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化学学报
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化学学报 ›› 1991, Vol. 49 ›› Issue (6): 540-545. 上一篇    下一篇

研究论文

RCH=CH2与过氧甲酸反应的量子化学研究

洪三国;傅孝愿   

  1. 江西师范大学化学系;北京师范大学化学系
  • 发布日期:1991-06-15

A quantum chemical study of RCH=CH2 epoxidation by peroxyacid

HONG SANGUO;FU XIAOYUAN   

  • Published:1991-06-15

PDF

1087

被引次数

7

本文用MINDO/3方法研究了烯烃RCH=CH2(R=H, CH3, CHO和NO2)与过氧甲酸反应的机理。研究结果表明, RCH=CH2与过氧甲酸反应是亲电反应, 在加热条件下较容易进行。乙烯与过氧甲酸反应的过渡态具有局部对称结构; 若R为取代基时, 这种对称性不复存在, 对于R为给电子基, 过氧基的氧偏向与取代基相连的乙烯碳原子, R为吸电子基, 过氧基氧偏向乙烯的另一碳原子; 取代基的给、吸电子能力越强, 过渡态偏离对称结构越显著, 活化势垒降低或升高也越大。

关键词: 反应机理, 丙烯, 丙烯醛, 乙烯, 量子化学, 乙烯 P, 分子轨道理论, 甲酸 P, 过氧化物, 硝基烃

MINDO/3 MO method has been used to study the reactions of peroxyformic acid with ethylene and substituted ethylenes. The results show that the reactions of RCH=CH2 (R = H, Me, CHO, NO2) with peroxyformic acid are electrophilic reactions. The activation energy decreases with R being electron donating substituent, while it increases by electron withdrawing substituents. Besides, when R = H, the transition structure (TS1) possesses local symmetry, as for R = Me, CHO, NO2, this symmetry no longer exists.

Key words: REACTION MECHANISM, PROPENE, PROPENAL, ETHYLENE, QUANTUM CHEMISTRY, ETHYLENE P, MOLECULAR ORBITAL THEORY, FORMIC ACID P, PEROXIDE, NITRO HYDROCARBON

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