β-Chlorovinyl ketones are known to be very reactive toward nucleophilic substilutione In the present study, β-chlorovinyl sulfones were synthesized and their reactions investigated. Thus, condensation of arylsulfonyl chloride with vinyl chloride followed by dehydrochlorination with the aid of triethylamine gave the following; β-chlorovinyl-p-tolyl sulfone (3a) (mp 4347°C), β-chlorovinyl-2, 4-dimethylphenyl sulfone (3b) (bp 135142°C/0.12 mmHg), β-chlorovinyl-2, 5-dimethylphenyl sulfone (3c) (mp 99.5102.5°C), and 4, 4'-bis- (β-chlorovinylsulfonyl) -phenoxybenzene (3d) (mp 127132°C). All those β-chlorovinyl sulfones were trans-isomers. The reactions of (3a) with Bisphenol-A or cyclohexylamine, (3b) with methanol, and (3d) with diethylamine were studied. (3d) was also condensed with hexamethylenediamine, ethylenediamine, and Bisphenol-A to obtain polymers with intrinsic viscosities of 0.20 dl.g-1 (dimethylformamide, 30°C), 0.16 dl.g-1 (dimethylformamide, 30°C), and 0.09 dl.g-1 (dioxan, 30°C), respectively.
Catalytic effects of several metal oxides of periodic groups V and VI on the hydroperoxide-epoxidation of olefins have been studied. It has been shown that molybdenum (VI) oxide is most selective for the epoxidation of octenes when cumene hydroperoxide or tert-butyl hydroperoxide is used. Tungsten (VI), on the other hand, showed only a poor selectivity, and the oxides of vanadium, niobium, selenium, and chromium, etc. were almost without effect. Results of the kinetic studies on the MoO3-catalyzed epoxidation of 1-octene and cyclohexene with hydroperoxides indicated that the reaction rate was proportional to the concentrations of olefin and of hydroperoxide. The effect of the amount of the catalyst was rather complex. It was suggested that the epoxidation proceeds via preliminary formation of complexes between the hydroperoxide and the catalyst. The structure of the intermediate complex and the solvation of hydroperoxide have been discussed. This epoxidation method was also applied to various olef ins.
The reactions of p-substituted benzoic anhydrides with dimethyl sulf oxide (DMSO) in dioxane gave the corresponding α-benzoyloxymethylmethyl sulf ides. Results of the rate measurements indicated that this reaction followed second-order integrated equation. Hammett's ρ value was positive. The activation energy and the frequency factor were obtained in the reaction of p, p'dinitrobenzoic anhydride with DMSO. The kinetic isotope effect of this reaction with DMSO-d6 was small (kH/kD=1.21 at 100.2°C) and it seemed to be a secondary one. In the reaction of mixed benzoic anhydrides, two sulfides were obtained. The yield of the sulfide with a more electron-attractive substituent was higher than that with a less electron-attractive substituent. The mechanism of this reaction is discussed, and the nucleophilic attack of the DMSO-oxygen (=S→O) on the anhydride-carbon (=C=O) appears to be the rate determining step.