1,3,5,7-四乙酰基-1,3,5,7-四氮杂环辛烷的硝解反应机理

摘要

为了更好地指导五氧化二氮(N2O5)硝解1,3,5,7-四乙酰基-1,3,5,7-四氮杂环辛烷(TAT)制备奥克托今(HMX)的生产,研究了TAT在N2O5/HNO3体系中的硝解反应机理.采用柱层析从硝解产物中分离得到了两个副产物,并采用1H NMR、IR以及元素分析进行了结构表征,确证其为1,5-二乙酰基-3,7-二硝基-1,3,5,7,-四氮杂辛烷( DADN)和1-乙酰基-3,5,7-三硝基-1,3,5,7-四氮杂环辛烷(SEX).rAT先迅速硝解形成一硝基化合物,再快速硝化形成DADN,DADN中酰胺碱性降低,反应慢慢硝化形成SEX,SEX再以更慢的速度硝化形成HMX,其中k2＞k1,k2＞k3＞k4.%In order to provide better guidance to the preparation of HMX by nitrolysis of 1 ,3 ,5 ,7-tetraacetyl-1 ,3,5 ,7-tetrazacyclooctane (TAT), the nitrolysis mechanism was investigated. Two byproducts 1 , 5-diacetyl-3 , 7-dinitro-1 , 3 , 5 , 7-tetrazacy-clooctane (DADN) and 1-acetyl-3 ,5 ,7-trinitro-1 ,3 ,5 ,7-tetrazacyclooctane (SEX) were obtained by flash column chromatogra-phy and were indentified by ' H NMR, FTIR and elementary analysis. The results reveal that TAT is nitrated in succession to form HMX, and the order of the reaction rate is k2 > k, , k2 > k3 > k4.