3,3'-二硝基双呋咱醚(FOF-1)合成、晶体结构及理论研究

以二硝基呋咱(DNF)为原料,碱性条件下通过DNF分子间硝基醚化合成了3,3'-二硝基双呋咱醚(FOF-1),产率67%,采用红外光谱、核磁共振、质谱及元素分析进行了结构表征.初步探讨了硝基分子间醚化合成FOF-1反应机理,确定了分子间醚化的最佳条件.培养了FOF-1单晶,X射线单晶衍射分析结果表明:FOF-1晶体结构属正交晶系,空间群为P2(1)2(1)2(1),a=6.507(3)nm,b=7.342(4)nm,c=18.721(9)nm,α=90°,β=90°,γ=90°,Dc=1.813g·cm-3;用B3LYP方法在6-31G(d,p)基组水平上对FOF-1的结构进行了计算,得到了其稳定的几何构型和键级.在振动分析的基础上求得体系在不同温度下的热力学性质,并得到了温度对热力学性能影响的关系式.探讨了其热解机理,计算出醚键断裂时的的活化能为234.12kJ·mol-1.

Synthesis, Crystal Structure and Theoretical Research of 3,3'-Dinitrodifurazanyl ether (FOF-1)

3,Y-Dinitrodifurazanyl ether (FOF-1) was synthesized in a yield of 67.0% using 3,4-dinitrofumzan (DNF) as a starting material through intermolecular etherification. The structure was confirmed by IR,~1H NMR,~(13)C NMR, MS and elemental analyses. The reaction mechanism of intermolecular etherification of nitro-group to synthesize FOF-1 was preliminarily discussed. The optimal conditions of intermolecular etherification were confirmed. The single crystal of FOF-1 was cultivated and tested by single-crystal X-ray diffraction. The crystal belongs to orthorhombic system, space group P2(1)2(1)2(1) with crystal parameters a=6.507(3) nm, b=7.342(4) nm, c= 18.721(9) nm, α=90°, β=90°,γ=90°, Dc=1.813 g·cm~(-3). The structure of FOF-1 was also estimated by a B3LYP method based on 6-31G(d,p) basis set and the stable geometric configuration and bond order were obtained. The thermodynamics properties at different temperatures were obtained from vibrational analysis, and the relationship between temperature and thermodynamics properties was deducted. Pyrolysis mechanism of FOF-1 was discussed, and the activation energy of the breaking of ether link is 234.12 kJ·mol~(-1).