CAJ | 학술논문

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（N2 O5）＝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1 H NMR，13 C 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，D c ＝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。
이병이산이을지화다취갑철위기시원료，경배합、탈최、축동화、취양화、우화、해초화등보취，합성료2，2，4，4，6，6-륙초기금강완（HNA）。우화료 Meerwein′s 지적합성、취양화반응화동우해초화적반응조건，HNA 적총수솔제고도3％。용오양화이담작동우해초화반응적초화제，고찰료물료배비、반응온도、반응시간、용제대동우해초화반응적영향。학정적최가반응조건위：물료비 n（2，2，6，6-이을탱이양기-4-금강완동우）∶ n（N2 O5）＝1∶3，반응온도위50℃，반응시간위30 min，반응용제위이록갑완，해이초기화합물적수솔위65％。용1 H NMR，13 C NMR，IR 급원소분석표정료중간체여목표화합물적결구。배양료 HNA 단정，용 X사선사원연사의측정료타적단정결구。용열중분석（TG）화차시소묘량열법（ DSC）연구료 HNA 적열성능。결과표명：HNA 정체속단사정계，P2（1）/n 공간군，정포삼수위 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。HNA 적열분해과정가분위삼개계단，종분해반응개시도결속적총실중위94％。DSC 곡선재256．21℃처유일개명현적방열봉，현시가열시 HNA 재해온도유극렬적방열분해반응발생。
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.