Thermal Decomposition of Nitrate Esters

Article abstract of DOI:10.1021/j100163a013

Rates of thermal decomposition and solvent rate effects have been measured for a series of nitrate esters.The alkoxy radicals formed by homolysis together with some of their further degradation products have been stabilized by hydrogen donation.Internal and external return of nitrogen dioxide have been demonstrated by solvent cage effects and isotope exchange.Radical-stabilizing substituents favor β-scission.Dinitrates in a 1,5 relationship behave as isolated mononitrates.Dinitrates in a 1,3 or 1,4 relationship exhibit intramolecular reactions.Tertiary nitrate esters in diethyl ether undergo elimination rather than homolysis.