化学学报 ›› 1993, Vol. 51 ›› Issue (12): 1185-1190. 上一篇    下一篇

研究论文

α-氰基苄基碳负离子钠盐与碳酸二乙酯的单电子转移反应动力学和机理

杨第伦;赵文轶;金景;刘有成   

  1. 兰州大学化学系;兰州大学应用有机化学国家重点实验室
  • 发布日期:1993-12-15

Kinetics and mechanism of the SET reaction of α-cyanobenzyl carbanion sodium salt with diethyl carbonate

YANG DILUN;ZHAO WENYI;JIN JING;LIU YOUCHENG   

  • Published:1993-12-15

测定了α-氰基苄基碳负离子钠盐与碳酸二乙酯缩合反应产物的结构及其分布,反应中间体的EPR谱,反应过程中产物和溶剂的CIDNP效应和反应动力学,为这一缩合反应提出了单电子转移-负离子自由基分解-自由基偶合的非链式自由基机理

关键词: 缩合反应, 反应机理, 乙酯, 苄基, 乙腈 P, 阴碳离子, 碳酸酯, 电子顺磁共振谱法, CIDNP, 单电子转移

Based on EPR observation of di-Et carbonate ketyl radical, CIDNP signals due to both the product Et a-cyanophenylacetate and DMSO impurity in the solvent DMSO-d6, as well as the fit to successive first-order kinetics, an electron-transfer initiated nonchain radical mechanism is proposed for the reaction between a-cyanobenzyl carbanion sodium salt (1) and di-Et carbonate (2) in DMSO.

Key words: CONDENSATION REACTION, REACTION MECHANISM, ETHYL ESTER, BENZYL GROUP, ACETONITRILE P, CARBANION, POLYCARBONATE, QUARTZ, CIDNP

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