procedure yielded phenylglyoxime which, after two recrystallizations from chloroform, melted at 168°alone or mixed with authentic phenylglyoxime prepared from , -dibromoacetophenone. This shows the oil to be , -dichloroacetophenone and the dimethoxy compound to be l-phenyl-l,l-dimethoxy-2,2-dichloroethane. In accord with this structure the dimethoxy compound is stable toward potassium hydroxide in methyl alcohol solution.By refluxing a solution of 1 g. of pure compound and 3 g. of potassium hydroxide in 15 cc. of absolute methyl alcohol for four hours, evaporating the solvent and extracting the potassium hydroxide from the residue with cold distilled water, 85% of the pure dimethoxy compound was recovered.Summary Phenylacetylene reacts rapidly with chlorine and absolute methyl alcohol to produce about a 70% yield of l-phenyl-l,l-dimethoxy-2,2-dichloroethane of m. p. 66°, which is evidently formed by the addition of two molecules of methyl hypochlorite to the triple bond of the unsaturated compound.
ammonia was allowed to remain in a thermostat at 30" for three days. Twenty-five cc. aliquots of this solution were refluxed for seven hours with 15 cc. of concentrated hydrochloric acid, after which the solution was codled in an ice-bath and made alkaline by the addition of solid sodium hydroxide. The alkaline solution was extracted with two 50-cc. and one 25-cc. portion of ether. The ether extracts were washed with 30 cc. of water and extracted with one 60-cc. and two 20-cc. portions of a solution of 15 cc. of concentrated hydrochloric acid in 85 cc. of water. The acid solution was boiled to expel ether. To the cooled acid solution was added 12 cc. of 10% potassium bromide solution, after which it was titrated with approximately 0.15 N standard potassium bromate solution. The end-point was determined by spotting on starch-potassium iodide paper. One cubic centimeter of 0.1 N potassium bromate is equivalent to 1.551 mg. of aniline. This method gave results reproducible to within 0.8%.The yield of amine from benzoyl p-methoxybenzhydroxamate, benzoyl p-methylbenzhydroxamate, mnitrobenzoyl p-methylbenzhydroxamate, m-nitrobenzoyl P-methoxybenzhydroxamate, benzoyl m-methylbenzhydroxamate, benzoyl m-methoxybenzhydroxamate and mfluorobenzoyl benzhydroxamate was determined by dissolving 1 to 2 g. of the potassium salt of the dihydroxamic acid in the amount of 0.1 N ammonia calculated to make a 0.026 molar solution and allowing the salt to decompose in the thermostat at 3 0 ' . The solution was then made acid with 20 cc. of concentrated hydrochloric acid and refluxed for seven hours. The solution was concentrated to about 50 cc. by distillation, cooled in an ice-bath and made alkaline by addition of solid potassium hydroxide. The alkaline solution was extracted with two 50-cc. and one 25-cc. portion of ether and the combined ether extracts washed with 30 cc. of water. The ether solution was extracted 6 t h two 25-cc. portions of 3 N hydrochloric acid. The acid solutions were combined in a weighed beaker, evaporated to dryness on a water-bath and finally dried in a desiccator over Drierite until their sveight did not change after a day in the desiccator. The yield of amine was calculated from the weight of amine hydrochloride obtained in this way. This method gave results that were reproducible to within 2%.1. The rates of decomposition of the potassium salts of a series of meta and para substituted dibenzhydroxamic acids, R-&-A-+&-R~, have been determined at 30'. A qualitative inverse relationship has been found between the ionization constants of benzoic acids corresponding to R and the rates of decomposition of dihydroxamic acid salts in which the effect of substituents in R alone was considered. A quantitative direct relationship has been found between the ionization constants of benzoic acids corresponding to R' and the rates of decomposition of dihydroxamic acid salts in which the effect of substituents in R' alone was being considered.2. These results support the hypothesis that the rate determining step in a Hofma...
Reduction of Dibenzoylethenol 2065 2-Bromodecene-l.-A mixture of 45 g. of 2-bromodecene, 400 ml. of ammonia, and 200 ml. of ether was vigorously agitated and treated with a solution of 12 g. of sodium in 200 ml. of ammonia. On working up the product two fractions were obtained: Fraction I, 16 g., b. p. 75-78°at 30 mm., 1.4215, da 0.743; Fraction II, 10 g., b. p. 138-146°at 23 mm., n2£ 1.4296. Fraction I was soluble and Fraction II insoluble in ethanol. Fraction I is undoubtedly decene-1 as indicated by the following values recently reported10 for this compound: b. p. 171-173°, da 0.7447, n2£ 1.4259. Fraction I did not give even the slightest opalescence with alkaline mercuric cyanide solution. On bromination the decene took the calculated quantity of bromine and gave 27 g. of material: b. p. 145-160°at 18 mm., da 1.324, n2¡ 1.4891. On treatment with sodamide11 in liquid ammonia the bromide gave a good yield of decyne-1.(10) Waterman, van't Spijker and von Westen, Rec. irav. chim. 48, 1097 (1929. (11) Vaughn, Vogt and Nieuwland, to be published.Fraction II was refractionated and gave 7 g. of material: b. p. 142.5°at 28 mm., n2£ 1.4308, da 0.7636, 725 26.46 dynes/cm. The material was insoluble in ethanol, water and hydrochloric acid and reacted very slowly or not at all with bromine in carbon tetrachloride. It gave no precipitate with alkaline mercuric cyanide solution.
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