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本文报道一类新型大环聚醚的合成.在以1,7-二氧杂-4,10-二氮杂环十二烷(1a)及1,7,10,16-四氧杂-4,13-二氮杂环十八烷(1b)中的两个仲胺上进行含醚键的卤代烷取代反应,获得一批带有两个含有侧链醚键的新型冠醚.以碳酸钾为缩合剂,所得冠醚碱金属配合物经酸分解及四甲基氢氧化铵处理后,得游离的大环聚醚. 用溶解度法初步测定了这类冠醚对碱金属的配位性能.结果指出,其母环及侧链上氧原子数的多少及碱金属离子半径的大小均影响配合物的稳定性,其中有些冠醚对碱金属有良好的配位能力,有的还具有优异的选择性,例如N,N′-β-甲氧基乙基-1,7-二氧杂-4,10-二氮杂环十二烷(13a)对钾及钠离子的选择比大于18-c-β,并比4,4′(5′)-二甲基苯并-30-c-10还高.
This paper reports the synthesis of a new type of macrocyclic polyether. In the synthesis of 1,7-dioxa-4,10-diazacyclododecane (1a) and 1,7,10,16-tetraoxa-4 , 13-diazacyclooctaoctadecane (1b), two new secondary crown ethers with pendant ether linkages were obtained.Using potassium carbonate as Condensing agent, the resulting crown ether alkali metal complexes by acid decomposition and tetramethylammonium hydroxide treatment, free macrocyclic polyether obtained by the solubility method for the preliminary determination of such crown ether coordination properties of alkali metal.Results It is pointed out that the number of oxygen atoms in the mother ring and the side chain and the size of the radius of the alkali metal ions all affect the stability of the complex. Some of the crown ethers have good coordination ability with alkali metals, and some also have excellent choices Such as N, N’-β-methoxyethyl-1,7-dioxa-4,10-diazacyclododecane (13a) have a selectivity to potassium and sodium ions greater than 18-c -β and higher than 4,4 ’(5’) -dimethylbenzo-30-c-10.