N-羟甲基叔胺的乙酰解反应及其在DAPT合成TAT反应机理中的应用  

Acetolysis of N-hydroxymethyl Tertiary Amines and its Application in the Reaction of TAT from DAPT

作　　者：邹坡 万子娟 罗军[1] 

机构地区：[1]南京理工大学化工学院,江苏南京210094

出　　处：《含能材料》2015年第11期1079-1083,共5页Chinese Journal of Energetic Materials

摘　　要：为研究3,7-二乙酰基-1,3,5,7-四氮杂双环[3.3.1]壬烷（DAPT）乙酰解制备1,3,5,7-四乙酰基-1,3,5,7-四氮杂环辛烷（TAT）的反应机理,以仲胺为原料与甲醛进行缩合反应合成了N-羟甲基叔胺,并在乙酸酐中研究其乙酰解反应。结果表明：N-羟甲基叔胺在进行乙酰化时,反应发生在氮原子而不是氧原子,脱去羟甲基得到相应的N-乙酰化产物。DAPT乙酰解先得到7-乙酰氧基亚甲基-1,3,5-三乙酰基-1,3,5,7-四氮杂环辛烷,再经水解、乙酰化得到TAT;考察了硝酸铵在N-羟甲基叔胺乙酰解过程中的作用,发现硝酸铵在乙酰解过程中参与反应,释放的硝酸与仲胺反应生成硝酸盐,抑制了乙酰化反应的进行;加入硝酸铵后,乙酰化收率降低了18%~41%。In order to understand the reaction mechanism of TAT from DAPT, N-hydroxymethyl tertiary amines were prepared with secondary amines and formaldehyde as starting materials. The effect of ammonium nitrate on acetolysis reaction of N-hydroxym- ethyl tertiary amines was also studied. Results show that the acetolysis reaction occurres via N-attack instead of O-attack, then the N-hydroxymethyl is removed to obtain N-acylated product. Preparation of TAT was accomplished by hydrolysis and acetylation of 7-acetoxymethyl-1 , 3,5- triacetyl-1 , 3,5,7-tetraazacyclooctane, which was converted from DAPT. The acetolysis reaction can be deactivated by nitrate, which is obtained from secondary amine and nitric acid, which is generated by acetolysis reaction of am- monium nitrate. The acetylation yield reduces 18%-41% in the presence of ammonium nitrate.

关 键 词：乙酰解 N-羟甲基叔胺 N N-二烷基乙酰胺 3 7-二乙酰基-1 3 5 7-四氮杂双环[3.3.1]壬烷(DAPT) 1 3 5 7-四乙酰基-1 3 5 7-四氮杂环辛烷(TAT) 反应机理 硝酸铵 

分 类 号：TQ560.1[化学工程—炸药化工]