Functional analysis of sulfonamide-type chelating agents as separation agents

以带负电荷的氮原子为Lewis供体的磺胺类螯合剂作为萃取剂，进行了功能分析。具体而言，本文进行了以下基础性研究。为了评价磺酰胺型单阴离子N，N双齿配体作为二价金属阳离子萃取分离剂的可能性，以几种具有对甲苯磺酰胺基团的N- ca -N双齿配体为模型体系，研究了铜（II）阳离子在氯仿中的螯合萃取行为。所研究的四种N-C2-N-配体对铜（II）均具有定量萃取性，萃取物中金属与配体的比例为1:2。此外，铜（II）与配体的萃取常数的顺序表明，N-C_2-N-结构中π电子的数目是获得高络合能力和萃取性的重要因素。以离子液体1-丁基-3-甲基咪唑六氟磷酸（[bmim][PF_6]）为萃取相，研究了8-磺酰胺喹啉衍生物作为螯合萃取分离剂用于溶剂萃取几种二价金属阳离子的可能性，为离子液体萃取体系中新型萃取分离剂的开发提供了基本途径。所研究的药剂可作为[bmim][PF_6]萃取体系中金属阳离子的萃取剂。它们在[bmim][PF_6]体系中的提取率优于在氯仿体系中的提取率。提取的镉大部分为（水合）中性络合物，而利用含三氟甲基的衍生物，以阴离子络合物的形式提取二价镉，并伴有阴离子交换过程。

Functional analysis of sulfonamide-type chelating agents, which have negatively-charged nitrogen atom as Lewis donor, as extraction agents was performed. In concrete, the following fundamental studies were investigated.1. To evaluate the possible use of sulfonamide-type monoanionic N,N-bidentate ligands as extrative separation agents for divalent metal cations the chelate extraction behavior of copper(II) cation into chloroform with several N-Ca-N- bidentate ligands having the p-toluenesulfonamido group was investigated as a model system. All of the four N-C2-N- ligands studied showed quantitative extractability for copper(II) and the metal-to-ligand ratio in the extracted species was 1:2. Furthermore, the order of the extraction constants for copper(II) with the ligands suggests that the number of π-electrons in the N-C_2-N- structure is an important factor in achieving high complexation ability and extractability.2. Possible use of 8-sulfonamidoquinoline derivatives as chelate extractive separation agents for solvent extraction of several divalent metal cations using an ionic liquid, 1-butyI-3-methylimidazolium hexafluorophosphate ([bmim][PF_6]) as extraction phase was investigated as fundamental approach to develop novel extractive separation agents for ionic liquid extraction system. The studied agents were able to be used as extractants for the metal cations in the [bmim][PF_6] extraction system. Furthermore, their extractability in the [bmim][PF_6] system was superior to that in chloroform system. Most of the extracted species were (hydrated) neutral complexes, whereas, in use of the derivative having trifluoromethyl group, divalent cadmium was extracted as anionic complex accompanied with anion-exchange process.