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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (7): 567-571. 上一篇    下一篇

研究论文

氧化腈与丙炔1,3-偶极环加成反应中区域选择性的理论研究

张月梅1，王若曦1，徐为人2，刘成卜*,1   

  1. (1山东大学理论化学研究所 济南 250100)
    (2天津药物研究院天津药代动力学与药效动力学省部共建国家重点实验室 天津 300193)
  • 投稿日期:2004-06-23 修回日期:2004-12-14 发布日期:2010-12-10
  • 通讯作者: 刘成卜

Theoretical Study on the Regioselectivity of Nitrile Oxide 1,3-Dipolar Cycloaddition to Propyne

ZHANG Yue-Mei1, WANG Ruo-Xi1, XU Wei-Ren2, LIU Cheng-Bu*,1   

  1. (1 Institute of Theoretical Chemistry, Shandong University, Jinan 250100)
    (2 Tianjin Institute of Pharmaceutical Research, Tianjin State Key Laboratory of Pharmacokinetics and Pharmacodynamics, Tianjin 300193)
  • Received:2004-06-23 Revised:2004-12-14 Published:2010-12-10
  • Contact: LIU Cheng-Bu

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被引次数

2

用密度泛函(DFT)B3LYP/6-311＋＋G**方法研究了氧化腈(RCNO, R＝F, NO2, OCH3, OH, COOCH3, CHO, CONH2, H, CH3)与丙炔的1,3-偶极环加成反应, 并且计算了不同温度下的反应速率常数, 讨论了氧化腈上不同取代基R的取代效应和温度对反应区域选择性的影响. 结果显示, 氧化腈与富电子亲偶极体——炔烃反应, 5-取代反应占优势; 氧化腈上取代基R为强吸电子基团时或在较高温度下, 有利于4-取代反应的进行.

关键词: 1,3-偶极环加成, 氧化腈, 丙炔, 量子化学计算, 区域选择性

In order to discuss the regioselectivity of nitrile oxide 1,3-dipolar cycloaddition to propyne, 1,3-dipolar cycloaddition reaction of substituted nitrile oxide (RCNO, R＝F, NO2, OCH3, OH, COOCH3, CHO, CONH2, H, CH3) with propyne was studied using density functional theory at the 6-311＋＋G** level, and the reaction rates were calculated at different temperature from 200 to 400 K. The conclusions are that 5-substituted reaction of nitrile oxide with electron-deficient dipolarophile—propyne is dominant, while 4-substituted reaction of electron-deficient nitrile oxide with propyne is favored at relatively high temperature.

Key words: 1,3-dipolar cycloaddition, nitrile oxide, propyne, quantum chemical calculation, regioselectivity