物理化学学报 >> 1998, Vol. 14 >> Issue (11): 1001-1006.doi: 10.3866/PKU.WHXB19981108

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乙烯基炔与一氧化氮反应机理的理论探讨

陈丽涛, 陈光巨, 傅孝愿   

  1. 浙江工业大学化学工程学院，杭州 310014|北京师范大学化学系，北京 100875
  • 收稿日期:1998-02-23 修回日期:1998-05-22 发布日期:1998-11-15
  • 通讯作者: 傅孝愿

AM1 Studies of Two Pathways of Vinylacetylene React with Nitric Oxide

Chen Li-Tao, Chen Guang-Ju, Fu Xiao-Yuan   

  1. Institute of Chemical Engineering,Zhejiang Industrial University,Hangzhou 310014|Department of Chemistry,Beijing Normal University,Beijing 100875
  • Received:1998-02-23 Revised:1998-05-22 Published:1998-11-15
  • Contact: Fu Xiao-Yuan

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摘要：

利用半经验AM1方法，研究了乙烯基乙炔与一氧化氮反应生成丙炔腈（反应1）和丙烯腈（反应2）的两条竞争反应途径．采用Berny梯度法优化得到了反应势能面上的所有驻点，并逐一进行了振动分析确认．结果表明，反应互较反应Ⅱ易引发（即, NO比较容易与乙烯基乙炔进行分步的1，4-加成，形成六元环过渡态及中间体，最终消除CH2O和H自由基后生成丙炔腈），而反应Ⅱ较难引发（NO与乙烯基乙炔较难进行1，2-加成，形成四元环过渡态及中间体），但一经引发，就能较容易地进行分步裂解，生成丙烯腈和CHO自由基．

关键词: 乙烯基乙炔, 一氧化氮, 自由基, 丙烯腈

Abstract:

Two competitive pathways of the stepwise reaction of vinyl acetylene (VA) with nitric oxide were studied by UAM1 method. The calculations showed that the path Ⅰ(NO attacks VA to form a six-membered cyclic transition state through the 1,4-addition reaction for the first two steps, then decomposed at the last two steps to form CH2O, propionitrole and H ratical) is easier to initiate than path Ⅱ(NO approaches VA with a 1.2-addition to form a four-membered cyclic transition state at its first two steps). However, path Ⅱcall easily take place at its final two steps to form acrylonitrile once it has been initiated.

Key words: Vinylacetylene, Nitric oxide, Radical, Acrylonitrile