DFT study of nucleophilic substitution at sulfur

被引：0

作者：

Gai, JG ^{[1
]}

Ren, Y ^{[1
]}

机构：

[1] Sichuan Univ, Coll Chem, Chengdu 610064, Peoples R China

来源：

CHINESE JOURNAL OF ORGANIC CHEMISTRY | 2004年 / 24卷 / 10期

关键词：

nucleophilic substitution at sulfur; deprotonation; DFT theory;

D O I：

暂无

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A series of reactions, X- + CH3SCl (X = F, Cl, Br, I), were examined at B3LYP/6-311 + G(2df, p) level. Computational results indicate that X- (X = Cl, Br, 1) attacks preferably sulfur atom instead of carbon atom of CH3SCL The substitution reactions follow an addition-elimination mechanism. However, deprotonation reaction is much more favorable than substitution for reaction F- + CH3SCl.

引用

页码：1267 / 1270

页数：4

共 24 条

[1] THEORETICAL-STUDIES OF NUCLEOPHILIC-SUBSTITUTION AT PHOSPHORUS .1. PH3+H--]H-+PH3
BACHRACH, SM
MULHEARN, DC
[J]. JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (47): : 12229 - 12231
[2] Theoretical study of nucleophilic substitution at two-coordinate sulfur
Bachrach, SM
Gailbreath, BD
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (06): : 2005 - 2010
[3] NUCLEOPHILIC-SUBSTITUTION AT OXYGEN - THE REACTION OF PH3 AND NH3 WITH H3NO - AN ABINITIO INVESTIGATION
BACHRACH, SM
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (03): : 1016 - 1019
[4] Nucleophilic substitution at sulfur: S(N)2 or addition-elimination?
Bachrach, SM
Mulhearn, DC
[J]. JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (09): : 3535 - 3540
[5] THE ENDOCYCLIC RESTRICTION TEST - EXPERIMENTAL EVALUATION OF TRANSITION-STRUCTURE GEOMETRY FOR A NUCLEOPHILIC DISPLACEMENT AT NEUTRAL NITROGEN
BEAK, P
LI, JL
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (07) : 2796 - 2797
[6] GEOMETRY OF FORMAL NUCLEOPHILIC-SUBSTITUTION AT 1ST-ROW HETEROATOMS - THE TRANSFER OF OXYGEN FROM NITROGEN TO PHOSPHORUS
BEAK, P
LOO, D
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (13) : 3834 - 3835
[7] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE
BECKE, AD
[J]. JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07): : 5648 - 5652
[8] GAS-PHASE NUCLEOPHILIC DISPLACEMENT-REACTIONS
BRAUMAN, JI
OLMSTEAD, WN
LIEDER, CA
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1974, 96 (12) : 4030 - 4031
[9] REACTIONS OF TRIMETHYLCHLOROSILANE WITH VARIOUS NUCLEOPHILES IN THE GAS-PHASE USING THE FLOWING AFTERGLOW TECHNIQUE
DAMRAUER, R
DEPUY, CH
BIERBAUM, VM
[J]. ORGANOMETALLICS, 1982, 1 (11) : 1553 - 1554
[10] GAS-PHASE SN2 AND E2 REACTIONS OF ALKYL-HALIDES
DEPUY, CH
GRONERT, S
MULLIN, A
BIERBAUM, VM
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (24) : 8650 - 8655

← 1 2 3 →