含氟茂铁吡唑类衍生物的合成及燃速催化性能的研究

Synthesis and burning-rate catalysis performance of fluorine-containing ferrocenyl pyrazolines

以乙酰基二茂铁和取代苯甲醛为原料,利用羟醛缩合反应制备3种单二茂铁基的α,β-不饱和酮(1a^1c).然后将其与水合肼缩合成环合成吡唑啉(2a^2c),再与相应酰氯反应,引入具备强吸电子能力的含氟基团,合成5种3-二茂铁基-5-芳基-1-苯甲酰基吡唑啉(3a^3e),并运用IR、MS、1H NMR、19F NMR、13C NMR及HRMS对化合物结构进行表征.运用循环伏安法(CV)和差示脉冲伏安法(DPV)两种电化学手段探讨化合物3a^3e的氧化还原过程,利用热重分析(TG)、差热分析(DSC)两种热分析手段深入研究化合物3a^3e对高氯酸铵(AP)的燃速催化性能.电化学测试结果表明,化合物3a^3e均只含有一组氧化还原峰,归属于分子中茂环Fc/Fc+的氧化还原过程,且电极反应动力学基本受扩散控制.热分析结果表明,化合物3a^3e均对AP有优良的燃速催化效果,将原来的分解温度从450℃提前到300℃左右.

Three ferrocenyl chalcones（ 1 a-1 c） were synthesized by the aldol condensation reaction of acetylferrocene with substituted benzaldehyde. Then hydrazine hydrate was condensated with them to construct three kinds of pyrazolines（ 2 a-2 c）. Finally,2 a-2 c were acylated with corresponding benzoyl chlorides to obtain five novel 3-ferrocenyl-5-phenyl-1-benzoylpyrazolines（ 3 a-3 e）. These compounds were structurally characterized by IR,MS,1 H NMR,19 F NMR,13 C NMR,HRMS. Electrochemical properties of these compounds were studied by CV and DPV. Thermal behavior and catalytic performance for thermal decomposition of AP were studied by TG and DSC. The results indicated that synthetic molecules all have efficient catalytic effect on the thermal decomposition of AP. What ＇s more,when electron withdrawing group of fluorine was brought in,the polarity increased and the burning-rate catalysis performance slightly weakened.