An Efficient Synthesis and Preliminary Investigation of Novel 1,3-Dihydro-2H-benzimidazol-2-one Nitro and Nitramino Derivatives

The preparation and properties of a series of novel 1,3-dihydro-2H-benzimidazol-2-one nitro and nitramino derivatives are described. A detailed crystal structure of one of the obtained compounds, 4,5,6-trinitro-1,3-dihydro-2H-benzimidazol-2-one (TriNBO), was characterized using low temperature single crystal X-ray diffraction, namely an orthorhombic yellow prism, space group ‘P 2 21 21′, experimental crystal density 1.767 g/cm(3) (at 173 K). Methyl analog, 5-Me-TriNBO-monoclinic red plates, space group, P 21/c, crystal density 1.82 g/cm(3). TriNBO contains one activated nitro group at the fifth position, which was used for the nucleophilic substitution in the aminolysis reactions with three monoalkylamines (R=CH(3), C(2)H(5), (CH(2))(2)CH(3)) and ethanolamine. The 5-R-aminoderivatives were further nitrated with N(2)O(5)/ HNO(3) and resulted in a new group of appropriate nitramines: 1,3-dihydro-2H-5-R-N(NO(2))-4,6-dinitrobenzimidazol-2-ones. Thermal analysis (TGA) of three selected representatives was performed. The new compounds possess a high melting point (200–315 °C) and thermal stability and can find a potential application as new thermostable energetic materials. Some calculated preliminary energetic characteristics show that TriNBO, 5-Me-TriNBO, 5-methylnitramino-1,3-dihydro-2H-4,6-dinitrobenzimidazol-2-one, and 5-nitratoethylnitramino-1,3-dihydro-2H-4,6-dinitrobenzimidazol-2-one possess increased energetic characteristics in comparison with TNT and tetryl. The proposed nitrocompounds may find potential applications as thermostable high-energy materials.