2-(氟代己酰胺基)-苯甲醛与NH_3反应生成3-(1-亚胺基氟烷基)-1H-喹啉-2-酮的反应机理理论研究  

A Theoretical Study on the Reaction Mechanism of 2-(Perfluorohexanamidol)benzaldehyde with Ammonia to form 3-(1-Iminoperfluorobutyl)-1,2-dihydro-quinolin-2-one

作　　者：张福兰[1,2] 李来才[1] 徐伯华[2] 田安民[3] 

机构地区：[1]四川师范大学化学与材料学院,成都610066 [2]长江师范学院化学系,涪陵408003 [3]四川大学化学学院,成都610064

出　　处：《化学学报》2009年第1期45-53,共9页Acta Chimica Sinica

基　　金：四川省教育厅重点基金(No.07ZA097)资助项目

摘　　要：采用密度泛函方法(DFT)研究了2-(氟代己酰胺基)-苯甲醛与NH3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,通过振动分析确认了过渡态的结构,并用内禀反应坐标方法(IRC)确认反应途径.应用分子中的原子理论(AIM)分析了这些物质的成键特征.报道了可能的反应通道,其中Re→TS1→IM1→TS2→IM2→TS3→IM3→TS4→IM7→TS11→IM9→TS12→IM10→TS13→IM11→TS14→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.采用连续介质模型(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 2-（perfluorohexanamidol）benzaldehyde with ammonia was studied by density functional theory. The geometries of the reactants, transition states, intermediates and products were optimized at the B3LYP/6-31G＊ level. Vibrational analysis was carried out to confirm the transition state structure, and the intrinsic reaction coordinate （IRC） method was used to search the reaction path. In addition, atoms in molecules （AIM） theories have been used to discuss bond natures. Feasible reaction pathways were investigated, indicating that the reaction Re→TS1→IM1→TS2→IM2→TS3→IM3→TS4→IM7→TS11→IM9→TS12→IM10→TS13→IM11→TS14→P1 is the main pathway, the activation energy of which is the lowest. The dominant product predicted theoretically is in agreement with the results from the experiment. The reaction in ethanol solution has been investigated at the same level with polarizable continuum models （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：2-(氟代己酰胺基)-苯甲醛 3-(1-亚胺基氟烷基)-1H-喹啉-2-酮 反应机理 溶剂化效应 

分 类 号：O621.25[理学—有机化学]