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

制备了一些4位酰基取代的4-酰基-5-吡唑酮衍生物。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，Sc配合物中的配体间接触降低了稳定性，因为蒽羰基、乙酰基、苯甲酰和3,5 -二甲基苯甲酰衍生物的pKa值非常相似。离子半径较大的La （III）的萃取受取代基共振效应等电子效应支配。在三价Al、Ga和in的萃取过程中，观察了配体间接触和两个供氧之间距离的影响。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，并对各种金属离子的溶剂萃取进行了研究。采用易偶联反应设计合成了4-酰基-5-吡唑啉酮取代二苯并-16-冠-5、二苯并-19-冠-6、12-冠-4、15-冠-5、18-冠-6和双-（4-酰基-5-吡唑啉酮）取代重氮-18-冠-6。碱金属离子很容易被提取到氯仿中。选择性主要由冠醚部分决定，取决于腔的大小。碱土金属离子也很容易被提取到氯仿中，但选择性受酰基吡唑酮和冠醚基团的控制。在二价过渡金属离子中，Mn、Cd和Pb的可萃取性特别高。众所周知，传统螯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。酰基吡唑酮和冠醚分别协同萃取时也有这种异常萃取。

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.