【作者】 周波；

【导师】 秦圣英；

【作者基本信息】 四川大学 ， 有机化学， 2005， 硕士

【摘要】 氮杂冠醚因其冠环中氮原子的软碱性质及本身特殊的空间构型,使氮杂冠醚对许多金属离子具有较强的选择络合作用;另外,氮杂冠醚不仅被用作仿酶基体,而且还可以作为取代基挂接到其它的仿酶模型中,以调控活性中心的微环境。将氮杂冠醚引入Schiff碱氧载体人工模型中,以此来考查氮杂冠醚环可能赋予模型化合物新的特点与功能,是冠醚化学和仿生化学又一新的发展方向。为了进一步探索其中的规律性,我们从苯并-10-氮杂-15-冠-5和吗啉出发,通过改良的Mannich反应,设计合成了一系列共11个N-取代的氮杂冠醚单Schiff碱新型配体及相应的Co（II） 、Mn（III）配合物作为仿生氧载体模型,以MS、IR、1^HNMR和元素分析予以表征,获得了一些创新性成果。模拟生物氧载体,研究了氮杂冠醚在不同取代位置和其它不同取代基的配体对Co（II）配合物氧合性能的影响。以二甘醇二甲醚作溶剂,吡啶作轴向配体,在-5℃～25 ℃范围内测定了它们的氧合反应平衡常数K_O2,并计算除了它们的热力学参数?H⁰, ?S⁰;考查了添加碱金属离子对二氧亲合性能的影响。以空气为氧源,考查了其Mn（III）配合物中氮杂冠醚及其取代位置、其它取代基以及添加NHPI 对对二甲苯的催化氧化反应诱导期和选择性能的影响。并对以上的实验结果作了合理的解释。由EDTA二酐和二氮杂冠醚合成了未见报道的3个EDTA-二氮杂冠醚缩聚物,考查了它们对难溶盐BaSO₄ 的增溶性能。结果表明,它们对BaSO₄ 的溶解效率达60%⁷5%,远远优于类似物对BaSO₄ 的增溶性能。这说明合适的环腔尺寸、合适长度的羧甲基侧链及其数目以及配体适度的柔韧性都有利于提高它们对BaSO₄ 的增溶性能。更多还原

【Abstract】 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%.更多还原