双环[3.3.1]壬烷-2,6,9-三酮的合成
Synthesis of Bicyclo[3.3.1]nonane-2,6,9-trione
Received date: 2013-09-06
Revised date: 2013-10-22
Online published: 2013-10-25
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
任晓莉 , 凌亦飞 , 罗军 . 双环[3.3.1]壬烷-2,6,9-三酮的合成[J]. 有机化学, 2014 , 34(2) : 376 -381 . DOI: 10.6023/cjoc201309009
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 cyclization 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 conditions, high yield and environmental friendship.
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