2,2,4,4,6,6-六硝基金刚烷的合成、表征及晶体结构  

Synthesis,Characterization and Crystal Structure of 2,2,4,4,6,6-Hexanitroadamantane

作　　者：张萍萍[1] 凌亦飞 孙露[1] 罗军[1] 

机构地区：[1]南京理工大学化工学院,江苏南京210094

出　　处：《含能材料》2014年第5期646-653,共8页Chinese Journal of Energetic Materials

摘　　要：以丙二酸二乙酯和多聚甲醛为起始原料,经环合、脱羧、缩酮化、臭氧化、肟化、偕硝化等步骤,合成了2,2,4,4,6,6-六硝基金刚烷(HNA)。优化了Meerwein's酯的合成、臭氧化反应和酮肟偕硝化的反应条件,HNA的总收率提高到3%。用五氧化二氮作酮肟偕硝化反应的硝化剂,考察了物料配比、反应温度、反应时间、溶剂对酮肟偕硝化反应的影响。确定的最佳反应条件为:物料比n(2,2,6,6-二乙撑二氧基-4-金刚烷酮肟)∶n(N2O5)=1∶3,反应温度为50℃,反应时间为30 min,反应溶剂为二氯甲烷,偕二硝基化合物的收率为65%。用1H NMR,13C NMR,IR及元素分析表征了中间体与目标化合物的结构。培养了HNA单晶,用X射线四圆衍射仪测定了它的单晶结构。用热重分析(TG)和差示扫描量热法(DSC)研究了HNA的热性能。结果表明:HNA晶体属单斜晶系,P2(1)/n空间群,晶胞参数为a=1.2011(2)nm,b=2.1129(4)nm,c=1.1967(2)nm,α=90°,β=90.59(3)°,γ=90°,V=3.0368(11)nm3,Z=8,Dc=1.777 g·cm-3,μ=0.166 mm-1,F(000)=1664。HNA的热分解过程可分为三个阶段,从分解反应开始到结束的总失重为94%。DSC曲线在256.21℃处有一个明显的放热峰,显示加热时HNA在该温度有剧烈的放热分解反应发生。2,2,4,4,6,6-Hexanitroadamantane（HNA）was synthesized via cyclization,decarboxylation,ketalization,ozonation, oximation,and oxidative nitration etc. steps,using diethyl malonate and paraformaldehyde as raw materials. The reaction condi-tions of the preparation of Meerwein′s ester,ozonation and nitration were optimized,and the overall yield of HNA was promoted to 3% . The effects of substrates ratio,reaction temperature,reaction time and solvent on the gem-nitration reaction were investiga-ted using nitrogen pentoxide as nitrating agent of gem-nitration reaction of ketoxime. The optimum reaction conditions were deter-mined as with the yield of gem-dinitro compound being 65% ：n（compound 7）∶ n（ N2 O5 ）= 1 ∶ 3,reaction temperature 50 ℃, reaction time 30 min and methylene chloride as solvent. The structures of intermediates and target compound were characterized by 1 H NMR,13 C NMR,IR and elemental analyses. The single crystal of HNA was cultivated and its single crystal structure was determined by a four-circle X-ray diffractometer. The thermal decomposition properties of HNA were studied by thermogravimetry （TG） and differential scanning calorimetry（ DSC）. Results show that the crystal belongs to monoclinic system,space group P2（1）/n with crystal parameters of a =1. 2011（2）nm,b =2. 1129（4）nm,c =1. 1967（2）nm,α =90°,β =90. 59（3）°,γ =90°, V =3. 0368（11）nm3 ,Z =8,D c =1. 777 g·cm -3 ,μ =0. 166 mm -1 ,F（000）= 1664. The thermal decomposition process of HNA can be divided into three stages and the total mass loss from start to the end of decomposition reaction is 94% . There is an obvious exothermic peak at 256. 21 ℃ on DSC curve of HNA,revealing that an intense exothermic decomposition reaction of HNA would occur on heating.

关 键 词：有机化学 晶体结构 [2  2  4  4  6  6-六硝基金刚烷(HNA)] 五氧化二氮 硝化 

分 类 号：O621.3[理学—有机化学]