MEDIUM AND STRUCTURE EFFECTS ON THE ANODIC-OXIDATION OF ARYL ARYLMETHYL SULFIDES

被引：51

作者：

BACIOCCHI, E ^{[1
]}

ROL, C ^{[1
]}

SCAMOSCI, E ^{[1
]}

SEBASTIANI, GV ^{[1
]}

机构：

[1] UNIV PERUGIA,DIPARTMENTO CHIM,I-06100 PERUGIA,ITALY

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 19期

关键词：

D O I：

10.1021/jo00019a005

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The anodic oxidation of a number of XC6H4CH2SC6H4Y has been investigated under a variety of conditions (AcOH/AcO-,AcOH/NO3-,AcOH/ClO4-,CH3CN/ClO4-) and the relative weight of the various reaction paths available to the intermediate radical cation (C-alpha-H deprotonation, C-S bond cleavage, attack on sulfur) evaluated via product analysis. It has been observed that in AcOH/AcO- (presence of a strong base) the main reaction is C-alpha-H deprotonation, which is also favored when X is an electron-withdrawing substituent and depressed by electron-donating Y. The C-S bond cleavage reaction is particularly important in CH3CN/ClO4-; its relative contribution is enhanced by an electron-donating X, which makes the benzyl carbocation more stable. The pathway leading to sulfoxides is favored in AcOH/NO3- and, to a lesser extent, in AcOH/ClO4-. Formation of sulfoxide is also favored when Y is an electron-donating group.

引用

页码：5498 / 5502

页数：5

共 31 条

[1]

ALDMAL K, 1984, SULFUR LETT, V2, P1

[2] STABILIZATION OF OXIDIZED SULFUR CENTERS IN ORGANIC SULFIDES - RADICAL CATIONS AND ODD-ELECTRON SULFUR-SULFUR BONDS [J].