COPPER SALT-CATALYZED REACTION OF BUTENES WITH PERESTERS
COPPER SALT-CATALYZED REACTION OF BUTENES WITH PERESTERS
复制标题
DOI：
10.1021/ja00864a020
复制
发表时间：
1962-01-01
影响因子：
15
通讯作者：
KOCHI, JK
中科院分区：
文献类型：
--
作者：
KOCHI, JK
研究了铜盐催化过酸酯反应的机理。铜盐在这些自由基反应中的作用是通过一系列单电子氧化还原步骤来描述的：首先，亚铜离子被过酸酯氧化成烷氧基和羧酸铜；其次，通过烷氧基与氢供体化合物之间的链转移反应产生的自由基来还原铜盐。对于丁烯，丁烯基中间体显示出平衡，产生α-甲代烯丙基酯和巴豆酯的混合物，与反应物正常丁烯异构体无关。检查溶剂和外来亲核试剂的影响。阐述了铜物质氧化烯丙基自由基的性质。
The mechanism of the copper salt-catalyzed reactions of peresters has been studied. The role of copper salts in these free radical reactions is described by a series ofone-electron oxidation-reduction steps: first, the oxidation of cuprous ion by perester to alkoxy radical and cupric carboxylate; and second, reduction of the cupric saltby a free radical generated by the chain transfer reaction between the alkoxy radical and an hydrogen donor compound. With butenes, butenyl radical intermediates are shown to equilibrate to produce a mixture of a-methallyl and crotyl esters independent of the reactant normal butene isomer. The effect of solvent and foreign nucleophiles is examined. The nature of the oxidation of allylic radicals by cupric species is elaborated.