3,5-二氯-2,4,6-三硝基苯胺及其衍生物的合成

Synthesis of 3,5-Dichloro-2,4,6-trinitrobenzenamine and Its Derivatives

分别以3,5-二氯苯胺为原料,经N保护、硝化、水解以及以1,3,5-三氯-2,4,6-三硝基苯(TCTNB)为原料,经叔丁胺化,再在三氟乙酸中脱叔丁基2种方法合成了3,5-二氯-2,4,6-三硝基苯胺。与甲胺反应,合成了3,5-二甲氨基-2,4,6-三硝基苯胺,收率85%,再用混酸硝化合成了3,5-二甲硝胺基-2,4,6-三硝基苯胺的硝酸盐,收率70%。采用核磁共振、质谱、红外和元素分析等进行了结构表征。探讨了不同参数下TCTNB的氨化结果。优化的条件为:n(TCTNB)∶n(叔丁胺)=1∶2,CuO为催化剂,KHCO3为碱。

Two synthetic methods have been developed for the synthesis of 3, 5-dichloro-2, 4, 6- trinitrobenzenamine. In the first process, 3,5-dichlorobenzenamine was selected as precursor, followed by N- protection, nitration, and hydrolysis. In another process, 1,3,5-trichloro-2,4,6-tri-nitrobenzene （ TCTNB ） reacted with 2-amino-2-methylpropane and then trifluoroacetic acid to deprotect. The condensation between 3,5 -dichloro-2,4,6-trinitrobenzenamine and methylamine gave 3,5 -dimethylamino-2,4,6-trinitrobenzenamine in 85 % yield which can be converted to the nitrate of 3,5-dimethylnitramino-2,4,6-trinitrobenzenamine in 70% yield. The structure of the product was confirmed by ^1H NMR, MS, IR and elemental analysis. The results of selective of TCTNB under different conditions were discussed. The optimized conditions are： n（TCTNB） ：n（t-butylamine） = 1：2, CuO as catalyst, KHCO3 as base.