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1957年Bradshaw等人合成了一系列大环内酯类化合物,并以这类化合物为配体制得了碱金属、碱土金属的配合物。β-二酮冠醚配合物也有研究,发现不仅冠醚环上的醚氧与金属离子配合,环外的羰基也有一定的作用,但含四羰基冠醚配合物尚未见到报导。可以预料,由于羰基增多冠醚与金属离子的配合作用将变得复杂。为此,本文合成了1,4-二氧-9,12-二氮环十六烷-5,8,13,16-四酮(简写为TKC)与硝酸镧、钐的配合物,并进行了元素分析、红外光谱,紫外光谱、核磁共振、溶解性能及摩尔电导和差热分析测试,对配合物的合成条件进行了探索,以研究冠醚环上的氧、氮原子以及环外羰基与RE(Ⅲ)的配合性能。TKC的结构如左。
In 1957, Bradshaw et al. Synthesized a series of macrolide compounds, and used such compounds as ligands to make alkali metal and alkaline earth metal complexes. β-diketone ethers have also been studied. It is found that not only the ether oxygen on the crown ether ring cooperated with the metal ions, but also carbonyl groups outside the ring. However, tetracarbonyl crown ether complexes have not been reported yet. It is expected that the complexation of crown ether with metal ions will be complicated by the increase of carbonyl group. For this purpose, a complex of 1,4-dioxo-9,12-diazacyclohexadecane-5,8,13,16-tetraone (abbreviated as TKC) with lanthanum nitrate and samarium was synthesized and carried out The synthesis conditions of the complexes were explored by elemental analysis, infrared spectroscopy, ultraviolet spectroscopy, nuclear magnetic resonance, solubility and molar conductance and differential thermal analysis. The results showed that the oxygen and nitrogen atoms in the crown ether ring, RE (Ⅲ) with the performance. The structure of TKC is left.