为合成高能不敏感含能化合物,以3,4-二硝基吡唑为原料,经异常亲核取代氢(VNS)反应合成5-氨基-3,4-二硝基吡唑(ADNP),ADNP经重氮化后与硝基乙腈的钠盐偶合、分子内环化,合成多硝基氮杂芳香稠环含能化合物4-氨基-3,7,8-三硝基吡唑并[5,1-c]1,2,4-三嗪(PTX); 采用红外光谱(IR)、核磁共振(NMR)、元素分析表征了产物结构,优化了ADNP合成、分离条件和PTX环化反应条件; 采用差示扫描量热(DSC)研究了PTX的热性能及与HMX、RDX、Al粉、硝化棉(NC)的相容性; 采用BAM撞击感度测试仪测试了PTX的撞击感度。结果 表明,DNP与偏三甲基肼碘化物、叔丁醇钾(t-BuOK)的物质的量比为1:2.5:3.5,反应时间为8h,ADNP收率可达73.7%; 利用DNP与ADNP的溶解度差异可以提高ADNP的提纯效率; 合成PTX中间体后直接环化可将反应收率从55.6%提高至90.7%; 对PTX合成条件的优化将总收率从文献值的29.8%提高至66.8%; PTX的热分解峰温为288.5℃; PTX与Al粉和NC具有良好的相容性,与HMX、RDX不相容; 其撞击感度为15J。表明PTX为一种热稳定性较好的高能不敏感含能化合物,有望应用于高能不敏感弹药中。
To obtain high energy insensitive compounds, 5-amino-3,4-dinitro-pyrazole(ADNP)was synthesized via vicarious nucleophilic substitution(VNS)from 3,4-dinitro-1H-pyrazole(DNP). Azocoupling of diazopyrazole of ADNP with sodium cyanonitromethanide, followed by intramolecular cyclization resulted in polynitropyrazole[5,1-c][1,2,4]triazine energetic compound 4-amino-3,7,8-trinitropyrazole[5,1-c][1,2,4]triazine(PTX). The structure of PTX was confirmed by IR, NMR and elemental analysis. The reaction conditions of the synthesis and purification of ADNP and the cyclization of PTX were optimized. The thermal property and compatibilities of PTX with RDX, HMX, Al powder and NC were investigated by DSC method. The impact sensitivity of PTX was measured by the BAM drop hammer apparatus. The results show that the yield of ADNP is up to 73.7% when n(DNP): n(1,1,1-trimethylhydrazinium iodide):n(t-BuOK)is 1:2.5:3.5, and reaction time is 8h. ADNP can be purified efficiently by using the difference of solubility. The yield of PTX can be improved from 55.6% to 90.7% via the immediate cyclization after azocoupling. The decomposition peak temperature of PTX is 288.5℃. It has a good compatibility with Al powder and NC, but is incompatible with HMX and RDX, and its impact sensitivity is 15 J. It is indicated that PTX is an high energy insensitive compound with high thermal stability and is promising in insensitive high ammunition.
