OXIDATION OF SULFIDES AND PHOSPHINES BY AROMATIC SELENONIC AND SELENINIC ACIDS

被引:29
作者
FAEHL, LG [1 ]
KICE, JL [1 ]
机构
[1] TEXAS TECH UNIV,DEPT CHEM,LUBBOCK,TX 79409
关键词
D O I
10.1021/jo01328a005
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Both alkyl sulfides and triphenylphosphine are readily oxidized by p-chlorobenzeneselenonic acid to alkyl sulfoxides and triphenylphosphine oxide, the selenonic acid itself being reduced to p-chlorobenzeneseleninic acid. The seleninic acid, in an acid-catalyzed reaction, then even more rapidly oxidizes additional sulfide to sulfoxide (or Ph3P to phosphine oxide) and is itself reduced to a diselenide. Study of the mechanism of this oxidation of sulfides by aromatic seleninic acids indicates that the rate-determining step is nucleophilic attack by the sulfide on the protonated seleninic acid, ArSe(OH)2 +, to give the sulfoxide, a proton, and the selenenic acid, ArSeOH. The selenenic acid can then disproportionate to the diselenide, ArSeSeAr, and the seleninic acid. Despite the strong inherent oxidizing power of p-chlorobenzeneselenonic acid and its facile oxidation of alkyl sulfides and Ph3P, it does not oxidize such other potentially oxidizable organic functionalities as alcohols, alkenes, or ketones. © 1979, American Chemical Society. All rights reserved.
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页码:2357 / 2361
页数:5
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