柑橘生物活性多甲氧基黄酮及其糖苷类的合成研究  

Synthesis of Citrus Bioactive Polymethoxyflavonoids and Flavonoid Glucosides

作　　者：汪秋安[1] 吴峥[1] 刘莉[1] 邹亮华[1] 罗茗[1] 

机构地区：[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

出　　处：《有机化学》2010年第11期1682-1688,共7页Chinese Journal of Organic Chemistry

基　　金：广东省教育部产学研结合(No.2009B090300146)资助项目

摘　　要：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,1b～4a,4b,5～9.其中1a,1b,2a,2b,3b,4a,4b和5～7,9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.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,1b～4a,4b,5～9 have been synthesized via reactions of bromination,methy-lation,aromatic nucleophilic substitution,Friedel-Crafts acetylation,aldol condensation,cyclization or Al-gar-Flynn-Oyamada reaction,DDQ dehydrogenation,selective demethylation,glycosidation and deacetylation.The natural products 1a,1b,2a,2b,3b,4a,4b,5～7,9 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 structures of all new compounds have been confirmed by MS,IR,1H NMR and 13C NMR spectra.

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 

分 类 号：O621.3[理学—有机化学]