Intramolecular sensitization within steroids:: Excited-state interaction of C-17 α and β carbon-bromine bonds with a C-6 carbonyl group

被引：4
作者：
Li, WS [1 ]
Torun, L [1 ]
Morrison, H [1 ]
机构：
[1] Purdue Univ, Dept Chem, W Lafayette, IN 47907 USA
来源：
CANADIAN JOURNAL OF CHEMISTRY | 2003年 / 81卷 / 06期
关键词：
photodehalogenation; bromosteroid; ketosteroid; intramolecular singlet-singlet energy transfer (ISSET);
D O I：
10.1139/V03-055
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The synthesis, photochemistry, and photophysics of 17alpha-bromo-3alpha-(triphenylsilyloxy)-5alpha-androstan-6-one (1) and 17beta-bromo-3beta-(triphenylsilyloxy)-5alpha-androstan-6-one (2) have been studied in aqueous tetrahydrofuran. The 17alpha-bromo isomer gives evidence (reduced phi(f), tau(1), and phi(isc) for the ketone) for interaction between the ketone and C-Br moieties in the excited singlet state. Some photodehalogenation is also observed upon excitation of the ketone chromophore. This interaction seems to be absent or minimal for the 17beta-bromo isomer.
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收藏
页码：660 / 668
页数：9
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