Synthesis, Structure And Properties Of Ferrocene And Coumarin Organotin Compounds

Organotin compounds have a widely range of application in agricultural production, industrial catalysis, environmental science, organic synthetic chemistry and coordination chemistry and other fields. In recent years, organiotin compounds have been paid more attention as antibacterial or anticancer drugs. In this thesis Ferrocene hydrazone and coumarin carboxylic acid are chosen as ligands to react with dialkyltin chloride or alkyltin oxides, and ferrocene and coumarin functional groups are introduced into organotin molecules. Two series of organotin compounds are synthesized and characterized by means of using elemental analysis, infrared spectrum, nuclear magnetic resonance spectrum, and X-ray single crystal diffraction techniques. Some novel structural organotin compounds are obtained. The electrochemical property, antibacterial activity and interaction with DNA of these compounds are studied preliminarily.Ferrocenecarbonyl hydrazone(1, 6 and 10) have been synthesized by the condensation reaction of ferrocenecarboxyl hydrazide with 2-hydroxyacetophenone or 1-benzoylacetone. Under conditions of triethylamine, ferrocenecarbonyl hydrazones reacts with diorganotin dichlorides to produce 11 kinds of new ferrocenecarbonyl hydrazone organotin compounds(2-13). Their structures are confirmed by elemental analysis, IR, 1H and 13 C NMR spectra. The crystal structures of 11 compounds are determined by X-ray single crystal diffraction. The results show that the reaction of ferrocenecarboxyl hydrazide with 1-benzoylacetone generates a product containing a pyrazole ring, which ring-open and bond to tin with enol and imine in the presence of triethylamine. In the ompounds, central tin atoms are five-coordinated and have the coordination geometry of distorted trigonal bipyramid. The axial position are occupied by a phenolic oxygen and a enol oxygen or two enol oxygen atoms, and two alkyl carbons and a imine N are located in the triangle plane. Electrochemical properties of the ligands and the oganotin compounds are determined by the cyclic voltammetry, and the results show that the oganotin compounds were oxidized easierly.The Knoevenagel condensation reaction of salicylaldehyde or substituent salicylaldehyde with diethyl malonate gets ethyl coumarin-3-carboxylate, which hydrolyses to form coumarin-3-carboxylic acid. Diorganotin dichlorides or diorganotin oxides react with coumarin-3-carboxylic acid to afford 7 kinds of organotin coumarin-3-carboxylates. The compounds are characterized by using infrared spectra, elemental analysis, nuclear magnetic resonance hydrogen spectrum and carbon spectrum. X-ray single crystal diffraction technology has been applied to the determination of crystal structures of the compounds. The results show that tin atom present different coordinated configurations due to the different substituent. Triphenyltin coumarin-3-carboxylate(17) contains a methanol molecule and Sn atom possesses trigonal bipyramid configuration, and a one-dimensional chain is formed by the intermolecular hydrogen bond between the carbonyl and methanol. In tricyclohexyltin coumarin-3-carboxylate(18) and 8-methoxycoumarin-3-carboxylate(20), one dimensional chain is formed by the coordination carbonyl oxygen of the neighboring molecule to tin atom, and tin atom has a five coordination configuration. The tin atom in fenbutatin coumarin-3-carboxylate(19) is four-coordinated tetrahedral configuration. Two tin atoms of dibutyltin coumarin-3-carboxylate(21) and 8-methoxycoumarin-3-carboxylate(22) have a seven-coordinated distorted pentagonal bipyramidal geometry and five-coordinated trigonal bipyramid configuration, respectively, and a four-nuclear ladder structure is formed through μ2O and carboxylate bridging. Both tin atoms of dibutyltin 7-diethylaminocoumarin-3-carboxylate(23) are five-coordinated trigonal bipyramid configurations.The interaction between organotin coumarin-3-carboxylates and calf thymus deoxyribonucleic acid(ctDNA) were determined with UV-absorption method, results indicate that dibutyltin 7-diethylamino- coumarin-3-carboxylate could intercalate into the base pairs of ctDNA. Micro-calorimetry is used to determine the antibacterial activity of orgnotin compounds, and the result shows that the orgnotin compounds have the antibacterial activity which is equivalent to penicillin.This thesis enrichs the structure types of organotin compounds, and provides the experimental basis of ferrocenecarbonyl hydrazone organotin compounds and organotin coumarin carboxylate for other properties and applications.