The Research On The Synthesis, Characterization And Properties Of Organotin Carboxylates

The author have found that organotin compounds have many important significance in different fields especially anticancer activities based on reading a number of literatures. More and more organometallic scientists paid attention to the anticancer activities of organotin compounds since the scientists Crown and his coworks found organotin compounds exhibited better anticancer activity in the early 1980s. So two series of di-n-butyltin carboxylates(32e - 32j and 16a - 16d, 17a - 17d) were synthesized by the reaction of di-n-butyltin oxide with corresponding aromatic carboxylic acids.The author also have found that retinoids play an essential role in vertebrate growth and development, supporting cell differentiation, embryonic development, vision, the immune response and reproduction especially anticancer activities. Therefore in order to enhance the activities of organotin compounds, we synthesized a series of di-n-butyltin retinoates by the reaction of di-n-butyltin oxide with corresponding retinoids in 1: 2(16a - 16d) and 1: 1 (17a - 17d) molar ratio. Study of their biological activity in Hela,Liver Cancer Cell(LCC),A549 cancer cell showed that compound 17a had better anticancer activity.A series of di-n-butyltin dicarboxylates[n-Bu₂Sn(OOCAr)₂(32a - 32j)] were synthesized by the reaction of di-n-butyltin oxide with corresponding aromatic carboxylic acids in 1: 2 molar ratio. The anticancer activities of these compounds indicated that all of them exhibited good activities. In order to research the relations between their structures and anticancer activities, compound 32b and 32e were determined by X-ray single crystal diffraction. The crystal 32b belongs to rhombohedral with space group R-3, a = 25.388(3) A, b = 25.388(3) A, c = 19.081(4) A,β= 90°, V = 10651(3) A³, Z = 12, R = 0.0492, wR = 0.1257. The crystal 32e belongs to monoclinic with space group P2(1)/c, a = 9.3215(8) A, b = 23.9936(19) A, c = 10.8225(9) A,β= 107.8480(10)°, V = 2304.0(3) A³, Z = 4, R = 0.0585, wR = 0.128. In the crystals of 32b and 32e each tin atom is six-coordinated in a distorted octahedron geometry structure. The structures of 32b and 32e exist in their crystals by intermolecular and intramolecular hydrogen bonds. 32b presented better anticancer activity than 32e because the hydrogen bonds in 32b are longer and weaker, so that the species R2Sn²⁺ of 32b in bio-system is released more easily to combine with DNA of cancer cells.In order to reveal the anticancer mechanism of organotin compounds, di-trideca-fluorooctayltin dichloride[(C₆F₁₃CH₂CH₂)2SnCl₂] was synthesized and the cyclic voltammetric and spectrophotometric methods were used to study the interaction of (C₆F₁₃CH₂CH₂)₂SnCl₂ and DNA. The results suggested that compound (C₆F₁₃CH₂CH₂)₂SnCl₂ mainly reacts electrostatically with the phosphate backbone of DNA.We have synthesized 30 compounds and 15 of them were not reported in literatures until now. Their structures were characterized and confirmed by IR, 1H NMR, 13C NMR, 19F NMR and 119Sn NMR spectra.