Synthesis, Characterization and Energetic Performance of Oxalyl Diazide, Carbamoyl Azide, and N,N'-Bis(azidocarbonyl)hydrazine.

As pure compounds, small carbonyl azides enjoy a bad reputation, due to the high explosive sensitivity and instability they demonstrate. Consequently, most reported examples have only been poorly characterized. The compounds oxalyl diazide (1), carbamoyl azide (2), as well as N,N'-bis(azidocarbonyl)hydrazine (3) were obtained by performing a diazotation reaction on the corresponding hydrazo precursor. Carbamoyl azide (2) could also be obtained from oxalyl diazide via Curtius rearrangement to the reactive isocyanate, followed by reaction with water. Further, different trapping reactions of the isocyanate with hydroxyl (methanol, oxetan-3-ol) and amino (2-amino-5H-tetrazole) functions are described. All products were extensively analyzed using IR, EA, DTA and multinuclear NMR spectroscopy, and the crystal structures elucidated using single crystal X-ray diffraction. In addition, the sensitivities toward friction and impact were determined and the energetic performances of the carbonyl azides were calculated using the EXPLO5 code.