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

研究论文 上一篇    下一篇

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

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