白杨素衍生物的合成和晶体结构及与DNA的作用

以白杨素为先导化合物经羟甲基化反应合成中间体5,7-二羟基-6,8-二羟甲基黄酮(1)，进而合成了5,7-二羟基-6,8-二(甲氧基甲基)黄酮(2)，5,7-二羟基-6,8-二(乙氧基甲基)黄酮(3)，5,7-二羟基-6,8-二(丁氧基甲基)黄酮(4)，5,7-二羟基-6,8-二(戊氧基甲基)黄酮(5)和5-羟基-7-甲氧基-6,8-二(乙氧基甲基)黄酮(6)；采用IR，¹H NMR，¹³C NMR和元素分析对1～6进行了表征，同时用X-射线单晶衍射法对6进行了晶体结构测定。利用荧光法分别对1～4与CT-DNA的作用进行了研究，根据Stern-Volmer方程，它们对EB-DNA体系的荧光猝灭常数分别为k_q1=9.71×10³ L·mol^-1，k_q2=2.25×10⁴L·mol^-1，k_q3=1.03×10⁴L·mol^-1和k_q4=7.96×10³ L·mol^-1。1～4与白杨素相比，对DNA更具亲和力，为开发更有效的黄酮类化合物提供了实验依据。

Synthesis of chrysin derivatives and their interaction with DNA

Using chrysin as a leading compound, intermediate 5, 7-dihydroxy-6, 8-bis (hydroxymethyl) flavone (1) was synthesized by hydroxymethylation. The intermediate reacted with different alcohols to afford 5, 7-dihydroxy-6, 8-bis ( methoxymethyl) flavone (2), 6, 8-bis (ethoxymethyl) -5, 7dihydroxyflavone (3), 6, 8-bis-(butoxymethyl)-5, 7-dihydroxyflavone (4), 6, 8-bis (pentyloxymethyl) -5,7-dihydroxy flavone (5) and 6, 8-bis-(ethoxymethyl) -5-hydroxy-7-methoxyflavone (6). These compounds were characterized by IR, 1H NMR, 13C NMR and element analysis. The crystal structure of 6 was determined by X-ray crystal diffraction. The interaction of the derivatives with CT-DNA was studied by fluorescent spectroscopy. According to the Stern-Volmer equation, the quenching constants of the compounds 1 - 4 were measured, separately, they were K(q1) = 9.71 x 10(3) L x mol(-1), K(q2) = 2.25 x 10(4) L x mol(-1), K(q3) = 1.03 x 10(4) L x mol(-1) and K(q4) = 7.96 x 10(3) L x mol(-1). Compounds 1-4 showed higher binding affinity with DNA than chrysin did. The results provided the experimental basis for developing a more effective flavonoid and worthing further thoroughly study.