Thermolysis of Molecules Containing NO2 Groups

摘要

MINDO/3 calculations are reported for the thermal decomposition of nitromethane, methyl nitrite, methyl nitrate, nitroethylene, 1-1-dinitroethylene, cis-1,2-dinitroethylene, tetranitroethylene, nitroacetylene, and dinitroacetylene. The nitro compounds decompose most easily by first rearranging to isomeric nitrites. Methyl nitrite and methyl nitrate can decompose by fission into radicals (CH3O + NO or NO2) or by alternative routes involving cyclic elimination (CH3ONO yields CH2O + HONO) or intermolecular transfer of oxygen (CH3ONO2) + HCH20N02 yields CH3ONO + HOCH2ONO2). In the case of methyl nitrate, the latter alternative is likely to be favored under the conditions of a detonation shock wave. the activation energies calculated for the nitro yields nitrite rearrangements of tetranitroethylene and of dinitroacetylene suggest that neither will be thermally stable.