An in-depth kinetic analysis of the thermal conversion was conducted by Variable Temperature (VT) NMR measurements obtaining the reactant concentrations through the integrals of the diagnostic peaks in combination with DMF as internal standard. For AO conversion, both AO consumption and nitrile formation expectedly followed first-order kinetics (Figure and). Rate constants were extracted at 90, 95, and 100 °C giving Ea = 132 kJ mol -1 using Arrhenius fitting (Figure ). Since MKO and TKO were thermally stable and degraded non-specifically, their thermal Ea could not be determined. Carbamoylketoximes derived from secondary amines are not prone to thermally dynamic behavior, and hence this mechanistic interpretation was disregarded as an explanation. Considering the contrasting mechanochemical reactivity of the carbamoyloximes, these substantial deviations were thus surprising and suggested that the homolytic mechanochemical reaction pathway deviated from the thermal reaction pathway for AO.