MICELLAR EFFECTS UPON OXIDATION OF ORGANIC SULFIDES BY ANIONIC OXIDANTS

被引:28
作者
BACALOGLU, R [1 ]
BLASKO, A [1 ]
BUNTON, CA [1 ]
FOROUDIAN, H [1 ]
机构
[1] UNIV CALIF SANTA BARBARA,DEPT CHEM,SANTA BARBARA,CA 93106
关键词
D O I
10.1002/poc.610050402
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Peroxymonosulfate ion (HSO5-) rapidly oxidizes 2-chloroethyl phnyl sulfide (1). Dilute micelle-forming cationic surfactants slightly speed the reaction but the reaction rate decreases sharply with increasing surfactant concentration. Rate-surfactant concentration profiles in solutions of cetyltrimethylammonium hydrogensulfate can be treated quantitatively by estimating concentrations of 1 and HSO5- at the micellar surface with allowance for competition between HSO5- and HSO4-. The second-order rate constant in the micellar pseudo-phase is lower that in water by a factor of ca 400. Similar rate-surfactant concentration profiles were observed for the oxidation of di-n-propyl sulfide by periodate ion in solutions of cetyltrimethylammonium bromide, chloride and mesylate, and second-order rate constants in the micellar pseudo-phases are lower than in water by factors of ca 400. These oxidations are slowed by a decrease in the water content of aqueous acetonitrile and solvent, and micellar rate effects are consistent with transition states in which positive charge builds up on sulfur.
引用
收藏
页码:171 / 178
页数:8
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