Quantification of the Nucleophilic Reactivities of Ethyl Arylacetate Anions

被引：18

作者：

Corral-Bautista, Francisco ^{[1
]}

Mayr, Herbert ^{[1
]}

机构：

[1] Univ Munich, Dept Chem, D-81377 Munich, Germany

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2013年 / 2013卷 / 20期

关键词：

Carbanions; Kinetics; Linear free-energy relationships; Michael addition; Substituent effects; BOND-DISSOCIATION ENERGIES; POLAR ORGANIC-REACTIVITY; C-H BONDS; DIMETHYL-SULFOXIDE; ELECTROPHILICITY PARAMETERS; STABILIZED CARBANIONS; MICHAEL CONDENSATION; RADICAL CATIONS; ENOLATE ANIONS; ONE-POT;

D O I：

10.1002/ejoc.201300265

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

<title content-type="main">Abstract The kinetics of the reactions of substituted ethyl arylacetates with quinone methides and structurally related diethyl benzylidenemalonates have been studied in DMSO. The second-order rate constants (lgk(2)) correlated linearly with the electrophilicities E according to the linear free-energy relationship lgk(2) = s(N)(N + E), allowing us to determine the nucleophilicity parameters N and s(N) for these anions. The nucleophilic reactivities of the carbanions vary from N = 27.5 for the parent compound to N = 20.0 for the 4-nitro-substituted derivative.

引用

页码：4255 / 4261

页数：7

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