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Keywords:

  • nitro derivatives of phenols;
  • pyrolysis initiation reactions;
  • impact sensitivity;
  • UHF–SCF–AM1 MO method;
  • activation energy.

Abstract

The UHF–SCF–AM1 MO method was applied to the study of two kinds of pyrolysis reactions of six nitro derivatives of phenols (homolysis reaction by rupture of the C—NO2 bond into radicals and isomerization reaction involving phenolic hydrogen transferring to oxygen on the NO2 group). The molecular geometries of reactants, transition states and products were fully optimized. The potential energy curves and activation energies were first obtained. The results show that this category of compounds is more easily initiated via isomerization reactions than by homolysis reactions. The parallel relationship among the Wiberg bond order of the pyrolysis-initiation H—O bond in the molecule of a reactant, the activation energy of the isomerization reaction breaking the H—O bond and impact sensitivity of the reactant gives ‘the principle of the smallest bond order’ (PSBO) powerful support. The sensitizing effect of a phenol group was elucidated based on calculation results. The different influences of OH and NO2 groups on the heat of formation of a molecule are discussed. © 1998 John Wiley & Sons, Ltd.