4-氟苯甲醛、β-萘胺和Meldrum酸-锅反应生成1-(4-氟苯基)-1,2-二氢苯并[f]喹啉-3(4H)-酮的反应机理理论研究

采用密度泛函理论(DFT)研究了4-氟苯甲醛、β-萘胺和Meldrum酸一锅反应生成1-(4-氟苯基)-1,2-二氢苯并f]喹啉-3(4H)-酮的微观反应机理.在B3LYP/6-311G*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,并用内禀反应坐标(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.采用SCRF(PCM)方法研究了反应体系的溶剂化效应.报道了可能的反应路径,其中Re→TS1→IM1→TS2→IM2→TS3→IM3→TS4→IM5→TS7→IM9→TS13→IM10→TS14→P3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.

A Theoretical Study on the Reaction Mechanism of 4-Fluorobenzaldehyde, One-pot to Form 1-(4-Fluorophenyl)-1,2-Dihydrobenzo[f] Quino-lin-3(4H)-one

The reaction mechanism of 4-fluorobenzaldehyde, β-naphthylamine and meldrum's acid one-pot to form 1-(4-fluorophenyl)-1,2-dihydrobenzof] quinolin-3(4H)-one were studied by density functional theory. The geometries of the reactants, transition states, intermediates and products were optimized at theB3LYP/6-311G* level. Vibration analysis was carried out to confirm the transition state structure, and the intrinsic reaction coordinate (IRC) method was performed to search the reaction path. In addition, atoms in molecules (AIM) theories were used to discuss bond natures. The reaction in water solution was investigated at the same level with SCRF(PCM) method. Reaction pathways were investigated in this study. The result indicates that the reaction Re→TS1→IM1→TS2→IM2→TS3→IM3→TS4→IM5→TS7→IM9→TS13→IM10→TS14→P3 is the main pathway, the activation energy of which is the lowest. The dominant product predicted theoretically is in agreement with the experiment results.