UV light photolysis of dichloroacetyl chloride (CHCl2COCl) has been investigated by infrared spectroscopy in cryogenic Ar, Kr, Xe, and O2 matrices. The formation of CHCl3 and CO was found to be the dominant process ov...UV light photolysis of dichloroacetyl chloride (CHCl2COCl) has been investigated by infrared spectroscopy in cryogenic Ar, Kr, Xe, and O2 matrices. The formation of CHCl3 and CO was found to be the dominant process over the ketene formation. The C-C bond cleaved products CHCl2 and COCl were also observed. As the number of the chlorine atom substitution to methyl group of acetyl chloride increased, the C-C bond cleaved product yield in the triplet state increased, which can be attributed to an internal heavy-atom effect where the intersystem crossing rate was enhanced.展开更多
A [2+2] cycloaddition adduct 2 and a novel ring-opening product 3 were obtained from the reactions of 2,3-benzothiazepines 1 with dichloroacetyl chloride and triethylamine. The relative ratios of 2 and 3 were affected...A [2+2] cycloaddition adduct 2 and a novel ring-opening product 3 were obtained from the reactions of 2,3-benzothiazepines 1 with dichloroacetyl chloride and triethylamine. The relative ratios of 2 and 3 were affected by the addition order of reactants and reaction temperature. The structures were determined by spectral data and the reaction mechanisms for the formation of 2 and 3 were elucidated.展开更多
文摘UV light photolysis of dichloroacetyl chloride (CHCl2COCl) has been investigated by infrared spectroscopy in cryogenic Ar, Kr, Xe, and O2 matrices. The formation of CHCl3 and CO was found to be the dominant process over the ketene formation. The C-C bond cleaved products CHCl2 and COCl were also observed. As the number of the chlorine atom substitution to methyl group of acetyl chloride increased, the C-C bond cleaved product yield in the triplet state increased, which can be attributed to an internal heavy-atom effect where the intersystem crossing rate was enhanced.
基金This work was supported by the National Natural Science Foundation of China (No. 29972001).
文摘A [2+2] cycloaddition adduct 2 and a novel ring-opening product 3 were obtained from the reactions of 2,3-benzothiazepines 1 with dichloroacetyl chloride and triethylamine. The relative ratios of 2 and 3 were affected by the addition order of reactants and reaction temperature. The structures were determined by spectral data and the reaction mechanisms for the formation of 2 and 3 were elucidated.
