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The hydrochloride forms crystals melting at 86°, and giving up hydrogen chloride very easily. The nitrile dissolves in boiling water with partial decomposition into its components. Neither hydrochloric acid nor potash causes hydrolysis, but when heated with these reagents the nitrile undergoes decomposition. When the nitrile is slowly added to concentrated sulphuric acid, a-anilidopropionamide is formed; this melts at 140-141°, and is decomposed when heated with strong potash. With hydrochloric acid, it yields a-anilidopropionic acid, which melts at 163° and sublimes unchanged.

Ortho- and para-toluidine form compounds similar to the above. a-Paratoluidopropionitrile melts at 82°; the amide,


melts at 145°, and is more unstable than the anilido-amide; the free acid forms colourless, hygroscopic scales melting at 152°.

a-Orthotoluidopropionitrile melts at 72-73°, the amide at 125°, and the acid at 116° when separated from alcoholic, but at 123° from aqueous solutions.

The hydrochlorides of these nitriles yield unstable, crystalline platinochlorides.

Bromine forms tribromo-substitution products. a-Tribromanilidopropionitrile, CH2Br, NH CHMe CN, forms yellow needles melting at 130°; a-orthotoluidodibromopropionitrile melts at 105°, and a-paratoluidodibromopropionitrile at 117°. L. T. T.

Derivatives of Methyl Carbanilate. By W. HENTSCHEL (J. pr. Chem. [2], 34, 423-427).-In a former communication (Abstr., 1885, 792), the author has described the formation of methyl amidosulphobenzoate from methyl carbanilate by the action of sulphuric acid. When the substance is decomposed with excess of brominewater, and the solution allowed to remain for some days, a substance of the formula C,H,O,NBr, separates, which crystallises in needles, and melts at 96 5°.

This substance, in which two atoms of bromine have taken the place of the sulphonic group, when warmed with sulphuric acid yields dibromaniline sulphate, which on decomposition with sodium hydroxide gives ordinary dibromaniline (1: 24).

When treated with nitric acid of sp. gr. 145, the brominated substance gives a nitro-compound, crystallising in silky needles, melting at 152°, and having the constitution

OMe CO NH-C,H2Br2 NO2 [NH: Br2: NO2 = 1:2:46]. When heated with aqueous ammonia in a sealed tube, the nitrocompound yields dibromonitraniline (m. p. 127.5°).

The acid liquid containing methyl amidosulphobenzoate yields a nitrocarbanilide when treated with strong nitric acid. This forms colourless plates or prisms, melts at 189°, and when heated with strong hydrochloric acid in sealed tubes, yields a dinitraniline which agrees in all respects with unsymmetrical metadinitraniline.

G. H. M.

Ethyl Phthalylacetoacetate. By C. Bülow (Annalen, 236, 184 —194).—Ethyl phthalylacetoacetate, prepared by the method described by Fischer and Koch (Abstr., 1883, 806), is decomposed by the action of sulphuric acid at 65° for half an hour, yielding alcohol and acetic and phthalylacetic acids. It is also decomposed by prolonged boiling with water or with alkalis, but with a cold alcoholic solution of potassium hydroxide it yields a deliquescent crystalline compound, C1,H12K,O. + C2H,O, which is very soluble in water. At the ordinary temperature, ammonia converts ethyl phthaly lacetoacetate into phthalyldiamide, but at a temperature of 100° phthalimide is formed.



Ethyl phenylhydrazinephthalylacetoacetate, C20H1N2O, forms thick plates, soluble in alcohol, in strong acetic and sulphuric acids, and in alkalis. It melts at 236-238°, and on reduction with zincdust and acetic acid yields the ethylic salt of benzylacetoaceticorthocarboxylic acid. This compound melts at 92°, and dissolves freely in hot water, alcohol, ether, chloroform, and acetic acid. It is decomposed by boiling with baryta-water, yielding benzylacetoneorthocarboxylic acid, COOH-C,H, CH, CH, COMe. This acid dissolves freely in the usual solvents, and melts at 114°. The phenylhydrazine compound of ethyl benzylacetoaceticorthocarboxylate, COOH CH, CH2CH(COOEt)·CMe N2HPh, forms pale - yellow, needle-shaped crystals. It melts with decomposition at 235°, and dissolves freely in alcohol, ether, chloroform and carbon bisulphide. At the ordinary temperature, and more rapidly at 100°, the compound splits up into alcohol, water, and a new substance, CH16N2O3, which melts at 228-229°. W. C. W.

Benzoic Sulphinide. By I. REMSEN and A. G. PALMER (Amer. Chem. J., 8, 223-227).-Benzoic sulphinide may be sublimed; it is decomposed by simple evaporation with strong hydrochloric acid or by boiling with strong baryta-water, yielding orthosulphobenzoic acid. The following salts are described :-C,H,SO,NK + H2O, very soluble crystals; C,H,SO,NAg, sparingly soluble in boiling water, and separating in long needles; (C,H,SO,N),Ba + 14H2O, easily soluble in water and difficult to crystallise; the methyl salt has also been prepared, but not completely examined. H. B.

Parethoxybenzoic Sulphinide. By I. REMSEN and A. G. PALMER (Amer. Chem. J., 8, 227-229).-Ethoxy toluenesulphonamide (this vol., p. 136) was oxidised in warm dilute aqueous solution with potassium permanganate; from the filtered and concentrated solution, hydrochloric acid precipitated parethoxybenzoic sulphinide,

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The substance forms needle-shaped crystals, melting at 257-258°; it has not a sweet taste. The potassium and silver salts, C,H,SO,NK and C,H,SO,NAg, are described.

H. B.

Parabromobenzoic Sulphinide. By I. REMSEN and W. S. BAYLEY (Amer. Chem. J., 8, 229-235).-Parabromotoluenesulphonamide (Hübner and Post, this Journal, 1874, 57) was oxidised with potassium permanganate in considerable excess, when besides the sulphinide, there is also formed a considerable quantity of parabromosulphobenzoic acid; this substance is not formed if potash is also added during the oxidation. Parabromobenzoic sulphinide is sparingly soluble in cold water, volatilises at about 200°, melts at 217°, and is characterised by an extremely sweet taste, followed by an after-taste of extreme bitterness. The following salts are described :-(C,H,O,SN Br),Ba + 7H2O; (C,H,O,SNBr),Ca + 7H2O; C-H2O,SNBrAg + 2H2O. When treated with phosphorus pentachloride, and then with alcohol, the ethyl salt, C,H,O,SNBrEt, is obtained as a substance which after recrystallisation from hot alcohol melts at 199-199.5°. Attempts to prepare the ethyl salt from the silver salt and ethyl iodide were unsuccessful, a mixture of at least two substances being obtained. H. B.

Benzoyltoluenesulphonamide and some of its Derivatives. By I. REMSEN and C. S. PALMER (Amer. Chem. J., 8, 235-243).— Somewhat similar to the sulphinides is the class of substances represented by benzoylbenzenesulphonamide, Ph.CO.NH SO, Ph, and benzoyltoluenesulphonamide, Ph·CO·NH SO2 C,H,Me, obtained by the action of benzoic chloride on the corresponding amides. But the constitution of these substances has not been definitely proved, and Wolkow has shown that benzamide when treated with benzenesulphochloride yields not benzoylbenzenesulphonamide, but toluenesulphonic acid and phenyl cyanide, and it is, therefore, possible that the above two substances are represented, not by R.SO, NH COR, but by R-SO, N: C(OH)R. On the first of these suppositions, two ethyl salts should be obtained, one, R.SO, NEt COR, from the silver or lead, salts and ethyl iodide, and the other, R.SO, NCR.OEt, by acting on the sulphonamide with phosphorus pentachloride and alcohol; on the second supposition, only one ethyl salt can be prepared by either method, namely, R.SO2N CR.OEt. It has already been shown, and is confirmed by the authors, that ethereal salts of benzoyltoluene-sulphonamide cannot be obtained by the action of phosphorus pentachloride and alcohol. Neither can they be obtained by the action of ethyl iodide on the lead or silver salts of the sulphonamide; similar n gative results have been recorded by other writers.

But although the ethereal salts of the sulphonamides cannot be obtained from the sulphonamides, they may nevertheless be prepared indirectly. Benzoylmethyltoluenesulphonamide, C,H,O-NMe-C,H,SO2, crystallises with difficulty; it melts at 58°, and is prepared by the action of benzoic chloride on methylparatoluenesulphonamide, NHME SO2 C,H,. On adding water to its alcoholic solution, the latter crystallises in plates melting at 75°, is very stable, and is obtained by treating paratoluenesulphochloride with methylamine.

Benzoylethyltoluenesulphonamide was prepared, but not analysed; it is obtained from benzoic chloride and ethylparatoluenesulphonamide,

NHET SO2 C,H,, melting at 58°, and prepared like the above methylcompound.

Benzoylphenyltoluenesulphonamide crystallises readily from alcohol; the crystals melt at 149°; when boiled with alcoholic potash, it yields benzoic acid and toluene-sulphanilide. It is prepared from phenylparatoluenesulphonamide, NHPh.SO,C,H,, melting at 103, and already prepared by Müller. H. B.

Separation of the Two Isomeric Toluidinesulphonic Acids. By E. A. SCHNEIDER (Amer. Chem. J., 8, 274). The potassium and sodium salts of paratoluidinemetasulphonic acid are very soluble in water, but insoluble in cold aqueous potash, whilst the potassium and sodium salts of paratoluidineorthosulphonic acid are very easily soluble in the same liquid at ordinary temperature.

H. B.

Action of Concentrated Sulphuric Acid on Hydrazinetoluenesulphonic Acids. By E. A. SCHNEIDER (Amer. Chem. J., 8, 271-273).—It was hoped that condensation might be effected between the hydrazine- and sulphonic-groups. Parahydrazinetolueneorthosulphonic acid apparently underwent no change. Parahydrazinetoluenemetasulphonic acid reacts violently with sulphuric acid at 80°; the product poured into water gives a bright red precipitate, not further examined, and the filtrate, with excess of soda, gives a yellow precipitate which resembles in all its properties the basic substance obtained by Gallinek and Richter (Abstr., 1886, 236) by heating paratolylhydrazine with sulphuric acid, and is probably identical with it. H. B.

Oxidation by Means of Potassium Permanganate. By I. REMSEN and W. H. EMERSON (Amer. Chem. J., 8, 262-268).—It has been stated "that acid oxidising agents tend to transform paragroups (hydrocarbon-chains) and leave ortho-groups unchanged, and that alkaline oxidising agents tend to transform ortho-groups and leave para-groups unchanged," and R. Meyer and Baur (Abstr., 1881, 46) have adduced in favour of this the case of cymenesulphonic acid [Me: SO2H: Pr = 1:2:4], which with permanganate yields hydroxypropylsulphobenzoic acid [COOH: SO,H: C,H,O= 1:2:4], but with nitric acid yields sulphoparatoluic acid [CH,: SO,H: COOH = 1:2:4]. On the other hand, Jacobsen has shown that metaxylenesulphonamide [SO,H: Me: Me = 1: 2: 4] yields the same product of oxidation [SO,H: Me: COOH 1:2:4] with either chromic acid or potassium permanganate.



Jacobsen's work is fully confirmed, and it is also shown that paraxylenesulphonic acid and paraxylenesulphonamide yield the same oxidation products with permanganate, namely, sulphoterephthalic acid and a sulpho- or sulphamido-paratoluic acid. By fusing the last-named compounds with potash, they are both converted into one and the same hydroxytoluic acid, a-orthohomometahydroxybenzoic acid [Me: OH: ČOOH = 1:2:4], and hence the methyl-group first oxidised is not that which is in the ortho-position relatively to the sulphonic group.

The work of Meyer and Baur was then repeated and fully confirmed, and finally the behaviour of cymene itself with alkaline permanganate was examined. It was found that the products of the oxidation were almost equal quantities of terephthalic acid and of hydroxypropylbenzoic acid, COOH.C2HC,H,O, which was recognized by converting it into propenylbenzoic acid and isopropenylbenzoic acid. Cymene treated with chromic acid yields as the first product toluic acid, and hence the cause of the different behaviour of cymenesulphonic acid towards alkaline permanganate solution, and towards acid oxidising agents (nitric acid) is not to be sought for in the influence of the sulphonic group on the hydrocarbon side-chains (Meyer), but in the difference between the side-chains themselves, the isopropylgroup yielding most easily to acid oxidising agents, the methyl-group yielding most easily to alkaline oxidising agents. (Compare Abstr., 1886, 541.) H. B.


Action of Bromine and Water on a-Metaisocymenesulphonic Acid: Constitution of a- and ẞ-Metaisocymenesulphonic Acids. By W. KELBE and N. v. CZARNOMSKI (Annalen, 235, 272-299).—In addition to the results which have previously appeared in this Journal (Abstr., 1882, 619; 1884, 1355; and 1886, 355), the authors describe the following compounds :

Lead B-bromometisocymenesulphonate, Pb(C10H12BrSO3)2 + H2O, crystallises in needles, and is soluble in alcohol and in hot water. The barium salt forms colourless plates; the copper salt glistening green plates containing 4 mols. H2O; and the potassium salt, CH12Br SO3K + H2O, silky needles. The sulphonamide,

C10H12Br SO2 NH2,

melts at 162° and dissolves in strong alcohol, from which solvent it is deposited in transparent needles.

a-Bromisocymenesulphonic acid is very hygroscopic. After drying over sulphuric acid, it melts at 126°. Its salts are much more soluble than those of the B-acid. The barium and copper salts crystallise with 7 mols. H2O. The potassium salt crystallises in needles containing 1 mol. H2O. It dissolves readily in water or alcohol. The sodium salt contains 2 mols. H2O. The sulphonamide forms long, white, needle-shaped crystals. It melts at 170.5°, and dissolves in hot water and alcohol.

Pure a-bromisocy mene, C10H13Br, boils at 225° instead of 235° as previously stated (Abstr., 1882, 618).

Dibromocymene is prepared by the action of bromine on an aqueous solution of a-bromocymenesulphonic acid. It is an oily liquid boiling at 272-273°. Pure bromocymene is obtained as a strongly refractive liquid when potassium ß-bromometaisocy menesulphonate is decomposed by superheated steam. It boils at 224°, one degree lower than the a-compound, and is slowly oxidised by nitric acid, yielding bromometatoluic acid (m. p. 152°), C,H,MeBrČOOH [1:4:3].

General Conclusions.-When metaisocymene dissolves in sulphuric acid, the SO,H group displaces the H atoms at 4 or 6.


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