was mixed with a long layer of lead chromate, with the following results: 0.2194 gave 0.3238 CO, and 0.0515 H2O. C-40-23; H=2·63. 0.3452 17.2 c.c. nitrogen at 13° and 756 mm. N = 5.86. = 0.516 liberated I=437 c.c. N/10 iodine. Cl, as :NCI, 14.88. CH,NOCI, requires C-40-26; H=2·54; N=5·88; Cl = 44·65; Cl, as NCI, 15.02 3 =33 per cent. Two determinations of the molecular weight by Raoult's method were made, using 10 grams of benzene as solvent. 0.2010 lowered the freezing point 0:42°. 0.6442 M. wt. 234.5. 1.295°. M. wt. = 243.7. CH,NOCI, requires a molecular weight of 238·45. The behaviour of Witts's oil is identical in every respect with that of our crystalline 2: 4-dichlorophenyl acetyl nitrogen chloride. When prepared by his method, it frequently solidifies with the greatest difficulty, owing to the presence of impurity, probably parachlorophenyl acetyl nitrogen chloride, which can only be removed by the treatment described above. Phenyl Benzoyl Nitrogen Chloride, CH, NCI CO CH ̧. This substance is prepared by the general method from benzanilide and bleaching powder in the presence of potassium bicarbonate, but the reaction takes place less readily than with the formyl and acetyl compounds. It crystallises in colourless plates from a mixture of chloroform and light petroleum, and melts at 77°. 0.2014 gave 0.1228 AgCl. Cl=15.08. C13H10NOCI requires Cl 15.33 per cent. On heating the melted chloride to 120-130°, benzoyl chloride is given off, whilst a portion is converted into parachlorobenzanilide. The latter change is brought about quantitatively if the nitrogen chloride is heated under water for some time. Parachlorophenyl Benzoyl Nitrogen Chloride. We have not succeeded in obtaining this substance pure, as parachlorobenzanilide is not attacked at the ordinary temperature by hypochlorous acid. At 70-80°, either in the presence of potassium bicarbonate or acetic acid, a reaction takes place, but at this temperature the chloride becomes partly converted into 2:4-dichlorobenzanilide, which in turn forms, with the hypochlorous acid, 2: 4-dichloro VOL. LXXV. 4 B phenyl benzoyl nitrogen chloride. On extracting the product with chloroform, an oil is obtained which solidifies only with great difficulty. Analysis of the recrystallised product showed that it consisted of about 30 per cent. of parachlorophenyl benzoyl nitrogen chloride, together with 70 per cent. of 2:4-dichlorophenyl benzoyl nitrogen chloride. 2: 4-Dichlorophenyl Benzoyl Nitrogen Chloride, CH,Cl2 NCI-CO-CH5. This compound, like the corresponding formyl and acetyl derivatives, can either be obtained directly from benzanilide or from 2 : 4-dichlorobenzanilide, by the action of bleaching powder in the presence of acetic acid at a temperature of from 80-90°. It resembles other members of the group in appearance and properties, and melts at 86°. On heating at 150-200°, benzoyl chloride is evolved and a tarry mass is left from which 2: 4-dichlorobenzanilide can be isolated. 0.2096 gave 0.2992 AgCl. Cl = 35.3. C13H,NOCI, requires Cl = 35.44 per cent. We have obtained similar compounds from many other substituted anilides, from secondary amines, and from other substances in which hydrogen is attached to nitrogen, and we desire to reserve the investigation of these compounds. We have also obtained substituted nitrogen bromides resembling the nitrogen chlorides very closely in properties. CHEMICAL LABORATORY, ST. BARTHOLOMEW'S HOSPITAL, E. C. CV.-Synthetical Preparation of Glucosides. By HUGH RYAN, M.A., 1851 Exhibition Scholar of the Queen's By the action of alcohols and mercaptans on hexoses and pentoses in the presence of hydrochloric acid, Emil Fischer succeeded in preparing the glucosides of methylic, ethylic, propylic, isopropylic, amylic, and benzylic alcohols, of ethyleneglycol, glycerol, and ethyl, amyl, and benzyl mercaptans (Ber., 1893, 26, 2400; 1894, 27, 674, 2483, 2985). Similarly, Emil Fischer and Jennings obtained amorphous condensation products by the action of resorcinol, pyrogallol, and orcinol on different sugars. The method was found to be inapplicable for the preparation of glucosides of the monohydric phenols (Ber., 1894, 27, 1358). Phenol and its homologues can be converted into well crystallised glucosides by Michael's method (Compt. rend., 1879, 89, 355); this, however, is troublesome, and as it gives poor results, its employment hitherto has been very limited. I sought to improve the process by employing inactive pentacetylglucose, which is more easily prepared than acetochloroglucose, but could not isolate any crystalline compound from the product of its reaction with potassium phenolate. The best results were attained by a slight modification of Michael's method. The phenol (1 mol.) was dissolved in alcoholic potash (1 mol.) and to the clear solution was added acetochloroglucose (1 mol.) dissolved in absolute alcohol. The yield was satisfactory. The acetochloroglucose required was prepared by Colley's method (Ann. Chim. Phys., 1870, [iv], 21, 363), with some slight alterations which render it more easily accessible. Pure, crystallised, anhydrous glucose (18 grams), after passage through a fine sieve, was mixed with acetyl chloride (39 grams) in a well-dried Volhard tube; this was sealed off at once and shaken during 24-30 hours at the ordinary temperature. The colourless solution was dissolved in chloroform, and shaken with ice cold sodium carbonate. The chloroform solution was filtered, dried with calcium chloride, and, after evaporation in a vacuum, gave a colourless, semi-solid mass of acetochloroglucose. It may be mentioned that attempts to prepare acetochloroglucose in an open vessel protected from atmospheric moisture by a calcium chloride tube were unsuccessful. When 20 mols. of acetyl chloride were employed with 1 mol. of glucose, the principal product was the dextrorotatory pentacetylglucose previously made by Erwig and Königs by the action of acetic anhydride and zinc chloride on grape-sugar (Ber., 1889, 22, 1464). It melted at 110°, and on analysis gave the following result: 0.1389 gave 0.2490 CO2 and 0·0717 H2O. C=48·9; H=5·7. C16H22O11 requires C=49.2; H=5.6 per cent. 5 B-Naphthylglucoside, CH110.0°C10H.—A solution of acetochloroglucose (70 grams) in absolute alcohol (150 c.c.) was added to B-naphthol (28 grams) and potassium hydroxide (11 grams) dissolved in absolute alcohol, the total volume of the well-cooled mixture being about 300 c.c. After a few minutes, the solution became turbid, owing to the separation of potassium chloride. After remaining for three days at the ordinary temperature, the yellowish-brown solution, which smelt strongly of ethylic acetate, was heated to boiling for 45 minutes under a reflux condenser, cooled, and filtered. After removal of the alcohol on the water-bath, a little water was added, and the solution, on cooling, solidified. The product (46 grams), which contained some unchanged naphthol, was recrystallised from boiling water, and finally from absolute alcohol. It separated in groups of long needles melting at 184-186°, and was dried at 105° before analysis. 0.1806 gave 0.415 CO, and 0.0944 H,O. C-62-67; H=5.81. C16H1806 requires C = 62·74; H=5.88 per cent. B-Naphthylglucoside is soluble in alcohol or hot water, sparingly so in acetone, and almost insoluble in benzene, light petroleum, cold water, or ether. It is readily hydrolysed by dilute acids or emulsin, reduces Fehling's solution only after hydrolysis, and is stable towards dilute alkali, in which it is scarcely soluble. The taste is disagreeable. A similar experiment with paranitrophenol did not lead to the formation of a glucoside. In order to find whether the failure of the reaction was due to the nature or position of the nitro-group, I examined the behaviour of paracresol towards acetochloroglucose, with results which show that the position of the radicle does not explain the failure in the case of nitrophenol. Paracresylglucoside, CH1105.O.CH.CH.-Acetochloroglucose (36 grams), dissolved in absolute alcohol, was added to a solution of paracresol (11 grams) and potassium hydroxide (6 grams) in alcohol. The mixture, which became yellow, was left for 14 hours in ice water, and then at the ordinary temperature for a day. The resulting crystalline magma was diluted with absolute alcohol to 500 c.c., left for two days, and then boiled gently for 1 hours. The filtrate, when left in an evaporating dish for a few days, gave a separation of the glucoside in needles which were scarcely soluble in ether, benzene, light petroleum, or chloroform, sparingly so in acetone, and soluble in alcohol or water. It melted at 175-177°, after drying at 100°, and did not reduce Fehling's solution before, but readily after, hydrolysis, with emulsin or dilute acids. The yield of pure product amounted to 40 per cent. of the theoretical. 0.1737 gave 0.3652 CO, and 0·1045 H2O. C=57·34; H=6·74. C13H180 requires C=5777; H=6.66 per cent. 6 2 Orthocresylglucoside, CH1105 OCH CH2, was prepared from orthocresol in a similar manner. It crystallised from water in beautiful needles, melted at 163-165°, was scarcely soluble in ether but easily so in water or alcohol, and did not reduce Fehling's solution before, but readily after, hydrolysis by dilute acids or emulsin. It had an intensely bitter taste. The yield was similar in amount to that obtained from the para-derivative. The crystals were dried at 105-110° before analysis. 0.1406 gave 0.2966 CO2 and 0.0894 H2O. C=57.53; H=7.06. C13H1806 requires C=57.77; H=6.66 per cent. Carvacrylglucoside, C ̧H12OO.C ̧H2(CH3)·С ̧H2+}H2O, was prepared 11 from carvacrol in a similar manner. A yellowish, oily residue was obtained by the spontaneous evaporation of the filtrate from the potassium chloride formed in the reaction; this was evaporated with water several times on the water-bath until the odour of carvacrol disappeared, and afterwards crystallised from hot water. It separates in groups of beautiful needles, and when anhydrous softens at 118° and melts not quite sharply at 135°. The glucoside, after drying over calcium chloride, but not in a vacuum, was analysed. 0.1806 gave 0.3964 CO2 and 0·1279 H2O. C=59·8; H=7·9. 2 0.2384 lost 0.0064 H2O at 90° in a vacuum over phosphorus pentoxide. H2O=27. C16H2400+ H2O requires C=59·8; H-7·8; H20= 2.8 per cent. Carvacrylglucoside is easily soluble in alcohol or acetone but less readily so in cold water or ether, and is almost insoluble in benzene, chloroform, or light petroleum. It does not reduce Fehling's solution before, but readily after, heating with emulsin or dilute mineral acids. The behaviour of carvacrylglucoside towards dilute aqueous alkali is characteristic. Just as if it retained an unchanged phenolic hydroxyl group, it dissolves slowly, but completely, in dilute caustic soda. That its solubility is not due to decomposition of the glucoside into its components by the action of the alkali is shown by the fact that it scarcely reduces Fehling's solution even after prolonged boiling. Similar properties seem to be possessed by a galactoside obtained from B-naphthol and acetochlorogalactose, the latter substance having been prepared by the action of acetyl chloride on galactose. 11 As glucosides of the type CHO, R·OH, to which carvacrylglucoside and naphthylgalactoside apparently belong, are unknown, the investigation of these substances will be continued. Attempts to prepare glucovanillin and menthylglucoside have not been up to the present successful. Similar experiments will be made with anthranol and alizarin. It is noteworthy that all the glucosides hitherto prepared from acetochloroglucose in alkaline solution are readily hydrolysed by emulsin. My best thanks are due to Professor Emil Fischer for his advice during the course of this investigation. FIRST CHEMICAL INSTITUTE, |