Acta Phys. -Chim. Sin. ›› 1997, Vol. 13 ›› Issue (01): 36-41.doi: 10.3866/PKU.WHXB19970107

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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


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