Müller that in the above method benzamide is formed if the process is conducted quickly, but phenyl nitrile if slowly. In the course of the preparation of cumonitrile, a small quantity of cuminamide is obtained from the crude product of the reaction, if the aqueous solution, previously rendered alkaline by ammonia, is agitated with benzene. This amide crystallises in glittering lamina melting at 153.5°, insoluble in cold, sparingly soluble in hot water, soluble in alcohol. It is not decomposed by boiling with hydrochloric acid or potash of moderate concentration. With mercuric oxide, it yields a derivative, (C,H,PrCONH),Hg + 14H2O; this crystallises in needles melting at 190", insoluble in water, soluble in alcohol. V. H. V. Action of Alkyl Iodides on Dibenzylthiocarbamide. By C. REIMARUS (Ber., 19, 2348-2349).-Will has shown (Abstr., 1882, 723) that alkyl iodides react with diphenyl- and dibenzyl-thiocarbamide, with formation of hydriodides of bases in which the alkylgroup is directly combined with sulphur. The author has found that the isomeric dibenzylthiocarbamide behaves analogously. Benzylimidobenzylcarbaminethiomethyl, SMe C(NHC,H,): NC,H7, is formed when methyl iodide and dibenzylthiocarbamide are heated for 2-3 hours at 100°. The product is dissolved in water, treated with sodium carbonate, and extracted with ether. The sulphate of the base crystallises in lustrous needles readily soluble in water and alcohol; it melts at 145°. The hydrochloride forms large rhombic plates melting at 125°; the hydriodide crystallises in splendid octahedra melting at 99°, readily soluble in hot water. Benzylimidobenzylcarbaminethioethyl, SEt-C(NHC,H,): NC,H,, crystallises in wide prisms, apparently monoclinic, which melt at 93°; it dissolves readily in alcohol, sparingly in water. The sulphate forms large rhombic plates readily soluble in water and alcohol; the platinochloride crystallises in needles. Corresponding compounds were also prepared from propyl iodide and amyl iodide. N. H. M. Phenylseleniocarbimide and Diphenylseleniocarbamide. By H. STOLTE (Ber., 19, 2350-2352).-Phenylseleniocarbimide, CSe NPh, is prepared by passing hydrogen selenide into aqueous soda, evaporating, and adding isocyanophenyl chloride diluted with ether to prevent the reaction becoming too violent. After a day, the product is filtered, the ether evaporated, and the residue steam-distilled and dried in a vacuum over sulphuric acid. It is a yellowish-red oil, insoluble in water, readily soluble in alcohol and ether, and has only a slight odour. When the ethereal solution of the substance is treated with ammonia, it is converted into monophenylseleniocarbamide (Abstr., 1886, 781). Diphenylseleniocarbamide, CSe(NHPh)2, is prepared from phenylseleniocarbimide by treating its ethereal solution with aniline. The product is washed with ether, and crystallised from alcohol. It melts at 186° with decomposition. N. H. M. Substituted Nitrogen Chlorides. By G. BENDER (Ber., 19, ΝΗ 2272—2274).—When the compound C.H.<-O- >CO (this vol., p. 38) is treated with bleaching powder and hydrochloric acid the compound C,H,NO,Cl2 separates in colourless needles. When the latter is brought into contact with quinol, an odour of quinone is given off, and on cooling crystals of quinhydrone separate. The compound is decomposed by alcohol, alkalis, aniline, &c., into the NH compound C,H,Cl<^ >CO (loc. cit.). ·0 Acetanilide, when treated with bleaching powder in presence of acetic acid, yields the compound NPLCI COMe. The latter has the properties of the compound described above. It melts at 91°; when heated to 172°, it becomes yellow, effervesces violently and is converted into its isomeride, parachloracetanilide, melting at 172°. The same change takes place when the substance is treated with cold hydrochloric acid or when warmed with absolute alcohol; if more than 2 grams be employed, a violent explosion takes place. The compound reacts with paranitraniline, yielding acetanilide and orthochloroparanitraniline. .CH, CO The compound >NCI was prepared from succinimide: it crystallises from benzene in large colourless crystals melting at 148°. Benzamide yielded the compound COPh NHCl. This crystallises from water in long prisms melting at 116°. N. H. M. Condensation of Nitrobenzaldehyde with Hydrocarbons. By O. TSCHACHER (Ber., 19, 2463-2464).-Baeyer has shown that fatty aldehydes, in the presence of concentrated sulphuric acid, form condensation products with aromatic hydrocarbons, whilst aromatic aldehydes do not. The author finds that the introduction of a nitrogroup into the phenyl-ring gives to aromatic aldehydes the power of forming such condensation products. With benzene, metanitrobenzaldehyde yields metanitrotriphenylmethane, forming crystals melting at 90°. With toluene, metanitrophenylditolylmethane is formed. L. T. T. Compound of Pyruvic Acid with Hippuric Acid. By A. HOFFMANN (Ber., 19, 2554-2557).-6 grams of pyruvic acid were digested with 11 grams of sodium hippurate and 25 grams of acetic anhydride on a water-bath. In a short time, a vigorous reaction takes place and the temperature of the mixture rises to 108°. The product is dissolved in alcohol, the solution diluted with water, evaporated, and the brownish crystals recrystallised from petroleum. Analyses of the compound point to the formula C12H,NO,; the substance is therefore formed by the union of its two constituents (equal mols.) with elimination of the elements of water (2 mols.). It forms colourless, flat needles melting at 157°; it is very readily soluble in alcohol, ether, and acetic acid; insoluble in water. It yields salts corresponding with a bibasic acid, C12HNOs. The barium salt, C12H,ÑO,Br+ 2H2O, was prepared; when treated with acid, it yields the anhydride, C12H,NO, the acid not being capable of existing in the free state. When the anhydride is heated with hydrochloric acid at 140°, benzoic acid is formed. N. H. M. Phenyliodohydracrylic Acid. By E. ERLENMEYER and J. ROSENHEK (Ber., 19, 2464-2465).—Phenyliodohydracrylic (a-iodoB-phenylhydroxypropionic) acid, OH-CHPh-CHI-COOH, was obtained by the action of iodine chloride on cinnamic acid. A chloriodophenylpropionic acid is probably first formed, which is then converted into the hydroxy-acid by the action of water. The acid forms large crystals which melt with decomposition at 137-139°, and are soluble in benzene. When treated with hydrochloric acid, this acid yields a compound CiH16CUO, which the author believes to have the formula CHPh: CH-C(OH)<o>C(OH).CHI CHC1Ph. L. T. T. Creosolcarboxylic Acid. By H. WENDE (Ber., 19, 2324-2327). -Creosolcarboxylic acid, OH C,H,Me (OMe)·COOH [= 4:1:3: 5], is prepared by gradually adding 4 grams of sodium to 50 grams of creosol through which a current of dry carbonic anhydride is being passed. The reaction takes place slowly with evolution of hydrogen and slight development of heat, and is assisted by gently warming; much heat is then developed, and the reaction becomes rather violent. The product, when cold, is treated with dilute hydrochloric acid, extracted with ether, and the ethereal solution extracted with sodinm carbonate solution. It crystallises in needles melting at 180-182°, dissolves sparingly in water, readily in alcohol, ether, and chloroform, and is almost insoluble in benzene and light petroleum. It sublimes unchanged when carefully heated, and acquires a deep blue colour when treated with ferric chloride. The ammonium salt crystallises in globular groups of needles; the potassium salt forms small, readily soluble needles; the barium salt is sparingly soluble; the copper salt is a yellow powder; it is very electric when dry. The methyl salt forms small, rhombic crystals, a b c = 0·5285: 1: 0·7334; it melts at 92°, and gives a bluish-green coloration with ferric chloride. The ethyl salt crystallises in small needles or prisms melting at 77°. : : N. H. M. Derivatives of Opianic Acid. By C. LIEBERMANN (Ber., 19, 2275-2287; compare Abstr., 1886, 550).-AmidohemipinphenylC:N --NPh hydrazide (azopianphenylhydrazide), NH | `CH(OMe), CO , is prepared by the action of phenylhydrazine on azopianic acid. It separates from its solution in benzene in small, honey-coloured, tetragonal crystals, having a glassy lustre, ac 1: 0-5947. It melts at 222°, and dissolves in strong sulphuric acid and in fuming hydrochloric acid. = CONPh Amido-opianphenylhydrazide, NH, CH(OMe):<.CH:N>, is obtained by reducing the nitro-compound (loc. cit.) with tin and fuming hydrochloric acid, care being taken to prevent the reaction from becoming too violent from the heat developed. On adding water to its alcoholic solution, it crystallises in slender needles melting at 137 -143°. Normethylnitro-opianphenylhydrazide, .CONPh is formed when nitro-opianphenylhydrazide is boiled with alcoholic potash, and the potassium salt thus obtained treated with hydrochloric acid. It crystallises in yellow, glittering, rhombic plates melting at 1910. The potassium salt is a carmine-red powder. Opianoxime anhydride (hemipinimide), CH,NO, is prepared by boiling opianic acid (1 mol.) dissolved in nine times its weight of 80 per cent. alcohol with hydroxylamine hydrochloride (1 mol.) for two to three hours. It crystallises from alcohol in long, very slender, needles melting at 228-230°. An aqueous or alcoholic solution containing only a trace of the substance has a fine blue fluorescence. It sublimes unchanged, and can be heated with strong sulphuric acid without decomposition. Cold aqueous alkali dissolves it, forming a yellow solution which soon becomes colourless. When heated with alkali, it yields hemipinic acid and ammonia. The compound was also prepared by heating ammonium hemipinate. The potassium salt, CHONK, is a white compound almost insoluble in cold absolute alcohol. The silver salt was also prepared. Hemipinethylimide, CHO, NEt, is obtained by heating potassium hemipinimide with ethyl iodide at 150°. It crystallises from boiling water in colourless needles resembling hemipinimide; the solution shows the same fluorescence. It dissolves very readily in alcohol, acetone, and benzene, and melts at 96-98°. The formation of hemipinimide is interesting on account of its complete analogy with observations lately made in the phthalic acid series. The author assigns to the compounds phthalimide and hemipinimide the respective constitutional formula CO<H>C: NH and CO<C2H2(OMe)2>C:NH. Anilido-opianic acid, CHINO, is obtained by boiling a solution of equal weights of opianic acid and aniline, dissolved in glacial acetic acid, for 10 minutes. On cooling, the whole solidifies to a white mass, which is washed with water, dissolved in benzene, and precipitated with ether. It melts at 186-187°. It dissolves only in strong alkali solution. Anilidonitropianic acid, C16H1N2O6, is prepared from nitropianic acid in a manner similar to the above compound. It crystallises in needles melting at 183-184°. When treated with alkali, it yields a sparingly soluble potassium salt. Nitrohemipinic acid, NO CH(OMe)2(COOH)2, is very readily prepared by boiling nitropianic acid with fuming nitric acid (4 parts) for one hour. It melts at 166° (not 155°), but has all the other properties ascribed to it by Prinz (Abstr., 1882, 402). When heated above its melting point, it gives up water and yields a yellowish compound, probably the anhydride. Opianic anhydride, [CHO.C.H.(OMe)2 CO]2O, is formed when opianic acid is heated at 160° in a current of dry air. It crystallises well from acetone and melts at 234°. It is identical with the compound described by Wegscheider (Abstr., 1883, 996) as triopiamide, CHO. When boiled with alkali, it is gradually transformed into opianic acid. Strong nitric acid converts it into nitropianic acid. N. H. M. Opianic Acid Derivatives. By C. LIEBERMANN and S. KLEEMANN (Ber., 19, 2287-2299).—Acetylopianic acid, is prepared by heating opianic acid and dry sodium acetate with acetic anhydride. The excess of acetic anhydride is then removed by contact with cold water for 24 hours, and the remaining compound crystallised from boiling water. It melts at 120-121°. It is insolable in cold aqueous alkali, and when boiled with it, is decomposed into opianic and acetic acids. .CO. 0. Acetylnitropianic acid, CH(NO2) (OMe), >CHOAc, is prepared in a manner similar to acetylopianic acid. It is a yellow substance insoluble in cold sodium carbonate solution. Propionylopianic acid, CHO, crystallises in needles melting at 111°. Anhydracetamidohemipinic acid, C10H-ACNOs, and the propionylcompound, CH ̧(С2H ̧Ó)NO, melt at 164° and 139° respectively; they are very unstable. Meconine-acetic acid, <C,H2(OMe), >CH.CH, COOH, is obtained by heating opianic acid (3 parts), malonic acid (14 part), glacial acetic acid (2 parts), and sodium acetate (1 part) for five hours at 100°; the colourless, crystalline product is crystallised from water. It forms lustrous needles melting at 167°; it has an acid reaction and dissolves in ammonia. The silver, calcium, &c., salts were prepared. The ethyl salt crystallises in plates soluble in alcohol, ether, and hot water; it melts at 82.5°. The reactions of the acid are analogous to those of phthalylacetic acid. When boiled with baryta, and the excess of baryta afterwards removed by means of carbonic anhydride, barium opianylacetate is obtained; it forms lustrous prisms. The free acid is not capable of existence. When the silver salt is treated with methyl iodide, it yields, not methyl opianylacetate, but methyl meconine-acetate; the latter crystallises in lustrous plates melting at 124°. CO >CH-CH-COOH, is pre Normeconine-acetic acid, C.H2(OH)2 pared by heating meconine-acetic acid with hydriodic acid and phosphorus; the product is diluted with water and filtered. It crystallises from water in long plates melting at 228°. The calcium and barium salts form white crystalline precipitates. When the acid is • The formula and analysis given in the original dʊ not agree. |