Synthesis and metal ion complexation studies of proton-ionizable calix

A series of novel N-chromogenic calix4]arene azacrown ethers were synthesized as selective extractants of potassium ion. 1,3-Alternate calix4]arene azacrown ethers were prepared by reacting 25,27-dipropyloxy-26,28-bis(5-chloro-3-oxapentyloxy) calix4]arenes with p-toluenesulfonamide in the presence of potassium carbonate. The coupling reaction of calix4]arene azacrown ether with 2-hydroxy-5-nitrobenzyl bromide in the presence of triethylamine in THF gave the chromogenic calix4]arene azacrown ether in moderate yield. These compounds show high potassium selectivity over other metal ions as shown by two-phase extraction, bulk liquid membrane, and 1H NMR studies on a ligand-metal complex. It is assumed that the OH of the chromogenic group attached on nitrogen can assist the complexation by encapsulation of the metal.