有机化学 ›› 2010, Vol. 30 ›› Issue (11): 1682-1688. 上一篇    下一篇

研究论文

柑橘生物活性多甲氧基黄酮及其糖苷类的合成研究

汪秋安*,吴峥,刘莉,邹亮华,罗茗   

  1. (湖南大学化学化工学院 化学生物传感与计量学国家重点实验室 长沙 410082)
  • 收稿日期:2009-12-22 修回日期:2010-05-25 发布日期:2010-06-12
  • 通讯作者: 汪秋安 E-mail:wangqiuan@yahoo.com

Synthesis of Citrus Bioactive Polymethoxyflavonoids and Flavonoid Glucosides

WANG Qiu-An, WU Zheng, LIU Li, ZOU Liang-Hua, LUO Ming   

  1. (State Key Laboratory of Bio-chemical Sensing and Chemometrics, College of Chemical and Chemistry Engineer-ing, Hunan University, Changsha 410082)
  • Received:2009-12-22 Revised:2010-05-25 Published:2010-06-12

多甲氧基黄酮是广泛存在于柑橘属植物中的一类具有显著抗癌、抗炎等生物活性的天然产物. 本工作以间苯二酚和甲氧基取代的苯甲醛为原料, 经过溴化、甲基化、芳基亲核取代、Friedel-Crafts乙酰化、羟醛缩合、环化或Algar-Flynn-Oyamada反应、DDQ脱氢、选择性脱甲基化反应, 以及随后的糖苷化和脱乙酰化反应, 合成了一系列多甲氧基黄酮及其糖苷类化合物1a, 1b4a, 4b, 59. 其中1a, 1b, 2a, 2b, 3b, 4a, 4b57, 9是全合成的天然产物. 此外, 在对五甲氧基苯的合成过程中, 发现了一种由间二苯酚经溴代、甲基化和芳香亲核取代等三步反应高产率制备有机合成中间体2,3,4,6-四甲氧基苯酚(12)的新方法. 所合成新化合物的结构由MS, IR, 1H NMR和13C NMR进行了表征.

关键词: 黄酮类, 多甲氧基黄酮, 合成, 生物活性, 2,3,4,6-四甲氧基苯酚

Polymethoxyflavonoids (PMFS) are a class of natural products, which widely exist in citrus plants possessing distinguished anticarcinogenic and antiinflammatory activities. A series of polymethoxyflavonoids and flavonoid glucosides 1a, 1b4a, 4b, 59 have been synthesized via reactions of bromination, methylation, aromatic nucleophilic substitution, Friedel-Crafts acetylation, aldol condensation, cyclization or Algar-Flynn-Oyamada reaction, DDQ dehydrogenation, selective demethylation, glycosidation and deacetylation. The natural products 1a, 1b, 2a, 2b, 3b, 4a, 4b, 57, 9 were first total synthesized. Moreover, a new method for the preparation of organic synthetic intermediate 2,3,4,6-tetramethoxyphenol 12 by bromination, metylation and aromatic nucleophilic substitution from resorcinol in high yields was found during synthesizing pentamethoxybenzene 13. The struc-tures of all new compounds have been confirmed by MS, IR, 1H NMR and 13C NMR spectra.

Key words: flavonoids, polymethoxylated flavone, synthesis, bioactivity, 2,3,4,6-trtramethoxyphenol