Thermal ring-opening reaction of N-polynitromethyl tetrazoles: facile generation of nitrilimines and their reactivity

Thermal ring-opening reaction of N-(R-dinitromethyl)-5-nitrotetrazoles (R=NO2, F, Cl ) yielded highly reactive N-(R-dinitromethyl)-nitrilimine intermediates under mild conditions. These species underwent facile and regiospecific reaction with nitriles and acetylenes to afford the corresponding nitrotriazoles and nitropyrazoles in 50-90% yields. Treatment of N-(chlorodinitromethyl)-5-nitrotetrazole with the excess of azide led to a unique compound with the molecular formula C2N14. Based on the analytical data, it was assigned a structure of diazidomethylenecarbonohydrazonic diazide. (C) 2009 Elsevier Ltd. All rights reserved.