TRANSITION-STATE FOR 1,2-HYDROGEN HALIDE ELIMINATION FROM ETHYL HALIDES

被引：47

作者：

TOTO, JL ^{[1
]}

PRITCHARD, GO ^{[1
]}

KIRTMAN, B ^{[1
]}

机构：

[1] UNIV CALIF SANTA BARBARA,DEPT CHEM,SANTA BARBARA,CA 93106

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1994年 / 98卷 / 34期

关键词：

D O I：

10.1021/j100085a016

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

On the basis of extensive quantum chemical calculations for 1,2 elimination of HX from C(2)H(5)X (X = F, Cl, Br, and I) we have obtained a strongly asymmetric transition state that differs greatly from previous models for this reaction. The effect of alpha-chloro/fluoro substitution was also investigated, specifically for HF and HCl elimination. We confirm the electron donor/acceptor property of these substituents but find the conventional explanation of their effect on the activation energy to be unsatisfactory.

引用

页码：8359 / 8370

页数：12

共 45 条

[1]

ANDZELM J, 1984, J COMPUT CHEM, V5, P147

[2]

[Anonymous], 1972, UNIMOLECULAR REACTIO

[3]

Benson S. W., 1970, KINETIC DATA GAS PHA, P342

[4] A SIMPLE SELF-CONSISTENT ELECTROSTATIC MODEL FOR QUANTITATIVE PREDICTION OF ACTIVATION ENERGIES OF 4-CENTER REACTIONS [J].

BENSON, SW ;

HAUGEN, GR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1965, 87 (18) :4036-&

[5] STURCTURAL ASPECTS OF KINETICS OF 4-CENTER REACTIONS IN VAPOR PHASE [J].

BENSON, SW ;

BOSE, AN .

JOURNAL OF CHEMICAL PHYSICS, 1963, 39 (12) :3463-&

[6] STATIC AND SHOCK TUBE PYROLYSES OF ALKYL FLUORIDES .3. THERMAL DECOMPOSITION OF 1-CHLORO-2-FLUOROETHANE, 1,1-DIFLURORETHANE, AND 1,1,1-TRIFLUOROETHANE [J].

CADMAN, P ;

DAY, M ;

TROTMAND.AF .

JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1971, (09) :1356-&

[7] UNIMOLECULAR REACTION AND COLLISIONAL DEACTIVATION OF CHEMICALLY ACTIVATED 1,2-DIFLUOROETHANE PRODUCED BY MERCURY PHOTOSENSITIZATION OF CHLOROFLUOROMETHANE AT 300 DEGREES K AND 475 DEGREES K [J].

CHANG, HW ;

SETSER, DW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1969, 91 (27) :7648-&

[8] THEORETICAL-STUDY OF THE ADDITION OF HYDROGEN HALIDES TO OLEFINS - REACTION OF DIMERIC HYDROGEN-FLUORIDE WITH ETHYLENE [J].

CLAVERO, C ;

DURAN, M ;

LLEDOS, A ;

VENTURA, ON ;

BERTRAN, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (05) :923-928

[9] THEORETICAL-STUDY OF THE ADDITION OF HYDROGEN HALIDES TO OLEFINS - A COMPARISON BETWEEN (HCL)2 AND (HF)2 ADDITIONS TO ETHYLENE [J].

CLAVERO, C ;

DURAN, M ;

LLEDOS, A ;

VENTURA, ON ;

BERTRAN, J .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 1987, 8 (04) :481-488

[10] SIZE CONSISTENCY IN DILUTE HELIUM GAS ELECTRONIC-STRUCTURE [J].

DAVIDSON, ER ;

SILVER, DW .

CHEMICAL PHYSICS LETTERS, 1977, 52 (03) :403-406

← 1 2 3 4 5 →