Synthesis Of N-Substituted Azacrown Ethers And Studies Of Their Some Special Functions

As the soft base nature of nitrogen atom and the unique configuration, azacrown ethers not only have been using as enzyme-mimic organism, but also have been binding with others enzyme-mimic models to mimic and control the microenviroment around the reactive site. To introduce the azacrown ethers into Schiff base-type synthetic oxygen carriers to investigate the new characteristics are a trend of current crown chemistry and biomimetic chemistry. For the purpose to employ the cooperativity of the azacrown ethers in enzyme-mimic aspects, A series of benzoazacrown or morpholino substituted mono-Schiff base ligands and their Cobalt (Ⅱ), manganese (Ⅲ) complexes have been designed and synthesized successfully. They all had been characterized by IR, MS,1HNMR and elemental analysis, And obtained some creative results. The Cobalt (Ⅱ) complexes have been employed as synthetic oxygen carriers. Their equilibrium constants KO2 and thermodynamic parameters ?H0 and ?S0 for oxygenation over a range of -5℃to 25℃have been determined and calculated. And the alkali ions addition to the solutions to investigate their influence of the dioxygen affinities also has been done. The Schiff base manganese (Ⅲ) complexes have been employed as catalyst to catalytic oxidation of p-xylene to p-toluic acid using air as oxidant source. The influence of the substituted position of the azacrown and the other substituents in the ligand of the manganese(Ⅲ) complexes and the addition of NHPI on the selectivity and catalytic activity to oxidation reaction has been examined. The experimental phenomenons have been explained reasonably. For the purpose to investigate the solubilization of diazacrown ether derivatives to barium sulfate in water, three novel water-soluble EDTA-diazacrwn ether polymers have been synthesized. The effects of azacrown ether ring in the polymer chains including its cavity size on the solubilization of barium sulfate to water were investigated by comparison with several analogues. The results indicated that the EDTA-diazacrown ether polymers are the efficient solubilizers of barium sulfate and the diaza-18-crown-6 derivative EDTA-type polymer with the highest solubilization efficiency of the barium sulfate to water is up to 75.26%.