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

Abstract

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, (1)H, (13)C, and (14/15)N 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.

Toxicity Assessment of Energetic Materials by Using the Luminescent Bacteria Inhibition Test

“…The synthesis of meso‐erythritol tetranitrocarbamate ( 41 ) started from corresponding sugar alcohol by an economically benign two‐step synthesis [44]. Primary nitrocarbamates form a new class of energetic materials with good detonation performances and lower sensitivities than the commonly used nitrate ester explosive PETN.…”

“…Therefore, 43 has to be classified as toxic. The toxicity of another water-soluble trinitroalkyl compound, trinitropropylammonium chloride (44), is lower and in the range of very toxic compounds (EC 50 < 0.10 g L À 1 ) [48]. A further trinitroalkyl substituted compound, (bis(2,2,2-trinitroethyl)-hydrazodicarboxylate), was reported to show high aquatic toxicity against Aliivibrio fischeri (EC 50 (30 min) = 0.02 mg L À 1 ) [18].…”

Synthesis, Characterization and Properties of Ureido‐Furazan Derivatives

“…The reaction of amines with CSI leads to ureido moieties (Scheme ), which further could be nitrated to a nitro ureido derivative. The CSI reaction conditions and mechanisms have been investigated in our research group to synthesize carbamates from alcohols .…”

Insensitive ionic bio-energetic materials derived from amino acids

“…Certain NBEMs derived from sugar alcohols and glycine were reported by Klapötke et al . 22 , 23 . However, studies on this bio-based species focus primarily on neutral compounds.…”