orange-red needles, melting at 116°. The third product melting at 89° is only formed in small quantity, but is practically the sole product of nitrating dibromocymene with fuming nitric acid at 100°. It is a dibromonitrotoluene, C,H,Br2Me NO2 [Me: Br2: NO2 = 1:2:5:4], and can be readily further nitrated with formation of the compound above described melting at 142°. It is very soluble in petroleum and alcohol, from which it crystallises in long, colourless needles, and is identical with the substance described by Nevile and Winther (Trans., 1880, 429); and furnishes by reduction first a dibromotoluidine (m. p. 83-85°) and finally toluidine. The formation of dibromodinitrotoluene (m. p. 142°) by nitration of paracy mene is remarkable, the propyl-group being oxidised and then replaced by a nitro-group.

When dibromocymene is heated in sealed tubes for eight hours at 180° with 20 times its weight of nitric acid of sp. gr. 1.12, it is converted into dibromoterephthalic acid, which on treatment with phosphorus pentachloride yields a chloride

CH2Br2(COCl)2 [(COCI)2: Br2 = 1 : 4:2: 5],

readily soluble in carbon bisulphide and chloroform, and crystallising from ether in prisms melting at 80--81°. The corresponding amide, CH2Br2(CONH2)2, is insoluble in alcohol, ether, chloroform, and light petroleum, but dissolves sparingly in carbon bisulphide, from which it crystallises in fine needles; these carbonise at 300° without previously melting. By gentle oxidation, dibromocymene yields a monobasic acid of the formula C10H10Br2O2. The sodium salt forms beautiful colourless needles. The ammonium salt is only slightly soluble in water, and melts at 172°. The calcium salt crystallises in stellate groups of needles with 4 mols. of water, whilst the silver salt separates from a hot aqueous solution in needles containing 3 mols. H2O. This acid is either dibromocumic acid, CH2PrBr2 COOH [COOH : Pr: Br2 = 1:4:3:6], or dibromotolylpropionic acid, C,H,Bг2Me C2H, COOH. The author gives reasons in favour of its being the latter.

G. T. M. Derivatives of 1:2:34 Tetramethylbenzene (Prehnitene). By A. TÖHL (Ber., 21, 904-908).-Prehnitene combines with picric acid to form a fairly stable compound, which crystallises from alcohol in yellow needles and melts at 92-95°.

Nitroprehnitene, C10H13 NO2, is obtained when a thin layer of prehnitene is allowed to remain in contact with ordinary nitric acid for three to four days, and is purified by distillation with steam. It crystallises in stellate groups of flat needles, melts at 61°, boils with partial decomposition at 295° (thermometer in vapour), and is readily soluble in ether, alcohol, light petroleum, and acetic acid. On reduction with iron and acetic acid, it yields prehnidine, C10H13 NH2. This crystallises in large, lustrous, colourless scales, melts at 70°, is readily soluble in alcohol, ether, and light petroleum, and is volatile with steam. The hydrochloride, CH3NH2,HCl, crystallises from water in tufts of very long, colourless needles; the sulphate, (C10H13NH2)2, H2SO4, crystallises in large scales, and is sparingly soluble in cold water; the nitrate crystallises from water in sixcornered prisms. Acetoprehnidine, CH3NHAc, crystallises from

dilute alcohol in colourless needles, melts at 172°, is readily soluble in alcohol, and on treatment with ordinary nitric acid yields the nitroderivative, NO2 C10H12 NHAC. This compound can also be obtained by the action of acetic chloride on nitroprehnidine, and crystallises from dilute alcohol in hair-like, branching needles, melting at 225°. When reduced with tin and hydrochloric acid, it is converted into ethenylprehnityleneamidine hydrochloride, CH1<>CMe, HCl + 2H2O, which crystallises in slender, colourless needles, and is readily soluble in water; the base is flocculent and contains 2 mols. H2O.

NH

N

Nitroprehnidine, NO, C10H12 NH2, is prepared by the reduction of dinitroprehnitene (Abstr., 1886, 694) with alcoholic ammonium sulphide. It crystallises in lustrous, red needles, melts at 131o, and is soluble in alcohol and concentrated hydrochloric acid. On reduction, it yields prehnitylenediamine, C10H12(NH2)2, which crystallises from water in large, lustrous scales, from alcohol in long, colourless needles, melts at 140°, is sparingly soluble in ether and light petroleum, and gives the reactions characteristic of an orthodiamine. The hydrochloride, C10H12(NH2)2,2HCI + H2O, crystallises in large, lustrous scales, and in dilute aqueous solution is coloured dark-red by ferric chloride and by potassium chromate.

Prehnitol, CH3OH, obtained by fusing sodium prehnitenesulphonate with potassium hydroxide, crystallises from light petroleum in very long, colourless, silky needles, melts at 86-87°, boils at 266° (thermometer in vapour), and is very readily soluble in alcohol and ether. It is not coloured by ferric chloride. The acetylderivative, C10H13 OAc, crystallises in large, well-formed prisms, and melts at 56-57°; the bromo-derivative, C10H12Br-OH, crystallises in long, slender needles, and melts at 151°.

When oxidised with a dilute aqueous solution of permanganate at 100°, prehnitene is first converted into prehnitylic acid (loc. cit.), and finally yields prehnitic acid; a potassium salt of the latter,

C&H2(COOH)3 COOK + H2O,

was obtained by treating the oxidation-product, after filtration, with acetic acid and lead acetate, decomposing the lead salt with hydrogen sulphide, and evaporating the filtrate; it crystallises in large aggregates. W. P. W.

Bromodichlorophenol and Dibromodichlorobenzene. By L. GARZINO (Chem. Centr., 1887, 1546–1547; from Rend. Acc. Lincei [4], 3, 202–209).—Bromometadichlorophenol, C,H,BrCl2 OH [? OH : Cl2: Br = 1:24: 6], is obtained by adding the calculated quantity of bromine to a cooled solution of dichlorophenol (15 grams) in glacial acetic acid (10 grams). The separation of the product causes the mass to become semisolid. It is exposed to the air until the small excess of bromine has volatilised, then washed with plenty of water, dried, distilled in a vacuum, and finally sublimed. The pure product forms white needles, melting at 68°, and boiling with decomposition at 268°. Under a pressure of 200 mm., it distils unchanged at 220°. It sublimes moderately well at 130-140°. It is readily soluble in benzene,

ether, and chloroform, also in concentrated acetic acid and alcohol, but is nearly insoluble in water. It is carried over with water vapour. Ferric chloride produces a light-blue colour in an alcoholic solution, but no colour in watery solution. It has hardly any smell and very little caustic action. No isomeride seems to be formed. Ammonium, sodium, potassium, barium, and silver salts, as well as the benzoate (m. p 67.5°) and phthalate (m. p. 216-217°), were prepared.

For the preparation of dibromodichlorobenzene, CH Br2Cl2 [? = 1624], a mixture of 20 grams of the above bromodichlorophenol, and 45 grams of phosphorus pentabromide was slowly distilled. The part distilling between 200° and 350° was heated with a 25 per cent. solution of potash, dried, and repeatedly crystallised from a mixture of light petroleum (b. p. 30-80°).

The pure product forms needles melting at 67-68°, very easily soluble in ether, light petroleum, and benzene. These crystals can be moderately easily sublimed.. Besides this, another product is formed in small quantity, melting at 1905-192°; this dissolves casily in ether and light petroleum, separates from benzene in small needles, and contains both chlorine and bromine.

J. P. L.

Compounds of Phenoxides with Cuprous and Mercurous Chlorides. By A. G. POUCHET (Compt. rend., 106, 276—277).—A solution of phenol in sodium hydroxide when mixed with mercuric chloride yields a white precipitate of the composition (C,H,O),Hg, HgCl2 + 4H,O. B-Naphthol and a-anthrol yield respectively the compounds (CH,O) Hg, Hg.Cl2 + 4H2O and (Č1H,O),Ég,Hg2Čl2 + 4H2O.

Strictly analogous compounds of cuprous chloride are obtained in precisely the same way.

C. H. B.

Action of Aniline on Epichlorhydrin. By A. FAUCONNIER (Compt. rend., 106, 605-607).-Aniline (3 mols.) was heated at 140° and gradually mixed with epichlorhydrin (1 mol.). If the two liquids are first mixed and then heated, the reaction becomes explosively violent below 100°. The product is a brownish oil, which is dissolved in hydrochloric acid and reprecipitated by ammonia to remove aniline. The base is dissolved in ether, washed with water, then extracted with dilute hydrochloric acid, and the solution concentrated to a syrup, which gradually crystallises. It is purified by recrystallisation from alcohol. The hydrochloride thus obtained, CH2N2Cl2O, forms colourless needles, very soluble in water, and somewhat soluble in alcohol, especially on boiling, but insoluble in ether. They become brown at 180°, soften at 196°, and melt with decomposition at 201—202°. The base is obtained by treating the hydrochloride with alkaline hydroxides, carbonates, or hydrogen carbonates, or even with sodium acetate, and forms a colourless, non-crystallisable oil, soluble in alcohol or ether, but insoluble in water. It seems to be isomeric with the dianilinehydrin obtained by Claus by the action of aniline on glycerol dichlorhydrin. The author proposes to call it dianilglycerol, and ascribes to it the constitution NHPh.CH, CH(NHPh) CH2 OH. It gives the general reactions for alkaloids, and reduces auric chloride and potassium ferricyanide in the cold. It gives a precipitate with

mercuric chloride only in presence of sodium carbonate. The platinechloride forms pale-yellow lamella. Picric acid produces an amorphous, yellow precipitate soluble in acids; bromine-water or sodium hypochlorite, a dull green precipitate; potassium dichromate an intense brown coloration; potassium permanganate a very intense violet coloration. C. H. B.

Metahydroxyparanitrosodiphenylamine. By L. KOHLER (Ber., 21, 908-910).—Metahydroxydiphenylnitrosamine, C12H10N2O2, is obtained by dissolving hydroxydiphenylamine in alcohol, and adding the calculated quantities of dilute sulphuric acid and of an aqueous solution of sodium nitrite to the well-cooled solution. It crystallises in slender, yellow needles, melts with decomposition at 115°, and is readily soluble in ether, alcohol, and acetic acid, soluble in benzene and light petroleum. When it is dissolved in a mixture of 2 parts by weight of absolute alcohol and 7 parts of ether, and heated in the cold with 1 part of alcoholic hydrogen chloride, brown scales of a hydrochloride separate, from which metahydroxyparanitrosodiphenylamine, NHPh

OH CH

N

CO [NHPh: OH: N = 1:3': 4], can be obtained by

suspending them in water, adding a slight excess of aqueous soda, and precipitating the filtrate with carbonic anhydride. It crystallises from benzene in beautiful, red needles, and is soluble in acetone, benzene, and alcohol, sparingly soluble in ether, and very sparingly soluble in light petroleum. Ammonia and aqueous soda dissolve it readily, and its solution in concentrated sulphuric acid is coloured red. On reduction with tin and hydrochloric acid at the ordinary temperature, it yields metahydroxyparamidodiphenylamine, C12H12N2O, which crystallises in pale bluish scales, melts at 135°, and is readily soluble in alcohol, chloroform, and acetone, soluble in benzene and ether, and very sparingly soluble in light petroleum.

Hydroxyazophenine, CHNO, is formed by heating metahydroxyparanitrosodiphenylamine with aniline and aniline hydrochloride at 100° for three hours. It crystallises from toluene in brown needles, melts at 197°, is insoluble in aqueous, but soluble in alcoholic potash and soda, and dissolves in concentrated sulphuric acid with a reddishbrown colour.

W. P. W.

Condensation of Chloral Hydrate with Secondary Aromatic Amines. By P. BOESSNECK (Ber., 21, 782-783).-With aniline, chloral hydrate yields trichlorethylidenediphenylamine, with elimination of water (Wallach, this Journal, 1872, 611; Cech, ibid., 1876, ii, 66), whilst tertiary amines undergo the aldol-condensation with chloral hydrate (Boessneck, Abstr., 1883, 976; 1884, 458. Knöfler and Boessneck, this vol., p. 267); the reaction with secondary amines is now shown to be similar to that of the tertiary compounds.

Methylamidophenylhydroxytrichlorethane, CCL, CH(OH)·C2H ̧·NHMe, is obtained by mixing chloral hydrate and methylaniline in molecular proportion, moderating the violent reaction by cooling, and afterwards allowing the mixture to remain at about 40-50° for

24 hours; it is then supersaturated with ammonia, distilled with steam to remove unaltered methylaniline, and the hydrochloride precipitated by addition of concentrated hydrochloric acid; after washing with alcohol and recrystallising from hot water, this is decomposed by ammonia. It is crystalline, and melts with decomposition at 112°. The hydrochloride forms thick prisms, sparingly soluble in cold water. The nitroso-compound, CCl, CH(OH)·CH, NMe.NO, prepared by the action of sodium nitrite on the hydrochloride, crystallises in needles, melts at 117-118°, begins to decompose at 140°, and is soluble in alcohol, acetic acid, and ether.

Ethylamidophenylhydroxytrichlorethane, CC, CH(OH)·CH, NHEt, prepared in a manner similar to the methyl compound, is crystalline, and melts at 98°. The hydrochloride forms stellate group of needles, the nitroso-compound melts at 138°. A. J. G.

Reaction between Metaphenylenediamine and Carbon Bisulphide. By P. GUCCI (Chem. Centr., 1887, 1547; from Atti Soc. Toscano Sc. Nat., 5, 291-293).-Thiocarbonylmetaphenylenediamine thiocarbonate separates out in crystals after heating metaphenylenediamine and carbon bisulphide in sealed tubes for six hours with alcohol at 50-55°. After six hours' heating at 100°, a small quantity of a golden-yellow compound is formed in addition to the above. A further six hours' heating at 150° results in the latter substance alone being formed. The crystals are monoclinic, and do not give off hydrogen sulphide when boiled with alcohol. This compound is insoluble in water, ether, benzene, carbon bisulphide, and chloroform, and only sparingly soluble in ethyl and amyl alcohols.

At 280°, it remains unchanged, turns brown at 300°, and decomposes at a higher temperature. The author regards the compound as sulphocarbonylmetapheneylenediamine, C.H:N2H2:CS. J. P. L.

Diazo-compounds. By P. GRIESS (Ber., 21, 978-984).-The author has experimented on the behaviour of the three isomeric diazobenzoic acids towards methyl and ethyl alcohols and phenol. In the first two cases, 1 part of the acid, in the form of sulphate, was heated with 10 parts of the alcohol until the evolution of nitrogen ceased; in the experiments with phenol, 1 part of the sulphate was added to 2 to 3 parts of phenol, heated to its melting point, and the well-mixed mass warmed gently until the commencement of the reaction, which is always very energetic.

By methyl alcohol, metadiazobenzoic acid is completely converted into methylmetahydroxybenzoic acid. The product crystallises in white needles, which are very sparingly soluble in cold water, and melt at 107°.

Paradiazobenzoic acid and methyl alcohol yield methylparahydroxybenzoic acid, which melts at 183-184°, whilst orthodiazobenzoic acid yields only benzoic acid.

With ethyl alcohol, metadiazobenzoic acid yields a mixture of benzoic and ethylmetahydroxybenzoic acid. The products can be easily separated as the latter is almost insoluble in water; it forms white, crooked needles, melting at 137°.