EFFECT OF LEAVING GROUP ON RELATIVE REACTIVITY AND PRODUCTS IN SOLVOLYSIS

被引：34

作者：

SMITH, SG

GOON, DJW

机构：

[1] Department of Chemistry, Chemical Engineering, University of Illinois, Urbana

[2] Ph.D. Thesis, University of Illinois, Urbana, Ill

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1969年 / 34卷 / 10期

关键词：

D O I：

10.1021/jo01262a071

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Phenyldimethylcarbinyl chloride, p-nitrobenzoate, and thionbenzoate have been found to be more reactive than the corresponding benzhydryl compounds by factors of 5.5, 23, and 4700, respectively, in ethanolysis at 50°. For the cumyl derivatives, kinetic isotope effects and solvolysis products are consistent with an ionization-type reaction for the three leaving groups. The results are interpreted in terms of an observed kinetic isotope effect containing contributions from the isotope effect on elimination from the carbonium ion because of ion-pair return. The high reactivity of cumyl thionbenzoate is attributed to a decrease in the importance of ion-pair return in this system relative to the model compounds. © 1969, American Chemical Society. All rights reserved.

引用

页码：3127 / &

共 38 条

[1]

ANDERSON RF, UNPUBLISHED WORK

[2] THE DECOMPOSITION OF SECONDARY ALKYL CHLOROSULFITES .3. THE ELIMINATION REACTION AND ISOTOPE EFFECTS [J].