1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷的合成

Synthesis of 1,4-Diazido-2,3-Bis-Azidomethyl-2,3-Dinitro-Butane

以硝基甲烷为原料合成了1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷,总收率为37.8%。采用1HNMR﹑IR和MS对目标产物及中间体的结构进行了表征。在三羟甲基硝基甲烷的合成中,结合反应机理确定了氢氧化钙的用量为:n(CH3NO2)n(Ca(OH)2)=1001;通过对催化剂浓硫酸﹑三氟化硼—乙醚络合物和对甲苯磺酸的比较,得出对甲苯磺酸为中间体2,2-二甲基-5-羟甲基-5-硝基-1,3-二氧杂环己烷合成的较优催化剂;分别采用2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯和2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四对甲苯磺酸酯与NaN3反应,发现磺酸酯基易离去,叠氮化反应更易进行,收率较高;叠氮化反应的较优溶剂为DMSO。DSC分析表明,1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷的分解峰温为223.46℃。

The 1,4-diazido-2,3-bis-azidomethyl-2,3-dinitro-butane was synthesized from nitromethane. The overall yield is 37.8%. The characterization methods of 1H NMR, IR and MS were applied to confirm the structures of the intermediates and the product. Based on the reaction mechanism, the best process condition for synthesizing tris-（hydroxymethyl）-nitromethane was determined as n（CH3NO2） ： n（Ca（OH）2） = 100 ： 1; Comparing three different catalysts including concentrated sulfuric acid, boron trittuoride etherate and p-toluenesulfonie acid, p-toluenesulfonie acid served the best cata- lyst for forming the intermediate, 2,2-dimethyl-5-hydroxymethyl-5-nitro -1,3-dioxane; Both the reactants, 2, 3-bis （hydroxymethyl） -2,3-dinitro -1,4-butanediol tetranitrate and 2,3-bis （hydrox-ymethyl） -2,3-dinitro-1,4-butanediol etrasul- phonate, were used for the azide reaction with NAN3, and the phenomena is observed that it is easy for the leaving of sulphonate group and azide substitution with high yield in comparison with the methods using nitrate with sulphonate; A better solvent of azide reaction is DMSO. The results of DSC show that the temperature peak of decomposition of 1,4-diazido-2,3- bis-azidomethyl -2,3-dinitro-butane is 223.46℃.