REACTION OF ANIONS WITH ACTIVATED OLEFINS IN THE GAS-PHASE - A FLOWING AFTERGLOW SELECTED ION FLOW TUBE STUDY

被引：14

作者：

BERNASCONI, CF ^{[1
]}

STRONACH, MW ^{[1
]}

DEPUY, CH ^{[1
]}

GRONERT, S ^{[1
]}

机构：

[1] UNIV COLORADO,DEPT CHEM & BIOCHEM,BOULDER,CO 80309

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1990年 / 112卷 / 25期

关键词：

D O I：

10.1021/ja00181a003

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Reactions of anions with acrylonitrile, acrolein, methyl vinyl ketone, and methyl acrylate at room temperature under SIFT conditions are described. Stabilized carbanions such as benzyl anion, cyanomethyl anion, cyclohexadienide, acetone cnolate, and nitromethyl anion add to activated carbon-carbon double bonds in a process that is competitive with other modes of reaction. With acrylonitrile and methyl acrylate, addition is in a 1,4 or Michael fashion, while with acrolein and methyl vinyl ketone, 1,2 addition competes with 1,4 addition. Hydroxide, methoxide, fluoride, and cyanide do not add to activated olefins by cither mode (see Tables I-IV). A mechanism is proposed for hydride transfer from cyclohexadienide to activated olefins. © 1990, American Chemical Society. All rights reserved.

引用

页码：9044 / 9052

页数：9

共 65 条

[1] SELECTED ION FLOW TUBE (SIFT) - TECHNIQUE FOR STUDYING ION-NEUTRAL REACTIONS [J].