Pyrazolone Derivatives And Their Synthesis, Structural Characterization And Properties Of Organic Tin Compounds

Organotin compounds are widely used as fungicides, catalysts, PVC heat stabilizers, antifouling paints and wood preservatives. The structure and biological activity of organotin compounds, in particular anti-cancer activity, has become one of the hot research. Pyrazolone and its derivatives are an important heterocyclic compounds containing N, O and can be used as antipyretic, analgesic, anti-bacterial agent. Currently they are widely used in pharmaceutical and biological reagents, metallurgy, dyes, luminescent materials and other fields. This article will introduce pyrazolone into organotin molecules and hungry for new structure, the better biological activity of organotin compounds.This thesis focuses on the investigation on the preparation and properties of pyrazolone derivatives and organic tin compounds. We describe the synthesis of 1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-5-pyrazolone, and use it as raw material in the synthesis of 5 acylpyrazolone,4 4,4'-methylene hydrocarbon double pyrazolone, 1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-4-formaldehyde-5-pyrazolone,5 pyrazolone amino acid Schiff base,5 acylpyrazolone salicylhydrazone hydrazone and 5 pyrazolone formaldehyde hydrazone. And use pyrazolone derivatives as raw materials in the synthesis of pyrazolone organic tin compounds. We characterize their structure by using of elemental analysis, IR, NMR, X ray diffraction techniques and analysis the crystal structure of 15 compounds. Determination of the antibacterial activity of representative compounds and anti-tumor activity. Researching on the nature of their structural features and to explore its structure-activity relationships and provide guidance in order to design and synthesis of pyrazolone organic tin compounds.1.1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-5-pyrazolone, as an intermediate, were prepared from 2,3,4,5-tetrafluorobenzoic acid via acylchlorination, diethylmalonate condensation, partial hydrolysis and decarboxylation and cyclization.5 4-acylpyrazolone ketones were synthesized by using the chloride and the latter, under microwave irradiation,4,4'-hydrocarbon methylene-bis[1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-5-pyrazolone] were prepared with aldehyde and the latter.25 Pyrazoline Ketone compounds were synthesized by using acyl-pyrazolone and dialkyl tin dichloride. We characterize their structure by using of elemental analysis, IR, NMR. Their structures were characterized with X-ray diffraction determination of 9 compounds 1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-4-benzoyl-5-pyrazolone A, 4,4'-benzylidene-bis[1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-5-pyrazolone]H, 1-phenyl-3-(2,3, 4,5-tetrafluoroethane phenyl)-4-benzoyl-5-pyrazolone dibutyltin compounds Aa, dicyclohexyl compound Ac, dibenzyl compounds Ae, 1-phenyl-3-(2,3,4, 5-tetrafluorophenyl)-4-furan-formyl-5-pyrazolone dicyclohexyl ketone compounds Dc, bis(β-methoxycarbonyl-ethyl) tin compounds Dd, 1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-4-(2, 3,4,5-tetrafluorobenzoyl)-5-pyrazolone and dibutyltin compounds Ea, dibenzyl compounds Ee. The compounds Aa-Ee in addition to Dd the other six compounds, the tin atoms are six-coordinate distorted octahedral configuration., while compound Dd, as a result of ester-substituted functional groups to form intramolecular tin-oxygen bond, the tin atom is seven-coordinate distorted bipyramid configuration of the Pentagon.2.1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-4-formaldehyde-5-pyrazolone was prepared using 1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-5-pyrazolone as raw material and the four place of pyrazolone was introucduced aldehyde, pyrazolone aldehyde-a-amino acid Schiff were prepared usinga-amino acid and 1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-4-formaldehyde-5-pyrazolone, and then, dialkyl tin dichloride reacted with the latter preparing 25 pyrazolone aldehyde-a-amino acid organic compounds. Characterization of their structure and analysis of the two compounds, the crystal structure. In the compound pyrazolone formaldehyde and glycine Kc dicyclohexyl compounds involved in the coordination of solvent, making tin atoms form a distorted six-coordinated octahedral geometry. The compounds, pyrazolone aldehyde alanine La dibutyltin compounds were not coordinated with the solvent, the tin atom is distorted trigonal bipyramid configuration.3. The series of pyrazoline ketone hydrazone compounds was prepared using the acyl pyrazolone pyrazolone and formaldehyde as raw materials with salicylhydrazide and pyridine hydrazide, then a series of pyrazole hydrazone organic tin compounds was prepared by reacting the pyrazole hydrazone with dialkyl tin dichloride Analysis the crystal structure of four compounds. In the compound 1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-4-benzoyl-5-pyrazolone salicylhydrazone hydrazone dibutyltin compounds lAa, the central tin atoms was five-coordination distorted trigonal bipyramid configuration. The configuration of 1-phenyl-3-(2, 3,4,5-tetrafluorophenyl)-4-(2,3,4,5-tetrafluorobenzoyl)-5-pyrazolone salicylhydrazone hydrazone dibutyltin compounds 1Ea and pyrazolone formaldehyde hydrazone salicylhydrazone dibutyltin compounds 2a were similar with lAa. In the compound pyrazolone formaldehyde hydrazone salicylhydrazone bis ((3-methoxycarbonyl-ethyl) tin compounds 2d as a result of ester-substituted functional groups to form intramolecular tin-oxygen bond, the tin atom is seven-coordinate distorted pentagonal bipyramid configuration.4. Using of microcalorimetry method,we determine on the antibacterial activity of 4,4'-methylene-bis[1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-5-pyrazolone]F, H, Ac, Ea, 1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-4-furan-formyl-5-pyrazolone dibenzyl compounds De, 1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-4-furan-formyl-5-pyrazolone hydrazone salicylhydrazone dibutyltin compounds 1Da and lEa on the inhibition of E. coli, The measured results show that the organic tin compounds have some antibacterial activity, and the introduction of F atoms increased antibacterial activity. We determine anti-tumor activity of the pyrazoline ketones by using MTT method, 1-phenyl-3-(2,3,4,5-tetrafluorophenyl)-4-(2,3,4,5-tetrafluorobenzoyl)-5-pyrazolone E, Ea, pyrazolone formaldehyde glycine dibutyltin compounds Ka and pyrazolone salicylhydrazone formaldehyde hydrazone dicyclohexyl compounds 2c. E has obvious anticancer activity on the A549 and COLO205, but the anti-tumor activity of E was significantly lower than Ea, Ka and 2c. In particular, the anti-tumor activity of Ea, Ka, and 2c on the MCF-7 and COLO20 were significantly higher than cisplatin. Compound Ea, Ka, and 2c exhibit IC50s of 0.76±0.08μg/ml,0.51±0.04μg/ml and 0.010±0.001μg/ml against CoLo205. These results provide us experimental data about the research on seeking and screening organotin compound with much activity in anticancer and antifungal. We have studied catalytic activity of 1Ea and Aa on the condensation reaction of cyclohexanone and ,3-propanediol. Compound lEa are better than Aa on the catalytic activity and selective catalysts.This high selectivity of the catalyst we look to provide the basic data.