硝-硫混酸硝化四乙酰基六氮杂异伍兹烷制备CL-20反应机理

Reaction Mechanism of Preparation CL-20 from Tetraacetylhexaazaisowurtzitane Nitrated by Mixture of Nitric Acid and Sulfuric Acid

为了研究四乙酰基六氮杂异伍兹烷(TAIW)的混酸硝化反应机理,采用分阶段终止反应进程的方法,先后分离并表征了五种反应中间体:四乙酰基二硝基六氮杂异伍兹烷、三乙酰基三硝基六氮杂异伍兹烷、二乙酰基四硝基六氮杂异伍兹烷两种异构体以及一乙酰基五硝基六氮杂异伍兹烷。试验结果表明:TAIW笼底的两个游离仲胺基很容易首先发生硝化作用,在升温条件下,四个乙酰基再逐个发生硝解。运用薄层色谱(TLC)技术跟踪了反应进程,检测到了上述全部中间体。

In order to study the reaction mechanism of nitration/nitrolysis of tetraacetylhexaazaisowurtzitane （TAIW） of nitric acid and sulfuric acid, all of the intermediates, tetraacetyldinl two isomers of diacetyltetranitroh e, triacetyltrini with the mixture tane and monoacetylpentanitrohexaazaisowurtzitane were separated by means of quenching the reaction mixture at proper time and characterized by element analysis, NMR, FTIR, MS and X-ray diffraction. The results show that the two free secondary amines of TAIW are nitrated firstly and then the four acetyl groups of TAIW are nitrolysed one after one under conditions of elevating the reaction temperature. Moreover,all of the intermediates stated above of the nitration processeses were detected by thin layer chromatography（TLC） techniques.