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Trimethylanthragallol. By H. WENDE (Ber., 20, 867-870).— Trimethylanthragallol,

CH2MеO2(OH)3 [Me3: (OH), 1:3:4: 1': 2': 3'],


is obtained by heating a mixture of 2 parts of gallic acid, 3 parts of durylic acid, and 30 parts of concentrated sulphuric acid. The crude product is finally exhausted with benzene, which dissolves the trimethylanthragallol, leaving the rufigallic acid. The former crystallises in glistening, brown needles, melting at 244°, soluble in alcohol, sparingly soluble in benzene; it dissolves in concentrated sulphuric acid with a violet-red coloration; it resembles anthragallol in its absorption-spectrum and dyeing properties. Its triacetyl-derivative, C1H2MeзO2(OAc), crystallises in pale-yellow, rhombic tables, melting at 174. Trimethylanthragallol, on distillation over zinc-dust, yields a solid trimethylanthracene, identical probably with that obtained by Gresly, together with a liquid hydrocarbon which, though not fully examined, is considered to be a dihydride of trimethylanthracene.


V. H. V. Hydroxyanthraquinone Dyes. By C. LIEBERMANN and W. WENSE (Ber., 20, 862-866).-Liebermann and Kostanecki have shown that only those hydroxyanthraquinones which contain the hydroxyl-groups in the alizarin-position can be mordanted on fabrics. In order to confirm this view, a compound, at once an alizarin and a quinazin, has been prepared from hemipinic acid and quinol by heating a mixture of the two with concentrated sulphuric acid. There is thus formed a dimethyl ether of a quinalizarin, CH,(OMe)2(OH)2Ü2 [(OMe) 2 (OH), 1: 2: 1' : 4'], which crystallises in brown-red minute leaflets, melting at 225-230°, soluble in alkalis with violet coloration and in concentrated sulphuric acid with a blue coloration. With mordants, it gives but a faint colour. Its acetyl-derivative crystallises in small needles melting at 210-211°, sparingly soluble in cold alcohol and acetone, but more readily in hot. Quinalizarin, C1H.(OH),O2, obtained from the above by heating it with hydrochloric acid, crystallises in deep-red needles, exhibiting no signs of fusion at 275°. Its reactions with alkalis and with concentrated sulphuric acid are similar to those of the dimethyl ether; its barium and calcium salts are insoluble in water. It possesses strong dyeing powers, resembling those of alizarin. On distillation with zinc-dust at 210, it yields anthracene. Its tetracetyl-derivative, CH,(OAc),O2, crystallises in needles melting at 201°, soluble in chloroform, less soluble in alcohol. V. H. V.

Substituted Anthracene-y-carboxylic Acids; Behaviour of Carbon Oxychloride towards Anthracene Dihydride. By G. BEHLA (Ber., 20, 701-708; compare Abstr., 1886, 248).--Chloranthracene-y-carboxylic acid, CH,Cl·COOH, is obtained by heating 3 grams of anthracene with 5-6 grams of carbon oxychloride for 6-7 hours at 240-250°; the product is extracted with boiling sodium carbonate solution, precipitated with hydrochloric acid, dried, and recrystallised from benzene, from which it separates in long, greenishyellow, lustrous needles. It sublimes at 155°, and melts at 258-259°, with evolution of carbonic anhydride. It dissolves in alcohol, ether,

acetone, &c., sparingly in benzene and chloroform. The solutions have a blue fluorescence. Potassium permanganate and dilute nitric acid oxidise it to anthraquinone. Fuming sulphuric acid dissolves it with formation of a compound, crystallising in long, yellow needles, soluble in water; this is probably the disulphonic acid. Potassium y-chloranthracenecarboxylate, CH,Cl·COOK, forms very slender, yellow needles; the barium salt crystallises in lustrous, yellow prisms. The methyl salt crystallises in tufts of slender, yellow needles, which melt at 123°; it is insoluble in water, soluble in alcohol, ether, and chloroform.

Methyl anthracene--carboxylate, CH, COOMe, forms yellow prisms, melting at 111°; it resembles the chlorinated derivative in its solubility.

7-Chloranthracene-y-carboxylic acid can be obtained by passing dry chlorine through a solution of anthracene-7-carboxylic acid in chloroform; by the action of a second molecule of chlorine in the product, dichloranthracene, melting at 209°, is obtained.

7-Bromanthracene-y-carboxylic acid is prepared by adding the calculated amount of bromine to a solution of anthracene-y-carboxylic acid in glacial acetic acid; the product is treated with water, filtered, and the precipitate warmed with sodium carbonate solution; it is again filtered, precipitated with hydrochloric acid, dried, and crystallised successively from benzene and alcohol. It forms greenish-yellow, lustrous needles, which sublime at 160°, and melt at 266°, with evolution of gas. It is almost insoluble in water, soluble in ether, alcohol, and glacial acetic acid. The solutions show a blue fluorescence. It dissolves in fuming sulphuric acid, forming a reddish-yellow solution with green fluorescence; a yellow crystalline substance is formed, probably a disulphonic acid. Potassium-y-bromanthracene-y-carboxylate forms very slender, long, yellow needles; the barium and silver salts crystallise respectively in lustrous needles and microscopic prisms; both are yellow.

Anthracene--carboxylic acid monosulphonic acid, COOH CH, SO,H, is obtained by keeping a solution of the carboxylic acid in concentrated sulphuric acid surrounded by ice for 12 hours, and precipitating with water. It is purified by means of the barium salt. The free acid crystallises from alcohol in microscopic, slightly yellow prisms, which do not melt at 360°; it dissolves readily in water and alcohol, and is insoluble in ether and benzene. The aqueous solution shows a bluo fluorescence. The barium salt is very readily soluble in water.

The disulphonic acid, COOH-CH(SO,H), is prepared by dissolving the carboxylic acid in fuming sulphuric acid, and precipitating with water. It forms prisms, readily soluble in water and alcohol. The aqueous solution shows hardly any fluorescence; the solution in sulphuric acid has a yellowish-green fluorescence. The barium salt is very sparingly soluble.

When anthracene dihydride (Liebermann and Topf, this Journal, 1877, i, 86) is heated with carbon oxychloride at 200° for four hours, anthracene is regenerated; when the temperature is raised to 240°, and the heating continued for four hours, anthracenecarboxylic chloride and chloranthracenecarboxylic chloride are formed. N. H. M.

Nitrogen-derivatives of Terebenthene. By C. TANRET (Compt. rend., 104, 791-794).—The mother-liquor from terpin and the liquid hydrates formed from terebenthene by the action of nitric acid diluted with alcohol, were washed with water, neutralised, and distilled in a current of steam. The distillate consists of unaltered terebenthene, mixed with a continually increasing proportion of hydrate as the temperature rises. The nitrogen-derivatives are found in the last portions of the distillate. The liquid thus obtained is neutral to litmus, and colourless. With alcoholic potash, it yields potassium nitrite. A similar product is obtained by the action of nitric oxide on terpene hydrates, and hence it would seem that the compound is of the same nature as nitroethane, but less stable. When heated at 100°, it becomes acid, and decomposition increases as the temperature rises, and becomes rapid at 150°, nitrogen, nitric oxide, and watervapour being given off.

The liquid product of the reaction is agitated with dilute soda, and the latter is treated with sulphuric acid and agitated with chloroform. When the chloroform is distilled, and the residue treated with boiling water to remove tarry matter, a crystalline substance is obtained, which is recrystallised from alcohol. Direct treatment of the washed and neutralised mother-liquor in the same way yields the same product.

The solid product is a mixture of two isomerides of the composition C1HNO2, which can be separated by means of ether. The a-compound is comparatively insoluble in ether, and requires 30 parts of this liquid for solution. It dissolves in 6 parts of alcohol of 90°, 20 parts of water at 100°, and 68 parts at 13°, and is very soluble in chloroform. It melts at 210°, boils at 283° with partial decomposition, and crystallises in long, brittle, opaque, flattened prisms with a rhomboidal base. The ẞ-derivative crystallises in bulky, transparent, quadratic prisms, which begin to melt at 110°, are completely liquid at 114°, and boil at 274°. It appears to be a mixture of two isomerides. It dissolves in 7 parts of ether, 25 parts of alcohol, 7 parts of water at 100°, and 42 parts at 13°.

The rotary power of the x-compound is [a]D= +69°, of the B-compound [a]D +184°. Both are neutral to litmus, but have a distinctly acid function. They are not affected by strong sulphuric acid, nor by a solution of potassium hydroxide, but when fused with caustic alkalis they yield an alkaline carbonate and cyanide. When heated with soda-lime, only 76 per cent. of the nitrogen is evolved as ammonia.

With ferric salts, they give a deep violet coloration, owing to the formation of a compound (CH3N2O4)3(Fe2O3)2, which can be isolated. It dissolves in water, forming a reddish-brown solution which changes to red on addition of a trace of an organic acid.

If an excess of calcium saccharate is added to a solution of the a-compound, the salt (CH16NO,Ca); 3H2O is obtained in slender crystals, only very slightly soluble in water. C. H. B.

Terpenes and Ethereal Oils. By O. WALLACH (Annalen, 238, 78--89).—Schmidt (Arch. Pharm. [2], 141, 1) and Oglialoro (this

Journal, 1876, ii, 642) have pointed out that oil of cubebs contains two sesquiterpenes, C15H2, one of which yields a crystalline hydrochloride, CH22HCl, melting at 117-118°. The author has succeeded in obtaining this hydrochloride from oil of cubebs, patchouli (b. p. 270— 280°), oil of galbanum, Oleum cadinum, and Oleum sabina. It is best obtained by distilling Oleum cadinum in a current of steam, and treating the distillate with potash to remove phenols. The purified oil is distilled over potash, and the portion boiling between 260° and 280° is diluted with ether and saturated with hydrogen chloride. The hydrochloride can be recrystallised from ethyl acetate. It is deposited from ether in rhombic prisms, a : b: c = 0·61379: 1 : 0·41432. The solution is lævogyrate. The terpene is easily obtained by heating the hydrochloride with anhydrous sodium acetate and acetic acid. The sesquiterpene boils at 274-275°. Its sp. gr. at 16° = 0·921. It has a great tendency to resinify. The hydrochloride, hydrobro mide, and hydriodide are conveniently prepared by adding the corresponding acid to an acetic acid solution of the terpene. C15 H21,2HBr melts at 124-125°. C1H2,2HI melts with decomposition at 105106°. A solution of the terpene in a large excess of chloroform or acetic acid, gives on the addition of strong sulphuric acid first a green, and then a blue coloration. Attempts to prepare the sesquiterpene from isoprene were unsuccessful. W. C. W.

Ethereal Oils. By E. WEBER (Annalen, 238, 89-108).-Oil of rosemary not only contains camphor, borneol and a terpene, but also cyneol, C10H18O, which was discovered by Wallach and Brass in Oleum cyna (Abstr., 1885, 171).

Oil of cardamoms begins to boil at 164°, and the temperature gradually rises to 220°. A small quantity of a crystalline compound, which melts at 60–61o, is left in the retort. The liquid distilling over below 170° consists of water, acetic and formic acids.

The oil contains terpinene, boiling at 179-182, and another terpene, which boils at 180-183° (probably limonene or dipentene), and yields a hydrochloride which melts at 52°. The portion of the distillate coming over between 205° and 220° contains the compound CHIO, which is probably identical with Wallach's terpineol (Abstr., 1886, 71). W. C. W.

Active Camphene and Ethyl-borneol. By G. BOUCHARDAT and J. LAFONT (Compt. rend., 104, 693-695).-The monohydrochloride, C10H17Cl, with a rotatory power [a]D-28° 30', obtained from French essence of terebentaene, was heated in sealed tubes at 150° with somewhat less than its own weight of fused potassium acetate dissolved in very strong alcohol. After 48 hours, the product was precipitated with water, fractionated in a vacuum, and the unaltered hydrochloride was again subjected to the same treatment, twice at 150°, and finally at 175°. The rotatory power of the camphene obtained at each operation was—

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At a high temperature the potassium acetate and acetic acid either render part of the camphene altogether inactive, or diminish the general activity of the whole. The effect of temperature is very marked; the reduction in rotatory power was only 9-10° in the first two operations at 150°, whilst it was 30° in the last operation at 175°. In addition to the camphene, a certain quantity of some substance is formed which distils over with the hydrochloride. This is ethylborneol, CHEtO, isomeric with the compound obtained by Baubigny by the action of ethyl iodide and potassium hydroxide on borneol. It boils at 205-208° under ordinary pressure; sp. gr. at 0° = 0·9495; vapour-density, 58; rotatory power, [a]D= +26° 3'. It is not affected by potash, but if treated at 0° with a saturated solution of hydrochloric acid it forms a buttery mass, which when compressed yields a solid camphoraceous substance mixed with borneol and borneol hydrochloride. When heated at 100° with ten times its weight of saturated hydrochloric acid, ethylborneol is completely converted into ethyl chloride and inactive camphene hydrochloride. It is rapidly oxidised by ordinary nitric acid, with formation of camphor. C. H. B.

Determination of Position in the Pyrroline Series. By G. CIAMICIAN and P. SILBER (Ber., 20, 698-700); compare Abstr., 1886, 938). When tribromacetylpyrroline, methyl tribromocarbopyrrolate, dibromacetylmethylpyrroline, and dibromodiacetylpyrroline treated with nitric acid, dibromomaleïuimide is formed. In these compounds, the acetyl, methyl, or carboxyl must be attached to the carbon-atom next to nitrogen in the pyrroline-ring.


When brominated pyrrylene dimethyl diketone is heated with fuming nitric acid, dibromomaleïnimide is at once formed; if the reaction is allowed to take place at the ordinary temperature, dibromomononitracetylpyrroline, NO, CNHBr,Ac, is obtained. This crystallises in long needles melting at 206°. When dissolved in a mixture of sulphuric and fuming nitric acids at -18°, and precipitated with water, dibromodinitropyrroline, C,NHBr2(NO2)2 is formed, which changes at the ordinary temperature into dibromomaleïnimide. These reactions can only be explained by assuming that the acetyl-group is directly substituted by the nitro-group. N. H. M.

Tetraiodopyrroline. By G. CIAMICIAN (Gazzetta, 16, 543-548). -Tetraiodopyrroline, sold commercially under the name of "iodole," is readily obtained by the direct action of iodine on pyrroline; it forms yellow crystals, insoluble in water, sparingly soluble in alcohol. Its presence may be recognised by the action of concentrated sulphuric acid; this produces an intense green coloration, which after some

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