1⁃甲基⁃3,4,5⁃三硝基吡唑(MTNP)的简易合成  

A Simple Synthesis Method of 1⁃Methyl⁃3,4,5⁃trinitropyrazole(MTNP)

作　　者：张莉[1] 邹佳 陈政国 余思佳 李浩然[1] 石海川 黄明[2] 杨海君[1] ZHANG Li;ZOU Jia;CHEN Zheng-guo;YU Si-jia;LI Hao-ran;SHI Hai-chuan;HUANG Ming;YANG Hai-jun(School of Materials and Chemistry,Southwest University of Science and Technology,Mianyang 621010,China;Institute of Chemical Materials,China Academy of Engineering Physics,Mianyang 621999,China)

机构地区：[1]西南科技大学材料与化学学院,四川绵阳621010 [2]中国工程物理研究院化工材料研究所,四川绵阳621999

出　　处：《含能材料》2025年第4期317-323,共7页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金(22075260);四川省自然科学基金面上项目(2022NSFSC0288)。

摘　　要：为解决1⁃甲基⁃3,4,5⁃三硝基吡唑(MTNP)现有合成中的高温、高压等问题,开发了一种简易合成MTNP的新方法,即以4⁃氯吡唑(1)为原料,通过硝化、N⁃甲基化、苄胺化及氧化等反应合成MTNP。考察了物料比、温度、溶剂、脱苄试剂、氧化条件等因素对4⁃苄氨基⁃1⁃甲基⁃3,5⁃二硝基吡唑(4)、4⁃氨基⁃1⁃甲基⁃3,5⁃二硝基吡唑(5)和MTNP得率的影响;采用傅里叶变换红外光谱(FT⁃IR)、核磁共振(NMR)、高效液相色谱(HPLC)等对中间体及目标物进行结构表征。结果表明:合成中间体4时,采用摩尔比n(苄胺):n(4⁃氯⁃1⁃甲基⁃3,5⁃二硝基吡唑,3)=6∶1,反应温度35℃,石油醚/水为溶剂的反应条件,得率为89.6%;合成中间体5时,采用浓硫酸(98%)为脱苄试剂,得率为95.2%;合成目标物MTNP时,采用中间体4为底物以及脱苄/氧化“一锅法”,得率为60.5%。通过优化反应条件,从原料1经一锅法合成MTNP的总得率为41.5%。In order to solve the problems of high temperature and high pressure in the synthesis of 1⁃methyl⁃3,4,5⁃trinitropyr⁃azole(MTNP),a new method of simple synthesis of MTNP was developed,that is,4⁃chlorpyrazole(1)was used as raw materi⁃al,and MTNP was synthesized by nitration,N⁃methylation,benzylamine amination and oxidation.The effects of material ra⁃tios,temperatures,solvents,debenzylation reagents,and oxidation conditions on the yields of 4⁃benzylamino⁃1⁃methyl⁃3,5⁃di⁃nitropyrazole(4),4⁃amino⁃1⁃methyl⁃3,5⁃dinitropyrazole(5),and MTNP were investigated.Fourier transform infrared spectros⁃copy(FT⁃IR),nuclear magnetic resonance(NMR)and high performance liquid chromatography(HPLC)were used to charac⁃terize the structures of the intermediates and target compounds.The results showed that when the intermediate 4 was synthe⁃sized,the molar ratio of n(benzylamine):n(4⁃chloro⁃1⁃methyl⁃3,5⁃dinitropyrazole,3)=6∶1,the reaction temperature was 35℃,and petroleum ether/water was the solvent,the yield was 89.6%.In the synthesis of intermediate 5,concentrated sulfuric acid(98%)was used as debenzyl reagent,and the yield was 95.2%.The yield of MTNP was 60.5%by using intermediate 4 as substrate and“one⁃pot method”of debenzylation/oxidation.By optimizing the reaction conditions,the total yield of MTNP syn⁃thesized from raw material 1 by one⁃pot method was 41.5%.

关 键 词：1⁃甲基⁃3 4 5⁃三硝基吡唑(MTNP) 一锅法合成 苄胺化 氧化反应 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]