3,3’-二氰基二呋咱基醚(FOF-2)的合成、表征及量子化学研究

以3-氨基-4-酰胺肟基呋咱(AAOF)为原料, 经两次氧化、分子间醚化得到3,3’-二氰基二呋咱基醚(FOF-2), 收率90.9%, 并通过IR, 1H NMR, 13C NMR, MS, 元素分析, DSC等分析手段对其结构进行了表征. 初步探讨了硝基分子间醚化合成FOF-2的反应机理; 确定了Caro’s acid氧化、分子间醚化的最佳条件. 用B3LYP方法, 在6-31G(d,p)基组水平上对其结构进行了计算, 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的振动频率、IR谱及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活化能.

Synthesis, Characterization and Quantum Chemistry Study on 3,3'-Dicyanodifurazanyl Ether (FOF-2)

3,3’-Dicyanodifurazanyl ether (FOF-2) was synthesized in a yield of 90.9% using 3-amino-4-aminoximidofurazan (AAOF) as a starting material through twice oxidization and intermolecular etherification. The structure was confirmed by IR, 1H NMR, 13C NMR, MS, elemental analysis and DSC. The reaction mechanism of intermolecular etherification of nitro-group to synthesize FOF-2 was preliminar-ily discussed. The optimal conditions of Caro’s acid oxidization and intermolecular etherification were con-firmed. The structure of FOF-2 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 vibrational frequencies, IR spectrum and thermodynamics properties at different temperatures were obtained from vibrational analysis, and the relationship between temperature and thermodynamics properties was deducted. Pyrolysis mechanism of FOF-2 was discussed, and the activation energy of the breaking of ether link was calculated.