Page images

lenesulphonic acid, CH,N2SO3, a greenish-yellow, indistinctly crystalline powder, yields, when boiled with water, Bayer's B-naphtholsulphonic acid, from which 0-dichloronaphthalene (m. p. 61.5°) is obtained on treating its potassium salt with phosphorus pentachloride. B-Naphthylaminesulphonic acid, 2, dissolves in about 1300 parts of cold water, and is almost insoluble in alcohol. Its salts dissolve readily in water, yielding solutions fluorescing blue, and show great similarity in properties to the corresponding salts of the No. 1 acid. The potassium salt, with 1 mol. H2O, crystallises in small rhombohedra; the sodium salt, with 5 mols. H2O, crystallises in large tables; the barium salt, with 2 mols. H2O, forms small aggregates; the calcium salt, with 11 mols. H2O, crystallises in long, yellowish needles, and dissolves in about 11 parts of cold water: the amount of water of crystallisation in this salt varies with the temperature at which crystallisation takes place, and at about 10° crystals are obtained which at once effloresce when separated from the mother-liquor; the magnesium salt, with 8 mols. H2O, forms small, well-formed crystals; and the lead salt is anhydrous. The diazonaphthalenesulphonic acid is obtained as a green microcrystalline powder, and when boiled with concentrated hydrochloric acid yields a chloronaphthalenesulphonic acid, from which, on treatment of its potassium salt with phosphorus pentachloride, a dichloronaphthalene (probably 1': 2) is obtained, melting at 48°.

W. P. W.

Action of Phosphorus Pentachloride on a-Hydroxynaphthoïc Acid. By R. WOLFFENSTEIN (Ber., 20, 1966-1967).— a-Chlorocarboxylnaphthylorthophosphoric dichloride, POCI O C10H CC13, is obtained by warming a-hydroxynaphthoïc acid with phosphorus pentachloride (rather more than 2 mols.) in presence of a little phosphoric chloride, until the mixture is homogeneous. The product, when cold, is poured on to ice. It crystallises from light petroleum in transparent, colourless prisms melting at 115°. The compound is analogous to that obtained by Anschütz and More (Annalen, 239, 314) from salicylic acid and phosphorus pentachloride. N. H. M.


Indoles from -Naphthylhydrazine. By A. SCHLIEPER (Annalen, 239, 229-239).-The indoles from a-naphthylhydrazine are prepared by the same methods which the author employed in the preparation of the B-naphthindoles (this vol., p. 554).

a-Naphthylhydrazinepyruvic acid has been previously described by E. Fischer (Abstr., 1886, 554). The ethylic salt forms yellow prisms, and is freely soluble in benzene, chloroform, ether, acetic acid, and hot alcohol. It melts at 100°, and on fusion with zinc chloride yields ethyl a-naphthindolecarboxylate and small quantities of indole and a-naphthindolecarboxylic acid. Ethyl a-naphthindolecarboxylate can be distilled in a current of superheated steam. It melts at 170°, and dissolves freely in benzene, hot alcohol, and glacial acetic acid. a-Naphthindolecarboxylic acid, CH<CH>C-COOH, melts at 202°, and decomposes at 210-220°, yielding a-naphthindole; it is soluble in alcohol, ether, and acetic acid, and in alkalis. It is reprecipitated from the alkaline solution on the addition of an acid, and from the


ammoniacal solution on boiling. The nickel, cadmium, barium, and sodium salts are crystalline.

a-Naphthindole melts at 175°, and dissolves freely in alcohol, ether, and benzene. It is less soluble in hot water, dilute acetic acid, and light petroleum, and it is deposited from these solutions in colourless plates. The picrate crystallises in needles. The solution of the indole in acetic acid gives a red coloration with strong nitric acid, a colourless precipitate with hydrochloric acid, probably (CH,N),HCl, and a bluish-green precipitate on boiling with hydrogen peroxide.

a-Hydronaphthindole is obtained as a crystallisable oil on boiling the alcoholic solution of the indole with zinc-dust and hydrochloric acid. The alcoholic solution gives a red-violet coloration with silver nitrate, ferric chloride, and nitrous acid. The salts of the mineral acids are soluble in water. The oxalate is deposited from hot alcoholic solution in colourless needles melting at 166°. It is precipitated on adding oxalic acid to a solution of the base.


Methyl-a-naphthindole, CH<CH>CMe, obtained from acetonea-naphthylhydrazine (Abstr., 1886, 555), is soluble in alcohol, ether, benzene, acetic acid, and in hot water. It melts at 132°. The picrate is deposited from hot benzene in dark red needles, and melts at 167-168°. The acetic acid solution of the indole gives a cherryred coloration with ferric chloride, and on the addition of water a coloured precipitate is formed. W. C. W.

Nitroacenaphthene. By E. JANDRIER (Compt. rend., 104, 1858). -Nitric acid of sp. gr. 1.34 is added drop by drop to a warm saturated solution of acenaphthene in glacial acetic acid, and the product crystallised from alcohol, ether, or acetic acid. It forms white, silky needles which melt at 155°, and sublime at a low temperature, condensing in pale-yellow needles. . The nitro-derivative is easily reduced by zinc and hydrochloric acid or iron and acetic acid, and the amidoderivative yields a blue-violet product when carefully oxidised. With potassium dichromate and sulphuric acid, or with calcium hypochlorite, it yields a green solution and a green precipitate. The diazoderivative forms a yellow colouring matter with phenol, and scarlet and ponceaus with B-naphthol or its disulphonic acid. C. H. B. Methylerythrohydroxyanthraquinone. By W. BIRUKOFF (Ber., 20, 2068-2071).-Baeyer and Drewsen (Abstr., 1882, 1099) prepared methylery throhydroxyanthraquinone [Me: OH = 1:4] in very small quantity by the condensation of phthalic anhydride and paracresol with sulphuric acid. A yield of 5 per cent. of the paracresol employed can be obtained if phthalic anhydride (5 parts) is heated with paracresol (2 parts) and sulphuric acid (15 parts) for 10 minutes at 160°. The compound crystallises in yellowish-red, or from acetic acid in dark-brown, glistening needles, melts at 169-170°, and readily sublimes. In alkalis, it dissolves with a red colour; ammonia and soda do not dissolve it in the cold, and only sparingly on boiling; and with barium oxide and lime it yields insoluble brick-red lakes. Fusion with potassium hydroxide converts it with difficulty into a

coloured hydroxyanthraquinone, whilst sulphuric acid dissolves it with an orange-yellow colour, and the solution gives a spectrum corresponding entirely with that of erythrohydroxyanthraquinone. The acetyl-derivative crystallises in yellow needles and melts at 179


-Methylanthracene [Me = 1] is obtained on distilling methylerythrohydroxyanthraquinone with zinc-dust. It crystallises in white laminæ, melts at 199-200°, and is soluble in alcohol, yielding a solution fluorescing a pale blue. The picrate crystallises in red needles. When oxidised with chromic acid in acetic acid solution, it is converted into a-methylanthraquinone, together with the corresponding carboxylic acid if the reaction is allowed to become violent. The quinone crystallises in small, white needles, which speedily become pale-red on exposure to light; it melts at 166-167°, and is readily soluble in benzene and alcohol.

W. P. W.

Preparation of Anthranol and Dianthryl. By C. LIEBERMANN and A. GIMBEL (Ber., 20, 1854-1855).-These two compounds can easily be prepared by the reduction of anthraquinone by tin and acetic acid. If 10 grams of anthraquinone is dissolved in 500 grams of boiling glacial acetic acid, 25 grams of zinc added, and then a few c.c. of fuming hydrochloric acid added from time to time, almost all the CH

quinone is reduced to anthranol, CH,


CH, which is then

precipitated by pouring the solution into acidulated water. If, however, 10 grams of anthraquinone are added to just enough glacial acetic acid to form a thin paste, this then heated to boiling, 40 grams of tin added in two or three portions, and finally about half as much fuming hydrochloric acid as there was acetic acid, the reduction takes place almost entirely to dianthryl (dianthranyl), CH18, a small quantity of anthracene being formed at the same time. Dibromodianthryl is obtained by the action of bromine on a carbon bisulphide solution of dianthryl. It forms pale yellow prisms which melt considerably above 300°. L. T. T.

Terpenes and Ethereal Oils. Part V. Part V. By O. WALLACH (Annalen, 239, 1-54). The eight isomeric terpenes may be distinguished from each other by comparing the properties of their compounds with HCl, HBr, HI, &c., as shown in the following table (p. 966.)

The compounds of the terpenes with 2 mols. HBr, HI, &c., may be conveniently prepared on the small scale by saturating glacial acetic acid with hydrogen chloride, and adding this solution to the terpene dissolved in acetic acid. When the product is poured into ice-cold water, the compound separates in the pure state.

The bromides are prepared by adding bromine to the terpene diluted with ten times its volume of glacial acetic acid. They are purified by recrystallisation from warm ethyl acetate. The hydrochlorides are easily decomposed by boiling with glacial acetic acid and anhydrous sodium acetate, the chief product being the original

[merged small][merged small][merged small][ocr errors][ocr errors][ocr errors][merged small][ocr errors][merged small][ocr errors][merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][ocr errors][ocr errors][merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][ocr errors][merged small][merged small][ocr errors][merged small][merged small][ocr errors][merged small][merged small][merged small][merged small][merged small][merged small][ocr errors][merged small][merged small][merged small][merged small][merged small][merged small]

terpene. If pinene monohydrochloride is treated in this manner at 200° for four hours, it yields camphene. The conversion of pinene into dipentene, terpinolene, and terpinene, has been previously described (Abstr., 1885, 550, and 1886, 70). Pure pentene and all its derivatives are optically inactive. The dihydriodide, C10H16,2HI, is deposited from light petroleum in two distinct forms, namely, in rhombic crystals [a: b: 06644: 1], melting at 77°, and in monoclinic crystals [a b c = 10269 10.92619; B 49° 54'], melting


at 78-79°. Pure dipentene is converted into terpinene by treatment with alcoholic sulphuric, or hydrochloric acid.

Cineol, cajeputol, and eucalyptol are identical. This substance crystallises when it is cooled in a freezing mixture.

Terpinolene is obtained by boiling terpene hydrate, terpineol, or cineol, with dilute sulphuric or phosphoric acid. The melting point of the freshly prepared tetrabromide is 116°, but old specimens melt at about 112°. At the moment of fusion, a slight evolution of gas is perceptible. Solutions of the tetrabromide are optically inactive.

* Identical with the corresponding dipentene compounds.

+ Probably identical with the corresponding dipentene compounds.

By the action of hydrochloric, hydrobromic, or hydriodic acids on terpinolene, the hydrochloride, hydrobromide, &c., of dipentene are formed. Pure sylvestrene hydrochloride is obtained by saturating Swedish oil of turpentine (b. p. 174-178°) diluted with ether with dry hydrogen chloride. After an interval of two days, the ether is distilled off, and the residue is poured into shallow dishes, when the hydrochloride slowly crystallises out. The operation should be carried out in winter. After recrystallisation from warm alcohol, the hydrochloride melts at 72°. It is less soluble in ether and in light petroleum than dipentene hydrochloride. The ethereal solution is powerfully dextrogyrate. Sylvestrene boils at 175-178°; an intense blue coloration is produced by adding a drop of strong sulphuric or nitric acid to a solution of the hydrocarbon in acetic anhydride. Sylvestrene regenerated from the hydrochloride is identical with the hydrocarbon present in Swedish oil of turpentine. It is dextrogyrate. The hydrochloride, hydrobromide, and tetrabromide crystallise in the monoclinic system.

The hydrochloride forms plates, a b c = 2·0199 : 1 : 2·7641; B: = 76° 32'.


The hydrobromide also forms plates, a b c = 1.8887:1: 2.6937; = 73° 14'.

For the tetrabromide, a b c = 1.2166: 1: 1.6581; ß = 46° 9'. Terpinene is obtained by gradually adding 70 c.c. of strong sulphuric acid to two litres of oil of turpentine. The mixture is kept cool and is well shaken. After an interval of two days the acid is neutralised with soda, and the terpinene distilled over in a current of steam. Dipentene, phellandrene, and cineol also yield the same hydrocarbon.

Terpinene nitrite, C10H16 N2O3, is obtained in crystals by adding sodium nitrite in small quantities to a mixture of terpinene, acetic acid, and water. The compound is deposited in the course of two days at the ordinary temperature, or immediately in working on the small scale if the vessel containing the mixture is dipped for an

instant into hot water.

The nitrite melts at 155°. It is insoluble in water and light petroleum, but dissolves freely in alcohol, ether, and ethyl acetate.

The solutions are optically inactive. The nitrite dissolves in strong hydrochloric, sulphuric, and acetic acids, and is reprecipitated unaltered on diluting the acid solutions. On reduction with stannous chloride, the nitrite is converted into a base which has not yet been properly investigated. Terpinine is not converted into camphene or any other terpene by treatment with alcoholic sulphuric acid, or strong sulphuric acid.

The properties of phellandrene have been recently described by Pesci (Abstr., 1886, 1038). The aqueous solution is dextrogyrate. but the nitrite is lævogyrate. The nitrite behaves like a saturated compound, and does not destroy the colour of bromine-water. Phellandrene has not been obtained in a pure state. It easily changes into dipentene- or terpinene-derivatives.

The author proposes the following formulæ for the terpenes—

« PreviousContinue »