物理化学学报 >> 2000, Vol. 16 >> Issue (03): 243-247.doi: 10.3866/PKU.WHXB20000310

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乙烯亚胺与亚胺[2+2]环加成反应的理论研究

吴芃, 何绍仁   

  1. 北京师范大学化学系，北京 100875
  • 收稿日期:1999-07-20 修回日期:1999-11-16 发布日期:2000-03-15
  • 通讯作者: 吴芃

Theoretical Study on the Mechanism of [2+2] Cycloaddition of Ketenimine with Imine

Wu Peng, He Shao-Ren   

  1. Beijing Normal University,Beijing 100875
  • Received:1999-07-20 Revised:1999-11-16 Published:2000-03-15
  • Contact: Wu Peng

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摘要：

在HF/6-31G**和HP2/6-31G**水平上对乙烯亚胺和亚胺两模型分子的[2+2]环加成反应的三种环加成方式进行了理论探讨. 计算发现, 环加成方式(1)和环加成方式(2)反应途径的位垒较低 ,反应较易进行 ;而环加成方式(3)位垒较高 ,反应较难发生. 我们用前线轨道理论对其机理进行了初步探讨.

关键词: 环加成, 乙烯亚胺, 亚胺, 反应机理, 分布反应, 前线轨道理论

Abstract:

The three pathways of [2+2] cycloaddition of ketenimine with imine have been studied at HF/6-31G** and MP2/6-31G** levels of theory. The results indicate that the energy barriers of pathway (1) and pathway (2) are low. So the two reactions can proceed easily. While the energy barrier of pathway (3) is high, it is difficult to proceed. We explain the mechanisms of the first two pathways by the Frontier Orbital Theory at HF/6-31G** level.

Key words: Cycloaddition, Ketenimine, Imine, Mechanism, Stepwise reaction, Frontier orbital theory