A Study of Thermal Activation of N-Nitrosoamides

N-4-R-Benzyl-N-nitrosoamides were decomposed at various temperatures in selected solvents. From their decomposition rates, contributions from ΔH* and ΔS* evidently depend upon intramolecular and solvent effects consistent with an early metastable oxadiazetyl-type entity in the first and rate-determining step of nitrosoamide thermolyses as opposed to a first, slowest step to a trans-diazoester.