Comparison of the Electrophilic Reactivities of N-Acylpyridinium Ions and Other Acylating Agents

被引：8

作者：

Nigst, Tobias A. ^{[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 / 11期

关键词：

Kinetics; Linear free energy relationships; Acylation; Amines; Organocatalysis; ANION COMBINATION REACTIONS; X-SUBSTITUTED BENZOATES; NUCLEOPHILIC REACTIVITIES; PHENYL BENZOATES; RATE CONSTANTS; CARBON-ATOM; AMINOLYSIS; MECHANISM; KINETICS; CATION;

D O I：

10.1002/ejoc.201201540

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The kinetics of the reactions of carbanions, carboxylate anions, and primary and secondary amines with acylating agents were studied in acetonitrile and dimethyl sulfoxide (DMSO) under first-order conditions by UV/Vis spectrophotometry and conductimetry. Whereas reactions of a large variety of nucleophiles with ordinary carbanions and Michael acceptors generally follow the linear free energy relationship lgk(2) (20 degrees C) = s(N)(N + E), separate correlation lines for different types of nucleophiles were found when (lg k(2))/s(N) was plotted against N for the reactions with acyl derivatives 2-5. Even when nucleophilic attack is rate determining, the reactivities of acylating agents towards nucleophiles cannot be described by a single set of nucleophile-independent electrophilicity parameters.

引用

页码：2155 / 2163

页数：9

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