白杨素及其衍生物的合成

The synthesis of chrysin and its derivative

白杨素具有肿瘤预防和治疗作用,但因其在体内活性较低,须对其进行结构修饰,间苯三酚与冰醋酸发生Friedel-Crafts反应制备得到2,4,6-三羟基苯乙酮(1);1与硫酸二甲酯反应得到2-羟基-4,6-二甲氧基苯乙酮(2);2与苯甲醛在强碱性条件下发生羟醛缩合制备得到查尔酮(3);3在碘催化下生成黄酮(4);4脱去甲氧保护基后得到白杨素(5);5与2-溴代乙酸乙酯反应后,脱除乙氧基制得白杨素的衍生物(7),通过5步反应制备得到白杨素,再经过取代和去保护两步反应得到白杨素的衍生物,共合成得到7个产物,所有化合物的结构均经1H NMR,IR和MS表征和确定.

Chrysin can prevent and treat tumor. But its activities in vivo are so low that its structure must be modified. In this paper, 2,4,6-trihydroxyacetophenone （I） was prepared by Friedel-Crafts reaction between phloroglucol and glacial acetic acid. 2-hydroxy-4,6- dimethoxyacetophenone （2） was prepared by the reaction between 1 and dimethyl sulfite. Under strong alkaline conditions, chalcone （3） was prepared by aldol reaction between 2 and benzaldehyde. Under the catalysis of iodine, the flavone （4） was prepared using 3. Chrysin （5） was synthesized by the elimination of methoxyl group of 4. After 5 and ethyl bromoacetate reacted, the ethyoxyl group of the resulting product was removed to prepare chrysin derivative （7）. Chrysin was prepared through five steps. Its derivative was synthesized using chrysin through two steps of substitution and deprotection. There were seven compounds prepared. The structures of all compounds were characterized and confirmed by 1H NMR, IR and MS.