(南京理工大学化工学院, 江苏 南京 210094)
侯天骄(1990-),男,博士研究生,主要从事有机合成化学研究。e-mail: firstname.lastname@example.org 通信联系人: 罗军(1975-),男,教授,主要从事有机合成化学研究。e-mail: email@example.com
(School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China)
以间二硝基苯(DNB)为原料, 经硝化、还原、Henry反应、缩合合成了3, 5, 7-三硝基-1-氮杂金刚烷, 总收率为21.5%。采用熔点测定、IR、NMR对中间体及目标化合物进行了结构表征。研究了硝酸与硫酸摩尔比、混酸用量、加料方式对硝化反应收率的影响。分别采用“分步法”和“一锅法”合成了中间体1, 3, 5-三羟甲基-1, 3, 5-三硝基环己烷, 并通过提高反应温度缩短了Henry反应时间。研究了酸和碱对缩合反应的影响, 并改进了反应工艺。利用热重分析(TG)和差示扫描量热法(DSC)研究了目标化合物的热性能。结果表明, 硝化反应的最佳工艺条件为n(HNO3): n(H2SO4)=1: 1.5, m(混酸): m(DNB)=23, 加料方式为先加三分之二的混酸, 24 h后再补加三分之一, 硝化反应收率达70.7%;提高反应温度后Henry反应的时间缩短12 h, “分步法”的总收率为61.8%, “一锅法”的总收率为83.5%;改进后的缩合反应时间缩短至3天, 简化后处理方法依次为过滤、脱色、重结晶, 酸和碱都会降低缩合反应的收率; 3, 5, 7-三硝基-1-氮杂金刚烷从225 ℃左右开始分解, 热分解峰温为331℃, 表明其热稳定性较好。
3, 5, 7-Trinitro-1-azaadamantane was synthesized from 1, 3-dinitrobenzene via nitration, reduction, Henry reaction and condensation, the overall yield was 21.5%. The structures of intermediates and target compound were characterized by IR, NMR and melting point apparatus. The effects of molar ratio of HNO3 to H2SO4, mixed acid dosages and charging ways on the nitration reaction were investigated. Intermediate product 1, 3, 5-trihydroxymethyl-1, 3, 5-trinitrocylohexane was synthesized by "stepwise" and "one-pot" process and the reaction time of Henry reaction was shortened by increasing the reaction temperature. The effects of acids and bases on condensation of 1, 3, 5-trihydroxymethyl-1, 3, 5-trinitrocylohexane with ammonia were studied, the reaction conditions and workup procedures were modified. The thermal stability of 3, 5, 7-trinitro-1-azaadamantane was studied by thermogravimetry (TG) and differential scanning calorimetry (DSC). Results show that the optimum process conditions of nitration are determined as: n(HNO3): n(H2SO4)=1: 1.5, m(mixed acid): m(1, 3, -dinitrobenzene)=23 and the charging way is adding 2/3 mixed acid first followed by the other 1/3 after 24 h, with the yield of 70.7%. The time of Henry reaction is shorten by 12 h by increasing the reaction temperature, and the yields of "stepwise" and "one-pot" are 61.8% and 83.5%, respectively. The reaction time of improved condensation is shortened to 3 days, and the simplified workup procedures are filtration, decoloration and recrystallization successively, and both acids and bases reduce the yield of condensation. The decomposition of 3, 5, 7-trinitro-1-azaadamantane starts from about 225 ℃ and the exothermic peak temperature is 331 ℃, which demonstrates that the target compound possesses good thermal stability.
侯天骄,孙露,罗军.3,5,7-三硝基-1-氮杂金刚烷的合成工艺[J].含能材料, 2018, 26(7):585-589. DOI:10.11943/j. issn.1006-9941.2018.07.006.
HOU Tian-jiao, SUN Lu, LUO Jun. Synthesis Process of 3,5,7-Trinitro-1-azaadamantane[J]. Chinese Journal of Energetic Materials, 2018, 26(7):585-589. DOI:10.11943/j. issn.1006-9941.2018.07.006.