双甲基化大豆苷元磺酸盐的合成、晶体结构及活性研究

以大豆苷元为原料合成了强水溶性异黄酮类化合物7,4'-二甲氧基异黄酮-3'-磺酸钠(1)和7,4'-二甲氧基异黄酮-3'-磺酸铜(2).X射线单晶衍射分析表明,化合物1的分子组成为Na(H2O)2](C17H13O4SO3),Na的配位数为6,且相邻钠离子以7,4'-二甲氧基异黄酮-3'-磺酸根氧原子桥连,与两个磺酸根的3个氧原子和1个S原子组成六元环,六元环通过Na—O配位键彼此稠合,在晶体结构中形成延伸的锯齿状聚合八面体配位钠离子链;这些钠离子链之间又通过配位水与配位水、磺酸根之间的氢键作用自组装成二维结构的超分子离子聚合物.化合物2的分子组成为Cu(H2O)6](C17H13O4SO3)2.8H2O,Cu(Ⅱ)位于对称中心上.Cu(H2O)6]2+,C17H13O4SO3-和H2O之间存在多种氢键;并且异黄酮环反平行排列存在π…π的堆积作用.氢键和π…π的堆积作用使化合物2自组装成三维结构的超分子.抗缺氧缺血活性试验结果表明,它们的抗缺氧缺血活性比大豆苷元的高.

Syntheses, Crystal Structures and Biological Activity of Bimethylation Daidzein Sulfonates

The water soluble derivatives of daidzein sodium 7,4'-bimethoxylisoflavone-3'-sulfonate(1) and copper(Ⅱ) 7,4'-bimethoxylisoflavone-3'-sulfonate(2) were synthesized and their structures were characterized by IR,NMR,ESI-MS and X-ray diffraction analyses.In the crystal structure of compound 1,each sodium ion is six-coordinated by oxygens from the methoxyl and suflo-group of 7,4'-bimethoxylisoflavone-3'-sulfonate and H2O.Two adjacent sodium ions were bridged by the oxygen atoms from suflo-group and a six-membered ring is formed.The six-membered ring consists of two sodium ions,three oxygen atoms from two suflo-groups and a sulfur atom.The Na—O bonds of adjacent rings are paralleled with each other and form an one-dimensional zigzag sodium polyion chain along axis c of the unit cell. The sodium ions chains are also connected by the hydrogen bonds among coordination water molecules,between coordination water molecules and oxygen from suflo-group.The coordination interaction,hydrogen bonds and the electrostatic interaction between sodium ion and —SO-3 made compound 1 assemble supramolecular ion polymer with two-dimensional structure.The crystal of compound 2 consists of Cu(H2O)6]2+,C17H13O4SO-3 and H2O.Cu(Ⅱ) is at the symmetry center of structure of compound 2 and octahedrally coordinated by six water molecule.Cu(H2O)6]2+,C17H13O4SO-3 and H2O form several kinds of hydrogen bonds.The distance of 0.358 2 nm between anti-parallel isoflavone rings shows a π…π stacking interaction. The hydrogen bonds and π…π stacking interaction lead to supramolecular formation with three-dimensional network structure.The biological activities of resistance to hypoxia and anoxemia were tested,the results show that the biological activities of resistance to hypoxia and anoxemia of compounds 1 and 2 were better than that of daidzein.