Syntheses And Crystal Structures Of Soybean Isoflavone Derivatives

The soybean isoflavones are ubiquitous natural organic compounds, which are the products of botanic metabolizability. They display a wide range of biological activities. For instance, they have been pharmacologically shown with the effects of antidysrhythmic, antioxidant, potentialphytoestrogen, getting rid of hyperkinesias and inhibiting cancer cells growth, inhibiting cardiovascular disease and tyrosinekinases, and accelerating the formation of bone cells. Therefore, the soybean isoflavones have good value for development and application. However, their biological utilization rates are low and the doses are high for their poor solubilities, which limit their wide applications. Modifying the soybean isoflavones with chemical methods and enriching the species and properties of them are not only the important tasks in today's research field but also the sources to find new promising leading compounds and biologically active components. In the first part of this paper, the pharmacological actions and modifications of daidzein (4', 7-dihydroxyisoflavone) and genistein (4', 7-dihydroxyisoflavone), two effective principles of soybean isofiavone, are reviewed. The syntheses, crystal structures and properties of soybean isofiavone derivatives are studied in the following chapters.It is an important approach to find new medical components and to develop new drugs by modifying the structure of natural product. In order to enrich the species and properties of soybean isofiavone and improve the properties of them, in the second part of this paper, daidzein and genistein, two effective principles of soybean isoflavone, were modified by ethylating and sulfonation reaction. Six water soluble soybean isoflavone derivatives including sodium 4', 7-dimethoxyisoflavone-3'-sulfonate, sodium 7-ethoxy-4'-hydroxylisoflavone-3'-sulfonate, sodium 4', 7-diethoxyisoflavone-3'-sulfon-ate, sodium 4', 7-dimethoxy-5-hydroxyisoflavone-3'-sulfonate, sodium 7-ethoxy-4', 5-dihydroxyisoflavone-3'-sulfonate, sodium 4',7-diethoxy-5-hydroxyisofalvone-3'-sulfon-ate were obtained and characterized by 1H NMR and IR. In addition, considering the biological functions of microelement and the potential effects that they combines with natural medicine, six derivatives of 4', 7-dimethoxyisoflavone-3'-sulfonate and four derivatives of 4', 7-diethoxyisoflavone-3'-sulfonate were prepared, which are Cu2+, Co2+,Zn2+, Ni2+, Ii+ Ca2+ 4\ 7-dimethoxyisoflavone-3'-sulfonate and Co2+, Zn2+, Mg2+, Mn2+ 4', 7-diethoxyisoflavone-3'-sulfonate. The results showed that the skeletons of isoflavones have not been broken in the concentrated sulfuric acid, and the electrophilic substitution reaction is easy to be carried out.In the third part of this paper, firstly, seven derivatives of 4', 7-dimethoxyisoflavone-3l-sulfonate, Na+, Cu2+, Co2+, Zn2+, Ni2+, U* Ca2+ 4', 7-dimethoxyisoflavone-3'-sulfonate were determined by X-ray single-crystal diffraction analysis. In the crystal structure of sodium 4', 7-dimethoxyisoflavone-3'-sulfonate, there are sodium polyion chains and hydrogen bonds, which assemble the molecules into a two-dimensional network structure. And in the crystal structures of copper, cobalt, zinc, nickel 4', 7-dimethoxyisoflavone-3'-sulfonate, it ??? it stacking interactions and hydrogen bonds lead to the supramolecular formations with three-dimensional network. Besides, C-H*** n stacking interactions and hydrogen bonds exist in the crystal structure of calcium 4', 7-dimethoxyisoflavone-3'-sulfonate, and many hydrogen bonds exist in the lithium 4', 7-dimethoxyisoflavone-3'-sulfonate, they were also assembled into network structures in three-dimension. Secondly, four derivatives of 4', 7-diethoxyisoflavone-3'-sulfonate, Co2+, Zn2+, Mg2+, Mn2+ 4', 7-diethoxyisoflavone-3'-sulfonate were measured by X-ray single-crystal diffraction analysis. The results show that their molecular structural characteristic are very similar. And their molecular components are [M(H2O)]6(X)2-8H2O (X = C^HiyC^SCV, M = Co2+, Zn2+, Mg2+, Mn2+), respectively. Two isoflavone skeletons of them have two different conformations. Twelve H atoms of six coordinated water molecules form hydrogen bonds with four oxygen atoms of sulfo-groups of two isoflavone skeletons and eight oxygen atoms of eight lattice water molecules. In addition, the it ??? it stacking interaction exists between isoflavone skeletons in their crystal structures, which together with many kinds of hydrogen bonds lead to supramolecular formation with three-dimensional network structure. Finally, the crystal structures of other soybean isoflavone derivatives were studied, which mainly include 7-methoxy-4'-hydroxylisoflavone, 7-ethoxy-4'-hydroxy-isoflavone, 4',7-diethoxy-5-hydroxyisoflavone, manganese7-methoxy-4'-hydroxyisofla-vone-3'-sulfonate, 4'-methoxy-7-hydroxyisoflavone-3'-sulfonate and barium 4', 7-dimethoxyisoflavone-3'-sulfonate. Among them, it ??? it stacking interactions and hydrogen bonds exist in the crystal structure of 7-methoxy-4'-hydroxylisoflavone, 7-ethoxy-4'-hydroxyisoflavone and manganese 7-methoxy-4'-hydroxylisoflavone-3'-...