2-甲基嘧啶-4,6-二酮制FOX-7的副产物合成1,3,5,5-四硝基六氢嘧啶  

Synthesis of 1,3,5,5-Tetranitrohexahydropyrimidine with By-product of FOX-7 Prepared by 4,6-Dihydroxy-2-methylpyrimidine

作　　者：朱元玉 杜杨[1] 杜雨昕 ZHU Yuan-yu;DU Yang;DU Yu-xin(School of Chemical Engineering Nanjing University of Science and Technology,Nanjing 210094,China;Nanjing No.13 Middle School,Nanjing 210094,China)

机构地区：[1]南京理工大学化工学院,江苏南京210094 [2]南京市第十三中学,江苏南京210094

出　　处：《含能材料》2018年第4期329-333,共5页Chinese Journal of Energetic Materials

摘　　要：对2-甲基嘧啶-4,6-二酮(MPO)制备1,1-二氨基-2,2-二硝基乙烯(FOX-7)过程中的副产物二硝基甲烷进行了回收,经氢氧化钾水溶液中和制得了性质稳定的长针状晶体二硝基甲烷钾盐(KDNM),用KDNM、甲醛、叔丁胺作原料通过Mannich缩合反应制得了1,3-二叔丁基-5,5-二硝基六氢嘧啶,通过浓硫酸与浓硝酸的混酸体系硝解1,3-二叔丁基-5,5-二硝基六氢嘧啶制得了1,3,5,5-四硝基六氢嘧啶(DNNC),总产率达到78.9%(以二硝基甲烷钾盐计)。采用1H NMR、红外、质谱对DNNC和中间物的结构进行了表征。研究了p H值、溶剂、温度对Mannich缩合反应的影响以及硝化体系的选择对硝解反应的影响。确立了Mannich缩合反应的最佳工艺条件为:二硝基甲烷钾盐∶甲醛∶叔丁胺的摩尔比为1.0∶3.5∶2.0;10%甲醇水溶液为溶剂,室温下用盐酸调节p H值至8,随后升温至50℃,反应3 h,产率达到85.3%。硝解反应中采用20 m L 98%H_2SO_4与10 m L HNO_3的混酸体系作为硝解体系,产率达到92.5%。By-product dinitromethane in the manufacturing process of 1,1-diamino-2,2-dinitroethylene(FOX-7)from 4,6-dihydroxy-2-methylpyrimidine(MPO)was recovered,the long needle dinitromethane potassium salt(KDNM)crystal with stable property was prepared via neutralization using aqueous potassium hydroxide solution,1,3-dibutyl-5,5-dinitrohexahydropyrimidine was prepared via Mannich condensation reaction using KDNM,formaldehyde and tert-butylamine as raw materials,and 1,3,5,5-tetranitrohexahydropyrimidine(DNNC)was prepared via the nitrolysis of 1,3-dibutyl-5,5-dinitrohexahydropyrimidine with mixed acid system of concentrated sulfuric acid and concentrated nitric acid with total yield of 78.9%(Calculated by KDNM).The structure of DNNC and intermediate were characterized by 1H NMR,IR,MS.The effect of pH value,solvents and temperature on Mannich condensation reaction,and the effect of selection of nitration system on the nitating reaction were studied.The optimal conditions of Mannich condensation reaction were determined as:the molar ratio of KDNM,formaldehyde and tert-butylamine is 1.0∶3.5∶2.0,10%aqueous methanol solution is used as solvent and hydrochloric acid is used to adjust pH value to 8 at room temperature;and then temperature rises up to 50℃subsequently with reaction for 3 hours,and the yield reaches 85.3%.Using mixed acid composed of 20 mL 98%H 2 SO 4 and 10 mL HNO 3 By as nitrolysis system,the yield reaches 92.5%.

关 键 词：1 1-二氨基-2 2-二硝基乙烯(FOX-7) 二硝基甲烷钾盐 1 3 5 5-四硝基六氢嘧啶(DNNC) MANNICH反应 硝解反应 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]