双环[3.3.1]壬烷-2,6,9-三酮的合成有机化学.pdfVIP

DOI: 10.6023/cjoc201309009 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 双环[3.3.1]壬烷-2,6,9-三酮的合成 任晓莉 凌亦飞 罗 军* (南京理工大学化工学院 南京 210094) 摘要 研究了新化合物双环[3.3.1]壬烷-2,6,9-三酮以 1,3-环己二酮为起始原料的三条合成路线, 并对其反应机理进行了 初步推测. 第一条路线以 1,3-环己二酮与丙烯醛发生 Michael 加成、分子内 aldol 缩合以及氧化三步得到双环[3.3.1]壬 烷-2,6,9-三酮, 总产率为 43%. 第二条路线为 1,3-环己二酮先与吗啉反应生成烯胺, 再与丙烯酸乙酯进行环合, 以“一 锅煮”法得到目标产物, 产率为 20%. 第三条路线为 1,3-环己二酮先与丙烯酸乙酯经过 Michael 加成, 再进行酸催化分 子内 C-酰化得到目标产物, 总产率为 83%, 该路线具有操作简单、条件温和、产率高及环境友好等优点. 关键词 1,3-环己二酮; 双环[3.3.1]壬烷-2,6,9-三酮; 丙烯醛; 丙烯酸乙酯; 环化 Synthesis of Bicyclo[3.3.1]nonane-2,6,9-trione Ren, Xiaoli Ling, Yifei Luo, Jun* (School of Chemical Engineering, Nanjing University of Science Technology, Nanjing 210094) Abstract A novel compound bicyclo[3.3.1]nonane-2,6,9-trione was synthesized from cyclohexane-1,3-dione through three routes and some reaction mechanisms were proposed. The first route afforded bicyclo[3.3.1]nonane-2,6,9-trione in a total yield of 43% via Michael addition with cyclohexane-1,3-dione and acrolein, intermolecular Aldol condensation and oxidation. The second route gave target product in 20% yield via a one-pot process including formation of enamine with morpholine and cy- clization with acrylic ethyl ester. The third route also used cyclohexane-1,3-dione and acrylic ethyl ester as start materials and resulted bicyclo[3.3.1]nonane-2,6,9-trione with a high total yield of 83% via Michael addition and intermolecular C-acylation. This process has the advantages of simple operation, mild reaction co