Page images

tained in crystals which melt at 19° and boil at 143° under a pressure of 25 mm. C. H. B.

Synthesis of Aromatic Alkyl Polysulphides. By R. OTTO (Ber., 20, 2089).—When a warm alcoholic solution of benzenesulphinic acid is treated with hydrogen sulphide, a thick yellow oil of unpleasant odour separates, consisting chiefly of phenyl tetrasulphide. This compound is readily reduced to the bisulphide by the action of colourless ammonium sulphide in the cold. Paratoluenesulphinic acid yields toluene tetrasulphide when similarly treated; it crystallises in small scales, melts at 75°, and is not reduced by ammonium sulphide.

Benzenesulphonic chloride also yields phenyl polysulphides under W. P. W.

similar conditions.

Chlorine-derivatives of Phenyl Methyl Ether (Anisoïl). By L. HUGOUNENQ (Compt. rend., 104, 1807-1808).—When a current of chlorine gas is passed over phenyl methyl ether mixed with an equivalent quantity of ethyl alcohol, a solid product is obtained, crystallising from alcohol in long, white needles, which are soluble in ether, chloroform, benzene, carbon bisulphide, and glacial acetic acid. It melts at 59-60°, sublimes readily even at the ordinary temperature, and boils without decomposition at 240°, under a pressure of 738.2 mm. It is a trichloro-derivative, and is not attacked by boiling alcoholic potash, which indicates that substitution has taken place in the benzene-ring only. If the anisoil is heated and treated with chlorine in presence of iodine, it yields another trichloroderivative, which forms small needles melting at 56°. Other chlorinederivatives and various oxidation products have been obtained, and will be described subsequently. C. H. B.

Carvole-derivatives. By H. GOLDSCHMIDT and E. KISSER (Ber., 20, 2071-2078; compare this vol., p. 475).-If carvole is treated with hydrogen bromide, hydrobromocarvole, C10H15OBr, is obtained as a thick oily compound, which decomposes at about 50°, and resinifiest in the moist state with the evolution of hydrogen bromide. The oxime, C10H15Br: NOH, is formed by acting on hydrobromocarvole with the theoretical quantity of hydroxylamine, or by saturating a solution of carvoxime in methyl alcohol with hydrogen bromide; it crystallises from light petroleum in colourless, glistening prisms, and from alcohol in tufts of needles, melts at 116°, and when allowed to remain for some time darkens in colour, and eventually forms a viscid mass. The phenylhydrazide, C10H15Br: N2HPh, crystallises in slender, yellow needles, and melts at 119°.

Isocarvozime, C10H14 NOH, is obtained, together with a small quantity of carvoxime, when hydrobromocarvole or hydrobromocarvoxime in alcoholic solution is treated with an excess of hydroxylamine. It crystallises in needles, melts at 142-143°, and is sparingly soluble in alcohol. Isocarvoxime dissolves in acids and alkalis, and is more basic in its properties than carvoxime, but unlike that base it does not form additive compounds with hydrogen

chloride and hydrogen bromide. The benzoyl-derivative forms stellate, white, glistening scales, melts at 112°, and is readily soluble ir alcohol, ether, and benzene.

The authors have not succeeded in obtaining an isomeride of carvole corresponding with isocarvoxime from either hydrochlorocarvole or hydrobromocarvole, and find that carvole and carvacrol are the endproducts when the elements of hydrogen bromide are separated from the latter compound by repeated distillation, by heating with a mixture of anhydrous sodium acetate and acetic acid, or by the action of alcoholic potash in the cold. Isocarvoxime, when heated with dilute sulphuric acid, yields not the expected isocarvole (comp. Abstr., 1885, 1058) but carvacrol, hydroxylamine, and a compound, CH15NO, isomeric with carvoxime. This crystallises from hot water in glistening, transparent prisms, melts at 94°, has an odour resembling that of indole, and is insoluble in cold water, soluble in ether.

The remainder of the paper is devoted to a discussion of the possible formulæ for isocarvoxime, and of these the formula


CH2- -CH

is adopted as the most probable.


W. P. W.

Bromine-derivatives of Resorcinol. By J. ZEHENTER (Monatsh. Chem., 8, 293-298).-Monobromoresorcinol, C,H,Br(OH)2, is obtained by boiling monobromo-a-dihydroxybenzoic acid (1 part) with water (5 parts) for some hours in a reflux apparatus, adding excess of dilute sulphuric acid, and extracting with ether. The ethereal extract is then treated with a little dilute ammonium carbonate to remove any unaltered acid, and, after separation, slowly evaporated. The monobromoresorcinol remains as a solid crystalline mass, which, when purified, forms slightly yellow, more or less nodular groups of crystals. It melts at 91°, and cannot be sublimed without decomposition; it is readily soluble in water and ether, less so in alcohol, chloroform, benzene, &c. The aqueous solution gives with ferric chloride a bluish-violet coloration, which, after a time, gives place to a reddish-brown precipitate. It reduces alkaline silver solutions; with bromine-water, it gives a precipitate of tribromoresorcinol. When heated in a sealed tube with water, it gives up the whole of its bromine. When heated with water, potassium carbonate and tin chloride, it gives resorcinol and a-dihydroxybenzoic acid.

Dibromoresorcinol, CH2Br2(OH)2, is prepared by adding to resorcinol suspended in carbon bisulphide sufficient bromine dissolved in the same solvent, the greater part of the resorcinol is dissolved, and hydrogen bromide is given off, the liquid is quickly filtered, and the filtrate sets after a time to a crystalline mass. When purified by recrystallisation from water, dibromoresorcinol forms long, white needles, melts at 110-112°, and sublimes without decomposition. The air-dried crystals contain one mol. H2O. Dibromoresorcinol is sparingly soluble in cold water, readily in hot water, alcohol, and ether; with ferric chloride, the aqueous solution gives a pure blue coloration, which, after a time, gives place to a dark pre

cipitate; with neutral and basic lead acetate, it gives a white precipitate; with bleaching powder, a violet coloration, which changes first to red and then to gold. Bromine-water throws down a precipitate of tribromoresorcinol. It is soluble in alkalis, and is reprecipitated on adding an acid to the solution. In other respects, it resembles the monobromoresorcinol in behaviour.

This dibromoresorcinol differs from a-dibromoresorcinol prepared by Hofmann from eosin (this Journ., 1875, 571), and also from B-dibromoresorcinol previously described by the author (loc. cit.), both in its higher melting point, its reaction with ferric chloride, and also its readier solubility in water. From experiments made with a- and B-dibromoresorcinol, the author concludes that they are identical. G. H. M.

Action of Chlorine and Bromine on Pyrogallol. By A. HANTZSCH and K. SCHNITER (Ber., 20, 2033-2040).—When chlorine is passed into an aqueous or alkaline solution of pyrogallol, and the product after removal of the excess of chlorine by a current of air is treated with ether, an oil is obtained which contains chlorine, is acid in reaction, and is soluble in water. It cannot be distilled unchanged, and is readily reduced to pyrogallol by the action of zinc and sulphuric acid. Leucogallol, obtained by Stenhouse and Groves (this Journ., 1875, 704), by chlorinating pyrogallol in acetic acid solution, has the formula C18HC112O12 + 2H2O originally ascribed to it, and yields trichloropyrogallol, CHзCl2O, +3H,O, when dissolved in water and treated with zinc-dust in small portions at a time, rise of temperature being avoided. Trichloropyrogallol crystallises in long, white needles, and melts at 75°, whilst the anhydrous substance melts at about 185° with decomposition. It is very readily soluble in alcohol, ether, and chloroform, soluble in hot water, and dissolves in ammonia with a bright yellow colour. The aqueous solution gives insoluble precipitates of varying colours with most metallic salts, and ammoniacal silver nitrate yields with it a mirror of silver. The barium salt, (C,ClO3)2Ba + 6H2O, forms indistinct crystals; the copper salt, (C6Cl3O3)2Cu3 + 6H2O, is an amorphous green powder. The acetylderivative, CC,O,Ac, crystallises in slender needles, melts at 122", is soluble in alcohol, ether, and benzene, insoluble in water, and is very stable towards sulphuric and nitric acids. Leucogallol, on account of the ease with which it is reduced, cannot be regarded as a derivative of a hydrocarbon, CiH18, and is most probably formed of three benzene molecules united by oxygen-atoms. With hydroxylamine hydrochloride, it yields a nitrogenous compound which gives Liebermann's reaction, and also reacts with phenylhydrazine acetate, but owing to their great instability neither compound has been obtained pure.

Mairogallol (loc. cit.), although it differs from leucogallol by reason of its insolubility in water and greater stability, yields trichlorpyrogallol under similar conditions.

Xanthogallol (Stenhouse, this Journ., 1875, 1) is neither reduced by sodium amalgam nor by zinc and sulphuric acid, but yields trihydroxyxanthogallol, CH,BrОs(OH)3, when treated with dilute



aqueous soda. The barium salt has the formula (C1HBrO9),Baз; the acetyl-derivative, C1,H,Br1O,Ac3, crystallises in nacreous scales, and is soluble in all ordinary solvents, water excepted. Both xanthogallol and the trihydroxy-derivative yield compounds with phenylhydrazine acetate.

The second portion of the paper is devoted to a discussion of the probable constitution of these pyrogallol-derivatives, and in conclusion the authors state that the product obtained by Stenhouse on brominating bromanilic acid, and to which the formula C,HBrO was ascribed, is perbromacetone. W. P. W.

Anilic Acids. By S. SALZMANN (Ber., 20, 1997-1999).-Hantzsch showed (this vol., p. 719) that the acid formed by the bromination of quinonedihydroxyparadicarboxylic acid, which contains both bromineatoms in the para-position, is identical with ordinary bromanilic acid. By heating symmetrical tribromophenol with fuming sulphuric acid at 100-115°, the third possible bromanilic acid is obtained in which the bromine has the meta-position; this also seems to be identical with ordinary bromanilic acid. Bromanil is also formed in the reaction. The author considers that the chemical identity of the three acids is not established, and refers to a- and B-thiophencarboxylic acids as examples of compounds possessing the same physical properties. N. H. M.


Nitranilic Acid from Chloranil. By J. U. NEF (Ber., 20, 20272031).—When a hot solution of chloranil in acetone is gradually added to a concentrated aqueous solution of potassium or sodium nitrite heated at 80-90°, a dark reddish-brown coloration is at first produced, and after a short time a dark-yellow crystalline separation of the corresponding salt of nitranilic acid is obtained (Abstr., 1883, 465). The potassium salt forms microscopic crystals, which are probably monoclinic, and show feeble dichroism; the sodium salt forms characteristic dark-red monoclinic octahedra, a b c = 0·9463 : 1 : 0·98489; B 87° 5', and is strongly dichroic. All attempts to isolate the


reddish-brown intermediate product have failed. The action of a concentrated aqueous solution of potassium cyanide on chloranil dissolved in acetone results in the formation of several products, of which one crystallises well from acetic acid, and seems to have the formula C.(OH),Cl,(CN)2. W. P. W.

Cholesterin. By B. RAYMAN (Bull. Soc. Chim., 47, 898-901).The analogy of cholesterin to camphor is confirmed by the absence of any action when it is treated with hydroxylamine. The author failed in his attempts to prepare a sodium cholesterate, as also to prepare the cholesterin ether, (C2H43)2O. On heating cholesterin with acetic anhydride in a reflux apparatus, and cooling, cholesterin acetate separates in flocks; on crystallisation from benzene, it forms groups of needles which melt at 113° and decompose at a somewhat higher temperature, losing acetic acid; water acts on it in a similar manner.

Cholesteryl chloride may be prepared by heating cholesterin with

phosphoric chloride; it forms small scales and melts at 96°. On slowly evaporating the ethereal solution, it exhibits a fine violet fluorescence. Cholesteryl chloride dibromide, C26 HCI Br2, may be prepared by gradually adding bromine to an ethereal solution of cholesteryl chloride, when it is precipitated as a heavy white powder; it is insoluble in ether but soluble in most other solvents, and crystallises from its solution in carbon bisulphide in large, colourless crystals; it melts at 128° and is decomposed when heated to 158°. By digestion with sodium ethoxide or isobutoxide, or with a solution of potassium hydroxide, the bromine is removed and cholesteryl chloride regenerated.

By the action of potassium chlorate and hydrochloric acid on cholesterin an amorphous substance which appears to have the composition C26 HaCl2O, is formed. The reduction of nitro-derivatives of cholesterin by zinc powder has not yielded any satisfactory results.

A. P.

Combination of Aniline with Chromic Acid. By C. GIRARD and L. L'HOTE (Compt. rend., 104, 1725-1727).—When aniline is mixed with free chromic acid, oxidation takes place and no chromate is obtained. If, however, equal volumes of well-cooled saturated solutions of potassium dichromate and aniline hydrochloride are mixed together, a yellow crystalline precipitate is formed which must be immediately separated and drained by means of a filter-pump, then washed with small quantities of cold water, and dried on a porous plate over sulphuric acid in a vacuum. Sodium and ammonium dichromates give similar results.

The crystals are yellow monoclinic prisms which act strongly on polarised light and have a bright green lustre. They have the composition 2NH,Ph, H2Cr2O,, are slightly soluble in cold water, and are decomposed by boiling water. When moist, they decompose on exposure to air and light, but remain unaltered if dry. They are very slightly soluble in alcohol, which they gradually convert into aldehyde. The compound decomposes when heated to a moderate temperature, and it burns with formation of chromic oxide when ignited or struck on an anvil. It takes fire in contact with fuming nitric acid, and if moistened with concentrated sulphuric acid it burns like pyrophoric copper. When mixed with alkalis and agitated with ether or benzene, it gives up aniline. When treated with water, it yields violet colouring matters similar to mauve.

C. H. B.

Phenylparatoluidine. By A. BONNA (Annalen, 239, 55-64).— Phenylparatoluidine melts at 85-86° and boils at 317-318° (thermometer immersed in vapour). The nitroso-compound, NPh(C,H,).NO, is deposited from alcohol in yellow needles, soluble in ether and benzene. It melts at 82°. On the addition of bromine to the alcoholic solution, nitrosobromophenyltoluidine, CHBгN2O, is deposited. On recrystallisation from ether or chloroform, it forms yellow needles melting at 166°. The acetic derivative is formed when acetic chloride is added to a solution of phenyltoluidine in benzene, and also by the action of acetic anhydride on phenyltoluidine at 200°. The acetic derivative melts at 51°, and is freely soluble in alcohol and

« PreviousContinue »