Chin. J. Org. Chem. ›› 2014, Vol. 34 ›› Issue (8): 1595-1602.DOI: 10.6023/cjoc201403027 Previous Articles     Next Articles



张林a, 郑妍a, 潘晓晓a, 李来才a, 田安民b   

  1. a 四川师范大学化学与材料科学学院 成都 610066;
    b 四川大学化学学院 成都 610064
  • 收稿日期:2014-03-11 修回日期:2014-04-08 发布日期:2014-05-05
  • 通讯作者: 李来才
  • 基金资助:


Investigation the Reaction Mechanism from Phenylacetaldehyde and Benzylamine to Polysubstituted Imidazole Catalyzed by Ι2

Zhang Lina, Zheng Yana, Pan Xiaoxiaoa, Li Laicaia, Tian Anminb   

  1. a College of Chemistry and Material Science, Sichuan Normal University, Chengdu 610066;
    b College of Chemistry, Sichuan University, Chengdu 610064
  • Received:2014-03-11 Revised:2014-04-08 Published:2014-05-05
  • Supported by:

    Project supported by the Department of Education of Sichuan Province (No. 13ZA0150).

The reaction mechanism from phenylacetaldehyde and benzylamine to polysubstituted imidazole catalyzed by Ι2 was studied by the density functional theory. All of the reactants, intermediates, transition states and product were optimized at B3LYP/6-31+G(d) level. The single point energy and zero point energy correction were calculated for the optimized configuration of each compound at B3LYP/6-311++G(d,p) level. Transition states have been confirmed via vibration analysis and intrinsic reactions coordinate (IRC), and nature bond orbital (NBO) and atoms in molecules (AIM) theories have been used to analysis orbits interaction and bond natures. Our results showed that the activation energy of the rate-determining step was 514.32 kJ·mol-1 without I2-catalyzed, however, the activation energy of the rate-determining step was 145.94 kJ·mol-1 with I2-catalyzed. It indicated that I2 catalyst promoted reaction effectively, and the C—H bond of ethyl of phenylacetaldehyde was activated by I2. In addition, polarized continuum model (PCM) method was adopted to discuss the effects of solvation. All calculations were consistent with experiments. It is predicted that the organic solvent dimethyl sulfoxide (DMSO) can effectively improve the reaction yield.

Key words: iodine, polysubstituted imidazoles, reaction mechanism, solvation, density functional theory