GROUND-STATES OF MOLECULES .49. MINDO-3 STUDY OF RETRO-DIELS-ALDER REACTION OF CYCLOHEXENE

被引：189

作者：

DEWAR, MJS

OLIVELLA, S

RZEPA, HS

机构：

[1] Department of Chemistry, University of Texas, Austin

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1978年 / 100卷 / 18期

关键词：

D O I：

10.1021/ja00486a013

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The retro-Diels-Alder reaction of cyclohexene to form ethylene and butadiene has been studied, using MINDO/3. The transition state is predicted to be very unsymmetric, corresponding to weakening of one of the two breaking CC bonds. The calculated entropy of activation agrees well with experiment and the calculated secondary isotope effects for 4, 4-dideuteriocy-clohexene and 4, 4, 5, 5-tetradeuteriocyclohexene are similar to those measured for an analogous reaction by Taagepera and Thornton. Discrepancies between the conclusions reached here and those from recent ab-initio calculations are discussed. © 1978, American Chemical Society. All rights reserved.

引用

页码：5650 / 5659

页数：10

共 62 条

[1]

Baldwin J. E., 1970, FORTSCHR CHEM FORSCH, V15, P281

[2] KINETICS OF THERMAL UNIMOLECULAR REACTIONS OF CYCLOHEXENE AND 4-VINYLCYCLOHEXENE BEHIND REFLECTED SHOCK-WAVES [J].