Tang Yongxing, He Chunlin, Imler Gregory H, Parrish Damon A, Shreeve Jean'ne M
Department of Chemistry, University of Idaho, Moscow, Idaho, 83844-2343, USA.
Naval Research Laboratory, 4555 Overlook Avenue, Washington, D.C., 20375, USA.
Chemistry. 2017 Nov 16;23(64):16401-16407. doi: 10.1002/chem.201704446. Epub 2017 Oct 25.
N-Cyanoimidate (1) with hydroxylamine hydrochloride in the presence of triethylamine gives different products (2 a or 2 b) as a function of the sequence of reactant addition. Further oxidation/nitration/decarboxylation/acidification reactions of 2 a/2 b generate dinitromethyl-3(5)-1,2,4-oxadiazole derivatives, including a surprising energetic compound with high oxygen balance, 3-(dinitromethyl)-1,2,4-oxadiazol-5-one (5) as well as 5,5'-dinitromethyl-3,3'-azo-1,2,4-oxadiazole (9). Some salts of 5 and 9 as precursors were also prepared. All were fully characterized using multinuclear NMR and IR spectroscopy, and elemental analyses as well as low-temperature single-crystal X-ray diffraction for 4, 5, 7 and 8. In addition, their properties (thermal stability, detonation performance and sensitivity to impact and friction) were investigated. Among them, 5 and 8 show promising detonation performance as energetic materials.
在三乙胺存在下，N-氰基亚氨酸酯（1）与盐酸羟胺反应，根据反应物添加顺序的不同会生成不同的产物（2a或2b）。2a/2b的进一步氧化/硝化/脱羧/酸化反应生成二硝基甲基-3(5)-1,2,4-恶二唑衍生物，包括一种令人惊讶的具有高氧平衡的含能化合物3-(二硝基甲基)-1,2,4-恶二唑-5-酮（5）以及5,5'-二硝基甲基-3,3'-偶氮-1,2,4-恶二唑（9）。还制备了5和9的一些盐作为前体。所有产物均通过多核NMR和IR光谱、元素分析以及对4、5、7和8进行低温单晶X射线衍射进行了全面表征。此外，还研究了它们的性能（热稳定性、爆轰性能以及对冲击和摩擦的敏感性）。其中，5和8作为含能材料表现出有前景的爆轰性能。
