γ-Ray induced reduction of acid chlorides with trichlorosilane

Article abstract of DOI:10.1016/0022-328X(90)80108-C

The γ-ray induced reduction of various acid chlorides (RCOCl) with trichlorosilane was studied at ambient temperature.Trichlorosilyl radicals were found to attack acid chloride selectively at chlorine atom to produce acyl radicals at the first step.The preference of chlorine-atom attack to carbonyl-oxygen-atom attack is explained in terms of molecular orbital calculations (STO-3G); the SOMO (singly occupied molecular orbital) of trichlorosilyl radicals is more likely to interact with the energetically closer ?-HOMO (C-Cl) than ?-HOMO (C=O) of acid chlorides.The acyl radicals thus formed yield two kinds of products depending on the nature of the alkyl moiety involved.When the alkyl moiety (R) is tertiary, the acyl radical undergoes decomposition into carbon monoxide and an alkyl radical which finally yields an alkane (RH).When R is primary, the acyl radical abstracts a hydrogen atom from trichlorosilane producing an aldehyde, which, by subsequent hydrosilation, gives an alkoxysilane (RCH2OSiCl3) as a final product.Thus, the present reaction can be used as a complementary synthesis to the reported method in which initiators are used.