Synthesis, Characterization And Properties Of Aminosilane And Amino Acid Schiff Base Organotin Compounds

The organotin compounds are widely used in many fields, such as catalysts, PVC stabilizer, sterilization fungicides, antifouling coatings, wood preservative, anti-cancer drugs and so on. It is one of the smart spot of current research about its structure and biological activities, especially for its antitumor activities. Organosilicons are widely applicated in many fields. In recent years, silane coupling agents have been a hot spot in the field of chemical research. A series of Schiff base compounds have been synthesized by the reaction of salicylaldehyde with α-amino acid or aminosilane, and then react with organotin chlorides to afford the produts. In this thesis, 13 new amino-acid Schiff base organictin compounds and 15 new amino silane Schiff base ligands and their organotin compounds have been synthesized and characterized by means of element analysis, IR, NMR(1H and 13C), and X-ray single crystal diffraction. A series of novel structural organotin compounds are obtained. The antibacterial and anti-cancer activities of the representative compounds have been preliminary studied.The 1-(3-salicyliminopropyl)silatrane derivatives, 3,5-X2-2-OH-C6H2CH=N-(CH2)3Si(OCH2CH2)3N [X = H, Br](A1~A5), have been synthesized by the reaction of substituted salicylaldehyde with the 1-(3-aminopropyl)silatrane which were obtained by the condensation of(3-ami-nopropyl)triethoxysilane with triethanolamine. These compounds include 2-OH-C6H2CH=N(CH2)3Si(OCH2CH2)3N(A1), 5-Br-2-OH-C6H2CH=N(CH2)3Si(OCH2CH2)3N(A2), 3,5-Br-2-OH-C6H2CH=N-(CH2)3Si(OCH2CH2)3N(A3), 2-OH-C6H2C(CH3)=N(CH2)3Si(OCH2CH2)3N(A4), 3-CH3O-2-OH-C6H2CH=N(CH2)3Si(OCH2CH2)3N(A5). The 1-(3-salicyliminopropyl)silatrane organotin derivatives, [3,5-X2-2-OC6H2CH=NH(CH2)3Si-(OCH2CH2)3N]·Sn RnClm(B1~B10), have been synthesized by the reaction of the Schiff base ligands(A1~A5) with organotin chloride. The compounds include [2-OC6H2CH=NH(CH2)3Si(OCH2CH2)3N]2·Sn Et2Cl2(B1), [2-OC6H2CH=NH(CH2)3-Si(OCH2CH2)3N]2·Sn Bu2Cl2(B2), [2-OC6H2CH=NH(CH2)3Si(OCH2-CH2)3N]2·Sn Me2Cl2(B3), [2-OC6H2CH=NH(CH2)3Si(OCH2CH2)3N]·Sn Ph3Cl(B4), [5-Br-2-OC6H2CH=NH(CH2)3Si(OCH2CH2)3N]2Sn Me2Cl2(B5), [3-CH3O-2-OC6H2-CH=NH(CH2)3Si(OCH2CH2)3N]Sn Me2Cl2(B6), [2-OC6H2C(CH3)=NH(CH2)3Si-(OCH2CH2)3N]2·Sn Et2Cl2(B7), [3,5-Br-2-OC6H2CH=NH(CH2)3Si(OCH2CH2)3-N]·Sn Et2Cl2(B8), [3,5-Br-2-OC6H2CH=NH(CH2)3Si(OCH2CH2)3N]·Sn Ph3Cl(B9), {[3,5-Br2-2-OC6H2CH=NH(CH2)3Si(OCH2CH2)3N]·Sn(Me2Cl)OSn(Me2Cl)}2(B10). All compounds have been characterized by means of element analysis, IR, NMR and X-ray single crystal diffraction. In B4、B6、 B8、 B9、B1, 1:1 complexes are formed by the organotin derivatives and the Schiff base ligands. The tin atom is 5-coodinated with geometry of distorted trigonal bipyramid. The axial positions are occupied by O atoms of phenolic hydroxyl and Cl atom. In B1、 B2、 B3、B5 、B7, 1:2 complexes are formed, and the tin atom is 6-coodinated with geometry of distorted octahedral geometry. The axial positions are occupied by the two O atoms of phenolic hydroxyl goups. B10 is a novel four-nuclear ladder-type organotin compound with 5-coordinated tin atom.Seven organotin complexs of N-[(2-oxyphenyl)methylene]methionines, [3,5-X2-2-OC6H2CH=NCH(CH2CH2SCH3)COO]Sn R2(X = H, Br; R = Me, Et, Ph)(C1~C7), four diethyltin compounds of N-[(2-oxyphenyl)methylene]phenylalaninates, [3,5-X2-2-OC6H2CH=NCH(CH2Ph)COO]Sn(CH2CH3)2(X = H, Br)(D1~D4), and three cyclohexyltin complexs of N-(3,5-dibromosalicylidene)valines, [3,5-Br2-2-OC6H2CH=NCH(CH3)2COO]SnmCyn(E2~E4), have been synthesized by the reaction of organotin chlorides with N-[(2-oxyphenyl)methylene]aminoacids derived from substituted salicylaldehyde and α-amino acids. They are [2-OC6H2CH=NCH(CH2CH2SCH3)COO]Sn Me2(C1), [5-Br-2-OC6H2CH=NCH(CH2 CH2SCH3)COO]Sn Me2(C2), [3,5-Br-2-OC6H2CH=N-(CH2CH2SCH3)COO]Sn Me2(C3), [3-CH3O-2-OC6H2CH=NCH(CH2CH2SCH3)COO]-Sn Me2(C4), [5-Br-2-OC6H2 CH=NCH(CH2CH2SCH3)COO]Sn Ph2(C5), [3-CH3O-2-OC6H2CH=NCH(CH2CH2 SCH3)COO]Sn Et2(C6), [2-OC6H2CH=N-CH(CH2CH2SCH3)COO]Sn Me2(C7), [3,5-Br-2-OC6H2CH=NCH(CH2Ph)COO]-Sn(CH2CH3)2(D1), [5-Br-2-OC6H2CH=N CH(CH2Ph)COO]Sn(CH2CH3)2(D2), [2-OC6H2CH=NCH(CH2Ph)COO]Sn(CH2CH3)2(D3), [3-CH3O-2-OC6H2CH=N-CH(CH2Ph)COO]Sn(CH2CH3)2(D4), [3,5-Br-2-O C6H2CH=NCH(CH3)2COO]Sn Cy3(E2), [3,5-Br-2-OC6H2CH=NCH(CH3)2COO] Sn Cy2(E3), [3,5-Br-2-OC6H2CH=NCH(CH3)2COO]Sn Cy2 Sn Cy3(E4). All organotin complexes have been characterized by means of element analysis, IR, NMR and X-ray single crystal diffraction. C1, C2 and C6 are the weak-dimers with geometry of distorted octahedral geometry. C3 and D1 are composed of centrosymmetric dimers in which the two Sn-centres are linked by two asymmetric Sn-O???Sn bridges involving the phenolic O atom of the ligand and a long Sn???O. C4 and D4 are the weak-dimers with geometry of distorted trigonal bipyramid. C1, C2 and C6 have the structure of three monomers of self-assemble through the bidenate bridging coordination of carboxylate group to tin atoms to form a 12-membered macrocycle. C5 and E3 are the single-nuclear compounds with 5-coodinated tin atom. E4 is a novel two-nuclear compound in which the two different organotins are linked by O atom of carboxyl group.The anti-bacterial activity of the organotin compounds against E. Coli has been determind by using microcalorimetry method. The results show that the compounds have good antibacterial activity(MIC: 15.16 μg·m L-1). Diethyltin compounds display the activity against human lung tumor cell A549 and colon carcinoma cell COLO 205, but is worse than theat of cis-platinum.This work not only enriches the contents of organotin chemistry and structural chemistry, but also provides valuable information for studying and developing further the other properties and applications of the compounds.