Di-ionizable p-tert-butylcalix[4]arene-1,3-crown-4 ligands: synthesis and alkaline earth metal cation extraction

A series of di-ionizable calix[4]arene-1,3-crown-4 compounds has been synthesized. The ionizable groups are oxyacetic acid and N-(X)sulfonyl oxyacetamide groups with X=methyl, phenyl, 4-nitrophenyl and trifluoromethyl, which 'tunes' the acidity of the latter. The efficiency and selectivity of these novel ligands are assessed with competitive solvent extractions of alkaline earth metal cations from aqueous solutions into chloroform. The results are compared with those reported previously for calix[4]arene-crown analogues with crown-6 and crown-5 rings.