7-羟基异黄酮类化合物的“一锅法”合成及其糖苷化反应研究

"One Pot" Synthesis of 7-Hydroxylisoflavones and the Glycosidation of 7-Hydroxylisoflavone

以间苯二酚和芳乙酸为原料,用三氟化硼乙醚作溶剂和催化剂,在C1试剂DMF/PCl5体系中,以90%以上产率"一锅法"合成了4个7-羟基异黄酮类化合物1a^1d.将1a在DMF/丙酮(3∶2V/V)混合溶剂中,以K2CO3为碱性缩合剂、四丁基溴化铵(TBAB)为相转移催化剂,分别与α-溴代乙酰半乳糖和α-溴代乙酰麦芽糖发生糖苷化反应,以及随后在氨水存在下的脱乙酰基反应,得到了2种未见文献报道的新型7-O-β-D-异黄酮苷化合物2~3.所合成的产物已通过MS,1HNMR和IR等波谱方法进行了结构确认.该合成方法具有反应条件温和,后处理方便,产率较高和立体选择性强的优点,具有较大的应用价值.

Four 7-hydroxylisoflavones 1a-1d were synthesized by ＂one pot＂ from resorcinol and arylacetic acid, using C1 reagent and BF3/Et2O as the solvent and the catalyst with a yield of more than 90 %. la reacted with corresponding α-acetylglycosyl bromides through glycosidation and deacetylation reaction to form two new isoflavonoid 7-O-β-D-glycosides 2 - 3. The synthetic procedure of glycosidation was modified by using anhydrous K2 CO3 in a solvent mixture of DMF/acetone （3 ： 2 V/V） and tetrabutylammonium bromide （TBAB） as a phase transfer catalyst. This method has the advantages of mild reaction conditions, simple operation, high stereospecificticy and good yields. The structures of all compounds synthesized were determined by 1^HNMR, MS and IR spectra.