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alcohol, ether, chloroform, and benzene, sparingly soluble in boiling water. Prolonged boiling with water decomposes the acid and its salts with elimination of hydrobromic acid. Sulphuric acid dissolves it unchanged. The sodium salt, C10H1Br2O,Na, is a heavy white, crystalline substance, very readily soluble in water, from which it crystallises with 3 mols. H2O. The hydrogen potassium salt is almost insoluble in cold water; the barium (with 2 mols. H,O), calcium (with 2 mols. H2O), lead, silver, copper, and ammonium salts were also prepared. The methyl salt crystallises in small, lustrous, rhombohedric plates melting at 50° (uncorr.); the ethyl salt is a thin oil.

Hydroxysebaceic acid, C10H16Os, is prepared by boiling sodium dibromosebate with water, evaporating to dryness on a water-bath, digesting over sulphuric acid, and extracting with absolute alcohol. The filtrate is neutralised with alcoholic soda. The sodium salt so obtained is converted into the insoluble lead salt which is then decomposed with hydrogen sulphide. The acid is readily soluble in hot water and in cold alcohol, from which it separates in small crystalline grains melting at 143° (uncorr.); it is very sparingly soluble in ether, insoluble in benzene and chloroform. The sodium salt, CHO,Na2, forms a white, sandy powder very readily soluble in water.

Dihydroxysebacic acid, C10H1O6, is obtained by boiling an aqueous solution of dibromosebacic acid with freshly precipitated silver oxide; the product is filtered, treated with hydrogen sulphide, and evaporated to a syrup; this becomes crystalline when kept over sulphuric acid. It is very readily soluble in water, alcohol, and glacial acetic acid, sparingly soluble in ether, insoluble in benzene and chloroform; it melts at 130° (uncorr.) and is decomposed at a higher temperature. It is optically inactive. The sodium salt, C10H16O.Na, is very soluble in N. H. M.

water.

Constitution of Levulinic and Maleïc Acids. By A. MICHAEL (Amer. Chem. J., 9, 364-372).-The reactions brought forward by Anschütz (Abstr., 1887, 916) in favour of the new constitutional formulæ suggested by Roser for maleïc and levulinic acids are examined. It is shown that by assuming certain reactions for ketones or for aldehydes similar in kind to those already known, the syntheses and transformations of these two acids and also of several others such as their acetyl-derivatives, mucobromic acid, the dibromosuccinic acids, &c., are quite as easily explained by the old formulæ as by the new ones of Roser. H. B. Butenyltricarboxylic and Ethylsuccinic Acids. By G. POLKO Annalen, 242, 113-126).-Ethyl butenyltricarboxylate,

CH2Me CH(COOEt)·CH(COOEt)2,

is prepared by adding 48 grams of ethyl malonate to a warm solution of 6.9 grams of sodium in 77 grams of alcohol; 48.5 grams of ethyl a-bromobutyrate is added to the product. It is a pale-yellow liquid boiling between 271° and 281°. Its sp. gr. is 1065 compared with water at 17°. The free acid is soluble in water, alcohol, ether, and acetone. It melts at 119°, and begins to decompose at 124°.

The

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barium salt, Ba,(C,H,O1)2, and silver salt, Ag,C,H,О。 + 11⁄2Н2O, are amorphous. The normal calcium salt, Ca,(C,H,O6) is very hygroscopic. The acid salts, CaH.(C,H,O6), and CaH(C,H,O6) + 2H2O, are crystalline and insoluble in alcohol. The zinc, strontium, and potassium salts are amorphous.

Ethylsuccinic acid, COOH CHEt CH, COOH, is prepared by distilling butenyltricarboxylic acid. It is also formed in the saponification of ethyl butenyltricarboxylate. It melts at 97° and is identical with the a-ethylsuccinic acid described by Huggenberg (Abstr., 1878, 782). In addition to the salts described by Huggenberg, the crystalline strontium salt and the methyl salt were prepared. The latter boils at 202-205°. The anhydride remains liquid at -19'. Its sp. gr. at 34° is 1.165. The amide melts at 214° with decomposition. It is insoluble in cold water and in alcohol. W. C. W. Isobutenyltricarboxylic Acid and Unsymmetrical Dimethylsuccinic Acid. By F. BARNSTEIN (Annalen, 242, 126-140).— Ethyl isobutenyltricarboxylate, COOEt CMe, CH(COOEt), is prepared by the action of ethyl a-bromisobutyrate on ethyl sodiomalonate in alcoholic solution. It boils at 272-275°, and its sp. gr. is 106↓ compared with water at 17°. The free acid is difficult to obtain in the crystalline state. It is soluble in water, alcohol, ether, and acetone. On boiling the aqueous solution, carbonic anhydride is evolved. The acid melts at 120° with decomposition, yielding unsymmetrical dimethylsuccinic acid. The sodium, magnesium, barium and silver salts of isobutenyltricarboxylic acid are amorphous. The potassium sait, K ̧C,H,O。 + 2H2O, forms efflorescent prisms. The calcium salts, Ca3(C,H,O6)1⁄2 + 9H2O and Ca(C;H7O6)2 + 2H2O, are crystalline.

Unsymmetrical dimethylsuccinic acid, COOH CMe2 CH2 COOH, melts at 139°, and is freely soluble in alcohol, ether, acetone, and in hot water. It forms acid and normal salts. The normal salts of the heavy metals and alkaline earths are, as a rule, very sparingly soluble in water. The normal potassium salt is amorphous and deliquescent; the acid salt, CH,O,K+ 5H2O, crystallises in plates which effloresce on exposure to the air. The normal barium salt, C.H.O ̧Ва + 2H2O, is crystalline; the acid salt is also crystalline, and readily soluble in water. The cadmium salt, C.H,O,Cd + 6H2O, and the lead salt, CH2O,Pb+ H2O, are crystalline, and dissolve with difficulty in water. Dimethylsuccinyl chloride, CH,O,Cl2, boils at 200-202°. Diethyl dimethylsuccinate boils at 213-215°. Its sp. gr. at 17° is 10134 compared with water at the same temperature. The dimethyl salt boils at 200°; sp. gr. 1·0568 at 16°. Dimethylsuccinic anhydride boils at 215°. Thiophen-derivatives cannot be obtained by the action of phosphorus sulphide on unsymmetrical dimethylsuccinic W. C. W.

acid.

Furfuran Derivatives. By W. MARCKWALD (Ber., 20, 28112817; compare Abstr., 1876, ii, 444).-Furfuracrylic acid is best obtained by heating furfuraldehyde (1 part), sodium acetate (2 parts), and acetic anhydride (2 parts) at 250° for 11 hours; the yield amounts

to more than 80 per cent. of that theoretically possible. The ammonium salt of its reduction-product, furfuropropionic acid, is converted into furfuropropionamide, CH,O-CONH2, by heating for several hours in a closed tube at 220°; this crystallises in white needles, melts at 98°, distils at 270° withont decomposition, is soluble in water, alcohol, ether, and benzene, sparingly soluble in light petroleum, and on treatment with bromine and aqueous potash does not yield the corresponding amine, since the furfuran nucleus alone is attacked. When furfuracrylic acid (1 part) is heated with 95 per cent. alcohol (3.5 parts) and saturated with hydrogen chloride, the ethyl salt of a bibasic acid, C&HO(COOEt)2, is obtained as an oil which distils at 286°; this is heavier than and insoluble in water, soluble in alcohol and ether in all proportions, and has a pleasant, aromatic odour and a very bitter taste; the yield amounts to more than 80 per cent. of that theoretically possible. When saponified, it yields the corresponding acid, C,H0O5, which crystallises from water in large, colourless, transparent, thin prisms, melts at 138°, or with partial decomposition at about 110° when heated. for some time in an open vessel, and has a very bitter taste. On distillation, it is converted into oily decomposition-products of partly acid and partly neutral character. The barium, calcium, zinc, and copper salts were prepared; the silver salt, C,H,O,Ag2, forms microscopic needles. Since the ethyl salt yields a phenylhydrazide,

[blocks in formation]

the author ascribes to the acid the formula

COOH CH2 CH2 CO-CH2 CH2COOH,

and adduces the following evidence in its support; the acid is not reduced by sodium amalgam, does not form an additive compound with bromine, and on oxidation with dilute nitric acid is converted into succinic acid (the yield amounting to more than 40 per cent. of the acid employed), and a liquid fatty acid (? acetic or propionic acid). The acid is not acted on when heated at 200° with hydriodic acid saturated at 0°, whilst addition of amorphous phosphorus leads to experimental difficulties which have not yet been surmounted.

W. P. W.

Action of Nitric Acid on Symmetrical Trichlorobenzene. By C. L. JACKSON and J. F. WING (Amer. Chem. J., 9, 348–355).—In proving the constitution of benzenetrisulphonic acid (this vol., p. 152), it was found that with fuming nitric acid, symmetrical trichlorobenzene did not yield a mononitro-derivative melting at 68° (Beilstein and Kurbatow, Annalen, 192, 233), but the dinitro-derivative melting at 130°. If sulphuric acid was used at the same time, the trinitroderivative was obtained. Whether a mono-, di-, or tri-nitro-compound is obtained depends not only on the temperature and presence or absence of sulphuric acid, but also to a very considerable extent on the purity of the acid employed, an acid of sp. gr. 151, free from nitrogen peroxide, being more effective than one of sp. gr. 1534 conta ning much nitrogen peroxide.

Trichlorobenzene (1:3:5) is best formed by the chlorination of di

chloraniline prepared by Witt's method (this Journal, 1876, i, 264). Trichlorodinitrobenzene, C,HCl, (NO2)2, is produced at the ordinary temperature by the action of nitric acid of sp. gr. 1.505 on trichlorobenzene. It crystallises from alcohol in white prisms melting at 129.5°. The mononitro-compound is readily obtained by boiling with nitric acid of sp. gr. 1:46. Trichlorotrinitrobenzene, CC13 (NO2)3 is prepared by using a mixture of fuming sulphuric acid and nitric acid of sp. gr. 1-505. It crystallises from alcohol in nearly white needles melting at 187°. H. B.

Action of Sulphuric Acid on Bromodurene. By O. JACOBSEN (Ber., 20, 2837-2840).—When bromodurene is treated with eight times its weight of sulphuric acid at the ordinary temperature, and the mixture allowed to remain for 10 to 12 days, a thick brown liquid is obtained, which, on the addition of ice and subsequently of water, yields a residue consisting chiefly of dibromodurene, together with hexamethylbenzene and unaltered bromodurene. The aqueous solution was free from halogenated sulphonic acids, but contained at least three sulphonic acids, one of which on hydrolysis yields prehnitene, whilst the other two yield pseudocumene. From these results, the author concludes that sulphuric acid acts in this case as a brominecarrier, converting the bromodurene into dibromodurene and durene (compare Neumann, Abstr., 1887, 573), the latter of which in the presence of sulphuric acid yields psendocumene, prehnitene, and hexamethylbenzene in the manner already described by him (Abstr., 1887, 660).

Dibromodurene, under similar conditions, is not acted on by sulphuric acid.

Probably sulphuric acid acts as a bromine-carrier when in its presence bromobenzene and paradibromobenzene are converted into dibromobenzenesulphonic acid and a mixture of tetra- and hexabromobenzene respectively, as observed by Herzig (Abstr., 1882, 46). The author has also found that dibromometaxylene, [Me: Me: Br: Br = 1 : 3 : 4 : 6], when treated with chlorosulphonic acid, yields the chloride of its sulphonic acid together with a considerable quantity of tetrabromometaxylene, although but a small quantity of the latter results when the same dibromometaxylene is heated with sulphuric acid at 240°, an isomeric liquid dibromometaxylene being the chief product in this case.

W. P. W.

Aniline Salts. By A. DITTE (Compt. rend., 105, 813-816).— Aniline molybdate, 2NH,Ph,3M003,5H2O, forms hard, brilliant, transparent, prismatic crystals, which lose water when gently heated, and decompose at a higher temperature. It is obtained by mixing a warm concentrated solution of ammonium molybdate with excess of a concentrated solution of aniline hydrochloride. Oily drops separate and rapidly change to a crystalline precipitate, and when this is dissolved in hot water and the solution cooled, the salt crystallises in radiating groups.

Aniline tungstate, 2NH,Ph,4Wo03,3H2O, analogous to ammonium metatungstate, forms long, brilliant, transparent needles, which lose

water when gently heated, and at a higher temperature burn with a smoky flame leaving a residue of tungstic anhydride. When an

monium tungstate is mixed with a boiling solution of aniline hydrochloride, no reaction takes place, but if aniline is added, a portion of it dissolves, and when the still acid liquid is concentrated and cooled, the aniline tungstate crystallises.

Three aniline vanadates can be obtained. Warm solutions of ammonium vanadate and aniline hydrochloride yield a red liquid, acid to litmus; when this is cooled, it deposits yellow needles of the composition NH,Ph, V2O5,4H2O, which darken on exposure to light, and at 100° lose water and become green with a metallic lustre. At a higher temperature, the salt blackens and decomposes. If a small quantity of aniline is added to the mixed solutions in the experiment just described, and the black precipitate which forms filtered off, a reddish-brown liquid is obtained, which after some hours deposits brilliant, reddish-brown needles of the composition 4PhNH2,3V2O,, 18H2O. They lose water when heated, and decompose at a higher temperature. If aniline is added gradually in small quantities with constant agitation to a cold concentrated solution of equal equivalents of aniline hydrochloride and ammonium vanadate, small yellow crystals separate. The solution is diluted until these crystals dissolve, and aniline is added until it no longer dissolves. The liquid is then concentrated over sulphuric acid, when the compound 2NH,Ph, V2O,,2H2O crystallises in large pale-yellow plates mixed with reddish-brown crystals of the preceding compound.

Aniline iodate, NH2Ph,212O, is obtained by mixing a cold almost saturated solution of ammonium iodate with an excess of aniline hydrochloride. It forms brilliant, white, nacreous plates, which alter when exposed to light, but may be kept in the dark at a low temperature. When gradually heated, it at first seems to undergo no alteration, but below a red heat it detonates very violently. If ammonium diiodate is used instead of the normal salt, decomposition of the salt begins at the moment of its formation.

Aniline chlorate is obtained in needles by mixing cold concentrated solutions of sodium chlorate and aniline hydrochloride. It is very unstable, and decomposes rapidly even in the dark at 0°. ordinary temperature, it quickly becomes black, and detonates violently

at about 20°.

At the

Aniline borate, NH2Ph,2B2O3,4H2O, analogous to ammonium biborate, is obtained by mixing the ammonium salt with aniline hydrochloride, or more easily by adding aniline to a boiling saturated solution of boric acid, in which it is readily soluble. The filtered liquid when cooled first deposits unaltered aniline, and then unctuous, transparent, white lamelle, which lose water when heated, then intumesce and give off alkaline vapours, and finally take fire at a higher temperature. C. H. B.

Homologues of Aniline and their Separation on a Large Scale. By O. N. WITT (Chem. Ind., 10, 8-13).-In the present communication, the author, after detailing the progress made in the manufacture of pure benzene, toluene, and xylene, since 1880, refers

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