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Synthesis, Crystal Structure And Antitumor Activity Of Novel Di-and Tri-organotin Carboxylates

Posted on:2012-04-06Degree:DoctorType:Dissertation
Institution:UniversityCandidate:Adama Moussa SakhoFull Text:PDF
GTID:1221330368995638Subject:Organic Chemistry
Abstract/Summary:
The study of the chemical structure and biological activity of organotin carboxylate compounds has attracted considerable attention during the last few years; researchers focus on their preparation owing to their antitumor activity, catalytic activity, and the diversity of their structures.Eight new series of di- and triorganotin carboxylates have been synthesized and are collected in the chapters 4,5, and 6 respectively. The 2-(4-methyl benzoyl) benzoic acid (L’H),2-(4-ethyl benzoyl) benzoic acid (L2H),2-(4-isopropylbenzoyl) acid (HL1),2-benzoyl benzoic acid (HL3), and 4-oxobutanoic acid) (HL2) were prepared by Friedel Crafts reaction with of toluene, ethyl benzene, isopropyl benzene (cumene), benzene, and phtalic and maleic anhydride, respectively. All ligands have been characterized by elemental analysis, FT-IR, ’HNMR spectroscopy, and the structures of the complexes have been determined by X-ray crystallography diffraction analyses In chap 4, three new organotin carboxylates of composition [(R)2Sn(O2CC6H4C-OC6H4CH3)2] 1; [(R)2Sn(O2CC6H4COC6H4-C2H5)2]22 and R3SnO2CC6H4COC6H4CH33, were obtained by reactions of (R)2SnO [R= o-tolyl] with 2-(4-methyl benzoyl) benzoic acid and 2-(4-ethyl benzoyl) benzoic acid, and reaction of Cy3SnOH [Cy= tricyclohexyl] with 2-(4-methyl benzoyl) benzoic acid respectively. Single X-ray crystallography diffraction analysis show that the complex 1 has two folded symmetrical structure; the tin atom in 1 is found to adopt a distorted toward skew-trapezoidal bipyramidal geometry. Molecular structure of the complex 2 is centrosymmetric, and the internal tin atom is five-coordinated and is in distorted trigonal bipyramidal geometry. The crystal structure of the complex 3 is found to exhibit distorted tetrahedral geometry. Pilot studies have indicated that the complexes 1 and 2 have shown good anti-tumor activities.In 5, also Three diorganotin(IV) series and triorganotin (IV) complexes [(C6H11)2Sn]4(L1)2O2(OH)2 (1), (C6H11)3Sn(HL2) (2), and (CeH11)3SnL3(3) (where HL1 is 2-(4-isopropyl benzoyl) benzoic acid; (HL2) is phtalic acid and (HL3) is 2-benzoyl benzoic acid) were synthesized and their crystal structures were characterized. There are four crystal lographically unique Sn centers in the structure of 1, which consists of a SatO2(OH)2 ladder unit, and the ladder consists of four tins held together by twoμ3-oxygen atoms and twoμ2-oxygen atoms. The supermolecular motif of 1 is a two-dimensional structure linked by O-H…O hydrogen bonds. The asymmetric unit of 2 contains two crystallographically independent monomers. The supramolecular architecture of 2 is a 2-D layer structure linked by face-to-faceπ-πinteractions between phenyl rings of adjacent L2 anions. The structure of 3 contains one tri-cyclohexyltin cation and one L3 anion. The Sn…O interactions lead the whole structure to a supramolecular chain.In chapter 6, Two new supramolecular chains, namely [(C6H11)3SnL1] (1) and [(C6H11)3SnL2] (2) (where, HL1= 8-(ethoxycarbonyl)-1-naphthoic acid, HL2= 4-(oxo-4-phenyl butanoic acid), were synthesized by the self-assemble reaction of R3SnOH with the corresponding acids in a suitable mole ratios respectively. The tin atom in polymeric chain of the complexes 1 and 2 adopts distorted monocapped trigonal bipyramidal geometry with six-coordinated, and exhibits a one-dimensional supramolecular chain through intermolecular O→Sn interactions. The complexes 1 and 2 show antibiotic and anti-tumour activities in vitro experiments.
Keywords/Search Tags:Organotin carboxylates, synthesis, crystal structures, coordination, biological activity
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