三呋咱并氧杂环庚三烯便捷新法合成及量子化学研究

New facile synthesis and quantum chemistry studies of trifurazanooxacycloheptatriene

为解决目前三呋咱并氧杂环庚三烯(TFO)的合成方法难于工业化的问题,设计了TFO便捷合成新方法。以3,4-双(3’-硝基呋咱-4’-基)氧化呋咱(DNTF)为原料,经醚化、还原合成了TFO,总收率为71.1%,并利用红外光谱(IR)、核磁共振氢谱(1H NMR)、核磁共振碳谱(13C NMR)、质谱(MS)及元素分析等进行了结构表征;探讨了还原反应的关键影响因素,确定了最佳的反应条件为:还原剂为亚磷酸三乙酯,料比n(还原剂):n(BFFO)为2:1,反应温度为80℃,时间为18h。采用DSC研究了TFO的热性能,分解点为377.4℃。基于Gussian 98程序的B3LYP方法,在6-31G(d,p)基组水平上对TFO的结构进行了优化,得到了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,得到了温度对热力学性能影响的关系式,结果表明TFO分子结构稳定性较好。

A new facile synthesis method of trifurazanooxacycloheptatriene(TFO) was designed to be applied in industrial production.TFO was prepared with a total yield of 71.1% via etherification and reduction two-step reactions from the raw material of 3,4-bis(4’-nitrofurazano-3’-yl)furoxan(DNTF).The structure of TFO was characterized by infrared spectrum(IR),nuclear magnetic resonance 1 H spectrum(1 H-NMR),nuclear magnetic resonance 13 C spectrum(13C-NMR),mass spectrometry and elemental analysis.The influence of reaction conditions on the reduction was investigated,and the optimized conditions were obtained as following:(CH3 CH2 O)3 P is reductant,n(reductant):n(BFFO) is 2:1,the reaction temperature and reaction time were 80℃and 18 h respectively.The thermal behavior of TFO was studied by DSC,and the results show that the peak temperature of decomposition is 377.4℃.The structure of TFO was optimized at the group level of B3 LYP/6-31 G(d,p) based on B3 LYP/6-31 G(d,p) method,and the stable geometry and bond order were obtained.The thermodynamic properties at different temperatures were calculated based on vibration analysis,and the relationship between temperature and thermodynamic properties were achieved.All results indicate that the molecular structure of TFO has good stability.