SIOC English
有机化学
高级检索

有机化学 ›› 2010, Vol. 30 ›› Issue (03): 414-418. 上一篇    下一篇

研究论文

一锅法合成二硝基五亚甲基四胺反应机理的研究

宋红燕a，王鹏a，覃光明b，葛忠学b，王伯周b  孟子晖*,a，李清霞a   

  1. (a北京理工大学化工与环境学院 北京 100081) (b西安近代化学研究所 西安 710061)
  • 收稿日期:2009-05-22 修回日期:2009-06-29 发布日期:2010-03-28
  • 通讯作者: 孟子晖 E-mail:mengzh@bit.edu.cn

Reaction Mechanism of One-Pot Synthesis of Dinitro
Pentamethylene Tetramine

Song Hongyana,Wang Penga,Qin Guangmingb,Ge Zhongxueb,Wang Bozhoub
Meng Zihui*,a,Li Qingxiaa   

  1. (a School of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing 100081)
    (b Xi'an Morden Chemistry Research Insitute, Xi'an 710061)
  • Received:2009-05-22 Revised:2009-06-29 Published:2010-03-28

PDF

2356

被引次数

15 | 9

二硝基五亚甲基四胺(DPT)是高性能单质炸药奥克托金(HMX)的重要硝化前体. 以尿素为起始原料, 中间产物不分离, 经硝化、水解、Mannich缩合等反应得到DPT, 总收率63.2%. 通过分离、捕获中间体以及同位素示踪实验研究了一锅法合成DPT的反应机理. 分离出了稳定的中间体二硝基脲、硝酰胺和二羟甲基硝酰胺, 用苯磺酰氯捕获到了活性中间体1-硝基-六氢均三嗪. 以氘代甲醛、二羟甲基硝酰胺和氨缩合得到氘标记的DPT, 1H NMR和MS分析结果表明: 在反应过程中二羟甲基硝酰胺解离释放出甲醛和硝酰胺, 小分子碎片随机组合生成了三嗪化合物, 进而生成DPT.

关键词: 奥克托金, 二硝基五亚甲基四胺, 反应机理, 同位素标记

Dinitro pentamethylene tetramine (DPT) is an important precursor of octogen (cyclotetramethylene-tetranitramine. Starting from urea without isolation of intermediates, DPT was obtained by nitration, hydrolysis and Mannich condensation, in total yield of 63.2%. The reaction mechanism of one-pot synthesis of DPT was studied by isolating and capturing intermediates, and isotope tracing experiments. The stable intermediates dinitrourea, nitramide and bis(hydroxymethyl)nitroamine were isolated, and the active intermediate 1-nitro-hexahydrotriazine was captured by benzenesulfonyl chloride. The H2 labeled DPT (DPT-D) was synthesized by the reaction of CD2O with NH3 and bis(hydroxymethyl)nitroamine. The analysis results from 1H NMR and MS of DPT-D indicate that in the course of the reaction bis(hydroxymethyl)nitroamine is decomposed into CH2O and nitramide, and the small molecule species make up randomly to form triazine, then DPT.

Key words: octogen, dinitro pentamethylene tetramine, reaction mechanism, isotope tracing