| Halogenated polynitrobenzene is usually an intermediate for the synthesis of energetic materials,and condensation with nitropyrazole produces compounds with higher energy and lower sensitivity,so the combination of chloro-trinitrobenzene and pyrazole compounds,the introduction of picryl on pyrazole ring not only increases its energy,but also reduces the sensitivity.In this paper,two kinds of high energy and good heat-resistant energetic compounds,3-(3,4-dinitro-pyrazol-1-yl)-2,4,6-trinitrophenol and 3-(3,4-dinitro-pyrazol-1-yl)-2,4,6-trinitrobenzene,were synthesized by the C-N condensation reaction of chloro-trinitrobenzene and 3,4-dinitropyrazole(DNP)and the C-C coupling reaction between chloro-trinitrobenzene,and their structures were characterized.Firstly,1,3-dichloro-2,4,6-trinitrobenzene(DCTNB)was prepared with m-dichloro-benzene as initial material.And the reaction conditions of synthetic DCTNB were optimized.When the fuming sulfuric acid and the potassium nitrate was 100 mL and 35.5 g respectively,the reaction temperature was 160℃,the reaction time was 4 h,the yield of DCTNB was 75.4%.The purity of DCTNB was identified by thin layer chromatography and melting point test.The structure was characterized by IR,NMR and so on.Secondly,3-(3,4-dinitro-pyrazol-1-yl)-2,4,6-trinitrophenol was synthesized under influen-ce of acid binding agent by using DCTNB and 3,4-dinitropyrazole(DNP)as raw materials,which was separated and purified.The compound was characterized by thin layer chromatography,infrared spectrum,nuclear magnetic hydrogen spectrum,carbon spectrum and high resolution mass spectrum.The effects of acid binding agent,reaction temperature,reaction time and solvent on the condensation reaction were studied.The optimum conditions were obtained: the reaction base was triethylamine,the reaction temperature was 60℃,the reaction time was 2 h,the solvent was dimethyl sulfoxide,the yield of product was 62.4%.Besides,the possible mechanism of DCTNB and DNP condensation reaction was analyzed.3-(3,4-dinitro-pyrazol-1-yl)-2,4,6-trinitrobenzene was synthesized by using 2,4,6-trinitro-chlorobenzene(PiCl)and DNP as raw materials,which was separated and purified.And the structure of the product was characterized by IR,NMR and so on.Their performance and application prospects need further development.Thirdly,heat-resistant explosives 2,2′,2″,4,4′,4″,6,6′,6″-nonanitroterphenyl(NONA)was synthesized under high temperature and copper powder catalyst,with DCTNB and PiCl/DCTNB as raw materials.Then the copper powder was replaced with cuprous iodide,and dimethyl sulfoxide was used solvent instead of nitrobenzene.The Ullmann coupling reaction was carried out,and the product was isolated and purified.What’s more,the product was characterized and the reasons for not getting NONA were analyzed.Finally,the partial properties of the new compound 3-(3,4-dinitro-pyrazol-1-yl)-2,4,6-trinitrophenol were tested and calculated. |
