REMOTE PARTICIPATION DURING PHOTOOXIDATION AT SULFUR - EVIDENCE FOR SULFURANE INTERMEDIATES

被引:35
作者
CLENNAN, EL
YANG, K
机构
[1] Department of Chemistry, University of Wyoming, Laramie
关键词
D O I
10.1021/jo00042a031
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The photooxidations of geminally substituted gamma-hydroxy sulfides results in formation of unusual oxidative elimination products. Detailed spectral data and the independent synthesis of a close analogue provide compelling evidence for the structures of these olefins. The formation of the olefins is attributed to decomposition of sulfurane intermediates. This conclusion is supported by a detailed kinetic study which separated the chemical, k(r), and physical, k(q), components to the overall deactivation of singlet oxygen. Those sulfides with the best geometry for sulfide-hydroxyl interaction are also the substrates which react most rapidly with singlet oxygen to give oxidation products. In addition, sulfone yields are in excess of 50% for the hydroxy-substituted sulfides but less than 5% for their hydrocarbon analogues. Several mechanisms that provide explanations for these unusually high sulfone yields are presented.
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页码:4477 / 4487
页数:11
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