3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷的硝解副产物及硝解机理

Mechanisms and By-products of Nitrolysis of 3,7-dinitro-1,3,5.7-tetrazabicyclo[3.3.1]nonane

为了更好指导N2O5硝解3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷(DPT)制备奥克托今(HMX)的生产,研究了DPT在N2O5/HNO3和N2O5/CH2Cl2两种体系中的硝解产物,采用柱层析从硝解产物中分离得到了两个副产物,并进行了结构表征,确证其为:N,N′-二羟甲基硝胺和1,9-二硝酰氧基-2,4,6,8-四硝基-2,4,6,8-四氮杂壬烷。N2O5硝解DPT,当体系中溶解有硝酸铵时,N2O5浓度低时主要起硝化作用反应生成HMX,N2O5浓度高时主要起酯化作用反应生成直链产物;当体系中没有硝酸铵(或硝酸铵不溶解)时,N2O5主要起酯化作用也生成直链产物。

The main product of nitrolysis of 3,7-dinitro-1,3,5.7-tetrazabicyclo[3.3.1 ] nonane（DPT） in dinitrogen pentoxide/nitric acid/ ammonium nitrate with lower dinitrogen pentoxide concentration is HMX. While with higher dinitrogen pentoxide concentration,some of straight-chain by-products of both 1,9-dinitroxy-2,4,6,8-tetranitro-2,4,6,8-tetrazanonane and N, N＇-bis （ hydroxymethyl ） nitramide were obtained and separated by column chromatography,and the structures were confirmed with infrared spectroscopy（IR） ,nuclear magnetic resonance（HNMR） and mass spectrometry（MS）. Increasing dinitrogen pentoxide concentration leads to more by-products. Nitrolysis of DPT in dinitrogen pentoxide/nitric acid or dinitrogen pentoxide/methylene chloride afforded only straight-chain by-products.