Multiple Site N-Alkylation Reactivity of Hexaaza[3.3.3]propellane

Taking 2, 4, 6, 8, 9, 11-hexaaza[3.3.3]propellanes-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[3.3.3] 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.