Syntheses And Structural Analyses Of Organotin Compounds Containing The Hecarboxylic Acid And Heterocycle Thiol

Organotin(IV) compounds are attracting more and more interests due to their unique structures, the rich variety of shapes, extensively potential applications. Especially in the late 1980’s, some organotin(IV) compounds were found that they have potential antitumour activity more active than that of cis-platinum derivatives. Which opened the new era of the research on relationship of the structure-effect of organotin(IV) compounds. Its research range is expanding constantly, including organomet allic chemistry, coordination chemistry, structure chemistry, biochemistry and pharmacology, etc., thus it becomes the front field that has the development prospect. Today, it is the most advanced theme that the investigation on the biological activities and various structures of organotin(IV) compounds. Owing to its vacant d atom orbit, the center tin atom is able to accept single electron pair form such donor atoms as oxygen, nitrogen or sulfur to form new compounds. Synthesizing many kinds of organotin(IV) compounds are very important in discussing the relations of their construction and effect. Out of above considerations, this thesis studied a series of research on syntheses and characterizations of organotin(IV) compounds containing the hecarboxylic acid and heterocycle thiol. Forty-nine new organotin(IV) compounds are obtained and characterized by elemental analysis, IR and NMR, and forty-two of them are characterized by X-ray diffraction. Forteen of them’s antitumour activities are tested. The main contributions of the thesis are as following:1、Studies on the syntheses and X-ray structures of organotin(IV) compounds with three monacid. Twenty new compounds have been synthesized and characterized, and seventeen of them also characterized by X-ray diffraction. The results show that (1) Triorganotin (IV) compounds of monacid are usually 1D infinite chains, The cener tins are all five- coordinated bipyramid. While tri-benzyltin(IV) of 6-chloro-3-pyridin-eacetic acid and trimethyltin(IV) of 4,6-dimethyl-2- carboxymethythio compounds are monomers because of the crystal water’s coordination. (2)Diorganotin(IV) of monacid compounds show varity structure. The tin atoms of which are usually six-coordinated octahedron, which are found in the triorgantin(IV) of chloroacetic acid. But diorganotin(IV) of 6-chloro-3- pyridineacetic acid and dimethyltin of 4,6-dimethyl- 2-carboxymethythio are tetra-organodistannoxanes, which are also common. (3)Monorgnotin(IV) compounds of monacid is usually a typical drum structure.2、Studies on the syntheses and X-ray structures of organotin(IV) compounds with two biatomic acid. Five new compounds have been synthesized and characterized. The results show that organotin(IV) compounds are complicated. For example, triphenyltin(IV) of pamoic acid are 1D chain, while trimethyl-or tributhyl-tin compounds are monomer with di-tin-nuclear. The center tin atoms show four-coordinatinated tetrahedron or five-coordinated bipyramid conFig.uration. (2)When the trimethyltin(IV) chloride reacts with the (s)-(+)-Phenylsuccinic acid ligand under different condition, two different compounds are obtained. One is trimethyltin of (s)-(+)-Phenylsuccinic acid compound, which is a 3D polymer and the ligand coordinates to two center tin atom by O, O atoms and functions as a bridge ligand. While another is a dimethyltin of (s)-(+)-Phenylsuccinic acid compound, which is a 2D polymer containing big rings. In which the ligand functions not only as a bridge ligand but also as a bidentate equalized carboxyl group to coordinate to tins.3、Studies on the syntheses and X-ray structures of organotin(IV) compounds with heterocycle thiol. Twenty-frist compounds have been synthesized. The results show that heterocyle thilo ligand containing nitrogen atoms acts as variety coordinated mode under different envimoent. For example, it can coordinate to the tin atom by S and N atoms, also can by only S or only N atom. Moreover, both substitutional groups of the heterocycle and steric tendencies can influence them. For example, (1) 2-mercapto-4-methylpyrimidine ligand, which coordinates to tin center through different nitrogen atom because of the effect of 4-methyl group, steric exclusion, diffenent intermolecular interactions and so on. (2) While the centrosymmetric ligand, for example, 2,5-dimercapto-1,3,4- thiodiazole, containing two symmetrical nitrogen atoms and two sulfur atoms, can coordinate to tin center through different modes. Different compounds have been obtained by the reaction of the ligand with the same diorganotin dichloride under different conditions. Which are showed in the circumstances of Me2SnCl2 or (p-F-PhCH2)2SnCl2 reacting with the ligand.4、Studies on the syntheses and X-ray structures of organotin(IV) with mercaoto- carboxylate acid, three compounds have been synthesized. The results show that: triorganotin(IV) of 4-Mercaptophenylacetic acid compounds are 1D infinite chains. While dimethyltin(IV) of ligand is a 3D polymer containing big rings. 4-Mercaptophenylacetic acid ligand fountions as a tri-dentate ligand (S, O, O) in three organotin(IV) compounds.5、Studies on the antitumour activities of some obtained organotin(IV) compo- unds. The results indicate that theses compounds have tense antitumour activities and usually the in vitro activity was higher than that of cis-platin. The structure-activity relationship from the compounds are discussed preliminarily. Other organotin(IV) compounds’antitumour activities are testing now.