DFT study on the coupling process of CF3 radical addition to anilines derivative

• 作 者: XiangaiYuan;JinXie;ChengjianZhu;JingMa;
• 机 构: School of chemistry and chemical engineering,Nanjing University,Nanjing,China,210093
• 出 处: 中国化学会第29届学术年会
• 发表日期: 2014年期

　　The Ar-CF 3 moiety is a prominent structural class found among pharmaceuticals,agrochemicals and functional materials.It is interesting to understand the coupling process of CF 3 radical addition to anilines derivative from density functional theory(DFT)calculation.The computational results demonstrate that 4-methoxyaniline with strong electron-donor group has a slightly lower activation barrier(7.52 kcal/mol)than that(8.64 kcal/mol)with strong electron-acceptor group during the coupling process.In addition,taking 2-aminobenzamide for example,it is found that when the CF 3 radical adds to the ortho position can result in a relative lower free energy than that to para position(8.36 vs.11.36 kcal/mol).This may suggest that the ortho selectivity of un-symmetric anilines is relatively favored,which is in agreement with the experimental results(ortho vs.para = 2.5:1).Moreover,the low energy barrier for the transition-state(less than 10 kcal/mol)also demonstrates that CF 3 radical can easily attack the electron-rich position of anilines at room temperature.