摘要
本文采用密度泛函理论研究了苯甲醛和2-氨基吡啶在Cu(Ⅰ)催化下反应生成N-(吡啶-2-基)苯甲酰胺的微观机理.在PW91/DNP基组水平上优化了反应物、过渡态、中间体及产物的几何构型,通过振动分析确认了过渡态的结构.报道了四条可能的反应路径.结果表明:两种Cu(Ⅰ)催化剂中, CuI的催化效果优于Cu2O.通过四条路径速控步骤活化能比较得出路径Re→IMA1→TSA1→IMA2→TSA2→IMA3→TSA3→IMA4→IM6→TS4→P具有相对较低的活化能,是反应的主要通道,其速控步骤IM6→TS4→P的活化能是260.12 kJ·mol-1,反应热为93.01 kJ·mol-1.理论预测的主要产物与实验结果吻合.
The reaction mechanism of benzaldehyde and 2-aminopyridine Cu(Ⅰ)-catalyzed to form N-(pyridin-2-yl)benzamide was studied by density functional theory. The geometries of the reactants, transition states, intermediates and products were optimized at the PW91/DNP level. Vibration analysis was carried out to confirm the transition state structure. Four possible reaction pathways were investigated in this study. The result indicates that the CuI is better suitable catalyst for producing N-(pyridin-2-yl)benzamide through CuI and Cu2O of Cu(Ⅰ)-catalyzed. By comparison, the reaction Re→IMA1→TSA1→IMA2→TSA2→IMA3→TSA3→IMA4→IM6→TS4→P is the main pathway, its activation energy is the lowest. IM6→TS4→P is the rate-limiting step, with the activation energy being 260.12 kJ·mol-1 and the reaction heat being 93.01 kJ·mol-1. The dominant product predicted theoretically is in agreement with the experimental results.
作者
张福兰
刘艳
赵小辉
何树华
郭晓刚
ZHANG Fu-Lan;LIU Yan;ZHAO Xiao-Hui;HE Shu-Hua;GUO Xiao-Gang(College of Chemistry and Chemical Engineering,Yangtze Normal University,Chongqing 408100,China;Colledge of Green Intelligence Environmental,Yangtze Normal University,Chongqing 408100,China)
出处
《四川大学学报（自然科学版）》
CAS
CSCD
北大核心
2019年第6期1118-1124,共7页
Journal of Sichuan University(Natural Science Edition)
基金
教育部“春晖计划”资助项目(Z2016177)
重庆市教委科学技术资助项目(KJ1601215)
