有机化学 ›› 2012, Vol. 32 ›› Issue (01): 75-80. 上一篇    下一篇

研究论文

1,3,5-三硝基-六氢化-1,3,5-三嗪-2(1H)-酮(Keto-RDX)新法合成、晶体结构和热性能研究

周诚, 周彦水, 王伯周, 霍欢, 毕福强, 廉鹏, 樊学忠   

  1. 西安近代化学研究所 西安 710065
  • 收稿日期:2011-05-24 修回日期:2011-09-01 发布日期:2011-09-28
  • 通讯作者: 王伯周 E-mail:wbz600@163.com

A Novel Synthetic Route, Crystal Structure and Thermal Behaviors for 1,3,5-Trinitro-hexahydro-1,3,5-triazin-2(1H)-one (Keto-RDX)

Zhou Cheng, Zhou Yanshui, Wang Bozhou, Huo Huan, Bi Fuqiang, Lian Peng, Fan Xuezhong   

  1. Xi'an Modern Chemistry Research Institute, Xi'an 710065
  • Received:2011-05-24 Revised:2011-09-01 Published:2011-09-28

研究了1,3,5-三硝基-六氢化-1,3,5-三嗪-2(1H)-酮(Keto-RDX)的合成新方法, 以乌洛托品和硝基胍为原料, 通过Mannich 反应得到2-硝亚胺基-六氢化-1,3,5-三嗪盐酸盐(NIHT·HCl), 用HNO3/AC2O 硝化可得Keto-RDX, 并采用核磁共振、红外、质谱以及元素分析等进行了结构表征. 培养了Keto-RDX 单晶, 晶体结构解析表明: 晶体属于正交晶系, 空间群Pnma, 晶胞参数a=1.0057(17) nm, b=1.3483(2) nm, c=0.5982(10) nm, V=0.8112(2) nm3, Z=4, Dc=1.933 g/cm3,μ=0.188 mm-1, F(000)=480. 差示扫描量热(DSC)法和热失重(TG/DTG)法分析表明, Keto-RDX 分解峰温为211.4 ℃(DSC), 在185.00~202.79 ℃为固相分解阶段, 峰温为198.61 ℃, 质量损失为21.45%, 在202.79~230.00 ℃为液相分解阶段, 质量损失为77.83%, 峰温为213.78 ℃, 热稳定性较RDX 差.

关键词: 1,3,5-三硝基-六氢化-1,3,5-三嗪-2(1H)-酮, 合成, 热行为

1,3,5-Trinitro-hexahydro-1,3,5-triazin-2(1H)-one (Keto-RDX) was synthesized by a novel route of Mannich reaction and nitration reaction for nitroguanidine and urotropine, which were used as starting materials, with a yield of 72.0% and a purity of 98.5%. The structures of Keto-RDX were characterized by 1H NMR, 13C NMR, FT-IR, MS techniques and elemental analysis. It was found that Keto-RDX belongs to orthorhombic system with space group Pnma, and the crystal parameters were a=1.0057(17) nm, b=1.3483(2) nm, c=0.5982(10) nm, V=0.8112(2) nm3, Z=4, Dc=1.933 g/cm3, μ=0.188 mm-1, F(000)=480. The thermal decomposition behavior of Keto-RDX was studied by DSC and TG/DTG techniques. The results showed that there was a single sharp exothermic decomposition with peak maximum at 211.4 ℃ (DSC),and the thermal decomposition processes can be divided into two stages.

Key words: 1,3,5-trinitro-hexahydro-1,3,5-triazin-2(1H)-one, synthesis, thermal behavior