Whereas photolysis of acylsilanes in carbon tetrachloride has been shown to generate silyl radicals which yield chlorosilanes exclusively, and photolyses in alcohols yield siloxycarbenes which yield "mixed acetal" insertion products, it is shown that photolysis of acylsilanes in non-polar, non-halogenated solvents such as cyclohexane give complex mixtures of products which result primarily from the attack of silyl radicals on the carbonyl oxygen of an acylsilane, followed by conventional disproportionation or recombination reactions. Under some circumstances silyl radicals add to carbon–carbon double bonds. The structures of the products formed and the mechanism of their formation are described.
在碳四
氯化物中,酰
硅烷的光解已被证明会产生
硅基自由基,其仅生成
氯硅烷;而在醇中的光解会产生
硅氧卡宾,从而生成“混合
缩醛”插入产物。结果表明,在非极性、非卤代溶剂(如
环己烷)中,酰
硅烷的光解会产生复杂的产物混合物,主要是由
硅基自由基对酰
硅烷的羰基氧发起攻击,随后进行传统的不均化或
重组反应。在某些情况下,
硅基自由基会加成到碳-碳双键上。描述了所形成产物的结构和形成机制。