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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (10): 930-936. 上一篇    下一篇

研究论文

苯甲醛肟与炔丙醇偶极环加成反应的理论研究

林宪杰1, 徐为人2, 武剑1, 刘成卜*,1   

  1. (1山东大学化学与化工学院 济南 250100)
    (2天津药物研究院 天津 300193)
  • 投稿日期:2005-12-22 修回日期:2006-08-28 发布日期:2007-05-28
  • 通讯作者: 刘成卜

Theoretical Study on the Dipole Cycloaddition Reaction of Benzaldoxime with Propinol

LIN Xian-Jie1; XU Wei-Ren2; WU Jian1; LIU Cheng-Bu*,1   

  1. (1 College of Chemistry and Chemical Engineering, Shandong University, Jinan 250100)
    (2 Tianjin Institute of Pharmaceutical Research, Tianjin 300193)
  • Received:2005-12-22 Revised:2006-08-28 Published:2007-05-28
  • Contact: LIU Cheng-Bu

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被引次数

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用密度泛函理论(DFT)方法在B3LYP/6-31G*水平上研究了苯甲醛肟与炔丙醇加成反应的微观机制和热力学、动力学行为. 结果表明, 在苯甲醛肟与炔丙醇加成反应过程中, 8个可能反应通道的过渡态中均形成非平面五元环结构, 其中苯甲醛肟的Z、E构型特征得到了部分保留, 但主要部分的键长、键角均发生了变化, 电荷也进行了重新分布. 苯甲醛肟以羟基型参与反应的4个反应通道均为吸热反应和热力学非自发过程, 它们均具有较高的反应势垒、较慢的反应速率和较小的平衡常数; 而以离子型参与反应的四个反应通道均为放热反应和热力学自发过程, 它们的反应势垒较低, 反应速度较快, 平衡常数也较大, 故苯甲醛肟应主要以离子型参与反应. 炔丙醇的两种取向对应着加成反应的两种产物, 反应达到平衡后, 3-羟甲基二氢异噁唑为主要产物.

关键词: 苯甲醛肟, 炔丙醇, 加成反应, 机制, 理论研究

The reaction mechanism, thermodynamic and kinetic behavior of the dipole cycloaddition reaction of benzaldoxime with propinol have been studied by DFT method at B3LYP/6-31G* level. The results show that there are eight reaction channels, corresponding to eight transition states, in the reaction process. The main parts of all transition states are non-planar five-membered ring, in which the geometry of Z-benzaldoxime and E-benzaldoxime is maintained partially, but the bond length, bond angle and charge are all changed. The four reaction channels including hydroxyl-type benzaldoxime are endothermic reaction, thermodynamically non-spontaneous process, but the other four reaction channels including ion-type benzaldoxime participation are exothermic reaction and thermodynamically spontaneous process. The latter four reaction channels, which have lower reaction barriers, faster reaction velocities and bigger equilibrium constants than those of the former fours, are the chief reaction channels. Two kinds of products can be obtained in the addition reaction of benzaldoxime with propinol, in which 3-hydroxymethyl-dihydroisoxazol is the main product when reaction equilibrium is reached.

Key words: benzaldoxime, propinol, addition reaction, mechanism, theoretical research