A THEORETICAL AND EXPERIMENTAL INVESTIGATION OF THE ELECTROPHILIC OXIDATION OF THIOETHERS AND SULFOXIDES BY PEROXIDES

被引：30

作者：

BONCHIO, M ^{[1
]}

CAMPESTRINI, S ^{[1
]}

CONTE, V ^{[1
]}

DIFURIA, F ^{[1
]}

MORO, S ^{[1
]}

机构：

[1] UNIV PADUA,DIPARTIMENTO CHIM ORGAN,CNR,CTR STUDIO MECCANISMI REAZ ORGAN,I-35131 PADUA,ITALY

来源：

TETRAHEDRON | 1995年 / 51卷 / 45期

关键词：

D O I：

10.1016/0040-4020(95)00780-C

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

In the electrophilic oxidation by peroxides the reactivity of sulfoxides is considerably less affected by structural effects than that of thioethers. This feature has not been, so far, rationalized. We have calculated by semiempirical methods the charge on the sulfur atom, Q(S), and the energy of the HOMO for a series of thioethers and sulfoxides. Then we have correlated the rate constants for the oxidation of thioethers by H3O2+ and of sulfoxides by perbenzoic acid with Q(S) and with F (F = (E(LUMO)(Ox) - E(HOMO)(Sub))(-1) respectively. We find that the reactivity of thioethers is mainly dependent on Q(S), while that of sulfoxides is dominated by F.

引用

页码：12363 / 12372

页数：10

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