A Melt⁃cast Explosive 3⁃Azido⁃1 ， 3⁃dinitroazetidine （ AzDNAZ ） with Gem⁃azidonitro of Novel Energetic Group ： Synthesis and Performance

： Starting from （ 1 ‑tert‑butyl‑3 ‑nitroazetidin ‑3 ‑yl ） methanol ， a melt‑cast explosive of 3 ‑azido ‑1 ， 3 ‑dinitroazetidine （ AzDNAZ ） with novel gem‑azidonitro energetic group was obtained through an improved azidation‑salinization‑nitration strate‑ gy with a total yield of 58.8%. Structures of the intermediates and AzDNAZ were characterized by 1 H NMR ， 13 C NMR ， IR and el‑ ement analysis. One of the intermediates ， 1‑t‑butyl‑3‑azido‑3‑nitro‑azetidinium nitrate （ compound 22 ）， was obtained for the first time with the single crystal determined by X‑ray single crystal diffraction ， which reveals that it crystallizes in monoclinic ， space group P 2 （ 1 ） / n with a =0.8281 （ 314 ） nm ， b =0.8607 （ 2 ） nm ， c =1.7195 （ 2 ） nm ， α =90° ， β =94.983 （ 2 ） ° ， γ =90° ， V =1.2210 （ 6 ） nm 3 ， Z =4 ， M r =262 ， D c =1.427 g·cm -3 ， μ =0.174 mm -1 ， F （ 000 ） =552 ， R =0.0418 and ω R =0.1168. Meanwhile ， thermal behaviors of AzD‑ NAZ were studied by subsequently differential scanning calorimetry （ DSC ） and thermal gravimetric analyzer （ TG ） methods. Based on the measured values of density and heat of formation ， the detonation parameters were calculated by Gaussian 09 program and Kamlet‑Jacobs equations. Results show that the melting point ， decomposition point ， density ， heat of formation ， detonation velocity and detonation pressure are 78.2 ℃ ， 180.7 ℃ ， 1.75 g·cm -3 ， 331.73 kJ·mol -1 ， 8460 m·s -1 and 31.83 GPa ， respectively ， indicating AzDNAZ can be applied as a promising melt‑cast explosive or an energetic plasticizer with satisfactory performances.