journal6 ›› 2012, Vol. 33 ›› Issue (2): 89-92.DOI: 10.3969/j.issn.1007-2985.2012.02.021

• 化学化工 • 上一篇    下一篇

肟和环戊二烯杂Diels-Alder反应的理论计算

  

  1. （华东交通大学基础科学学院，江西 南昌 330013）
  • 出版日期:2012-03-25 发布日期:2012-05-28
  • 作者简介:徐文媛（1975-），女，江西南昌人，华东交通大学基础科学学院教授，博士，主要从事工业催化、有机硅反应及其量化计算研究.
  • 基金资助:

    国家自然科学基金资助项目(21163005；31160187 )

Theoretical Study on the Hetero-Diels-Alder Reaction of Oxime and Cyclopentadiene

  1. (School of Basic Sciences,East China Jiaotong University,Nanchang 330013,China)
  • Online:2012-03-25 Published:2012-05-28

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摘要：应用量子化学中的密度泛函（B3LYP/6-311G(d,p)）和二级微扰（MP2/6-311G(d,p)）方法对肟和环戊二烯的杂Diels-Alder反应机理进行了计算.结果表明，碳氮键先于碳碳键生成，碳氮键和碳碳键的生成与断裂属非同步的协同过程，C=O键在反应中钝化，不参与反应；反应符合前线轨道理论，利于反应进行；从热力学和动力学角度分析，此反应可以进行，优化计算的结果意义较大；反应计算数据与已有实验结果一致.

关键词： 肟, 环戊二烯, 杂Diels-Alder反应, B3LYP, MP2

Abstract: B3LYP/6-311G(d,p) theory and MP2/6-311G(d,p) theory  were used to calculate the Hetero-Diels-Alder reaction’s mechanism of oxime and cyclopentadiene.The results indicate that C—N bonds’ formation was prior to C—C bonds’;the formation and fracture of C— N bonds and C—C bonds were asynchronous collaborative processes；C=O bond which was passivated did not participate in the reaction.Reactions agree with frontier orbital theory which is favorable for the hetero-Diels-Alder reaction’s  progress.From the perspective of thermodynamics and kinetics,the reaction is feasible and the optimization results are of great significance.Reaction’s calculated data is in full agreement with literature’s.

Key words: oxime, cyclopentadiene, Hetero-Diels-Alder reaction, B3LYP, MP2

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