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obtained in a state approaching purity, but when heated with sulphuric acid it is converted into the corresponding anhydride, C10H9N3O3. This crystallises in snow-white plates of fatty lustre, is insoluble in ether and hot water, sparingly soluble in hot alcohol, benzene, acetic acid, and acetone, more readily in chloroform and hot concentrated hydrochloric acid; it dissolves readily in alkalis and alkaline carbonates, and in concentrated sulphuric acid. The solutions become red or violet on exposure to air. The alkaline solution reduces Fehling's solution on gently heating, and mercuric oxide in the cold, the solution in the latter case showing an intense orange-red coloration. From its reactions, it is very probably amido-oxyquinizinecarboxylic acid.

If the reduction of the diphenylhydrazide with sodium amalgam is pushed further, Lehrfeld's diamidosuccinic acid (Abstr., 1882, 162) is obtained. A. J. G.

Gluconic Acid. By L. BOUTROUX (Compt. rend., 104, 369-370). -The crystallised ammonium gluconate recently described by Volpert (Ber., 19, 2621) had previously been obtained by the author, and described by him as ammonium zymogluconate. Zymogluconic acid obtained from glucose by acid fermentation (Abstr., 1885, 682), is, however, identical with the gluconic acid of Hlasiwetz and HaberC. H. B.

mann.

Constitution of Trimethylenetricarboxylic Acid. By A. MICHAEL (J. pr. Chem. [2], 35, 132-136).-When ethyl sodiomalonate is treated with ethyl a-bromacrylate by Conrad and Limpach's method, a very violent reaction takes place, and an ethyl salt is formed identical with that obtained by Conrad and Guthzeit from ethyl a-8-dibromopropionate. The latter compound must therefore have the constitution CH, C(COOEt)·CH(COOEt).

When treated with sodium ethoxide and benzoic chloride, no substitution took place; the ethyl salt was recovered unchanged. This behaviour is analogous to that of the compound obtained by Perkin from ethylene bromide and ethyl sodiomalonate. This negative result can therefore no longer hold good as evidence against the constitution CH, CH-CH(COOEt), for ethyl vinaconate. N. H. M.

Amides of Ethylsulphonic Acid. By A. P. N. FRANCHIMONT and E. A. KLOBBIE (Rec. Trav. Chim., 5, 274-280).-In continuation of the experiments of Romburgh on the action of nitric acid on the replaced amides of phenylsulphonic acid, corresponding derivatives of ethylsulphonic acid are described, and the action on them of nitric acid is investigated. As regards the preparation of ethylsulphonic acid, preference is given to the oxidation of ethyl bisulphide. The acid is converted into the chloride, which is dissolved in ether, and an ethereal solution of the amine added. The amide formed is then fractionally distilled. The mono- and di-methylamides of ethylsulphonic acid, and the corresponding ethyl-compounds, are all colourless liquids, miscible with water, and of peculiar odour. Their physical properties are given in the following table :

[blocks in formation]

gravity.

1.216

1.146

Ethylsulphonomethylamide, EtSO, NHMe 276°
Ethylsulphonodimethylamide, EtSO,NMe, 240
Ethylsulphonethylamide, EtSO,NHEt .. 272
Ethylsulphonodiethylamide, EtSO,NEt2..

254

1.154

1.080

Ethylsulphonomethylamide, when treated with nitric acid (sp. gr. 1-5), yields a nitramide, EtSO, NMe NO2, a colourless liquid solidifying at 11°; it cannot be distilled without decomposition, and deflagrates with violence when heated at 100°. Ethylsulphonodimethylamide yields under the same conditions nitrodimethylamine. So also ethylsulphonethylamide yields a nitramide, EtSO, NEt NO2, a crystalline substance melting at 15°, sparingly soluble in water. The same compound is also obtained from ethylsulphonodiethylamide.

Thus the action of nitric acid on the replaced amides of ethylsulphonic acid is precisely analogous to the action on the corresponding derivatives of phenylsulphonic acid. V. H. V.

Calcium Urate. By S. DELÉPIN (Physiol. Soc., 1887, 2-3).Urine containing calcium oxalate, with perhaps an excess of uric acid, sometimes contains small acicular crystals differing from the generally known urates. They sometimes occur also in the urine of gouty subjects. Crystals of uric acid and natural sediments of acid urates when allowed to stand in hard water become transformed into small masses of acicular crystals very insoluble even in hot water. This change does not occur when distilled water is used. This led to the conclusion that the crystals were urate of calcium, and that this salt might be of more importance in the economy than has been supposed. Pure urate of calcium was therefore prepared from uric acid and calcium hydroxide, and a crystalline substance was obtained similar in appearance to the crystals observed in urine, and formed by adding hard water or calcium hydroxide to a deposit of uric acid or urates in urine.

Urate of calcium is colourless or white when seen in large quantities. It forms long, needle-shaped crystals which are generally grouped in stars, but it may also be amorphous. It is more insoluble in hot water than other urates, and less easily decomposed by acids. Strong acid, however, like sulphuric acid, displaces the uric acid, which crystallises readily. The murexide reaction is easily obtained.

It was also found that in gouty deposits in the cartilages, which are generally spoken of as sodium urate, urate of calcium was found to be present in all cases, both by chemical tests and microscopical appearances. W. D. H.

Chloropyromucic Acid. By H. B. HILL and L. L. JACKSON (Ber., 20, 252-255).-When ethyl pyromucate tetrachloride, prepared in the cold, is treated with concentrated alcoholic soda, sodium B-7-dichloropyromucate is in the main formed; if, however, in the preparation of the tetrachloride, the temperature has been allowed to rise too high, further substitution occurs, and the sodium salts obtained

contain not inconsiderable quantities of sodium trichloropyromucate. B-y-Dichloropyromucic acid, CH2Cl2O3, crystallises in slender interlaced needles, melts at 168-169°, is readily soluble in alcohol, ether, and hot water, moderately in boiling benzene or chloroform. The following salts are described:-Barium (+ 3H,O), calcium (+ 4H2O), silver and potassium (both anhydrous). The ethyl salt crystallises in slender needles and melts at 176°; the amide also crystallises in slender needles and melts at 176°. The free acid when treated with bromine-vapour does not give a stable additive compound, but is converted with evolution of bromine into an acid of high melting point (dichlorobromopyromucic acid?). With bromine-water, it is converted into mucochloric acid with evolution of carbonic anhydride. It is only completely oxidised with nitric acid after boiling for several hours; monochloric and dichloromaleic acids were identified amongst the products of the reaction. A. J. G.

Transformation of Furfuran into Pyrroline. By F. CANZONERI and V. OLIVERI (Gazzetta, 16, 486-497).-Although it is generally assumed that furfuran, C.H.O, and pyrroline are derivatives of a fundamental group, C.H., yet the transformation of one into the other has not as yet been effected. When pyromucic acid is heated with ammoniacal zinc chloride and lime, and the products of the change are collected successively in a tube surrounded by a freezing mixture, in another containing hydrochloric acid, and a third containing bromine, there are obtained pyrroline, furfuran, and methylamine hydrochloride. The last is a product of a more profound change. The formation of pyrroline results in the displacement of oxygen by the NH-grouping, thus: C.HO+ NH, C,H,N + OH. Its identity was established by the analysis of its potassium-derivative and by the pyrroline-red reaction. The furfuran was obtained as a colourless mobile liquid, of ethereal odour, boiling at 32°.

=

In order to throw some further light on the relative arrangement of the atoms in the CH, residue, the authors have effected the synthesis of a-naphthylamine by heating in sealed tubes pyromucic acid, lime, zinc chloride, and aniline; this result tends to show that the atoms are arranged thus: CH: CH·CH: CH. Further, as furfuran undergoes condensation with the benzene nucleus with elimination of water, it may probably be regarded as a glycide or rather as an anhydride of the unsaturated glycol CH(OH): CH·CH: CH (OH).

V. H. V. Furfurylamine. By J. TAFEL (Ber., 20, 398-400).-This compound is easily obtained by the reduction of C. Fischer's phenylfurfurazide (Abstr., 1878, 310) with sodium amalgam and acetic acid, as follows:-45 grams of phenylfurfurazide is dissolved in 600 grams of alcohol and then 1350 grams of 24 per cent. sodium amalgam slowly added, the solution being kept constantly acid by the addition of acetic acid, and the temperature not being allowed to rise above 3°. The product is then supersaturated with potash, and, after driving off the alcohol, is steam-distilled. The distillate is acidified with hydrochloric acid and evaporated to a small bulk. A red resin separates, and the filtrate, after being made slightly alkaline, is treated with

ether to remove aniline, re-acidified, and evaporated until crystallisation commences. The residue is then mixed with dry powdered potash and distilled. Furfurylamine distils over as a colourless liquid, boiling at 135° under 754 mm. The hydrochloride is easily soluble in water, alcohol, and hydrochloric acid; but this latter solution does not turn green when heated as stated by Ciamician and Dennstedt. The sulphate forms minute needles, the acid oxalate, C,H,NO,C2H2O1 + H2O, characteristic narrow scales. The picrate forms goldenyellow prisms which decompose without previous fusion at 150°. When exposed to the air, the amine absorbs carbonic anhydride, forming a crystalline mass melting at 75° and decomposing at a higher temperature with evolution of carbonic anhydride. L. T. T.

Thiophen in Aniline. By M. T. LEKO (Chem. Centr., 1887, 41). -The author endeavoured to find an amido-compound of thiophen in aniline by converting commercial aniline into the phenylhydrazine compound, and testing this for thiophen. The results were negative. G. H. M.

Reduction of a-Thiophenic Acid. By F. ERNST (Ber., 20, 518-520).-a-Thiophenic acid is the sole product of the oxidation of propiothienone, and is best prepared by this method; when reduced with sodium amalgam in alkaline solution, it yields tetrahydro-a-thiophencarboxylic acid, C,SH,COOH. This acid crystallises in large, tabular, colourless laminæ, melts at 51° (corr.), has an intensely acid taste, and an intolerable odour; it is very readily soluble in water and alcohol, and is volatile with steam. It is decomposed on distillation, shows all the properties of a hydro-acid, and, like the tetrahydrodicarboxylic acid (this vol., p. 237), gives the indophenine reaction on heating. The methyl salt is a colourless, oily liquid, boiling at 206° without decomposition; the ethyl salt is a yellow liquid. The calcium salt, (C,SH, COO),Ca + 3H2O, is crystalline; the silver salt, C.SH, COOAg, forms small, glistening crystals, sparingly soluble in W. P. W.

water.

Constituents of Coal-tar. By K. E. SCHULZE (Ber., 20, 409414). The author finds that amongst the benzene-derivatives (hydrocarbons and phenols) present in coal-tar, meta-compounds largely predominate. Thus, for instance, of the trimethylbenzenes the 1: 3:5 compound (containing 3 meta-positions) is very largely in excess of the 1: 3:4 and 1:2:3 compounds (containing each 1 meta-position: and the quantity of metacresol is much larger than that of ortho- or para-cresol.

The author has isolated from coal-tar pyridine, Ladenburg's a-alutidine (Abstr., 1885, 557), a-y-lutidine, and y-picoline.

L. T. T.

Reciprocal Transformation of Cumene- and Cymene-derivatives. By M. FILETI (Gazzetta, 16, 497-503).-This paper is merely an answer to Widman's criticisms (this vol., p. 133) on the author's view regarding the mutual transformations of cumene- and cymene-derivatives. V. H. V.

Oxidation of the Methyl Ethers of Mono- and Di-bromoorthoisopropylphenols. By A. PERATONER (Gazzetta, 16, 420-424). -Methyl bromisopropyl oxide, when heated with nitric acid of sp. gr. =13, yields dibromo- and nitrobromo-methoxysalicylic acids, OMe C,H2Br2 COOH, and OMe C&H2Br(NO2) COOH; it appears that the greater part of the compound is completely burnt in the oxidation process, and the formation of a dibromo- from a monobromocompound is due to the subsequent action of bromine liberated by the nitric acid.

Methyldibromisopropylphenyl oxide, under similar treatment, yields dibromomethoxysalicylic acid, identical with that obtained V. H. V.

above.

Compound of Orthotoluidine with Cupric Chloride. By E. POMEY (Compt. rend., 104, 365-366).-Orthotoluidine is mixed with hydrochloric acid, and, after combination has taken place, a saturated solution of cupric chloride in hydrochloric acid is added to the warm liquid, an abundant, pale-yellow, crystalline precipitate is formed. This is recrystallised from hydrochloric acid and dried below 100°, at which temperature it begins to decompose. It has the composition CuCl2,5(C,H,N,HCI), and is very soluble in water. The copper is completely precipitated from the solution by potassium hydroxide, and the chlorine by silver nitrate.

The compound which paratoluidine hydrochloride forms with cupric chloride contains 2 mols. of the former to 1 mol. of the latter.

C. H. B. Compound of Paratoluidine with Cupric Chloride. By E. РOMEY (Compt. rend., 104, 300).-If cupric chloride is added to a solution of paratoluidine it produces a brown precipitate, but if both solutions contain free hydrochloric acid no precipitate is formed. If, however, the mixture is heated to boiling and is then allowed to cool, it deposits very brilliant, golden-yellow crystals which are purified by recrystallisation from hydrochloric acid, and are then dried at 100° until no more hydrogen chloride is given off. They have the composition CuCl2,2(C,H,N,HCI), and are soluble in water.

C. H. B.

Thioparatoluidine. By J. TRUHLAR (Ber., 20, 664-679, and Chem. Centr., 1887, 8-10).-Thioparatoluidine melts at 103-104°, and is basic. When an alcoholic solution is treated with an excess of hydrobromic acid, the hydrobromide, CH,N,S,2HBr, is thrown down. It forms small, white needles, easily soluble in hot alcohol, less soluble in cold alcohol, and easily in water. The hydriodide is obtained in a corresponding manner; it forms light-brown needles easily soluble in water, alcohol and ether; when heated at 100°, it is decomposed with separation of iodine.

Thioparacetotoluide, NHAC C,H,Me S.C,H,Me NHAc, is obtained by treating thioparatoluidine with an excess of acetic anhydride; it crystallises from alcohol in snow-white, stellate groups of needles, and melts at 211°; it is easily soluble in alcohol and benzene, less easily in ether, and insoluble in water.

Thioparabenzoyltoluide, NHBzCH2Me•S•C2H2Me•NHBz, is obtained

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