Investigations of the Vicarious C-Aminations of 5,7-Dinitrobenzotriazole and 4,6-Dinitrobenzotriazol-3-ium-1-oxide and Their Energetic Properties.

This combined experimental and theoretical study details the vicarious nucleophilic substitution by amination of 5,7-dinitrobenzotriazol (1) and 4,6-dinitrobenzotriazole-3-ium-1-oxide (4) with trimethylhydrazinium iodide to afford the new corresponding one- and two-time aminated compounds and investigations of its mechanism by EPR spectroscopy. The preferred position for the first amination is computed by spin density population and verified by X-ray crystallography. The zwitterionic structure of 4 is investigated in solution by (1) H NMR spectroscopy and in solid state by X-ray diffraction. Furthermore, the crystal structure of 1 is presented. The energetic behavior of the aminated products as well as the starting materials 1 and 4 was investigated, regarding sensitivities and performance.