3,3′-二硝基-4,4′-偶氮氧化呋咱的合成及性能

Synthesis and Properties of High Energetic Compound 3,3'-Dinitro-4,4'-azofuroxan

以丙二酸单酰肼单钾盐为原材料,经硝化和亚硝化反应"一锅法"合成了4-氨基-3-叠氮羰基氧化呋咱(AN-FO),然后通过ANFO合成出3,3′-二氨基-4,4′-偶氮氧化呋咱(DAAFO),DAAFO在双氧水/浓硫酸溶液中氧化为DNAFO。用元素分析、IR、MS和DSC-TG对其结构进行了表征。结果表明,丙二酸单肼单钾盐在25～30℃硝化30min,然后在-22±2℃亚硝化60min,生成3,4-二叠氮羰基氧化呋咱(AAF)。AAF在80℃环氧六烷/水溶液中异构化重排得到ANFO,DAAFO在30℃经硝酸/硫酸氧化转化为DNAFO。DNAFO的密度为2.002g/cm3,生成焓为640.30kJ/mol。

4-Amino-3-azidocarbonylfuroxan（ANFO） was first synthesized via nitration and nitrosation in ＂one-pot＂,using malonic acid monohydrazide monopotassium salt as starting material.Then 3,3＇-diamino-4,4＇-azofuroxan（DAAFO）was prepared using ANFO.Finally,DAAFO were directly oxidized to DNAFO by hydrogen peroxide/sulfuric acid solution.The structures of these compounds were characterized by elementary analyses,FTIR,MS and DSC-TG.The reaction condition for ANFO and DNAFO was found to be： malonic acid monohydrazide monopotassium salt was nitrated at 25-30℃ for 30 min,and nitrosated at-22±2℃ for 60 min,in which furoxan-3,4-dicarboxylic acid diazide（AAF） was synthesized.ANFO was obtained by isomerization of AAF at 80℃ in dioxane/H2O.DNAFO was obtained by oxidating the DAAFO by HNO3/H2SO4 at 30℃.The density and enthalpy of formation of DNAFO are 2.002 g/cm3,and 640.30 kJ/mol,respectively.