知识与财富的链接
以间二氯苯胺为起始原料,用氯乙酰基保护氨基的方法,经乙酰化、硝化、叠氮化及脱氮、水解4步合成了7-氨基-6-硝基苯并二氧化呋咱(ANBDF),其中叠氮化及脱氮反应不经分离一锅完成,脱氮反应在80℃完成,其余反应均在0℃至室温下完成。4步反应的得率分别为97.7%,70.0%,82.5%和80.0%。以IR1、HNMR、MS及元素分析对目标化合物的结构进行了表征。制备并测定了ANBDF的晶体结构,其晶体结构属正交晶系,空间群P2121/n;晶胞参数:a=1.3626(3)nm,b=0.6961(13)nm,c=0.95745(3);Dc=1.931 g.cm-3。晶体结构分析表明,ANBDF是一平面分子,分子内存在氢键,分子结构紧密,密度大。DSC分析结果证明,ANBDF在199.3℃达到最大放热峰,是热稳定性能极佳、极具前途的高能量高密度化合物。
7-Amino-6-nitrobenzodifuroxan(ANBDF) was synthesized from 3,5-dichloroaniline and chloroacetyl chloride through the process of acetylation,nitration,azidation and denitrogenation,and hydrolysis.Azidation and denitrogenation reactions were finished in one pot.The denitrogenation reaction took place at 80 ℃,while all the other reactions were completed at 0 ℃ to room temperature.The yields of four reactions were 97.7%,70.0%,82.5% and 80.0% respectively.The structure of ANBDF was characterized by IR,1HNMR,MS and elementary analysis.The single crystal of ANBDF was prepared and its structure was determined by X-ray diffractometer.The crystal belongs to orthorhombic system,space group P2121/n with cell dimensions:a=1.362 6(3) nm,b=0.696 1(13) nm,c=0.957 45(3),Dc=1.931 g·cm-3.The crystal structure shows that all the atoms of ANBDF are nearly on the same plane and there are intramolecular hydrogen bonds,resulting in the high density of the molecule.DSC data demonstrate that the exothermal decomposition rate reaches peak value at 199.3 ℃,which characterizes that ANBDF possesses excellent thermal stability and can act as a promising energetic compound.
