Alternative mechanisms of thermal decomposition of o-nitrotoluene in the gas phase

摘要: The density functional theory methods were used to demonstrate that during the thermal decomposition of o-nitrotoluene, with formation 5-methylene-6-aci-nitrocyclohexa- 1,3-diene (aci-form) being primary event, rotation =N(O)OH group around CN double bond in aci-form is key importance. activation enthalpy lower for this step than alternative process H atom transfer between O atoms group. This accounts competitive experimentally observed products о-nitrotoluene decomposition, namely, hydroxyl radical and water. barriers reactions estimated over a broad temperature range, which indicated possible contribution other event mechanisms (nitro—nitrite rearrangement, bicyclization) efficient rate constant. results account differences parameters determined at various temperatures by different authors.