Efficient Synthesis of Primary Nitrocarbamates of Sugar Alcohols: From Food to Energetic Materials

The synthesis of various new polyvalent nitrocarbamates derived from sugar alcohols was accomplished by an economically benign two-step synthesis. The precursor carbamates were synthesized with the reagent chlorosulfonyl isocyanate (CSI) and further nitrated using mixed acid. The starting materials, sugar alcohols, are renewable biomass, mainly used in food and cosmetic industry. The structures of one carbamate and one nitrocarbamate were exemplary described by single-crystal X-ray-analysis. The heat of formation is calculated by the use of isodesmic reactions and the energetic performance data were estimated. All compounds were fully characterized by elemental analysis, vibrational spectroscopy, H-1, C-13, and N-14/15 NMR spectroscopy and thermal analysis (DSC). The nitrocarbamates exhibit good detonation performance and have significantly lower sensitivities compared to the commonly used nitrate ester explosive PETN.