一锅法合成二硝基五亚甲基四胺反应机理的研究  

Reaction Mechanism of One-Pot Synthesis of Dinitro Pentamethylene Tetramine

作　　者：宋红燕[1] 王鹏[1] 覃光明[2] 葛忠学[2] 王伯周[2] 孟子晖[1] 李清霞[1] 

机构地区：[1]北京理工大学化工与环境学院,北京100081 [2]西安近代化学研究所,西安710061

出　　处：《有机化学》2010年第3期414-418,共5页Chinese Journal of Organic Chemistry

基　　金：爆炸科学与技术国家重点实验室开放基金(No.KFJJ09-4)资助项目

摘　　要：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,1HNMR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.Dinitro pentamethylene tetramine （DPT） is an important precursor of octogen （cyclotetrame- thylene-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 in- termediates dinitrourea, nitramide and bis（hydroxymethyl）nitroamine were isolated, and the active interme- diate 1-nitro-hexahydrotriazine was captured by benzenesulfonyl chloride. The H2 labeled DPT （DPT-D） was synthesized by the reaction of CD20 with NH3 and bis（hydroxymethyl）nitroamine. The analysis results from IH NMR and MS of DPT-D indicate that in the course of the reaction bis（hydroxymethyl）nitroamine is decomposed into CH20 and nitramide, and the small molecule species make up randomly to form triazine, then 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 

分 类 号：TQ560.1[化学工程—炸药化工]