Yu Qiong, Cheng Guangbin, Ju Xuehai, Lu Chunxu, Lin Qiuhan, Yang Hongwei
School of Chemical Engineering, Nanjing University of Science and Technology, Xiaolingwei 200, Nanjing, Jiangsu, China.
Dalton Trans. 2017 Oct 24;46(41):14301-14309. doi: 10.1039/c7dt02098h.
Herein, the 1,4,2,5-dioxadiazine ring is combined with two furazan rings. Interestingly, the structure of the 1,4,2,5-dioxadiazine-furazan system can be modified by incorporating versatile functionalities. The N-trinitroethylamino functionalization derivatives and energetic salts based on 3,6-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,4,2,5-dioxadiazine are investigated. Derivatives of these functionalities are synthesized and fully characterized via multinuclear NMR spectroscopy, IR spectroscopy, and elemental analysis. The structures of compounds 1-7 are further confirmed by single-crystal X-ray diffraction. Compounds 1-12 have moderate thermal stabilities (143-177 °C, except 2 (114 °C), and 3 (88 °C)) and exhibit acceptable sensitivities (IS 3.52-16.3 J and FS 100-240 N). Based on the measured densities (1.73-1.95 g cm) and heats of formation (573.5-2065.4 kJ mol), the detonation velocities (D 8519-9563 m s) and pressures (P 29.3-43.3 GPa) are calculated. Among them, the trinitroethylamino derivative 1 and ammonium salt of 3,6-bis(4-nitroamino-1,2,5-oxadiazol-3-yl)-1,4,2,5-dioxadiazine 5 show a layered assembly of the 1,4,2,5-dioxadiazine-furazan system. These two compounds show good thermal stabilities (1, 154 °C and 5, 177 °C) and relatively low sensitivities (1, 16.3 J and 5, 13.4 J). These properties indicate that the layer assembly structure is helpful to improve the thermal stabilities and result in low sensitivities for the corresponding compounds.
在此，1,4,2,5-二恶二嗪环与两个呋咱环相结合。有趣的是，1,4,2,5-二恶二嗪-呋咱体系的结构可通过引入多种官能团进行修饰。对基于3,6-双(4-氨基-1,2,5-恶二唑-3-基)-1,4,2,5-二恶二嗪的N-三硝基乙氨基官能化衍生物和含能盐进行了研究。合成了这些官能团的衍生物，并通过多核核磁共振光谱、红外光谱和元素分析对其进行了全面表征。化合物1-7的结构通过单晶X射线衍射进一步得到证实。化合物1-12具有中等热稳定性(143-177℃，2除外(114℃)，3除外(88℃))，并表现出可接受的感度(IS 3.52-16.3 J，FS 100-240 N)。基于测得的密度(1.73-1.95 g/cm)和生成热(573.5-2065.4 kJ/mol)，计算了爆速(D 8519-9563 m/s)和压力(P 29.3-43.3 GPa)。其中，三硝基乙氨基衍生物1和3,6-双(4-硝基氨基-1,2,5-恶二唑-3-基)-1,4,2,5-二恶二嗪5的铵盐呈现出1,4,2,5-二恶二嗪-呋咱体系的层状组装。这两种化合物表现出良好的热稳定性(1为154℃，5为177℃)和相对较低的感度(1为16.3 J，5为13.4 J)。这些性质表明层状组装结构有助于提高相应化合物的热稳定性并导致低感度。
