specimen, free from water of crystallisation, was prepared by recrystallising from alcohol, and gave the following result: a= -2°30', l = 1 dem., c=2-240, [a = -111·5o. The sulphate was prepared by treating the hydrochloride with a solution of silver sulphate and evaporating the filtrate very nearly to dryness. It is excessively soluble in water, but insoluble in alcohol, and could not therefore be recrystallised. For this reason, its properties were not accurately determined, but it differs very markedly from the neutral sulphate of morphine. Isomorphine was originally prepared by treating a concentrated solution of the hydrobromide with aqueous ammonia in the presence of ether; the freshly precipitated base is dissolved by the ether, from which, however, it rapidly separates again in a beautiful, crystalline form. Only a portion of the base could be obtained in this way, even after 15 or 20 extractions with ether. The rest remained in the alkaline liquid, and on evaporating the latter to dryness in a vacuum, a mixture of the hydrobromide with ammonium bromide was obtained. The base is best obtained, however, by decomposing the hydrochloride by sodium methoxide in methyl alcohol. Sodium chloride is precipitated, and after filtration the nearly pure base is obtained from the mother liquor. Isomorphine is free from any bitter taste. It dissolves in large quantities of ethyl alcohol, is readily soluble in methyl alcohol, but not very readily so in most other organic reagents, and can best be recrystallised from a mixture of methyl alcohol and ethyl acetate, from which it separates in the form of small, white, glistening needles melting at 246-248°. It is also soluble in, and can be recrystallised from, hot water. 0.1638 gave 0.4320 CO, and 0-1004 H2O. C=71.92; H=6.81. 0.2690 11.8 c.c. moist nitrogen at 24° and 757 mm. N = 4.90. C17H19ON requires C=716; H=6·66; N=4.91 per cent. A determination of the specific rotation was made with a solution of the base in methyl alcohol, and gave the following result: Morphine is similar to isomorphine in many respects, and melts at 254°. A specimen, recrystallised from methyl alcohol, from which it separates in beautiful groups of radiating crystals, gave the following * It does not seem to be generally known that morphine can be readily recrystallised from various solvents, especially methyl alcohol, in which it is quite readily soluble. numbers when its specific rotation in methyl alcoholic solution was determined. - 3°0′, 71 dcm., c = 2.292, [a] = −130.9. The colour reactions of isomorphine are similar to those of morphine. Isomorphine Methiodide.-4.2 grams of isomorphine and 5 grams of methyl iodide were dissolved in 150 c.c. of methyl alcohol and the mixture boiled on a water-bath. After about 20 minutes, the methiodide commenced to separate. The boiling was continued for 1 hour, at the end of which time the crystals of the methiodide were filtered off. A further small quantity was obtained from the mother liquors. After drying at 80°, the substance was found to melt with some decomposition at 276°. It is soluble in hot water, from which it separates on cooling in the form of white, glistening needles. It dissolves readily in 25 per cent, caustic soda solution. 0.3980 required 9.35 c.c. N/10 AgNO, solution. I=30-0. C17H19ON,CH,I requires I=30.6 per cent. A determination of the specific rotation in water gave the following results: Morphine methiodide melts at nearly the same temperature as the isomorphine derivative. A determination of its specific rotation in water gave the following result: = ap -0°51′, l = 1 dem., c=1·162, [a] = -72·9°. Action of Acetic Anhydride on Isomorphine Methiodide.-Four grams of isomorphine methiodide were suspended in 40 grams of acetic anhydride, to this was added gram fused sodium acetate, and the whole boiled on a sand-bath until solution was effected, when 1.6 grams of silver acetate (1 mol.) were introduced. Immediate precipitation of silver iodide occurred, and the mixture was boiled in an oil-bath for 6 hours. Silver iodide was then filtered off, and the filtrate heated in a sealed tube for 3 hours at 180°. The acetic anhydride was then distilled off at 170° in an oil-bath, and the concentrated, light brown solution poured into twice its volume of water. A small quantity of a brown oil separated, which quickly solidified, and was collected, powdered, and dried. The crude substance only amounted to 0.3 gram. This was dissolved in glacial acetic acid, the solution boiled with animal charcoal, and filtered. On cooling, the filtrate deposited small, glistening needles, which were collected and found to melt at 154-155°. They were then recrystallised from a large quantity of dry ether, from which they separated in small, white needles melting at 158-158.5°. O. Fischer and Vongerichten obtained an acetyl di hydroxyphenanthrene from morphine methiodide which melted at 159° (Ber., 1886, 19, 792). The filtrate from the solid product, which contains the main product of the action of acetic anhydride and silver acetate on morphine methiodide, when made alkaline, deposits a base which has not yet been investigated. Further reactions of Isomorphine Methiodide.-2.1 grams of isomorphine methiodide were dissolved in hot water, and to this an aqueous solution of 0.78 gram of silver sulphate was added. The precipitated silver iodide was filtered off, and to the filtrate an aqueous solution of 0.8 gram of crystallised barium hydroxide was added, and the whole boiled. Carbon dioxide was passed through for a short time to precipitate the very slight excess of baryta. After filtration from the precipitated barium sulphate, the strongly alkaline solution was evaporated to a syrup, which, when placed in a vacuum, deposited a mass of fernlike crystals. On further evaporation in a vacuum, the crystals dissolved, and a syrup was obtained which, on standing overnight, became a hard, solid mass. This, when powdered and dissolved in methyl alcohol, gave a strongly alkaline solution. Excess of methyl iodide was added, and the mixture allowed to stand for 2 days. At the end of this time, it was still strongly alkaline, and did not become neutral until boiled on a water-bath for 1 hour. The methyl alcohol, with excess of methyl iodide, was evaporated off, leaving a syrup which was dissolved in water, and the solution boiled with animal charcoal, filtered, evaporated on a water-bath to a syrup, and placed in a vacuum over sulphuric acid. The resulting varnish gradually became quite hard, and could be powdered; it was deliquescent, and almost insoluble in ethyl alcohol, but readily soluble in methyl alcohol or cold water. It did not agree in any of its properties with codeine methiodide. 0.3908 required 8.7 c.c. N/10 AgNO。. I=28·2. C17H18(OCH3)O2N,CH,I requires I= 28.8 per cent. A determination of the specific rotation in water gave the following result : = - 96.4°. a = −2°0′, l = 1 dcm., c = 2·074, [ [ a ]35 Preliminary experiments have been made for the preparation of the acetyl compound, and the results will be communicated in a later paper. Addendum. Since the communication of the above paper to the Society, Pschorr and Sumuleanu have published their synthesis of morphol (Ber., 1900, 33, 1810), and confirmed the formula assigned to this substance by Vongerichten. THE WELLCOME CHEMICAL RESEARCH LABORATORIES. XCII.-The Oxime of Mesoxamide and some Allied Compounds. By MARTHA ANNIE WHITELEY, B.Sc. By the action of nitrosyl chloride on malonamide a substance is obtained which is characterised by the intense violet coloration it gives when mixed with ferrous sulphate and an alkali (Tilden and Forster, Trans., 1895, 67, 490). This substance can be prepared by the action of liquid nitrosyl chloride on malonamide in sealed tubes at the ordinary temperature. After several days there is evidence of considerable pressure, for, on opening the tubes, hydrogen chloride escapes together with unchanged nitrosyl chloride. It was more conveniently prepared, however, by passing a current of gaseous nitrosyl chloride through chloroform in which malonamide was suspended. The gas was rapidly absorbed, but the amide was attacked very slowly at the ordinary temperature, and it was necessary to warm the liquid from time to time to about 45-50°; a brisk evolution of gas then occurred, and the liquid became colourless. The white, crystalline powder was filtered off, washed with chloroform, and spread on a clock glass to dry; it continued to evolve hydrogen chloride for some time. The crude product thus obtained was readily soluble in water, and the concentrated solution decomposed with evolution of carbon dioxide when evaporated on a steam-bath. The aqueous solution was therefore allowed to evaporate in a vacuum over sulphuric acid, and the dry residue extracted repeatedly with boiling ethyl acetate. A small quantity of insoluble matter was left, which was found to be ammonium chloride. From the ethyl acetate solution, a white, crystalline powder was deposited, which gave very strongly the characteristic colour reaction with ferrous sulphate. After recrystallisation from ethyl acetate, the substance melted with decomposition at 187. It is readily soluble in water or alcohol, forming acid solutions from which, by spontaneous evaporation, it crystallises in small, clear prisms. It is also soluble in boiling acetone, ethyl acetate, or acetic acid, crystallising from the last in well-developed prisms containing acetic acid, which is given up on exposure to the air, the crystals efflorescing. It is insoluble in benzene, ether, or light petroleum. The aqueous solution assumes a bright yellow colour on the addition of ammonia, soda, or potash. The substance contains no chlorine. After boiling with hydrochloric acid, 'it reduces Fehling's solution. It does not respond to Liebermann's test. On analysis: 0.0919 gave 26 c.c. moist nitrogen at 20.5° and 766.7 mm. 0.0766 5 3 3 In a molecular weight determination : N = 32.58. N = 32.45. 0.0981 in 23.93 acetic acid gave a depression 0·135°. Mol. wt. = 118·4. 0.1351 in 23.93 0.187°. Mol. wt. = 117·7. The molecular weight of C,H,ON is 131. 5 3 The substance is therefore an oxime having the formula (CO-NH2)2C:N OH. 2/2 3 Acetyl Derivative, (CO·NH2)2C:N•O•CO⚫CH,.—The oxime dissolved in acetic anhydride on warming, and from the solution bright, well-formed, prismatic crystals separated; these were filtered off, washed with. acetic anhydride, and dried in a desiccator. The acetyl derivative melts, with decomposition, at 190°, and dissolves sparingly in cold, but readily in hot water, doubtless suffering hydrolysis, as the solution is coloured yellow by an alkali, and gives the characteristic violet coloration on the addition of ferrous sulphate. On analysis: 0.1473 gave 30.5 c.c. moist nitrogen at 17° and 767-65 mm. N=24.28. CH2ON, requires N = 24.28 per cent. Salts.-The acid character of the oxime is strongly marked. One hydrogen atom is readily replaced by metals, giving rise to salts which, with one or two exceptions, are of a bright yellow colour. The alkali salts are readily soluble in water, and are precipitated in the form of silky, yellow needles on the addition of alcohol to the solutions. The silver, lead, barium, and calcium salts are less soluble, and separate in a crystalline form from concentrated solutions. The silver salt, (CO.NH2)2C:N OAg, was analysed, with the following result : 0.1650, on ignition, gave 0.0744 Ag. Ag=45·09. CHON ̧Ag requires Ag = 45 34 per cent. The potassium salt, (CO-NH2),C:N.OK, was prepared by adding excess of potash to the concentrated aqueous solution of the oxime, and precipitating the salt by the addition of alcohol, filtering, and washing with alcohol until free from alkali. 0:5652 gave 0.2905 K2SO4. K = 23.08. 2 Ferrous Potassium Salt, (CO·NH2)2°C:N•OK,[(CO•NH2)1⁄2C:N•O]1⁄2Fe. -The capacity of forming coloured salts is certainly the most striking property of the oxime. The characteristic violet coloration with VOL. LXXVII. 4 B |