N-(2-苯甲亚胺基)-3-氨基-氟代己酰胺-2-烯环合的反应机理  

The Reaction Michanism of Ring-like Reaction of N-(2-benzimino)-3-amino-fluorohexanamide-2-ene

作　　者：徐伯华[1] 张福兰[1] 吴兴发[1] 

机构地区：[1]长江师范学院化学系,重庆408003

出　　处：《西南师范大学学报（自然科学版）》2009年第1期35-41,共7页Journal of Southwest China Normal University(Natural Science Edition)

基　　金：重庆市教委自然科学基金资助项目(KJ071303)

摘　　要：采用密度泛函方法(DFT)研究了N-(2-苯甲亚胺基)-3-氨基-氟代己酰胺-2-烯环合的微观反应机理.在B3LYP/6-31G*水平上优化了反应物、过渡态、中间体及产物的几何构型,然后通过振动分析确认了过渡态的结构,并通过内禀反应坐标方法(IRC)确认能量最低的反应途径,应用分子中的原子(AIM)理论分析了这些物质的成键特征.报道了4条可能的反应通道,2条直接协同环合反应和两条先H原子转移后成环的反应途径,其中通道Re→TS1→IM1→TS2→P1具有相对较低的活化能,是反应的主要通道.理论预测的主要产物与实验吻合.采用SCRF(PCM)方法研究了反应体系的溶剂化效应,结果表明反应过程中各物质的能量比气相要低.溶剂化效应使转化能垒有一定程度的升高.The microcosmic reaction mechanism of ring-like reaction of N-（2 -benzimino）-3 -amino-flu- orohexanamide - 2 -ene were studied by density functional theory. The geometries of the reactants, transition states, intermediates and products were optimized at the B3LYP/6 -31G ＊ level. Vibration analysis was carried out to confirm the transition state structure, and the intrinsic reaction coordinate （IRC） method was performed to search the minimum energy path. In addition, atoms in molecules （AIM） theories have been used to discuss bond natures. Four feasible reaction pathways were investigated in this study, including two concerted reactions of direct ring-like and two indirect channels in which the reactant first a transfer step of hydrogen atom of the imino moiety, followed by becomed a ring-like. Analysis indicated that the reaction Re→TS1→IM1→TS2→P1 was the main pathway ,the activation energy of which was the lowest. The dominant product predicted theoretically is in agreement with the results in the experiment. The reaction in ethanol solution has been investigated at the same level with SCRF （PCM） method, and the results show that the energy of each compound is lower than that in the gas phase. The solvent effects enhance the energy barrier to some extent.

关 键 词：N-(2-苯甲亚胺基)-3-氨基-氟代己酰胺-2-烯 3-(1-亚胺基氟烷基)-1H-喹啉-2-酮 反应机理 协同反应 溶剂化效应 

分 类 号：O643.12[理学—物理化学]