柚皮苷半合成生物活性黄酮醇和橙酮类化合物研究

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以柚皮苷为原料,经过糖苷水解、脱氢、苄基保护、O-甲基化、过氧丙酮(DMDO)氧化或阿尔格-弗林-大山田(Algar-Flynn-Oyamada)反应和脱苄基保护等反应步骤,半合成了山萘酚(1,Kaemferol),5,7,4’-三甲氧基黄酮醇(2)、3,5-二羟基-7,4’-二甲氧基黄酮醇(3),鼠李柠檬素(4,Rhamnocitrin)等4种天然黄酮醇类和4,6,4’-三羟基二氢橙酮(5)、4-羟基-6,4’-二甲氧基二氢橙酮(6)两种新的橙酮类化合物.重点探讨了过氧丙酮(DMDO)直接氧化黄酮制备黄酮醇和Algar-Flynn-Oyamada反应制备橙酮的合成方法,改进优化了反应条件.所有合成化合物的结构已通过1H NMR,MS和IR等波谱方法进行了确认.该合成途径原料易得,工艺简便,收率较高,具有较高的应用价值. Using naringin as raw material, glycoside hydrolysis, dehydrogenation, benzyl protection, O-methylation, DMDO oxidation or Algar-Flynn-Oyamada reaction and off Benzyl protection and other reaction steps, semisynthetic mountain naphthol (1, Kaemferol), 5,7,4’-trimethoxy flavonol (2), 3,5-dihydroxy-7,4’- dimethoxy 4 kinds of natural flavonols such as flavonol (3), Rhamnocitrin (4) and 4,6,4’-trihydroxydone (5), 4-hydroxy- Dimethoxydioxone (6) two new orange ketone compounds.We focused on the direct synthesis of flavonols from aldehydes and acetone (DMDO) flavonoids and Algar-Flynn-Oyamada reaction, The reaction conditions were confirmed.The structures of all the synthesized compounds were confirmed by 1H NMR, MS and IR spectral methods.The raw materials were easily obtained, the process was simple, the yield was high, and had high application value.
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