Studies On The 1,2,3-Bistriazole Formation Reaction Of Catenated Nitrogen Chains Compounds

Compared with traditional energetic materials,catenated nitrogen chains compounds are ideal high energy density materials due to their owing high heat of formation and clean decomposed product of nitrogen gas.However,a serious lack of nitrogen-nitrogen bond forming reactions has hidered the development of energetic compounds containing catenated N-N bonds.Meanwhile,synthesis of 1,2,3-triazole compounds has been made certain development,in which the condensation cyclization reaction with C-NH₂ and tosylhydrazones that could be use to extend to nitrogen amino（N-NH₂）and tosylhydrazone to synthesis of catenated nitrogen chains compounds.In this thesis,the bond-formation reaction of 1,2,3-bistriazole catenated nitrogen chains compounds was studied on the basis of condensation and cyclization reaction of dichlorotosylhydrazone and N-amino-azoles.It described in the following three parts:1.Optimization of the reaction conditions for the construction of N6 compound with 1,2,3-bistriazole structureBased on the condensation cyclization reaction of I,1’-dichloroacetonetosylhydrazone and 1-amino-1,2,3-triazole,the six-nitrogen chains compound with 1,2,3-bistriazole structure were synthesized by two-step method and one-stp method respectively.Because the former yield was significantly less than the latter,and the separation of the former is more complex,too.It is appropriate to synthesize catenated nitrogen chains compounds containing 1,2,3-bistriazole structure by two-step process.Also,we screened conditions of the second-step cyclization reaction in the two-step method,and studied the effects of basic reagents,temperatures,solvents and other factors on the reaction.Finally,the optimum reaction conditions were obtained.2.Construction of catenated nitrogen chains compounds containing 1,2,3-bistriazole structure from N-NH₂ triazolesBased on the above optimal conditions in the two-step method,we further investigated the suitability of the reaction conditions for different substrates.The effect of electronic on the bonding reaction of nitrogen-nitrogen bonds was studied by the reaction of dichloroaryl-acetotosylhydrazones and N-NH₂ triazoles with different substituents.The single-crystal data obtained by the separation of some intermediate products and studied the mechanism of cyclization reaction.The thermal stability of catenated nitrogen chains compounds were studied,and concluded that a large amount of energy was released upon decomposition and six-nitrogen copmounds was less stable than four-nitrogen compounds.3.Based on the N-NH₂ tetrazoles,N7 energetic compounds containing 1,2,3-triazole-tetrazoles structure were synthesized.Two energetic compounds with seven-nitrogen chain were synthesized by the reaction of dichlorotosylhydrazone and N-NH₂ tetrazoles.By investigating the reactivity of different N-NH₂ tetrazoles,studied the effect of substituents attached to the N-NH₂ azoles on the nitrogen-nitrogen bonding cyclization reactions.In addition,the detonation parameters of these energetic compounds were calculated,which provided a safety and feasible methods for the synthesis of longer catenated nitrogen chain compounds.