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摘要有机笼状高能密度化合物，具有高能量、低感度，同时热稳定性良好，可同时应用于军事和民事领域。其中多硝基金刚烷骨架上含有较多的碳原子，可设计性强，是一种潜在的高能量密度材料（HEDMs）。然而，随着金刚烷骨架上偕二硝基的引入，分子空间位阻增加，使多硝基金刚烷的合成变得更加困难。因此研究高位阻下偕二硝基引入反应工艺对多硝基金刚烷的合成具有十分重要的意义。34005
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以丙二酸二乙酯、多聚甲醛为起始原料，先经过环合、加热脱羧、羰基α位甲酰化、Aldol缩合构建金刚烷骨架，再通过缩酮化、氧化等步骤合成了2,2,4,6,6-五硝基金刚烷，反应总收率为13.9%；并研究了五硝基金刚烷钠盐在不同硝化体系中的高位阻硝化工艺。在-60 ℃用NO2Cl对2,2,4,6,6-五硝基金刚烷的钠盐进行硝化时，以85%的收率合成了2,2,4,4,6,6-优尔硝基金刚烷，从而实现了高位阻条件下多硝基金刚的硝化，为多硝基金刚烷的合成提供了一种有效的途径。
关键词 有机笼状高能密度化合物 高能量密度材料（HEDMs） 多硝基金刚烷 高位阻硝化
毕业论文设计说明书外文摘要
Title Studies on the synthesis of 2,2,4,4,6,6-Hexanitroadamantane
Abstract
High energy density cage compounds were widely used as propellants, explosives, pyrotechnics due to their high energy, good thermostability and insensitivity. Among them, polynitroadamantanes are potential High Energy Density Materials (HEDMs), which were attributed to the good designable structure with numerous C-H bonds on the adamantane skeleton. However, developments in the synthesis of polynitroadamantanes were limited owing to the increase of steric hindrance arised from the introduction of gem-dinitro groups. So, it’s very significant to develop high sterically hindered nitration methods to overcome the above-mentioned steric problems.
We designed and synthesized a high sterically hindered polynitroadamantane 2,2,4,6,6-pentanitroadamantane and studied the nitration of sodium salt of 2,2,4,6,6-pentanitroadamantane under different nitration systems. The synthesis of 2,2,4,6,6-pentanitroadamantane was accomplished from diethyl malonate and paraformaldehyde in 11 steps with an overall yield of 13.9%, and 2,2,4,6,6-pentanitroadamantane was successfully converted to 2,2,4,4,6,6-hexanitroadamantane in 85% yield with NO2Cl as the nitration reagent at -60 ℃. The strategy achieved the nitration of high sterically hindered compounds and paved a convenient way for the synthesis of other polynitroadamantanes.
Keywords high energy density cage compounds High Energy Density Materials (HEDMs) polynitroadamantane high sterically hindered nitration
目 次
1 绪论 2
1.1 金刚烷概述 2
1.2 多硝基金刚烷的合成研究进展 2
1.3 偕二硝基引入反应研究进展 2
1.4 本论文的研究思路和研究内容 2
2 2,2,4,4,6,6-优尔硝基金刚烷的合成 2
2.1 引言 2
2.1 实验药品与仪器 2
2.2 Meerwein’s酯（2.1）的合成 2
2.3 双环[3.3.1]壬烷-2,6-二酮（2.2）的合成 2
2.4 双环[3.3.1]壬烷-2,6-二酮-3-甲醛（2.3）的合成 2
2.5 4-羟基-2,6-金刚烷二酮（2.4）的合成 2
2.6 2,2,6,6-二乙撑二氧基-4-金刚烷醇（2.5）的合成 2
2.7 2,2,6,6-二乙撑二氧基-4-金刚烷酮（2.6）的合成 2
2.8 2,2,6,6-二乙撑二氧基-4-金刚烷酮肟（2.7）的合成 2