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.

已经制备了一些在4位时具有笨重的酰基取代基的4-酰基-5-吡唑酮衍生物。随着酰基较大的较大，离子半径较小的SC（III）的提取降低。显然，SC络合物中的料理接触降低了稳定性，因为蒽苯酚，乙酰基，苯甲酰，苯甲酰基和3、5-二甲基苯甲酰基衍生物的PKA值非常相似。具有较大离子半径的LA（III）的提取受电子效应（例如取代基的共振效应）的控制。在提取tervalent al中，可以看到间间接触的影响和两个捐赠的氧气之间的距离。 GA和IN.NOVEL 4-酰基-5-吡唑酮具有冠状部分作为分子内协同作用，并且已经研究了各种金属离子的溶剂提取。 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.将碱金属离子容易提取到氯仿中。选择性主要由冠状部分根据腔体大小控制。碱土金属离子也很容易提取到氯仿中，但是选择性均由酰基吡唑酮和冠状醚部分控制。在二价过渡金属离子中，对于Mn，CD和Pb，可见非常高的提取性。众所周知，这些金属离子的萃取性远低于带有常规螯合提取物的其他二价过渡金属离子。在与酰基吡唑酮和单独使用的冠状醚的协同提取中，也给出了这种异常提取。