Silyl radicals. XV. Stereochemical course of chlorine abstraction by 1-methyl-4-t-butyl-1-silacyclohexyl radicals from polychloroalkane.
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概要
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The isomerically pure <I>cis</I> and <I>trans</I> 1-methyl-4-<I>t</I>-butyl-1-silacyclohexane were subjected to the free radical chlorination with carbon tetrachloride in the presence of a catalytic amount of benzoyl peroxide under UV irradiation at 0 °C, affording the corresponding chlorosilanes with retention of configuration. With less reactive polyhalocarbons, however, less stereospecific products were obtained. A mechanism that inversion of silyl radicals competes with chlorine abstraction is proposed. Relative rates of each reaction were analyzed with a steadystate assumption.
- 公益社団法人 日本化学会の論文
著者
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Murakami Masashi
Department Of Biochemistry Cancer Institute Okayama University Medical School
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Sakurai Hideki
Department Of Chemistiy Faculty Of Science Tohoku University
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