ELECTROREDUCTIVE DEHALOGENATION OF CHLORINATED AROMATIC ETHERS - UNEXPECTED ELECTROGENERATED BASE-CATALYZED REACTIONS

被引：34

作者：

KIMURA, M ^{[1
]}

MIYAHARA, H ^{[1
]}

MORITANI, N ^{[1
]}

SAWAKI, Y ^{[1
]}

机构：

[1] NAGOYA UNIV,FAC ENGN,DEPT APPL CHEM,CHIKUSA KU,NAGOYA 46401,JAPAN

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1990年 / 55卷 / 12期

关键词：

D O I：

10.1021/jo00299a037

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The electroreductive dehalogenation of several mono- and polychlorinated aromatic ethers that serve as modelsof dioxins has been studied. The dechlorination was achieved by a simple constant-current electrolysis using a lead cathode in dimethylformamide. It was shown that 2,4,6-trichloroanisole undergoes successive dechlorination and the chlorine in the 2-position is selectively eliminated. Competitive reactions and cyclic voltammetric measurements suggested the increasing reactivity order of mono- < di- < trichloride for the reductive dechlorination. Use of allyl 2-chlorophenyl ether as a probe for radical cyclization indicated that free radical intermediates are of little importance. Thus, incipient radicals are immediately reduced to anionic intermediates. The electrolyses in the presence of deuterium oxide revealed proton sources for the present dechlorination. In these attempts, novel phenomena due to electrogenerated base (EGB) were found: di- and trichlorides underwent an unexpected overincorporation of deuterium in their dechlorinated products; a selective formation of Z-enol ethers from the allylic ethers was encountered. The mechanistic features of the present electroreductive dechlorination are discussed. © 1990, American Chemical Society. All rights reserved.

引用

页码：3897 / 3902

页数：6

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