异构化合成顺-5-降冰片烯-外-2,3-二酸酐的研究
收稿日期: 2015-03-13
修回日期: 2015-04-29
网络出版日期: 2015-04-30
基金资助
国家自然科学基金(No. 21272156)资助项目.
Synthesis of Exo-norborn-5-ene-2,3-anhydride via Isomerization
Received date: 2015-03-13
Revised date: 2015-04-29
Online published: 2015-04-30
Supported by
Project supported by the National Natural Science Foundation of China (No. 21272156).
以解聚的环戊二烯单体与马来酸酐为原料通过Diels-Alder反应、异构化以及重结晶制备高纯度的顺-5-降冰片 烯-外(exo)-2,3-二酸酐. 主要对顺-5-降冰片烯-内(endo)-2,3-二酸酐的异构化进行详细研究, 对酸促进异构化、碱促进异构化及加热异构化进行比较. 通过对加热异构化的溶剂、反应时间、底物浓度进行优化, 得出了一种较好的异构化方法: 以邻苯二甲醚为溶剂加热异构化可得到高纯度的顺-5-降冰片烯-外-2,3-二酸酐, 总产率为66.5%.
关键词： 顺-5-降冰片烯-外-2,3-二酸酐; Diels-Alder反应; 异构化反应; 邻苯二甲醚
陈海霞 , 刘艳 , 胡北 , 赵梦梦 , 任凯 , 谢小敏 , 徐浩 , 张兆国 . 异构化合成顺-5-降冰片烯-外-2,3-二酸酐的研究[J]. 有机化学, 2015 , 35(8) : 1759 -1764 . DOI: 10.6023/cjoc201503018
High purity exo-norborn-5-ene-2,3-anhydride was synthesized by Diels-Alder reaction of freshly distilled cyclopentadiene and maleic anhydride, isomerization and recrystallization. Acid-promoted isomerization, base-promoted isomerization and thermal isomerization of endo-norborn-5-ene-2,3-anhydride were studied in detail. 1,2-Dimethoxybenzene was found to be a competent solvent in the thermal isomerization of endo-norborn-5-ene-2,3-anhy-dride, and reaction time and concentration of substrate were also optimized. Furthermore, an effective protocol was developed to obtain exo-norborn-5-ene-2,3-anhydride with high purity in a overall yield of 66.5%.
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