to the processes of separating the homologues of aniline on a commercial scale. The two nitrotoluenes are best isolated by freezing out part of the para-compound, and separating part of the orthoderivatives by fractional distillation with steam. The medium portion is then reduced, and the toluidines thus obtained are subjected to a separation process, based on the fact that on treating a mixture of ortho- and para-toluidine with sulphuric acid insufficient in quantity to saturate both isomerides, the para-compound is first attacked. Hence on subjecting such mixtures to distillation, aided by the introduction of steam, a distillate rich in orthotoluidine is obtained. The latter may then be further purified by repeating the above treatment. The residual paratoluidine sulphate is neutralised with caustic soda or lime, and the base separated by distillation and recrystallisation. The separation of para- and meta-xylidine may be effected by sulphonating both isomerides; metaxylidinesulphonic acid is insoluble, whilst the acid from the para-compound is freely soluble, but yields an almost insoluble sodium salt, from which the base may be obtained by distillation with addition of a small amount of lime. To isolate the base from the meta-acid, the latter is heated at 160180° under pressure with five times its weight of hydrochloric acid. The acid mixture is then saturated with soda or lime, and subjected to distillation with steam. D. B.

Butylenic Bases: Characteristics of Ethylenic Diamines. By A. COLSON (Compt. rend., 105, 1014-1016).-10 grams of isobutylene bromide, boiling at 147-149°, was heated to boiling for 10 minutes with 40 c.c. of aniline, the excess of aniline expelled by distillation in a vacuum, and the aniline hydrochloride removed by treatment with water. The residue was then dissolved in warm hydrobromic acid, and the crystals which separated on cooling were purified by washing with hydrobromic acid. Diphenylbutylenediamine hydrobromide, CH,(C,H,N)2,2H Br, is thus obtained in white crystals, which melt at 122° with decomposition. It dissolves in five times its weight of boiling water, and 10 times its weight of cold water with partial decomposition, which is prevented if hydrobromic acid is present. It is about twice as soluble in alcohol as in water, but is not soluble in ether. The hydrobromide is decomposed completely by alkaline hydroxides with liberation of the base as a colourless oil, insoluble in water, but soluble in alcohol, ether, and chloroform. It has a bitter burning taste, and is coloured brown by nitric acid; its sp. gr. is about 10. With hydrochloric acid it yields a hydrochloride crystallising in white nodules, which become blue when exposed to air, melt at 98°, and dissolve in 10 times their weight of cold water with some decomposition. With acetic acid, the base forms a viscous acetate which is soluble in water, and seems to be uncrystallisable.

The aqueous solution of the base has no action on any indicator, and the alcoholic solution has no action on phthaleïns, but decolorises methyl-orange. In this respect, it resembles ethylenediphenyldiamine and ethyleneditolyldiamine, and hence it would seem that secondary aromatic diamines containing ethylene are distinguished from primary amines such as aniline and toluidine, by the fact that

they are very feebly basic, and do not act on phthaleïns, but decolorise methyl-orange. The basic properties decrease as the molecular weight increases.

When diphenylbutylenediamine hydrobromide is treated with sodium nitrite at 0° it yields a nitroso-derivative in the form of a yellow precipitate which melts at 90°. C. H. B.

Azopseudocumene. By V. POSPĚCHOFF (Chem. Centr., 1887, 858 -859, from J. Russ. Chem. Soc., 1887, 113–118).-Nitropseudocumene when reduced with sodium amalgam, yields azopseudocumene, N2(CH,Me3)2, which forms yellowish crystals melting at 173-174°, and may be sublimed without decomposition. It is sparingly soluble in alcohol, more readily in ether and benzene; it dissolves in concentrated sulphuric acid, but is reprecipitated on dilution.

The corresponding hydrazo-derivative is obtained by reducing nitropseudocumene with zinc-foil; it melts at 124-125°, and is readily oxidised in the air to the azo-derivative. In both cases, cumidine is obtained as a bye-product. V. H. V.

Formation of Aniline Dyes by the Oxidation of Aromatic Amines. By J. BARZILOFFSKY (Chem. Centr., 1887, 855-857, from J. Russ. Chem. Soc., 1887, 132-149).-By the oxidation of aromatic amines, azo-compounds and polyamines are formed; by changing certain conditions, basic products are formed which play an important part in the aniline dye industry. In order to throw some light on the nature of the chemical changes involved, the products of the oxidation of paratoluidine were investigated. The principal compounds formed are parazotoluene and azotolyl, C2H26N, the latter of which may also be obtained from hydroparazotoluene by heating its alcoholic solution with concentrated hydrochloric acid, as also by the oxidation of toluidine. The formation of azotolyl by the oxidation of paratoluidine is explained thus: two atoms of hydrogen are removed from two molecules of toluidine with production of hydrazotoluene, of which one part is converted into azotoluene by further oxidation, whilst the other part is transformed into the isomeric tolidine, which passes by oxidation into azotolyl.

Azotolyl when heated with an alcoholic solution of ammonium sulphite is readily transformed into the corresponding hydro-derivatiue, which differs from its analogues in readily combining with acids, and being separable on addition of alkalis. The hydrochloride, (C,H,,HCI) + 1HO, is colourless in the pure state, but when damp is readily oxidised to a compound, pararosotoluidine,

which is also obtained by oxidation of a dilute solution of paratoluidine with large excess of chromic acid, and subsequent addition of soda to the resultant product.

V. H. V.

Formation of Dyes by means of Hydrogen Peroxide. By C. WURSTER (Ber., 20, 2934-2940).-Ammonia is added to an emulsion of phenol and water so that a part of the phenol remains undissolved; a solution of sodium carbonate and an equal volume of hydrogen peroxide are added, and the whole diluted with water. The mixture is well shaken, a crystal of a hydroxylamine salt added, and the whole again shaken; a bright-blue and then a deep-blue coloration is produced which in a day or two changes to green. The dye which is extracted with ether is shown to be phenolquinonimide.

Hydrogen peroxide is found in the sap of many plants; it is also produced by micro-organisms, especially by the non-pathogenic.

All the monatomic phenols of the benzene series examined, in which the para-position to the hydroxyl-group is free, gave quinone-imides with hydrogen peroxide and ammonia. Hydroxy-acids also yield dyes.

Lacmoïd is formed when an ammoniacal solution of resorcinol is boiled with a little hydrogen peroxide.

If sodium carbonate is added to a mixture of resorcinol and quinone, a deep-green solution is obtained which, when shaken with air becomes yellow, then reddish-yellow and brownish-red; when air is removed, the green colour is regenerated. A similar change of colour is observed in many leaves, especially those of Berberis which contain a considerable amount of hydrogen peroxide.

Pyrocatechol, orcinol, and some plant constituents, such as phloridzin, also give dyes with hydrogen peroxide.

N. H. M.

Formation of Safranines. By P. BARBIER and L. VIGNON (Compt. rend., 105, 939-941).-It has been shown that phenosafranine is formed by oxidising a mixture of paraphenylene diamine (1 mol.) and aniline (2 mols.), and it is known that amidoazobenzene yields paraphenylenediamine on reduction. It therefore seemed probable that the action of nitrobenzene or amidoazobenzene in presence of some reducing agent evolving hydrogen, should yield phenosafranine, and this supposition is confirmed by experiment.

Amidoazobenzene hydrochloride (1 mol.) is mixed with iron and hydrochloric acid in sufficient quantity to yield one molecular proportion (H2) of hydrogen, and sufficient nitrobenzene to form a paste, and heated at 188° for three hours. The product is diluted with water, and treated with a current of steam to remove unchanged aniline; the aqueous solution is then mixed with ammonia, filtered, and the safranine precipitated by adding sodium chloride. The phenosafranine which separates is purified by repeated precipitation by means of salt and recrystallisation from hot water.

Amidoazotoluene likewise yields a safranine when heated with nitrobenzene, and hence it seems that this constitutes a general reaction for the preparation of safranines. C. H. B.

Nitro-derivatives of Oxanilide. By W. G. MIXTER and F. O. WALTHER (Amer. Chem. J., 9, 355-361).-Huebner and Rudolph's work on paradinitro-oxanilide is confirmed. Tetranitrooxanilide, C2O2[NH.C.H2(NO2)2]2 [NH: (NO,), 1: 2: 4], is formed by the

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action of red fuming nitric acid on oxanilide; it melts at 300°, is but slightly soluble, and is easily saponified by weak potash. Heranitro-oxanilide, C2O2[NH CH2(NO2)3]2 [NH: (NO2), 1:2:4: 6], is obtained when a mixture of fuming nitric acid and strong sulphuric acid is employed; it is the highest substitution product obtainable. It melts at 300°, its best solvent is glacial acetic acid. When heated with sulphuric acid at 200°, it yields a trinitraniline melting at 188°, which is the melting point of the only known trinitraniline, NH2: (NO2), = 1:2:46. In alkaline solutions, it dissolves with formation of trinitrophenyloxanilide, trinitrophenol, and trinitraniline. Trinitrophenyloxamide, NH, CO.CO.NH·C,H2 (NO2)3, crystallises in white fibres, and melts with decomposition at 255-260°. It has strongly marked acid characters. The potassium and ammonium salts are described. H. B.

Nitro-derivatives of Dibromoxanilide. By W. G. MIXTER and C. P. WILLCOX (Amer. Chem. J., 9, 361–364).-Dinitrodibromoranilide, C2O2(NH·C2H ̧Br·NO2)2 [NH: NO2 : Br = 1 : 2 : 4], is obtained by the action of strong nitric acid on paradibromoxanilide. It is yellow, melts at 288°, and when saponified yields orthonitroparabromaniline, melting at 111-4°.

Tetranitrodibromoranilide, C2O2[NH·C2H2 (NO2), Br]2, is obtained with some difficulty by using red fuming nitric acid. It is white, melts at 285-287°, and does not yield dinitrobromaniline when saponified. H. B.

11.

Compounds of Alloxan with Aromatic Amines. By G. PELLIZZARI (Gazzetta, 17, 409-425).-Alloxan combines directly with the aromatic amines to form additive products from which, however, the base cannot be recovered as such. Thus when a concentrated boiling aqueous solution of alloxan is agitated with a-naphthylamine, and the solution cooled, a compound of the formula C1,H,,N,O, separates C1H2N2O+ C10H,NH2 = С1Н1NзО4. This compound, a-naphthylamine-alloxan, crystallises in transparent, colourless needles, insoluble in water, acids, aqueous ammonia, but soluble in ether, benzene, and chloroform; it is coloured greenish by concentrated sulphuric acid. When heated with alkalis, it dissolves, yielding ammonia and the potassium salt of an acid, CH10N2Os; on acidification, the acid separates in long, glistening needles, insoluble in ether, benzene, and chloroform, but very soluble in alcohol. At 110°, it loses the elements of a molecule of water, but takes it up again on recrystallisation from aqueous alcohol. B-Naphthylamine apparently does not combine with alloxan.

Aniline combines with alloxan to form phenylamine-alloran,

C10H,NO, C1H2N2O、 + PhNH2,

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which crystallises in scales, decomposing at 248°. It forms a hydrochloride, C10H,N,O,,HCl, which crystallises in transparent needles, and a silver salt, C10H,AgN3O4, a white, insoluble powder. Like the naphthyl-derivative, it yields an acid, C,H,N3O3, when boiled with

This

alkalis, thus: C10H9N3O4 + H2O = C‚H ̧Ñ2O3 + NH3 + CO2. acid crystallises in colourless needles which decompose at 180° without fusion; it is soluble in alkalis and their carbonates; its silver salt, C,H,AgN2Oз, is a white crystalline precipitate. On dry distillation, phenylamine-alloxan yields paratoluidine.

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Methylphenylamine-alloxan, CH1N ̧O1 = C‚Í‚Ñ2O1 + NHPhMe, crystallises in white scales soluble in alcohol, moderately soluble. in boiling water; its hydrochloride, CH1N3O,,HCl, forms colourless prisms.

Dimethylphenylamine-alloxan, C12H13N3O4 + H2O, crystallises in colourless needles, sparingly soluble in water, and decomposing at 230°. Its hydrochloride crystallises in transparent needles, the nitrate in lozengeshaped crystals, the oxalate in quadrangular tables; the silver salt is a white precipitate. This compound, like the preceding, is decomposed by alkalis with formation of an acid.

To these derivatives, of which that of aniline is selected as a typical example, the author ascribes either the formula

CO<NHCO>C(OH)CHÍNH,

or COOH-NH.CO.C(CONH2): CH3NH2, of which the latter illustrates at once the basic and acid character, as also its decomposition by alkalis to form an acid, C,H,N2O3, by elimination of ammonia and carbonic anhydride, thus: COOH NH.CO(CONH2) CH3NH2+ H2O = COOH·C(CONH2): C2H3°NH2 + NH3 + CO2. On the other

hand, the combination of the benzene nucleus with another grouping by two of its carbon-atoms is unusual. The other formula illustrates the formation of paratoluidine by the dry distillation of the aniline compound, whilst the production of the acid compound is explained as a result of two successive reactions, in the first of which a carboxylic acid is formed which subsequently gives off a molecule of water to NH.CO. produce an imide, thus: CO<NH.CO>C(OH).C2H ̧•NH2 + 2H2O =

COOH•C(OH)(CONH,)•C,H,NH, + CO2 + NH3, and

(ii) COOH-C(OH) (CONH2) C.H, NH, OH, =

NH<0>C(OH)-CHÍNH,.

If the latter formula be correct, then the above compounds might be considered as derivatives of dialuric acid or tartronyl carbamide.

V. H. V.

Benzylidenephthalide and Isobenzalphthalide. By S. GABRIEL (Ber., 20, 2863-2868).-Benzylidenephthalide crystallises in small, monoclinic forms; a b c = 1.9005: 1: 2·3830; ß = 76° 2.5'.

Benzylphthalimidine (Abstr., 1885, 902, 1229) is readily obtained by adding a mixture of benzalphthalimidine (12 grams) and amorphous phosphorus (6 grams) to 36 c.c. of boiling hydriodic acid (b. p. 127°), and subsequently heating for 45 minutes in a reflux apparatus. The yield amounts to 80 per cent. of that theoretically possible. When treated with phosphorus oxychloride,

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