【作者】 史娟；

【导师】 张尊听；

【作者基本信息】 陕西师范大学 ， 有机化学， 2006， 硕士

【摘要】 白杨素是一种重要的黄酮类化合物,具有广泛的药理作用,如抗氧化、抗病毒、抗癌等。超分子化学以分子间由非共价的弱相互作用结合而成的多分子体系为研究对象,可以被看作是推广了的配位化学,而能够直接将配位化学与超分子化学联结起来的桥梁则是配合物分子内和分子间的配体间弱相互作用。为了改善白杨素的性能、提高其生物利用度和与金属离子的配位能力,本文对白杨素进行了磺化,得到2种白杨素磺化物:白杨素-6-磺酸钠和白杨素-8-磺酸钠。以白杨素-6-磺酸根为配体与金属离子自组装得到4种白杨素磺化配合物,培养了它们的单晶,并对晶体结构和超分子作用进行了研究。此外,对白杨素全合成过程中出现的Baker-Venkataraman二次重排进行了探讨。 首先,对黄酮类化合物的分类及与金属离子的络合作用,白杨素的药理作用和超分子自组装研究进行了综述。其次,以白杨素为先导化合物对其进行磺化,得到两种白杨素磺化物:白杨素-6-磺酸钠和白杨素-8-磺酸钠的混合物,通过络合解聚使其分离。白杨素-6-磺酸钠为配体分别与Zn(Ⅱ)、Cd(Ⅱ)、Ba(Ⅱ)、Cu(Ⅱ)作用,得到了4个白杨素磺化配合物,它们分别是:白杨素双核锌配位化合物、白杨素四核镉配位化合物、白杨素磺酸钡配位聚合物和白杨素磺酸铜配位化合物。采用元素分析、IR、和~1H NMR进行了结构表征,X-射线单晶衍射法测定了晶体结构,研究了4个白杨素磺化配合物的晶体结构和超分子作用。同时,对白杨素双核锌和白杨素四核镉配位化合物的光致发光性能进行了测定,并讨论了它们的发光机制。 最后,在白杨素全合成过程中得到了间三苯甲酰氧基苯乙酮、白杨素和二苯甲酰基甲烷(DBM)三种物质,其中DBM是Baker-Venkataraman二次重排反应的产物,讨论了Baker-Venkataraman二次重排反应机理。 在白杨素6位及8位引入磺酸根不仅提高了白杨素的水溶性,还增强它了与金属离子的自组装能力。白杨素-6-磺酸根可作为双齿配体与金属离子Zn(Ⅱ)、Cd(Ⅱ)、Ba(Ⅱ)、Cu(Ⅱ)发生自组装作用,依靠白杨素-6-磺酸根与金属离子间的配位作用、阴阳离子之间的静电力、氢键与π-π堆积作用组装为具有三维结构的超分子化合物,所得到的多核配合物还具有光致发光性能。水溶性黄酮配体使得白杨素新药和新型荧光材料的研制开发成为现实。更多还原

【Abstract】 Chrysin is one of flavonoids widely spread in nature. It has extensive biological activities, such as antivirus, antioxidant, and anticancer. Supramolecular chemistry is an important extension of the chemical field. Its object is the multimolecular entities assembled by the weak no-covalence interaction between molecules. It can be defined as "extended coordination chemistry" and the bridge linked the coordination chemistry with supramolecular chemistry is the intermolecular forces in the coordination complex. In order to improve the coordination abilities of chrysin with metal ions, the chrysin was sulfonated. Two chrysinsulfonates, chrysin-6-sulfonate and chrysin-8-sulfonate were obtained. Chrysin-6-sulfonate acted a ligand and self-assembled with Zn(II), Cd(II), Ba(II), Cu(II). 4 kinds of the sulfonate coordination complexes were synthesized and determined. The crystal structures and supramoecular forces were studied, In addition to, the mechanism of twice Baker-Venkataraman rearrangement was discussed.Firstly, the classification and complexing action with metal ions of flavonoids, pharmacological actions of chrysin and supramolecular self-assembly were reviewed. Secondly, the mixture of chrysin-6-sulfonate and chrysin-8-sulfonate was obtained by sulfonated chrysin. By the method of coordination and depolymerization, two chrysinsulfonates were separated. The ligand, sodium 5,7-bihydroxyflavone-6-sulfonate coordinates with Zn( II), Cd( II), Ba( II), Cu( II), and 4 sulfonate complexes were obtained including a dinuclear zinc complex, a tetranuclear cadmium complex, a barium coordination polymer and a copper complex. They were characterized by ~1H NMR, IR and X-ray single-crystal diffraction analysis. The crystal structures and supramolecular forces of four complexes were discussed and the photoluminescent phenomena of the dinuclear zinc complex and the tetranuclear cadmium complex were observed and the photoluminescent mechanisms were discussed.Finally, 2,4,6-tribenzoyloxyacetophenone, chrysin and DBM were synthesized in the synthetic course of chrysin. And the mechanism of twice Baker-Venkataraman rearrangement was discussed.The water solubility and coordination ability of chrysin were strengthened byintroduced a sulfo-group in 6- or 8- position of chrysin. The bidentate ligand, chrysin-6-sulfonate, self-assembled with Zn(II), Cd(II), Ba(II) and Cu(II), and formed supramolecular complexes by coordination interactions, electrostatic interactions, hydrogen interactions and n-n stacking interactions. The dinuclear zinc complex and the tetranuclear cadmium complex have photoluminescent phenomena. It is possible to make developing new drug and novel photoluminescent materials because of the synthesis of the water-solubility ligand of flavonoids.更多还原