Thermal Decomposition of Nitramines: Dimethylnitramine, Diisopropylnitramine, and N-Nitropiperidine

Article abstract of DOI:10.1021/j100185a023

Kinetics and activation parameters of the solution thermolysis of nitramines dimethylnitramine, diisopropylnitramine, and N-nitropiperidine were determined over the temperature range 200-300 deg C.Each formed the corresponding nitrosamine as the only, or major, condensed-phase product.For dimethylnitramine the products were completely characterized.The observations of a large positive activation volume in the thermolysis of dimethylnitramine and of the slowing of the decomposition reaction with increased solvent viscosity both suggest that the rate-determining step is homolysis, the N-NO2 bond being the most obvious point for this.Nitrosamines could be produced by this route; however, when doubly 15N-labeled dimethylnitramine was heated with unlabeled dimethylnitramine, little scrambling of the label in the reactant was observed.Label scrambling was observed in the nitrosamine but could have resulted from subsequent N-NO homolysis.Scrambling of the label in the product gases and the observation of a kinetic isotope effect when perdeuterated dimethylnitramine was decomposed were explained in terms of a second decomposition route involving transfer of hydrogen from the α carbon to one of the NO2 oxygens.