Synthesis and evaluation of a novel ionophore based on a thiacalix[4]arene derivative bearing imidazole units

Zhao, Jiang Lin; Tomiyasu, Hirotsugu; Ni, Xin-Long; Zeng, Xi; Elsegood, Mark R. J.; Redshaw, Carl; Rahman, Shofiur; Georghiou, Paris E.; Yamato, Takehiko

Abstract

O-Alkylation of the flexible thiacalix[4]arene 1 with 2-chloromethyl-1-methyl-1H-imidazole 2 in the presence of Na₂CO₃ or K₂CO₃ afforded mono-O-alkylation product 3 in 29–51% yield, along with recovery of the starting compound. In contrast, the same reaction in the presence of Cs₂CO₃ gave only one pure stereoisomer, namely 1,3-alternate-4; other possible isomers were not observed. Alkali metal salts such as Na₂CO₃ and Cs₂CO₃ can play an important role in the conformer distribution via a template effect. The conformations of the receptors, mono-O-alkylation product 3 and that of 1,3-alternate-4, have been confirmed by X-ray crystallography. Furthermore, the complexation properties of the receptor 1,3-alternate-4 toward selected alkali/transition metal cations are reported. The two-phase solvent extraction data indicated that 1,3-alternate-4 exhibited a stronger extraction efficiency for transition metals over alkali metals. The dichromate anion extraction ability of 1,3-alternate-4 showed that it could serve as an efficient extractor of HCr₂O₇⁻/Cr₂O₇²⁻ anions at low pH.

Citation

Zhao, J. L., Tomiyasu, H., Ni, X.-L., Zeng, X., Elsegood, M. R. J., Redshaw, C., Rahman, S., Georghiou, P. E., & Yamato, T. (2014). Synthesis and evaluation of a novel ionophore based on a thiacalix[4]arene derivative bearing imidazole units. New journal of chemistry = Nouveau journal de chimie, 38(12), 6041-6049. https://doi.org/10.1039/c4nj01099j

• Journal Article Type: Article
• Acceptance Date: Sep 25, 2014
• Online Publication Date: Sep 29, 2014
• Publication Date: Dec 1, 2014
• Deposit Date: Jul 8, 2015
• Publicly Available Date: Jul 8, 2015
• Journal: New journal of chemistry
• Print ISSN: 1144-0546
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 38
• Issue: 12
• Pages: 6041-6049
• DOI: https://doi.org/10.1039/c4nj01099j
• Keywords: Novel ionophore; Thiacalix[4]arene derivative; Na₂CO₃; Cs₂CO₃; Calixarene family
• Public URL: https://hull-repository.worktribe.com/output/376118
• Publisher URL: http://pubs.rsc.org/en/Content/ArticleLanding/2014/NJ/C4NJ01099J#!divAbstract
• Additional Information: Author's accepted manuscript of article published in: New journal of chemistry, 2014, v.38, issue 12 at http://pubs.rsc.org/en/Content/ArticleLanding/2014/NJ/C4NJ01099J#!divAbstract
• Contract Date: Jul 8, 2015