Action of Phosphorus Pentachloride on Anilic Acids of Bibasic Acids. By R. ANSCHÜTZ (Ber., 21, 957).—Anilic acids (this vol., pp. 277 and 367) can be readily converted into the corresponding anils by the action of an equivalent quantity of phosphorus pentachloride on the acid suspended in chloroform. Succinanil, succinparatolil, succinorthotolil, and succin-a-naphthil, &c., were prepared by this method. Fumaranilic acid yields a product, the formula of which agrees with that of monochlorosuccinanil. F. S. K. Itaconanilic Acid. By R. ANSCHÜTZ and F. REUTER (Ber., 21, 958-959). The authors have shown that the itaconanilic acid. which they obtained (this vol., p. 277) is different from that prepared by Gottlieb (Annalen, 77) and by Michael. In this article they discuss the formula of Gottlieb's and Michael's acid, and give COOH-CH-CH, NPh F. S. K. Chloronitrobenzoic Acids. By A. CLAUS and H. KURZ (J. pr. Chem. [2], 37, 196-201).-The substances described in this paper have been prepared from the corresponding amido-compounds by Sandmeyer's reaction. CH, CO as the most probable. Parachlorometanitrobenzonitrile, NO C,H,CI-CN, dissolves readily in alcohol, ether, chloroform, and hot water, from which it crystallises in colourless needles, melting at 100-101° (uncorr.). When boiled with dilute sulphuric acid, it forms parachlormetanitrobenzoic acid, which crystallises in pale-yellow needles, melting at 178-179° (uncorr.). Parachlororthonitrobenzonitrile dissolves readily in alcohol, ether, and hot water. It forms colourless needles, melting at 98° (uncorr.). Parachlororthonitrobenzoic acid crystallises from hot water in long, colourless needles, melting at 139° (uncorr.). The sodium salt (6 mols. H2O) is very soluble in water, from which it crystallises in flat needles. The potassium, copper, barium, ammonium, calcium, and silver salts are described. Metachloroparanitrobenzonitrile crystallises from alcohol, ether, and hot water in colourless needles, melting at 87° (uncorr.). Metachloroparanitrobenzoic acid forms long, white needles, melting at 185186° (uncorr.), and is very soluble in alcohol, ether, chloroform, and hot water. The ammonium, silver, barium (2 mols. H2O), and calcium (2 mols. H2O) salts are all soluble in hot water, and crystallise in colourless needles. The ammonium salt dissociates at 100°. G. T. M. Hydroxy-ẞ-isodurylic Acid. By C. KROHN (Ber., 21, 884-886). -Hydroxy-B-isodurylic acid, OH C.H Me, COOH [Me, OH: COOH = 1:3:4:6:5], is obtained when the sodium-derivative of pseudocumenol is heated with excess of liquid carbonic anhydride at 170 to 180°. It crystallises in snow-white needles, melts at 181°, and at a slightly higher temperature decomposes into pseudocumenol and carbonic anhydride. It is readily soluble in ether, sparingly in the other organic solvents; the alcoholic solution gives a permanent blue coloration with ferric chloride. When treated with a mixture of acetic and nitric acids, it yields Auwers' nitropseudocumenol nitrate (Abstr., 1885, 380). When a solution of the acid in concentrated sulphuric acid is heated at 50-70°, carbonic anhydride in abundantly evolved, and Reuter's pseudocumenolsulphonic acid (Abstr., 1878, 413) is formed. A. J. G. Oxidation of Unsaturated Acids. By R. FITTIG (Ber., 21, 919 -921). The oxidation of the following unsaturated acids was effected by gradually adding the equivalent quantity (1 mol. to 1 mol. of the acid) of a 2 per cent. permanganate solution to a very dilute aqueous solution of the alkaline salt of the acid cooled to 0°. The yield is good, and the products can be purified with little difficulty. The a-B-unsaturated acids yield dihydroxy-acids, which do not undergo change when boiled with dilute hydrochloric acid. Cinnamic acid, for example, is converted into phenylglyceric acid together with small quantities of benzaldehyde and oxalic acid, and ethylcrotonic acid is oxidised to the dihydroxy-acid, OH CHMe CEt(OH).COOH, which crystallises well, melts at 95-96°, and is not identical with How's hexeric acid obtained in very small quantity in the decomposition of the dibromide of ethylcrotonic acid. CHPh The B--acids yield dihydroxy-acids which, when warmed with dilute hydrochloric acid, readily undergo conversion into the corresponding hydroxy-lactones. Thus, isophenylcrotonic acid forms the beautifully CH, CO、 crystalline phenylhydroxybutyrolactone, OH·CH< >0, + {H2O, which melts at 76-77°, or, when anhydrous, at 86-87°. The corresponding phenyldihydroxybutyric acid, OH CHPh•CH(OH)·CH, COOH, forms large crystals, and melts at 116°, with decomposition into the hydroxy-lactone. Isoctylenic acid, CHMe, CH2·CH.CH·CH, COOH, obtained by the distillation of isobutylparaconic acid, is in like manner converted into the liquid hydroxy-lactone, CHMe CH CH<CÒ CH, The y--acids, as, for example, cinnamenylpropionic acid and hydrosorbic acid, also yield hydroxy-lactones, which differ, however, in many respects from those obtained from the B-y-acids. The research, which has been carried on in conjunction with the author's pupils, is being continued. W. P. W. Iodophenolsulphonic Acids. By F. KEHRMANN (J. pr. Chem. [2], 37, 9-14).-When iodine (1 mol.), in the form of a mixture of potassium iodide and iodate, is added little by little to potassium paraphenolsulphonate (1 mol.) dissolved in excess of dilute hydrochloric or sulphuric acid, iodine at first separates, but is quickly reabsorbed, and after a short time the liquid crystallises to a dense mass of long, thin prisms of the formula C.H,I2O·SO2K + 2H2O. This salt begins to decompose at 270° without melting. The barium salt, (CH3L2O SO2) Ba + 3H2O, is only slightly soluble in cold water from which it crystallises in white, glistening needles. The copper salt forms pale green, monoclinic prisms. The anhydrous free acid melts at 120°, and decomposes with separation of iodine at 190°. It dissolves readily in water from which it is precipitated by hydrochloric or sulphuric acid. It probably has the constitution [HŌ : İ2: SO2H = 1:26:4]. The mother-liquor on evaporation yields a considerable quantity of unchanged potassium paraphenolsulphonate, and an amount insufficient for analysis of a substance containing iodine, and crystallising in gleaming scales. G. T. M. Iodophenolsulphonic Acids. By E. OSTERMAYER (J. pr. Chem. [2], 37, 213–216).—lf paraphenolsulphonic acid (1 mol.) is treated with iodine (1 mol.) in the way described by Kehrmann (this vol., p. 595), besides the chief product, diiodophenolsulphonic acid, a compound is produced which appears to be a moniodosulphonic acid. This acid forms thick, colourless crystals belonging to the rhombic system, and differs from the diiodosulphonic acid by its barium and calcium salts dissolving readily in water. The diiodosulphonic acid forms a zinc salt, (OH-C,H2I2SO3)2Zn + 60H2, which crystallises in long, colourless needles. The paper is mainly on the question of priority between the author and Kehrmann (loc. cit.). G. T. M. New Synthesis of Tetraphenylethylene. By J. H. ZIEGLER (Ber., 21, 779-781).-When equivalent quantities of sulphur and diphenylmethane are heated together, the former begins to dissolve at 110°, and the solution is complete at 150°; the scarcely yellow solution yields crystals of unaltered sulphur on cooling. On raising the temperature, the liquid slowly darkens at 200°, and an evolution of hydrogen sulphide begins; the reaction requires 10 hours' heating at 240-290° for completion. The residue consists mainly of tetraphenylethylene, and can be purified by treatment with ether in which unaltered diphenylmethane, &c., dissolve. The yield is about 75 per cent. of the diphenylmethane employed. A. J. G. Action of Chlorine on a- and 6-Naphthol. By P. T. CLEVE (Ber., 21, 891-896).-Dichloro-2-naphthol, C10HsCl2 OH (probably OH : C1: Cl = 1:2:4), is obtained, together with chloro-a-naphthol, by the action of chlorine on a cold solution of a-naphthol in acetic acid. It crystallises from alcohol, chloroform, and benzene in silky needles melting at 106°, and from acetic acid in prisms having the composition C10H5Cl2 OH + C2HO2; these lose the associated acetic acid completely at 40-50°. When heated at 170-180°, it loses hydrogen chloride, and is converted into a compound which probably has the composition C20HClO2, does not melt at 275°, and is insoluble in all the ordinary solvents. On oxidation with dilute nitric acid, dichloro-a-naphthol yields phthalic acid and a quinone-like compound crystallising in yellow needles, whilst chloronaphthaquinone, CH,CIO2, is formed when it is treated with chromic acid in acetic acid solution; this crystallises in lustrous, golden-yellow needles, melts at 116, is soluble in alcohol, and yields an anilide, CoH CIO, NH Ph, which forms sparingly soluble, purple-red crystals and melts at 202-203° (compare Knapp and Schultz, Abstr., 1882, 510; Claus, Ber., 18, 2929). When treated with phosphorus pentachloride, dichloro-a-naphthol is converted into a trichloronaphthalene (= 1 : 2 : 4?), which crystallises in needles and melts at 92. Chloro-a-naphthol (probably OH : Cl = 1 : 2), owing to its great solubility in the ordinary solvents, could only be crystallised from light petroleum. It could not, however, be obtained pure either by distillation or by fractional crystallisation; the impure crystals melted at about 54°. When treated in acetic acid solution with chlorine, it is converted into the dichloro-derivative, whilst phosphorus pentachloride reacts with it to form the above trichloronaphthalene. : Chloro-B-naphthol, CHCI-OH, is obtained under like conditions. from B-naphthol. It crystallises from chloroform in monoclinic forms, a b c = 19600:1: 1·9562; ß = 66° 54′; observed faces, OP, P, +Pcs, -Pcs, P, melts at 70°, and is readily soluble in alcohol, benzene, chloroform, acetic acid, and boiling light petroleum; it is also soluble in hot water from which it crystallises in talc-like scales. When heated with phosphorus pentachloride, it yields a dichloronaphthalene melting at 34° (compare Abstr., 1887, 961), and also the orthophosphate, (C10H&CIO)3PO, which crystallises from alcohol in microscopic needles, melts at 152°, is insoluble in water and only very sparingly soluble in hot alcohol. W. P. W. Investigation of the Second Van't Hoff Hypothesis. By K. AUWERS and V. MEYER (Ber., 21, 784-817).-The second hypothesis which Van't Hoff deduced from his arrangement of atoms in space is that two carbon-atoms united by a single affinity are free to rotate, the axis, of rotation being the bond of union, and that isomerism is only possible for those substances of the type =C-C=which cannot by rotation round the common axis be converted into the same form. As the existence of the two isomeric dioximes of benzil, discovered by V. Meyer and H. Goldschmidt, would, if for both the formula Ph.C(NOH):C(NOH) Ph were established, be in direct contradiction to the above hypothesis, the present paper contains a series of investigations by which the authors have sought to ascertain whether the composition of the above two compounds is identical. The preparation of the dioximes is that formerly described. By treating benzil in alcoholic solution with hydroxylamine hydrochloride, the a-dioxime is formed, and from this the B-dioxime may be easily obtained by simply heating with three times its weight of absolute alcohol at 170-190° for some hours. The a-dioxime separates from alcohol as a white, crystalline powder, melting with decomposition at 237°, insoluble in water, and nearly insoluble in acetic acid, ether, and alcohol, of which the last dissolves 0:05 part per 100 at 17°. The B-dioxime crystallises from alcohol in slender needles melting with decomposition at 206-207°, slightly soluble in water, and easily soluble in acetic acid,. ether, and alcohol, of which the last dissolves 15.26 parts per 100 at 17°. Of the two forms, the latter is the more stable into which the first is readily converted, but change in the opposite direction never takes place. Thus the a- is converted into the B-dioxime when it is heated with alcohol at 170°, or with water at 200°, also when it is treated with acetic chloride or with hydrogen chloride in acetic acid solution. Both are true derivatives of benzil, as both yield benzil and hydroxylamine hydrochloride when heated with concentrated hydrogen chloride in a sealed tube at 100°. The change takes place somewhat less readily with the B- than with the a-compound. The non-existence of true nitroso-groupings in either compound is shown by each yielding a diacetyl-derivative when treated with acetic anhydride. a-Diacetyldiphenylglyoxime melts at 147-148°, is insoluble in water, and sparingly soluble in alcohol and acetic acid. B-Diacetyldiphenylglyoxime melts at 124-125°, and is easily soluble in alcohol and acetic acid, from the hot solutions of which it crystallises in fine needles. On treatment with alkalis, both derivatives yield the oximes from which they were prepared. To further remove all doubt as to the possibility of merely physical isomerism, and to prove that the oximes are not only different from one another, but yield different derivatives, reconvertible into their respective oximes, the propionic and isobutyric derivatives were also prepared. Dipropionyldiphenylglyoxime.-The a-derivative is easily soluble in alcohol, acetic acid and ether, and crystallises in thin scales melting at 103-104°; the B-derivative is slightly soluble in alcohol and acetic acid, soluble in ether, crystallises in oblique prisms, and melts at 121°. Diisobutyryldiphenylglyoxime.-The a-derivative is easily soluble in alcohol, ether, and acetic acid, and crystallises in flat needles melting at 121-122°; the B-derivative is very soluble in alcohol, ether, and acetic acid, crystallises in quadratic prisms melting at 88-89°, below which temperature the substance begins to sublime. The two oximes were oxidised by means of potassium ferricyanide, and both were found to give the same oxidation-product-that described by Koreff (Abstr., 1886, 363). By reduction of this product with hydriodic acid, pure dibenzyl is obtained, thus proving the presence of the Ph C C Ph-group in the original compounds and the oxidationproduct, and confirming Koreff's view of the constitution of the latter. Hence it is a polymeride and not, as Gabriel (Abstr., 1886, 693) assumed, an isomeride of phenyl cyanate, which it furnishes on strongly heating. An attempt by reduction to again obtain either CPh.N. of the oximes failed, but a dioxime-anhydride, <CPh:N>0, melting at 94° was obtained. In order to ascertain whether there was any tendency towards the formation of the group <C>NOH, attempts were made to prepare compounds containing this group from stilbene bromide by treatment with hydroxylamine and nitrous acid. These, however, failed to yield any product of an oxime character, as also did the treatment with amyl /O C.Ph, nitrite and sodium alcoholate. Isobenzil, Ph.C 0/ when heated with hydroxylamine hydrochloride and absolute alcohol at 140 --150°, did appear to yield the B-dioxime, but under the conditions of the experiment it must be assumed that the isobenzil is converted into benzil, and that the latter yields the dioxime. |