甲胺盐酸盐/发烟硝酸体系中DPT硝解?亚硝解反应制备MNX

Preparation of MNX from DPT Through Nitrolysis?nitrosolysis Reaction in CH_3NH_2?HCl/Fuming Nitric Acid System

用CH_3NH_2·HCl代替NH4NO3作为3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷(DPT)与发烟硝酸反应的添加剂,考察了CH_3NH_2·HCl对生成1-亚硝基-3,5,7-三硝基-1,3,5,7-四氮杂环辛烷(MNX)的影响。研究了CH_3NH_2·HCl促进DPT与发烟硝酸反应制备MNX的工艺,考察了发烟硝酸和CH_3NH_2·HCl的加入量、反应时间和反应温度对反应的影响。结果表明,通过正交实验确定的最佳反应条件为:n(DPT):n(CH_3NH_2·HCl)=1:2.5,反应时间10 min,反应温度-25℃。在最优反应条件下MNX的收率为78.5%。本方法避免使用NaNO_2溶液和N_2O_4作为亚硝基来源,简化了MNX的制备工艺,且反应废液容易处理,硝酸回收率为75%。CH_3NH_2·HCl对DPT与发烟硝酸反应的促进作用比NH_4NO_3的显著,提出了CH_3NH_2·HCl(或NH_4NO_3)分解成CH_3NH_3(或NH_3)作为Lewis碱催化剂促进DPT与发烟硝酸反应的可能机理,其中涉及到硝酸通过氧化还原反应生成亚硝酸作为亚硝基来源的过程。

CH3NH2·HCl was used to replace NH4NO3 as an additive in the reaction of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane(DPT)in fuming nitric acid,and the effect of CH3NH2·HCl on the formation of 1-nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane(MNX)was investigated.The process of preparing MNX by CH3NH2·HCl promoting the reaction of DPT with fuming nitric acid was studied.The effects of loading amounts of fuming nitric acid and CH3NH2·HCl,reaction temperature and reaction time on the reaction were investigated.Results show that the optimum reaction conditions determined by orthogonal experiments are:n(DPT)∶n(CH3NH2·HCl)=1∶2.5,reaction time 10 min and reaction temperature-25℃.Under the optimum reaction conditions,the yield of MNX is 78.5%.This method avoids using NaNO2 solution and N2O4 as nitroso resource and simplifies the preparation process of MNX.The waste liquid is easy to be treated.The recovery of nitric acid is 75%.CH3NH2·HCl can promote the reaction of DPT with fuming nitric acid more significantly than NH4NO3.A possible mechanism of promoting the reaction of DPT and fuming nitric acid via decomposing CH3NH2·HCl(or NH4NO3)into CH3NH2(or NH3)as a Lewis base catalyst is proposed,which involves the process of nitrous acid formation from nitric acid through a redox reaction as nitroso resource.