A SEARCH FOR MAXIMAL NEIGHBORING GROUP PARTICIPATION IN SOLVOLYSES OF ALLYLIC SUBSTRATES - ETHANOLYSIS OF 2-(OMEGA-ALKYLTHIOALKYL)-3-METHYL-2-CYCLOHEXENYL P-NITROBENZOATES

被引：1

作者：

JURSIC, BS

LADIKA, M

SUNKO, DE

机构：

[1] Laboratory of Organic Chemistry, Faculty of Science, University of Zagreb Strossmayerov trg 14

来源：

TETRAHEDRON | 1993年 / 49卷 / 13期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1016/S0040-4020(01)86349-3

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The solvolysis of 2-(omega-methylthioalkyl)- and 2-(omega-benzylthioalkyl)-3-methyl-2-cyclohexenyl p-nitrobenzoates 5 and 6 in 80 vol % ethanol includes several competitive reactions. Path k1 is a stepwise process (k(H)/k(D) = 1.18-1.20) which includes allylic cation 9 as a reaction intermediate, while path k2 involves a neighboring sulfur participation (k(H)/k(D) = 1.01 - 1.03) and formation of an intermediate cyclic sulfonium cation 10. Esters 5 and 6 solvolyze in 80% EtOH with a greater neighboring group participation than in 97% TFE. IL has been concluded that in solvolytic reactions of allylic substrates a pronounced neighboring group participation (k2/k1= 900) may occur only with very strong internal nucleophiles, and in solvents which can not form strong hydrogen bonds with these nucleophiles.

引用

页码：2717 / 2728

页数：12

共 17 条

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