The Study On The Synthesis Of Tetrazole-based Energetic Derivatives

Recent years,nitrogen-rich heterocyclic energetic compounds have draw the eyesight of researchers,meanwhile,for the excellent energetic properties of tetrazole energetic compounds such as high nitrogen-content,high heat of formation,high density and eco-friendly,more attention has been focused on the study of tetrazole energetic compounds.Many strategies of introducing other energetic moieties on tetrazole ring to give new energetic compounds with excellent energetic proprieties have been developed.This work focused on the study of the synthesis of tetrazole-based trinitrobenzene energetic compounds,and the optimization of reaction parameters of hydrazonium(2-methyltetrazol-5-yl)diazotate.Firstly,the substitution reactions of 1,3,5-trichloro-2,4,6-trinitro-benzene(TCTNB)with tetrazole and 5-anmio-tetrazole were explored.Various conditions for the nucleophilic substitution reaction were investigated to summarize the effects by alkalis,solvents and tempreture.Meanwhile,5-methyl-2,4,6-trinitrobenzene-1,3-diamine(DATNT)was prepared and followed by treatment with BrCN,which was used to synthesize DATNT-tetrazole-based energetic derivatives by cyclization reaction.In addition,other synthetic routes were tried,such as multi-step synthesis.Secondly,reaction parameters of hydrazonium(2-methyltetrazol-5-yl)diazotate were optimized based on previous milligram results.The effects of concentration,temperature and time were investigated to achieve the optimal conditions.(1)In the case of methanol as the solvent,the optimal reaction concentration,reaction temperature and reaction time are 1.5mol/L,-8 ~oC,and 4 h respectively,and the yield is 68.8%.(2)In the case of ethanol as the solvent,the optimal reaction concentration,reaction temperature and reaction time are 3.0mol/L,-8 ~oC,and 4 h respectively,and the yield is 85.6%.Finally,the synthesis of hydrazonium(2-methyltetrazol-5-yl)diazotate was scaled up to10 grams level with ethanol as the solvent.Feeding speed,reaction temperature and reaction time were examined to achieve the optimal conditions.And the optimized reaction concentration,feeding time,reaction temperature and reaction time are 3.0 mol/L,20 min,-8 ~oC,and 4 h respectively.The maximum yield is 93.1%.