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rates as an oil, which gradually solidifies. It crystallises from alcohol in thick pointed needles, having a peculiar odour resembling that of benzophenone; it is readily soluble, melts at 58-59°, and distils slowly with steam.

Orthodichlorovinylbenzoic acid, C2HCl, C.H, COOH, is obtained by dissolving the trichloroketone in an alkali and adding acid. It crystallises from dilute alcohol in long, slender needles melting at 120 121°. It is reduced by sodium amalgam to orthoethylbenzoic acid melting at 68°. The methyl salt crystallises in thick needles which melt at 47°. N. H. M.

Hydro-derivatives of Aromatic Bases. By E. BAMBERGER (Ber., 20, 2915—2917).—B-Tetrahydronaphthylamine, CH NH2, prepared by the reduction of B-naphthylamine with sodium, is a very strong base, capable of displacing ammonia from its salts. It forms stable, crystalline salts with carbonic anhydride, and by carbon bisulphide is converted with explosive violence into tetrahydronaphthylamine tetrahydronaphthylsulphocarbamate. The isomeric a-derivative is a feeble base, which does not react alkaline or yield a carbonate. It reacts like a normal amine with nitrous acid.

It is suggested that the hydro-derivatives of the aromatic bases are related to bases of the camphor-group, and that tetrahydroB-naphthylamine and Leuckart and Bach's bornylamine (Abstr., 1887, 376) are similarly constituted. N. H. M.

Orthamidazo- and Hydrazimido-compounds. By T. ZINCKE and A. T. LAWSON (Ber., 20, 2896-2903; compare Abstr., 1886, 795, and 1887, 731).-Benzeneazo-B-naphthylamine is a much feebler base than orthamidazotuluene; the salts are readily decomposed by alcohol and water. The hydrochloride crystallises in yellowish needles; the sulphate, NH2 C10H N2Ph,H2SO4, forms brownish-yellow needles. The diazochloride is prepared by dissolving 1 part of the azo-compound in 15 parts of hot glacial acetic acid and adding 3 parts of strong hydrochloric acid; cold nitrous acid is then passed through, and the whole kept until a clear, dark-red solution is obtained. The platinochloride, (N2Cl·C1H2 N2Ph),PtCl, forms small, yellow, sparingly soluble needles. The diazosulphate is less soluble than the chloride; the perbromide, N,Br3 C10H, N2Ph, forms small, red needles. When the solution of the diazochloride in acetic acid is diluted with water, nitrogen is evolved, and benzeneazo-ß-naphthol is formed. When the wellcooled acetic acid solution of the diazochloride is treated with stannous chloride, heated on a water-bath, and filtered, the diazohydride, N2H CH, N2Ph, is obtained; this crystallises from benzene or alcohol in colourless, lustrous needles, melting at 204-205°. The acetyl-derivative, N2Ac-C1H N2Ph, crystallises from alcohol in lustrous needles which melt at 137-139°.



B-Amidazonaphthalene hydrochloride, CH, N2 C10H NH2,HCl, forms small, brownish-yellow needles; the sulphate crystallises in brownishyellow needles. The diazochloride is decomposed by water, with formation of B-hydroxyazonaphthalene (Nietzki and Goll, Abstr., 1886, 714) and evolution of nitrogen. The diazohydride, N2H·C10H6N2°C10H7,

crystallises in white needles melting at 202-204°, is readily soluble in hot alcohol and hot glacial acetic acid, sparingly soluble in benzene. N. H. M. Sulphonation of Acetonaphthalide. By M. LANGE (Ber., 20, 2940-2941).-a-Acetonaphthalide is sulphonated by adding it in fine powder to fuming sulphuric acid containing 20 per cent. of anhydride. The sulphonic acid is unstable, and loses the acetyl-group when boiled with alkalis or acids.

a-Naphthylaminesulphonic acid is obtained by treating the solution of acetonaphthalidesulphonic acid in sulphuric acid with twice the bulk of water. It crystallises in needles much more soluble than naphthionic acid; the salts are also much more soluble than those of the naphthionic acid. The solution shows a green fluorescence. The benzylidene compound crystallises in long needles. When the acid is diazotised and boiled with alcohol, a naphthalenesulphonic acid is formed, which yields a-naphthol when fused with potash.

N. H. M. x-Naphthalenedisulphonic Acid. By A. WEINBERG (Ber., 20, 2906-2911).-a-Naphthalenedisulphonic acid is converted by the action of soda into a new ẞ-naphtholsulphonic acid. This, when heated with ammonia, is converted into B-naphthylaminesulphonic acid, from which B-naphthalenemonosulphonic acid was obtained by means of the diazo-compound. Assuming that B-naphthalenedisulphonic acid has the constitution [2: 3'], the constitution of a-naphthalenedisulphonic acid would be [2: 2'1.

BB-Naphtholsulphonic acid, [2: 2'] (known as naphtholsulphonic acid F.), is prepared by heating sodium naphthalenedisulphonate (100 grams), soda (30 grams), and water (300 c.c.), for 12 hours at 250°. The product is recrystallised and converted into the barium salt; the free acid is recrystallised from strong hydrochloric acid, from which it separates in needles which melt, when dried, at 89°. It is readily soluble in water and alcohol, insoluble in ether and benzene. When the sodium salt is heated with phosphorus pentachloride (3 parts) at 165°, chloronaphthol phosphate melting at 215° is formed as chief product, together with a naphthalene dichloride, which crystallises from methyl alcohol in rhombic plates which melt at 114°. Sodium naphtholsulphonate crystallises with 2 mols. H2O in large plates; the potassium salt with 1 mol. H2O forms rhombic crystals. Both salts are readily soluble in water. The magnesium salt crystallises in plates with 54 mols. H2O; the barium salt is sparingly soluble, but more soluble than the barium salt of Schaeffer's B-naphtholsulphonic acid. Nitrous acid converts the sulphonic acid into a nitrosocompound; the sodium salt crystallises with 2 mols. H2O in golden needles.

Naphthylaminesulphonic acid [22] (F.), is obtained by the action of ammonia on the naphtholsulphonic acid; it dissolves in 350 parts of boiling water. The barium salt with 5 mols. H2O crystallises in well-formed needles; the magnesium salt crystallises with 5 mols. H2O.

Bayer and Duisberg's B-naphthylamine-6-sulphonic acid (Abstr., 1887, 732) is not identical with the acid [2: 2'], but is a mixture.

B-Naphthol-d-disulphonic acid, prepared from 2: 2' naphtholsulphonic acid, yields with diazobenzene a crystalline orange dye, and with a-diazonaphthalene a Bordeaux, which crystallises in violet plates. The sodium salt is readily soluble in water, from which it is precipitated by alcohol as a yellow powder; the barium salt with 24 mols. H2O crystallises in prisms soluble in 180 parts of boiling water. The solutions of the salts show a green fluorescence.

N. H. M. Derivatives of Dinaphthyl. By P. JULIUS (Chem. Ind., 10, 97 -99). The author has modified Dianin's method of preparing a- and B-dinaphthol. He proposes to treat an aqueous solution of sodium naphthoxide with a mixture of ferric chloride and hydrochloric acid, whereby the naphthol, which separates in a finely-divided state, is oxidised into dinaphthol as soon as it is brought into contact with ferric chloride. The following reaction occurs:-2C10H, OH + Fe2Cl, = C20H12(OH)2 + Fe2Cl + 2HCI. In practice it is necessary to use 2 mols. of hydrochloric acid to 1 mol. of ferric chloride. a-Dinaphthol thus prepared forms a white, crystalline powder melting at 296-299°. B-Dinaphthol forms pale-yellow, glistening needles melting at 217°. The yields of a- and B-dinaphthols are 70 to 75 and 85 to 95 per cent. respectively as compared with theory. On treating B-dinaphthol with sulphuric acid, and saturating the resulting sulphonic acid with barium carbonate, the barium salt of B-dinaphtholdisulphonic acid, C20H10(OH)2(SO3),Ba + 6H2O, separates, whilst the filtrate contains the barium salt of B-dinuphtholtetrasulphonic acid, C20H8(OH)2(SO3),Ba2. Dinitro-ẞ-dinaphtholdisulphonic acid,

C20H5(NO2)2(OH),(SO,H)2 + 3H2O,

is obtained by treating the barium salt of the disulphonic acid with nitric acid. It crystallises from alcohol in yellow, silky needles. B-Dinaphthol does not combine with diazo-compounds; a-dinaphthol, however, does so readily, giving rise to a series of dyes.

D. B.

Diamidopyrene. By R. JAHODA (Monatsh., 8, 449-451).—The hydrochloride of this base is obtained by the reduction of dinitropyrene (Goldschmiedt, Abstr., 1881, 206); it forms white needles. Diamidopyrene, C16H, (NH2)2, is very unstable in the free state, resinifying very rapidly. The sulphate forms a white substance, insoluble in water and alcohol, and decomposes when heated. L. T. T.

Diterebenthyl. By A. RENARD (Compt. rend., 105, 865-868).— The resin oils obtained by the destructive distillation of colophony consist mainly, of a hydrocarbon which boils above 300°, and can be isolated by successive washings with sodium hydroxide solution, and then with water, followed by fractionation. The liquid thus obtained has the composition C20H30, and boils at 343-346°; sp. gr. at 18° 0.9688; vapour-density 9.6; rotatory power for [a]D=+59°; refractive index 1:53. It seems to be diterebenthyl, formed by the condensation of 2 molecules of terebenthene with elimination of H2O. When exposed to air in thin layers for five days, it absorbs about one-tenth of its weight of oxygen and forms a varnish. Chromic anhydride in




boiling acetic acid oxidises the hydrocarbon to carbonic oxide and carbonic anhydride. Potassium permanganate in aqueous solution converts it into carbonic anhydride and formic, acetic, and propionic acids.

When the hydrocarbon is poured gradually into well-cooled, fuming nitric acid, there is no evolution of gases, and on adding water a trinitro-derivative, C20H27 (NO2)3, separates out. When dried in a vacuum, it forms a yellow powder soluble in alcohol and ether. If the ethereal solution of the hydrocarbon is treated with a current of hydrogen chloride, the compound 2C20H30, HCl is obtained. Bromine acts violently, but in solution in carbon bisulphide it yields the dibromide C20H30 Br2, and when the carbon bisulphide evaporates, the brominederivative decomposes with evolution of hydrogen bromide. The direct action of bromine on the hydrocarbon in presence of water yields the hexabromo-derivative C2H2Bre, a dark-brown, amorphous solid, which melts below 100°, and is soluble in alcohol and ether.

Ordinary concentrated sulphuric acid converts diterebenthyl into a sulphonic acid, which is isolated by agitating with water and light petroleum. The liquid separates into three layers, the lower of which is dilute sulphuric acid, the middle the sulphonic acid, and the upper layer a solution of the unaltered hydrocarbon in the light petroleum, which does not dissolve the sulphonic acid. A certain quantity of a new hydrocarbon is formed, which is not attacked by acids. The sulphonic acid is converted into the ammonium salt, which is precipitated by adding sodium chloride to the solution. The sulphonic acid, C20H SO,H, is obtained by decomposing the ammonium salt with sulphuric acid and extracting with benzene. It is a dark-brown mass, soluble in water, alcohol, ether, and benzene, but insoluble in light petroleum. Its solutions are highly fluorescent, and are brown by transmitted light, green by reflected light. It decomposes carbonates of the alkalis and alkaline earths. The free acid is precipitated from its aqueous solution by sodium chloride, sulphuric acid, sodium sulphate, and calcium chloride.

The ammonium salt is soluble in water, forming fluorescent solutions. The barium, calcium, copper, and lead salts, which can be obtained by double decomposition, are all insoluble in water. They all dissolve in alcohol, ether, and benzene, and burn with a smoky flame. C. H B.

Bitter Principle of Calamus Root. By H. THOMS (Annalen, 242, 257-260).—The author states that the reason Geuther (Abstr., 1887, 972) failed to obtain acorine and acoretine from calamus root is because he did not use the original process described by the author (Abstr., 1886, 895), and consequently obtained different results.

W. C. W. Bitter Principle of Calamus Root. By A. GEUTHER (Annalen, 242, 260—264).—A reply to the above.

Cubebin. By C. POMERANZ (Monatsh., 8, 466-470).-The author is investigating this compound from Piper cubeba, the formula of which was proved by Weidel to be C10H10O3. Attempts to eliminate

possible alkyl-groups by the action of hydrogen chloride or iodide proved unavailing, as the substance always carbonised. When oxidised with permanganate, it yielded piperonylic acid, C,HO. When treated with acetic anhydride, no aceto-derivative is formed, but an ether, (C10H10O), which crystallises in needles, is soluble in alcohol, and melts at 78°.

From these results, the author concludes that cubebin (i) is a derivative of a methylene ether of pyrocatechol; (ii) contains a side-chain, CH,O, yielding carboxyl on oxidation; and (iii) contains this sidechain in the same position relatively to the two etheric oxygen-atoms as the carboxyl in protocatechuic acid stands to the two hydroxyls. L. T. T.

Brominated Quinolines. By A. CLAUS and V. TORNIER (Ber., 20, 2872-2882).-y-Bromoquinoline (Claus and Collisehoun, Abstr., 1887, 158) boils at 274-276° (uncorr.; not 273-274°), solidifies when cooled to below 0° and melts at 12-13°. The oxalate crystallises in stellate groups of prisms, melting at 107° (uncorr.). The picrate forms a loose, bright yellow precipitate, consisting of slender needles; it melts at 190°. The ethobromide, C,NH,Br, Et Br, is obtained by heating the base with ethyl bromide and absolute alcohol at 100° for some hours; it separates on cooling in lemon-coloured needles with 2 mols. EtOH, and melts at 216° (uncorr.). -Bromoquinoline dibromide hydrobromide is obtained when bromine is added to a solution of y-bromoquinoline hydrobromide in chloroform, as a cinnabar-coloured mass of crystals, melting at 76° with decomposition; it was not analysed. When the hydrobromide is heated at about 200°, a new dibromoquinoline is obtained, together with its hydrobromide. The new base crystallises from alcohol in colourless, lustrous needles, which melt at 166° (uncorr.).

Parabromoquinoline is best purified by boiling with chromic acid. It is an almost colourless liquid which boils at 178° (uncorr.), solidifies when cooled to below 0°, and melts at 18-19° (uncorr.) When oxidised with potassium permanganate, it yields only quinolinic acid [(COOH), = 2:3]. The hydrobromide forms colourless needles, which soon become red, and melt at about 256°. The hydrochloride (with 1 mol. H2O) melts at 213° (uncorr.). The nitrate forms needles melting at 182°; the sulphate crystallises (with I mol. H,O) in small plates melting when dry at 176°; the chromate forms small, yellow needles melting at 179°; the oxalate, melting at 62°, the picrate, melting at 216-217°, and the ethobromide, melting at 230° (uncorr.), are also described. Parabromoquinoline dibromide hydrobromide is a very unstable, orange-red substance, which melts at 70°, and when heated at 200° yields dibromoquinoline, melting at 125-126° (La Coste, Ber., 14, 925; Claus and Küttner, Abstr,, 1887, 278).

Orthobromoquinoline, prepared from orthobromaniline and purified by chromic acid, forms a colourless oil boiling at 300-304° (uncorr.). The hydrochloride, C,NH,Br,HCl + H2O, melts with decomposition at 166°; the platinochloride crystallises from alcohol in small, bright yellow needles; the nitrate melts at 90°; the dichromate begins to decompose at 100°, and melts at 168°.

Orthobromoquinoline dibromide hydrobromide forms orange-red

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