Synthesis, Structural Characterization And Properties Of The Organotin Complexes Containing Heteroatom Carboxylic Acid

Organotin complexes have been used extensively as catalysts, stabilizers, biocides, anti-fouling agents and wood preservatives. In recent years, the investigations on the structure mode and biological activities, especially anti-tumor activity, of organotin complexes have become the focus on organometallic chemistry. In this thesis, more than 40 organotin carboxylates were synthesized by the reactions of triphenyltin hydroxide, cyclohexyltin hydroxide, dibutyltin oxide, 2-methyl-2-phenylpropyltin oxide with various aryloxyacetic acids , 2-(aryloxyacetyl hadrazone) acetic acid(or pyruvic acid) and 2-(2-hydroxy benzoyl hydrazono) acetic. These organotin carboxylates were characterized by elemental analysis, IR, NMR spectra, and 11 single crystal structures of the typical organotin compounds were determined, and their variations on structure and property were also discussed. The thesis contains the following works.First, 8 kinds of aryloxyacetic acid ligands were synthesized by the following method: m-dihydroxybenzene, p-dihydroxybenzene , o-nitrophenol, p-nitrophenol,salicylaldehyde , p-hydroxyl benzaldehyde and vanillic aldehyde react with sodium chloroacetate in the alkalescent solution. 20 organotin carboxylates were synthesized by the reaction of organotin hydroxide or oxide with the corresponding aryloxyacetic acid. The crystal structures of m-C₆H₄ (OCH₂COOSnGy₃)₂(1),p-C₆H₄(OCH₂COOSnCy₃)₂ (4) , 2-NO₂C₆H₄OCH₂COO Sn[C₆H₅C(CH₃)₂CH₂]₃ (9),[2-NO₂C₆H₄OCH₂COOSnBu₂]₂O(10), 4-NO₂C₆H₄O CH₂COOSnCy₃(ll) and 2-CHO-4-CH₃OC₆H₃OCH₂COOSn[C₆H₅C(CH₃)₂CH₂]₃ (20) were resolved and their coordination mode and structural features were discussed by combining spectroscopic analysis.Second, 21 organotin carboxylates with the 2-(aryloxyacetyl) hadrazone) acetic acid (or pyruvic acid) were synthesized by the reactions of riphenyltin hydroxide, cyclohexyltin hydroxide, dibutyltin oxide, 2-methyl-2-phenylpropyltinoxide with various hadrazone acetic acid which were synthesized from the aryloxyacetic acid prepared before. In the chapter the author also prepared 2-(2-hydroxy benzoyl hydrazono) acetic acid ligand and obtained several organotin carboxylates.The structures of five carboxylates such as C6H5OCH2 CO NHNCHCOOSnCys (21), CeHsOCHzCONHNCHCOOSnPhs (22) , [4-NO2C6H4 OCH2CONHN= CH COOSn]2O(31), C6H5(OSnCy3)CONHNCHCOOSnCy3 (33) and C6H5OCH2CO NHNC(CH3)COOSnCy3(38) were determined. In the series of organotin carboxylates,only the Nitrogen atom of 31 co-ordinate with Tin atom, the Nitrogen atom of all others don't co-ordinate with Tin atom.Third,the inhibitory effects on HeLa (cervix cancer) and MCF-7 cells , the bacteriostatic power on Escherichia coli and the catalytic power to acyloin condensation and to ester exchange reaction of several typical organotin carboxylates were measured and obtained good resuits.The data of the first experiment indicated that theses compounds have antitumour activities and usually the in vitro activity was much higher than that of cis-platin;and the data of the third experiment showed that some of these organotin carboxylates have catalytic power and high selectivity to acyloin condensation and to ester exchange reaction.