Aminolysis of a model carbamate insecticide: a theoretical reaction mechanism study of carbaryl via an isocyanate intermediate
作者: Chaoqing ZhangHui YinXiaoling LuoRong ChenGuoming Liang
作者单位: 1Chongqing Normal University
刊名: Theoretical Chemistry Accounts, 2017, Vol.136 (6)
来源数据库: Springer Journal
DOI: 10.1007/s00214-017-2102-2
关键词: Aminolysis mechanismCarbarylCatalytic effectsPCM
英文摘要: The possible aminolysis pathways of carbaryl are investigated by using the B3LYP/6-311++G(d,p), M06-2X/6-311++G(d,p) and MP2/6-311++G(d,p) levels. The uncatalyzed, base-catalyzed and water-catalyzed aminolyses are explored in our calculation. For each case, three alterative channels, the concerted, addition–elimination (BAC2) and elimination–addition (E1cB) channel via an isocyanate, are evaluated. Our results convincingly demonstrate that the most favorable mechanism is the E1cB channel for all of the aminolysis reactions in the gas phase. For BAC2 and E1cB routes, the first stage is the rate-determining step. The base-catalyzed and water-catalyzed aminolysis reactions have more advantages to the uncatalyzed one. The solvent effect for acetonitrile does not notably...
原始语种摘要: The possible aminolysis pathways of carbaryl are investigated by using the B3LYP/6-311++G(d,p), M06-2X/6-311++G(d,p) and MP2/6-311++G(d,p) levels. The uncatalyzed, base-catalyzed and water-catalyzed aminolyses are explored in our calculation. For each case, three alterative channels, the concerted, addition–elimination (BAC2) and elimination–addition (E1cB) channel via an isocyanate, are evaluated. Our results convincingly demonstrate that the most favorable mechanism is the E1cB channel for all of the aminolysis reactions in the gas phase. For BAC2 and E1cB routes, the first stage is the rate-determining step. The base-catalyzed and water-catalyzed aminolysis reactions have more advantages to the uncatalyzed one. The solvent effect for acetonitrile does not notably...
全文获取路径: Springer  (合作)
分享到:
来源刊物:
影响因子:2.233 (2012)

×
关键词翻译
关键词翻译
  • aminolysis 氨基分解
  • catalyzed 催化的
  • carbamate 氨基甲酸盐
  • isocyanate 异氰酸盐
  • reaction 反酌
  • theoretical 理论的
  • mechanism 机构
  • acetonitrile 乙腈
  • carbaryl 维因
  • intermediate 中频