bisulphide and carbon tetrachloride. This result is due in some way to the presence of ammonium chloride, since thiocarbonyl chloride is decomposed only to a very slight extent when heated alone at 200° for a similar period. Diphenylamine reacts with thiocarbonyl chloride in ethereal solution to form a compound which crystallises in small, pale-yellow needles, melts at 196°, and is probably identical with Bernthsen and Friese's tetraphenylthiocarbamide (Abstr., 1882, 1089). When thiocarbonyl chloride (5 grams), dissolved in benzene free from thiophen (25 grams), is treated with powdered aluminium chloride. (8 to 10 grams) and the mixture heated on a water-bath for some time until hydrogen chloride ceases to be evolved, a compound is obtained whose composition approximates to that required for thiobenzophenone, CSPh. This is a reddish-brown oil which dissolves readily in ether, benzene, and hot alcohol, and decomposes on distillation yielding a crystallisable distillate free from sulphur. When treated with hydroxylamine or with phenylhydrazine, it gives off hydrogen sulphide, and is converted into diphenylacetoxime or the phenylhydrazide of benzophenone respectively; hence it must be regarded as a thioketone. Behr (this Journal, 1873, 276) and Engler (Abstr., 1879, 61) have obtained compounds containing sulphur which have been described as thiobenzophenone; these substances, however, do not react either with hydroxylamine or phenylhydrazine, and cannot, therefore, be thioketones. The author suggests that Engler's compound (m. p. 146'5°) may be a polymeride of thiobenzophenone corresponding with Wislicenus' thioduploacetone. Thiocarbonyl chloride also reacts with zinc methyl and zinc ethyl, and the compound obtained from the latter is a pungent, red oil, which can be distilled with steam. On analysis it was found to contain only four-fifths the amount of sulphur required for the formula CSEt2, and the noncrystallisable oil obtained, together with hydrogen sulphide, on treating its alcoholic solution with phenylhydrazine, yielded only one-half the nitrogen required for the formula CEt:N,PhH; these results are, however, attributed to the difficulty of purifying the compound, which most probably is diethylthioketone. = Ethyl chlorothioformate is obtained by the action of thiocarbonyl chloride (1 mol.) on an alcoholic solution of sodium ethoxide (1 mol.). The boiling point of this compound is probably 130-135°, but the specimen obtained boiled at 130-160°; its identity was, however, established by its conversion into xanthogenamide on treatment with aqueous ammonia. When 2 mols. of sodium ethoxide are employed, ethyl thiocarbonate is obtained (compare Klason, Abstr., 1887, 1029). The reaction with a solution of phenol in aqueous soda results in the formation of phenyl thiocarbonate, CS(OPh)2, which forms white, lustrous crystals, and melts at 97°. The action of thiocarbonyl chloride on ketonic derivatives of the type of ethyl acetoacetate results in the displacement of both the hydrogen-atoms of the methylene-group by the thiocarbonyl radicle. Ethyl thiocarbonylacetoacetate (CS:CAc-COOEt), (compare Norton and Oppenheim, Ber., 10, 703), for example, is obtained from ethyl sodacetoacetate and from ethyl cnpracetoacetate; this compound does not react with phenylhydrazine or hydroxylamine, and probably is not a thioketone. An oil which could neither be crystallised nor distilled, and which contained sulphur but not chlorine, was formed when ethyl sodiomethacetoacetate in ethereal solution was treated with the chloride. Under like conditions, ethyl sodiomalonate yields the thiocarbonyl-derivative CS:C(COOEt)2, which crystallises in small, flesh-coloured needles, and melts at 177-178°. When this compound is saponified with alcoholic potash, and the product dis solved in water and treated with dilute sulphuric acid, hydrogen sulphide is evolved in small quantity, and a crystalline acid is obtained which cannot be recrystallised, since it decomposes partially on solution with the evolution of hydrogen sulphide. The analytical results are consequently only approximate, but they point to the formulæ CS:C(COOH), for the acid, and CS:C(COOAg)2, for the silver salt; the latter is pale-yellow in colour, and when touched with a small flame explodes like gunpowder, with the formation of silver sulphide, carbonic anhydride, and carbon. Thiocarbonyl chloride and ethyl sodiobenzoylacetate also react, forming ethyl thiocarbonylbenzoylacetate, (CS:CBz-COOEt)z, which crystallises in yellowish needles, melts at 162-164°, and dissolves in sulphuric acid with a yellow colour. Lastly, the sodium compound of desoxybenzoïn is converted, under similar conditions, into the thiocarbonyl-derivative, C15H10OS, which crystallises in small, golden-yellow needles, melts at 285-286°, is much more sparingly soluble in ether, carbon bisulphide, light petroleum, and hot alcohol than the thiocarbonyl-derivatives of ethyl acetoacetate and ethyl malonate, and dissolves in concentrated sulphuric acid with a deep bluish-violet colour, recalling that of permanganate in solution. W. P. W Calcium Copper Acetate. By F. RÜDORFF (Ber., 21, 279--281). -Calcium copper acetate, which was first prepared by Brewster (Schweigger's Jahresb., 33, 342), does not contain 8 mols. of H2O, but has the composition Ca(C2H3O2)2 + Cu(C2H3O2)2 + 6H2O. The crystals are stable at the summer temperature and do not lose water of crystallisation when exposed over calcium chloride for 48 hours; decomposition, however, sets in at 60°. The salt cannot be recrystallised from water, and is not formed when solutions containing equimolecular proportions of its constituents are mixed together, since in both cases the resulting solution on cooling or on spontaneous evaporation yields crystals either of copper acetate or a mixture of the double salt and copper acetate until the solution contains the constituent salts in the ratio of 1 mol. of copper acetate to 3 mols. of calcium acetate; when this point is reached, crystals of the pure double salt begin to separate. The double salt can readily be prepared by dissolving 25 grams (1 mol.) of copper acetate and 66 grams (3 mols.) of calcium acetate in 350 c.c. of warm water; on cooling, the pure salt separates in quadratic forms, and the mother-liquor on concentration continues to yield pure crystals until 10 mols. of calcium acetate are present. W. P. W BB-Methylethylpropionic Acid. By P. v. ROMBURGH (Rec. Trav. Chim., 6, 150-156).-Secondary butylmalonic acid was prepared by heating ethyl sodiomalonate with secondary butyl iodide for several hours. The ethyl secondary butylmalonate obtained on fractionation of the crude product, is a colourless liquid of a pleasant odour; it boils at 233-234° under a pressure of 774 mm.; sp. gr. at 75 = 0.988. When heated with alcoholic potash, acidified with hydrochloric acid, and extracted with ether, it yields secondary butylmalonic acid, CHMeEt CH(COOH)2, which forms compact, transparent crystals melting at 76° and becoming opaque in the air. It dissolves readily in water, ether, alcohol, and boiling benzene. With ammonium chloride and calcium chloride, it gives a precipitate almost insoluble in boiling water. The silver salt is white. = When secondary butylmalonic acid is gradually heated to 200°, it gives off carbonic anhydride, and yields BB-methylethylpropionic acid, CHMeEt CH2COOH, which boils at 196-198" under a pressure of 762 mm., and is optically inactive; sp. gr. at 15° 0·930; vapourdensity 3.99. The silver salt crystallises from hot water in curved needles; the calcium salt forms transparent needles which contain 3 mols. H2O, and become opaque when exposed to dry air. The amide, prepared by Hofmann's method, forms long, transparent needles which melt at 124°, and can be sublimed without altering the melting point. It dissolves in warm water, in alcohol, ether, and boiling benzene. The author concludes that ßß-methylethylpropionic acid has the same constitution as the caproic acid from the dextrogyrate hexyl alcohol obtained from Roman essence of camomile, but differs from it in being optically inactive. This alcohol would therefore have the constitution CHMeEt CH, CH, OH. C. H. B. Borneo Tallow. By A. C. GEITEL (J. pr. Chem. [2], 36, 515518). The author has examined an authentic sample of Borneo tallow (the produce of Shorea stenoptera and other dipterocarpons), from Java. It had a bright-green colour, which by long exposure to the air became at first yellow, and eventually white. At ordinary temperatures, it had the consistence of cacao-butter, which it somewhat resembled in taste and smell. It softened between the fingers, commenced to melt at 35-36°, and became perfectly fluid at 42°. On cooling, the oil did not solidify until the temperature had fallen considerably below the melting point. A portion of the tallow was saponified with potash, and the resulting soap decomposed with dilute sulphuric acid; the mixture of fatty acids thus obtained crystallised well, and, after repeated washings with warm water and careful drying, solidified at 54°. It consisted almost entirely of stearic and oleic acids, present in the ratio of two to one. The tallow contained about 10 per cent. of free stearic acid, and yielded a like quantity of glycerol. The author points out that the composition of Borneo tallow, and the ease with which it can be saponified, render it particularly well adapted to the manufacture of soap and candles. G. T. M. Action of Nitric Acid on Amides and Alkylamides. By A. P. N. FRANCHIMONT (Rec. Trav. Chim., 6, 140-149).—When nitric acid acts on amides and methylamides, it would seem that the radicle of the organic acid is displaced by that of nitric acid, or in other words, by NO2, but the amide of nitric acid is only stable when the two hydrogen atoms of the group NH, are displaced by a hydrocarbon radicle such as methyl. The three typical reactions may be represented by the equations: AcNH2 + HNO3 = AcOH + N2O + H2O; AcNHMe + 2HNO, AcOH + MeÑO, + N2O + H2O; and AcNMe2+ HNO1 = AcOH + Me2N NO. = Heptylamide, prepared by Hofmann's method and treated with the strongest nitric acid, yields a volume of nitrous oxide corresponding with 1 mol. of the amide; acetylglycocine behaves in a similar way. All compounds containing acetyl are not attacked, but in the majority of cases when any reaction takes place, the acetyl-group is removed in the form of acetic acid, as in the case of the amides. The same reaction seems to take place with propane-derivatives. Strong sulphuric acid does not decompose the amides in the same way as nitric acid. In most cases the reaction in question does not occur between the free amides and nitric acid, but between the acid and nitrates of the amides which are first formed. It is possible that the nitric acid merely acts as a dehydrating agent, and this view would seem to be supported by the fact that sulphuric acid decomposes the nitrates of the amides in a precisely similar way. It is probable, however, that a sulphate is first formed, and the decomposition which ensues is due to the liberated nitric acid, and in fact if an amide is dissolved in sulphuric acid, there is no action beyond the formation of a sulphate, but on adding nitric acid decomposition at once begins. When the organic acid is not liberated, a stable nitroderivative is formed, as in the case of dimethyloxamide. In other cases, a nitro-derivative may be formed in the first instance, but decomposes immediately. The action of acetic chloramide on silver nitrite yields acetic acid and nitrous oxide, a nitro-derivative possibly being formed as an unstable intermediate product. Another possible supposition is that the action of nitric acid on nitrates of the amides is analogous to the formation of diazo-derivatives, and that unstable oxydiazo-compounds are formed; thus, for instance, AcNHO NO2 gives AcNH(O·NO2): NO·OH; these oxydiazo-derivatives decomposing in accordance with the equations already given. This latter view is supported by the fact that a solution of dimethyloxamide in nitric acid evolves nitrous oxide after some time; that a solution of dinitrodimethyloxamide in nitric acid undergoes no change, and that if a solution of dimethyloxamide in nitric acid is poured into water immediately after its preparation, some little time elapses before the nitro-derivative separates. No one supposition, however, is capable of explaining all cases. The main point is that the nature of the reaction is to a great extent determined by the nature of the acid radicle in the amide, and in some cases the nature of the alkyl radicles substituted in the NH-group exerts a distinct influence, ethyl and methyl-derivatives not behaving in exactly the same way. C. H. B. Isomerism of Fumaric and Maleïc Acids. By R. ANSCHÜTZ (Ber., 21, 518-520).-Lossen (Ber., 20, 3310) suggests that the oxidation of fumaric and maleïc acids to tartaric and inactive tartaric acids may be explained with the help of the formulæ COOH CH: CH COOH and COOH·C CHCOOH, usually ascribed to fumaric and maleïc acids respectively. In the present paper, the improbability is shown of inactive tartaric acid having |