2,4,6,8-四硝基-2,4,6,8-四氮杂双环[3.3.0]辛烷的合成及表征  

Synthesis and Characterization of 2,4,6,8-Tetrachitro-2,4,6,8-tetraazabicyclic[3.3.0]octane

作　　者：侯静 吴俊越 詹乐武 李斌栋[1] HOU Jing;WU Jun-yue;ZHAN Le-wu;LI Bin-dong(School of Chemistry and Chemical Engineering,Nanjing University of Science&Technology,Nanjing 210094,China)

机构地区：[1]南京理工大学化学与化工学院,江苏南京210094

出　　处：《火炸药学报》2024年第7期601-605,I0001,共6页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.22271156)。

摘　　要：以氨基磺酸盐、甲醛、乙二醛为起始原料,对2,4,6,8-四硝基-2,4,6,8-四氮杂双环[3.3.0]辛烷(BCHMX)的合成工艺进行了优化,得到了无需中间体(2,4,6,8-四氮杂双环[3.3.0]辛烷磺酸盐)提纯的高效合成工艺;采用傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1H NMR)、核磁共振碳谱(13 C NMR)、热重-差式扫描量热(TG-DSC)等分析测试手段对目标产物的分子组成、晶体结构、热稳定性进行了分析表征。结果表明,最优缩合工艺条件为:每摩尔氨基磺酸钾加入1.07 mol甲醛、1.77 mol乙二醛,以8.4 mol的水作为溶剂,0.023 mol的甲酸作为酸催化剂,反应时间为12 h;硝化工艺条件为:以摩尔比为1.3∶1的发烟硝酸和乙酸酐为硝化体系,在40℃下进行反应。通过缩合和硝化两步反应,能够以65.29%的总收率得到纯度97.8%的2,4,6,8-四硝基-2,4,6,8-四氮杂双环[3.3.0]辛烷(BCHMX);BCHMX晶体属单斜晶系,空间群为P2(1)/c;BCHMX热分解温度为223℃。By using amino sulfonic acid salts,formaldehyde,and glyoxal as starting materials,an optimized synthesis process for 2,4,6,8-tetrachitro-2,4,6,8-tetraazabicyclic[3.3.0]octane(BCHMX)without purification of the intermediate(2,4,6,8-tetraazabicyclo[3.3.0]octane sulfonate)was developed.The molecular structure,crystal structure,and thermal stability of the target product were analyzed and characterized using Fourier transform infrared spectroscopy(FT-IR),proton nuclear magnetic resonance spectroscopy(1H NMR),carbon-13 nuclear magnetic resonance spectroscopy(13 C NMR),and thermogravimetric analysis combined with differential scanning calorimetry(TG-DSC).Results show that,the optimal process conditions are as follows:1.07 mole of potassium amino sulfonate per mole of formaldehyde,1.77 mole of glyoxal,8.4 mole of water as the solvent,and 0.023 mole of formic acid as the acid catalyst.The condensation reaction is carried out for 12 hours.The nitration reaction is performed using fuming nitric acid and acetic anhydride in a molar ratio of 1.3∶1 as nitrating agent at 40℃.By the condensation and nitration reactions,BCHMX with a purity of 97.8%is obtained with a total yield of 65.29%.BCHMX belongs to the monoclinic crystal system with space group of P2(1)/c,and the theraml decomposition temperature is 223℃.

关 键 词：有机化学 缩合反应 含能材料 氨基磺酸钾 2 4 6 8-四硝基-2 4 6 8-四氮杂双环[3.3.0]辛烷 BCHMX 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术]