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

doi:10.6023/cjoc201403027

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

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碘催化苯乙醛与苄胺合成多取代咪唑的反应机理研究

张林^a, 郑妍^a, 潘晓晓^a, 李来才^a, 田安民^b

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 E-mail:lilcmail@163.com
基金资助:
四川省教育厅重点基金（No.13ZA0150）资助项目.

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

Zhang Lin^a, Zheng Yan^a, Pan Xiaoxiao^a, Li Laicai^a, Tian Anmin^b

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 Ι₂was 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

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Zhang Lin, Zheng Yan, Pan Xiaoxiao, Li Laicai, Tian Anmin. Investigation the Reaction Mechanism from Phenylacetaldehyde and Benzylamine to Polysubstituted Imidazole Catalyzed by Ι₂[J]. Chin. J. Org. Chem., 2014, 34(8): 1595-1602.

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碘催化苯乙醛与苄胺合成多取代咪唑的反应机理研究

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

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