以2，4，6，8，9，11-六氮[3，3，3]杂螺桨烷-3，7，10-三酮（PTO）为原料，通过与亲电试剂发生烷基化反应，获得了具有含能化衍生前景的六烯丙基六氮杂螺桨烷、六乙氧羰甲基六氮杂[3，3，3]螺桨烷和六羧甲基六氮杂螺桨烷；系统研究了不同亲电试剂与六氮杂[3，3，3]螺桨烷之间的反应活性，探讨了不同取代基六氮杂螺桨烷化合物的酸碱稳定性和热稳定性。结果表明，不同取代基结构对于六氮杂[3，3，3]螺桨烷的骨架修饰具有显著影响，亲电试剂活性的增加和溶剂极性的增大对反应有利，但过高活性的亲电试剂因副反应过多无法获得相应的烷基化产物；烷基化取代后的六氮杂[3，3，3]螺桨烷体系的水解稳定性大大增加，酸性条件下可保持稳定而碱性条件下多数烷基化产物发生降解；烷基化取代的产物其热稳定性较PTO有所增强。
Abstract
Taking 2,4,6,8,9,11-hexaaza[3,3,3] propellane-3,7,10-trione (PTO) as raw material, the reactivity of the hexaaza[3,3,3] propellane with different electrophilic reagents was systematically investigated. N-hexallyl-hexaaza[3,3,3] propellanes, N-hexethylacetic -hexaaza propellanes and N-hexacetoxyl-hexaaza[3,3,3] propellanes with energetic derivative prospect were designed and synthesized for the first time. The acid-stability, base-stability and thermal stability of hexaaza[3,3,3] propellane with different substituent were discussed. The results show that different substituent structure has significant effect on the modification of the hexaaza[3,3,3] propellane skeleton.Increasing the activity of electrophilic reagent and solvent polarity enhanced the reaction process, but extremely high activity failed to obtain the corresponding alkylation products due to the adverse reactions. The hydrolytic stability of the N-alkylated hexaaza[3,3,3] propellane system is greatly increased. Most of them remained stable under acidic conditions while decomposed under alkaline conditions. The thermal stability of the products was enhanced by alkylation compared with PTO.
关键词
六氮杂[3,3,3]螺桨烷 /
空间位阻 /
多位点 /
烷基化 /
三维立体骨架
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Key words
hexaaza[3,3,3] propellane /
steric hindrance /
multiple reactive sites /
alkylation /
three-dimensional skeleton
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