UNIMOLECULAR REARRANGEMENTS OF CARBANIONS IN THE GAS-PHASE .2. CYCLOPROPYL ANIONS

被引：32

作者：

CHOU, PK ^{[1
]}

DAHLKE, GD ^{[1
]}

KASS, SR ^{[1
]}

机构：

[1] UNIV MINNESOTA, DEPT CHEM, MINNEAPOLIS, MN 55455 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1993年 / 115卷 / 01期

关键词：

D O I：

10.1021/ja00054a045

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We have examined the gas-phase unimolecular rearrangements of a series of substituted cyclopropyl anions (CHXCH2CY-; X = H, Y = Ph, CHO, and CN; X = Y = CO2CH3) with a variable temperature flowing afterglow device. The ring-opening barriers range from 19 to greater-than-or-equal-to 36 kcal mol-1 and are well reproduced by ab initio molecular orbital calculations. An analysis of eight monosubstituted cyclopropyl anions reveals that the flexibility (ease of inversion) and thermodynamic stability of these ions account for their tendency to isomerize.

引用

页码：315 / 324

页数：10

共 92 条

[1] DO DEPROTONATED SEMICARBAZONES UNDERGO THE NEGATIVE-ION BECKMANN REARRANGEMENT IN THE GAS-PHASE [J].