有机化学 ›› 2014, Vol. 34 ›› Issue (2): 376-381.DOI: 10.6023/cjoc201309009 上一篇    下一篇

研究论文

双环[3.3.1]壬烷-2,6,9-三酮的合成

任晓莉, 凌亦飞, 罗军   

  1. 南京理工大学化工学院 南京 210094
  • 收稿日期:2013-09-06 修回日期:2013-10-22 发布日期:2013-10-25
  • 通讯作者: 罗军 E-mail:luojun@njust.edu.cn

Synthesis of Bicyclo[3.3.1]nonane-2,6,9-trione

Ren Xiaoli, Ling Yifei, Luo Jun   

  1. School of Chemical Engineering, Nanjing University of Science & Technology, Nanjing 210094
  • Received:2013-09-06 Revised:2013-10-22 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

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.

Key words: cyclohexane-1,3-dione, bicyclo[3.3.1]nonane-2,6,9-trione, acrolein, acrylic ethyl ester, cyclization