物理化学学报 >> 1997, Vol. 13 >> Issue (01): 36-41.doi: 10.3866/PKU.WHXB19970107

研究论文 上一篇    下一篇

一元硝酸酯热解反应的理论研究

贡雪东,肖鹤鸣   

  1. 南京理工大学化学系，南京 210094
  • 收稿日期:1996-07-11 修回日期:1996-10-03 发布日期:1997-01-15
  • 通讯作者: 肖鹤鸣

Theoretical Study on Pyrolysis of Mononitrate Esters

Gong Xue-Dong,Xiao He-Ming   

  1. Department of Chemistry,Nanjing University of Science and Technology,Nanjing 210094
  • Received:1996-07-11 Revised:1996-10-03 Published:1997-01-15
  • Contact: Xiao He-Ming

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摘要：

运用SCF－AM1－MO方法，计算研究了十个一元硝酸酯的热解反应，揭示了烷基取代对反应过程的影响.UHF计算O－NO2键均裂产生RCH2O•和•NO2两个自由基的反应活化能较低，是硝酸酯热解的主要途径; RHF计算α-H转移环消除产生RCHO和HONO的反应具有较高活化能，且α-C上含两个以上取代基时不发生该反应.还探索性地进行了C－O键断裂的UHF和RHF计算.

关键词: 硝酸酯, 热解反应, AM1方法, RIF计算, UHF计算

Abstract:

The pyrolysis reactions of ten mononitrate esters have been studied by using SCFAM1-MO method. The effect of alkyl substitution on the mechanism of reactions is discussed. UHF calculations show that homolysis of O-NO2 bond into two radicals RCH2O•and•NO2 has lower activation energy and is the main way of pyrolysis. However, RHF calculations indicate that breaking of O-NO2 is a α-H transition elimination reaction with products RCHO and HONO and quite high activation energy, and can't occur when there are more than two alkyl substitution groups on α-C. The cleavage of C-O bond has also been studied by UHF and RHF calculations.

Key words: Nitric esters, Pyrolysis, AM1 method, RHF ealculation, UHF calculation