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Molecular Design of Organic Ligands with Highly Selective Recognition and Separation Function for Metal Ions

具有金属离子高选择性识别和分离功能的有机配体的分子设计

基本信息

批准号：
11640607
负责人：
UMETANI Shigeo
金额：
$ 2.11万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

Some 4-acyl-5-pyrazolone derivatives with bulky acyl substituent at 4-position have been prepared. The extraction of Sc (III) with smaller ionic radius decreased as the acyl group became bulkier. It is clear that the interligand contact in the Sc complex decreases the stability, since the pKa values of anthracenecarbonyl, acetyl, benzoyl and 3, 5-dimethylbenzoyl derivatives are very similar. The extraction of La (III) with larger ionic radius was governed by the electronic effect such as resonance effect by the substituents. The effect of the interligand contact and the distance between the two donating oxygens was seen in the extraction of tervalent Al. Ga and In.Novel 4-acyl-5-pyrazolones having the crown ether moiety as the intramolecular synergist have been synthesized and the solvent extraction of various metal ions has been examined. 4-Acyl-5-pyrazolone-substituted dibenzo-16-crown-5, dibenzo-19-crown-6, 12-crown-4, 15-crown-5 and 18-crown-6, and bis- (4-acyl-5-pyrazolone) -substituted diaza-18-crown-6 were designed and synthesized by facile coupling reactions. Alkali metal ions were readily extracted into chloroform. The selectivity was governed primarily by the crown ether moiety depending on the cavity size. Alkaline earth metal ions were also readily extracted into chloroform, however the selectivity is governed by both the acylpyrazolone and the crown ether moieties. Among the divalent transition metal ions, the extraordinarily high extractability was seen for Mn, Cd and Pb. It is well known that the extractability for these metal ions is much lower than the other divalent transition metal ions with the conventional chelating extractants. Such anomalous extraction was also given in the synergistic extraction with acylpyrazolone and crown ethers employed separately.

合成了一些4-酰基-5-吡唑啉酮类4-位取代基较大的衍生物。离子半径较小的Sc(III)的萃取量随着酰基体积的增大而减小。很明显，由于蒽甲酰、乙酰基、苯甲酰基和3，5-二甲基苯甲酰基衍生物的pKa值非常相似，所以配体间的接触降低了络合物的稳定性。离子半径较大的La(III)的萃取受取代基的共振效应等电子效应的控制。在三价铝的提取过程中，配体间的接触和两个供氧体之间的距离对萃取的影响很明显。合成了以冠醚为分子内增效剂的新型4-酰基-5-吡唑啉酮类化合物，并考察了它们对多种金属离子的萃取性能。通过简单的偶联反应，设计并合成了4-酰基-5-吡唑酮取代的二苯并-16-冠-5、二苯并-19-冠-6、12-冠-4、15-冠-5和18-冠-6以及双(4-酰基-5-吡唑酮)取代的二氮杂-18-冠-6。碱金属离子很容易被萃取到氯仿中。选择性主要由冠醚部分控制，取决于空腔的大小。碱土金属离子也很容易被萃取到氯仿中，但选择性由酰基吡唑酮和冠醚基团共同控制。在二价过渡金属离子中，对锰、镉、铅的萃取率极高。众所周知，用传统的络合萃取剂对这些金属离子的萃取率远低于其他二价过渡金属离子。在单独使用酰基吡唑啉酮和冠醚的协同萃取中，也出现了这种异常萃取。