Study On The Synthesis Of Nitrogen-rich Fused Heterocycles And TATB Internal Standard Candidate

Energetic nitrogen-rich fused heterocycles have become one important research hotspot in the field of energetic materials,because of their high density,high enthalpy of formation,high stability and low mechanical sensitivity.The synthesis study of novel nitrogen-rich fused heterocycles could provide energetic compounds with excellent properties.Besides,the quality control of TATB is extremely important during its production,storage,and application.The study of new TATB internal standard candidates could provide actually applicable internal standard material for TATB.It has a practical significance for the quality control of TATB production and equipments.In this thesis,the syntheses of azolo-fused heterocycles and TATB internal standard candidates were studied.（1）Synthesis of pyrazolo-fused heterocyclesStarting from 5-aminopyrazole（1）,3-tetrazolyl-4-aminopyrazolotriazine（3）was synthesized through diazotization and cycloaddition in a total yield of 71.6%.Besides,3-（5-methyl-1,2,4-oxadiazolyl）-4-aminopyrazolotriazine（6）and 3-（5-acetoxyl-1,2,4- oxadiazolyl）-4-aminopyrazolotriazine（7）were synthesized in 48.4%and 57.7%respectively by amidoximation and cyclization from 3-cyano-4-aminotriazine pyrazole（2）.Starting from 3-nitropyrazole（8）,4-cyano-4-amino-7,8-dinitropyrazo-lotriazine（11）was synthesized in 29.1%by nitration,VNS amination and diazo-cyclization.Nitration of compoud 11 gave 3-aminocarbonyl-4-nitroamino-7,8-dinitropyrazolotria- zine（13）in 63.9%.The intermediates and products were characterized and analyzed by IR,NMR,MS and DSC-TG.（2）Synthesis of triazolo-fused heterocyclesStarting from 5-aminotriazole（16）,3-tetrazolyl-4-aminotriazolotriazine（18）was synthesized in 55.4%by diazotization and cycloaddition.Interestingly,nitration of compound 18 with HNO₃/H₂SO₄gave 3-tetrazolyl-4-amino-7-nitrotriazolotriazine（20）as a new energetic compound in 72.3%.O-acetyl-4-aminotriazolotriazine-3-amidoxi- me（23）and O-acetoxyacetyl-4-aminotriazolotriazine-3-amidoxime（25）were obtain-ed in 47.6%and 52.7%by O-acylation from 3-cyano-4-aminotriazolotriazine（17）.Besides,3-cyano-4-amino-7-nitrotriazolotriazine（28）was synthesized in 17.3%from3,5-diaminotriazole（26）by diazotization,reduction,diazotization and cyclization reactions.The intermediates and products were characterized and analyzed by IR,NMR,MS and DSC-TG.（3）Synthesis of TATB internal standard candidatesStarting from 2,4,6-trinitrochlorobenzene（30,TNCB）or 1,3,5-trichloro-2,4,6-trinitr- obenzene（34）,2,4,6-trinitroaniline（31,TNAB）,2,4,6-trinitrophenylhydrazine（32,TNHB）,N-methyl-2,4,6-trinitroaniline（33,TNMAB）and 1,3,5-tris（methylamino）-2, 4,6-trinitrobenzene（35,TMATNB）were synthesized as TATB analogues,which were characterized and analyzed by IR,NMR and MS.The data of HPLC,UV-Vis and stability show that TNMAB could be used as the internal standard candidate of TATB.Besides,1,3,5-tris（methylnitroamino）-2,4,6-trinitrobenzene（36）was synthesized by nitration of compound 35.The synthesis conditions of compounds 35 and 36 were investigated.The crystal of compound 36 was analyzed by single crystal diffraction,and the detonation properties of compound 36 were calculated.