ducts; the liquid products, besides monobromobenzene, meta- and paradi-bromobenzene, contain two tribromobenzenes melting at 44° and 119.6° respectively, and yielding nitro-derivatives which melt at 93.5° and 125° respectively. It would seem that the aluminium chloride first reduces the paradibromobenzene to the monobromo-derivative, part of the bromine becoming free and acting on the mono-derivative with formation of the meta-di-derivative. At the same time, another portion of the liberated bromine forms tri-derivatives. These results are analogous to those obtained by Friedel and Crafts by the action of aluminium chloride on dichlorobenzene. C. H. B. Action of Sulphuric Acid on Chlorobenzenes. By ISTRATI (Bull. Soc. Chim., 48, 35-41).-300 grams of pentachlorobenzene was heated with 2000 c.c. of Nordhausen acid for seven to eight hours per day during 15 days. Hydrogen chloride, sulphurous anhydride, and some water, were given off. At the end of 15 days, the acid was decanted off, a fresh quantity added, and the heating continued 15 days longer. No carbonisation took place, but a deep marooncoloured substance gradually separated. The acid was neutralised by barium carbonate but no sulphonic acid was obtained. The maroon-coloured substance, after being washed with water, dissolved completely and rapidly in sodium or potassium hydroxide solution, forming a deep red liquid, and when this was filtered and acidified with hydrochloric or sulphuric acid, the substance was reprecipitated. When dried at 60°, it contracts and becomes dark green with a metallic lustre. It is insoluble in boiling water, which removes traces of a colourless, crystalline substance, but it is soluble in concentrated alcohol, very slightly soluble in ether, chloroform, or carbon bisulphide, quite insoluble in benzene. The alcoholic solution, which is cherry-red by transmitted light and yellowish-green by reflected light, and has very great tinctorial power, deposits no solid on cooling, hence it seems probable that a compound is formed. The substance will not crystallise from alcohol, and is not fusible. When heated to redness, it burns and leaves a residue of carbon which is only combustible at a very high temperature. It contains 36 83 per cent. of chlorine, and is free from sulphur. The potassium salt is deep brown with a metallic lustre, and is readily soluble in water, forming a deep red, non-dichroic solution. The barium, iron, tin, mercury, aluminium, magnesium, cadmium, nickel, and other salts, are obtained by double decomposition. They are all pale or deep red, and are insoluble in water, with the exception of the silver salt, which blackens rapidly, and of the mercuric salt, which separates slowly from the solution. The compound seems to have a phenolic function, and the author proposes to call it Francein. Francein is readily attacked and dissolved by cold fuming nitric acid. When heated in sealed tubes at 150° to 180° for six hours, large, colourless crystals, separate. Francein can also be obtained by the action of ordinary concentrated sulphuric acid, and in this case another substance of the same composition as francein, but much more soluble, is also formed at the same time. Tetrachlorbenzene (200 c.c.), when heated to boiling with concentrated sulphuric acid (1200 c.c.) for 105 hours, is completely dissolved with evolution of water, hydrogen chloride, and large quantities of sulphurous anhydride. No sulphonic acid is formed, but the chief product is a colonring matter which retains a volatile substance; this sublimes at 100°, crystallises in slender needles, and has an odour resembling that of benzoic acid. This substance is removed by treatment with boiling water, when a reddish-brown solid is left easily soluble in alkalis. A considerable portion is soluble in boiling water and especially in alcohol, forming a solution which is pale-brown by transmitted light, and dull-green by reflected light. The more soluble portion contains 33 12 per cent. of chlorine; the portion insoluble in water contains 38 72 per cent. In the preparation of trichlorobenzenesulphonic acid, when the sulphuric acid is diluted with water, it yields a red product insoluble in water, but easily soluble in alcohol; this is infusible and very darkcoloured with a metallic lustre. The formation of hydrogen chloride and sulphurous anhydride in these reactions is of special interest. It is probable that under the influence of the sulphuric acid, which plays the part of an oxidising agent, part of the chlorine leaves the benzene nucleus, the sulphuric acid being reduced. This action, which is quite secondary with the lower chlorobenzenes, becomes the dominant reaction with the higher derivatives. In the case of the trichloro-derivative, both reactions are well marked. When pentachloronitrobenzene is heated with concentrated sulphuric acid, water and hydrochloric acid are given off in large quantities, but very little sulphurous anhydride is liberated. On diluting with water, a crimson precipitate forms. This substance is not soluble in alkalis, but dissolves in warm alcohol from which it separates on cooling. A dilute alcoholic solution is golden-yellow by reflected light and pale-red by transmitted light. C. H. B. Nitrochlorethylbenzenes. By ISTRATI (Bull. Soc. Chim., 84, 41-43). Paradichlorethylbenzene when boiled with concentrated sulphuric acid and fuming nitric acid for 50 hours, fresh nitric acid being added each day, yields a solid, crystalline product completely soluble in the warm acids, from which it is precipitated by adding water. This nitro-derivative is readily soluble in a mixture of alcohol one part and ether two parts. When treated with boiling water, the compound, CH,Cl2Et NO2, is dissolved and is deposited on cooling. It is very soluble in alcohol and ether, and crystallises in lamellæ melting at 175°. Its solution is feebly acid, and is not precipitated by lead salts, and is not oxidised by potassium permanganate in the cold. Ferric chloride gives an abundant yellowish-white precipitate. The portion less soluble in water has the composition C&Cl2Et (NO2)3, and is easily soluble in alcohol, ether, and benzene. It forms small hard crystals which melt at about 195° with partial decomposition. The alcoholic solution mixed with an aqueous solution of ferric chloride yields a slight precipitate after some time. 100 grams of the compound C,H2Cl2Et NO2 was boiled for 12 hours with 500 c.c. of fuming nitric acid, and then with a mixture of fuming nitric and sulphuric acids. The product consists of two isomerides. which can be separated by treatment with warm alcohol. The less soluble compound forms hard, white crystals which dissolve in ether and melt at 82°. The more soluble compound has a strong aromatic odour and forms crystals melting at 150°. These compounds contain 21 per cent. of chlorine. C. H. B. Orthocyanotoluene. By S. GABRIEL and B. WEISE (Ber., 20. 3197-3199).-Orthocyanobenzal chloride, CN-CH, CHCl2, is prepared by boiling the oil obtained in the preparation of orthocyanobenzyl chloride (Abstr., 1887, 1035), whilst chlorine is being passed through. It boils at 260°. When heated with fuming hydrochloric acid at 170°, orthophthaldehydic acid, melting at 97°, is formed. Strong sulphuric acid converts it into diphthalide ether (m. p. 221°). Orthocyanobenzotrichloride, CN CH, CC,, is obtained by the further action of chlorine on the oil from cyanobenzene chloride, and crystallises from alcohol in monoclinic crystals of a vitreous lustre; a b c = 1-5464 1: 1·1056; ß = 73° 53'. It melts at 94-95°, and boils at about 280°. N. H. M. By M. Action of Nitric Acid on Pentamethylbenzene. GOTTSCHALK (Ber., 20, 3286-3288).-When oxidised with dilute nitric acid, pentamethylbenzene yields tetramethylbenzenecarboxylic acid, CHMe,COOH [COOH: Me, 1:2:3: 4:5]. This acid crystallises from alcohol in colourless needles, and melts at 165°. Its barium salt crystallises in anhydrous scales or in tufts of needles, (C1H3O2)2Ba + 2H2O. When the barium salt is heated with lime, it yields prehnitene. Small quantities of polybasic acids were also formed but were not examined. When dissolved in cold fuming nitric acid, pentamethylbenzene yields dinitroprehnitene. The author believes that the reaction is analogous to that noticed by Jacobsen (Abstr., 1886, 694), when durene is treated with fuming sulphuric acid, but he has not been able to isolate hexamethylbenzene from the products of the reaction. Nitropentamethylbenzene, C.Me, NO2, is obtained by the slow action of bromine vapour on a mixture of pentamethylbenzene and silver nitrate at ordinary temperatures. It crystallises from alcohol in long needles. melting at 202°. L. T. T. Phenylacetylene and Diphenyldiacetylene. By A. F. HOLLEMAN (Ber., 20, 3080--3082).-Phenylacetylene is prepared by boiling monobromocinnamene with alcoholic potash. The bromocinnamene was obtained from ethylbenzene by the method of Friedel and Bahlson (Bull. Soc. Chim., 35, 55). Diphenyldiacetylene is prepared by the method of v. Baeyer and Landsberg (Ber., 15, 57); it melts at 88° (not 97°, Glaser, Annalen, 154, 151). Bromine (4 mols.) acts on diphenyldiacetylene (1 mol.) with formation of a tetrabromide melting at 173°, and a compound melting at 149-153°; analyses of the latter point to the formula C16H10Br2 C16H10Bг. N. H. M. Iodophenols. By E. NÖLTING and T. STRICKER (Ber., 20, 3018— 3023; compare this Journal, 1874, 259; Zeit. für Chem. [2], 4, 322).— Orthiodophenol remains practically colourless after two years' exposure to the air and light. When treated with nitric acid, iodine is set free, but chloriodophenol is formed if chlorine is passed through its solution in carbon bisulphide. When fused with potassium hydroxide, orthiodophenol yields catechol free from resorcinol, even at temperatures above 250°. 2 Metiodophenol is formed by the usual reactions from metiodonitrobenzene and metamidophenol; it is necessary to diazotise metiodaniline in an excess of acid, otherwise a compound is obtained which crystallises in red needles, melts at 145°, and is possibly diiodoxyazobenzene, C,H,IN2°C2H2I·OH. Metiodophenol crystallises from light petroleum in white needles melting at 39°, or sublimes in small, snowwhite needles melting at 40°. It is readily soluble in the usual solvents, does not liberate iodine when treated with chlorine or fuming nitric acid, even when boiled with the latter, and on fusion with potassium hydroxide yields resorcinol free from catechol. Pariodophenol is readily obtained from paramidophenol. It forms long needles, melts at 93-94°, yields iodine when treated with nitric acid, but not with chlorine, and on fusion with potassium hydroxide at higher temperatures, yields resorcinol instead of quinol. To explain the formation in fusions with potash or soda of resorcinol from ortho- and para-derivatives, and of catechol from meta-derivatives without assuming the occurrence of intramolecular change, Nölting, recalling the fact that fused alkalis sometimes act as oxidising, and sometimes as reducing agents, suggests that both these actions occur during fasion; 1: 3 bromophenol, for example, being first oxidised to 1 2 3 dihydroxybromobenzene, which is then reduced to catechol. W. P. W. :: Solid Orthiodophenol from Iodine and Sodium Phenoxide. By C. SCHALL (Ber., 20, 3362-3364).-When the orthiodophenol obtained by the action of iodine on sodium phenoxide (Abstr., 1883, 1109) is kept for some months, crystals separate, melting at 42-43°. These dissolve sparingly in hot water, and separate as an oil which crystallises when a crystal is added. It then melts at 39-40°. An iodine determination and the vapour-density show that the substance is pure orthiodophenol. The crystals are at first lustrous and transparent, but become slightly red when exposed to air; they are doubly refractive, and are probably monoclinic (compare Neumann, Annalen, 241, 67). N. H. M. Occurrence of Catechol in Raw Beet-sugar. By E. O. v. LIPPMANN (Ber., 20, 3298-3301).—The author has examined a sample of raw beet-sugar which showed a strong reducing action on Fehling's solution, but from its mode of manufacture could not contain invertsugar. An ethereal extract yielded small quantities of catechol and of an acid, C,H10O, which showed most of the properties of catechol, and yielded that substance when heated. The author cannot tell whether these substances were derived from the beetroot, or were formed by the decomposition of part of the carbohydrates during the process of manufacture. Catechol reduces Fehling's solution, but not Soldaini's solution, and the author therefore advises the use of the latter in preference to Fehling's solution in sugar testing. L. T. T. Hydroxyquinones. By R. NIETZKI and F. KEHRMANN (Ber., 20, 3150-3153).—The authors try to prove experimentally that the formula of tetrahydroxyquinone is, C.(OH),O2 [0:01:4], and that of rhodizonic acid, Ce(OH),O, [OH: OH = 3:6]. By mixing an aqueous solution of tetrahydroxyquinone with a salt of orthotoluylenediamine, and adding sodium acetate, a green, crystalline substance is precipitated. This dissolves in alkalis and dilute mineral acids; when dried at increased temperatures, it turns brown, and is ultimately converted into the azine of rhodizonic acid; when oxidised it yields diquinoylazine, CON2C7H ̧. From its marked basic properties, it was thought that only one nitrogen-atom had entered into reaction, and that its formula was C.(OH),O:NC,H,NH2, analysis showed, however, that its true composition was C3H10N2O4, and two formulæ, N C.(OH).<>C,H. [N: N = 1:2], or C,O(OH),<N NH>CH. [N: NH: 0=1: 2: 4], are suggested. Now if tetrahydroxyquinone is an orthoquinone, it would react with diamines even when the hydrogen of the hydroxyl-group is displaced; but with tetrabenzoyltetrahydroxyquinone no reaction takes place. By heating tetrahydroxyquinone with acetic chloride, a yellow, crystalline diacetyl-derivative, CO2(OAc)2(OH)2, is obtained; it melts at 205°, is soluble in alcohol and ether, but less readily in water; it acts like a bibasic acid, and with orthotoluylenediamine yields a compound very similar to that obtained from tetrahydroxybenzene; it is moreover, in its whole behaviour, very similar to chloranilic acid, and has therefore the constitution [(OH)2 : (OAc), = 2:5:36]. From these results, it follows that tetrahydroxyquinone is a paraquinone, and that the second of the above formulæ shows the constitution of the compound formed with orthotoluylenediamine. F. S. K. Dinitrosocresorcinol. By S. v. KOSTANECKI (Ber., 20, 3133— 3137). As paraquinon-oximes are obtained by acting on monhydric phenol-derivatives with nitrous acid, it is usually accepted that when more than one isonitroso-group enters into a polyhydric phenol, each takes up the para-position with respect to a hydroxyl-group. The symmetrical formula C,H2O2(NOH), [O2 : (NOH), = 1:3: 5: 6] has therefore been given to dinitrosoresorcinol, and its correctness is the subject of this research. Resorcinol and orcinol give dinitroso-compounds when treated with only one molecule of nitrous acid, but from betorcinol CH2Me(OH), [Me, (OH), 1: 4:3: 5] a mono-derivative only is obtained even with an excess of nitrous acid, and this abnormal behaviour can only be explained by the supposition that the methyl : = |
