Facile synthesis of thiacalix[n]arenes (n=4, 6, and 8) consisting of p-tert-butylphenol and methylene/sulfide alternating linkage and metal-binding property of the n=4 homologue

2,14-Dithiacalix[4]arene 3₄ was conveniently prepared in 16% yield by acid-catalyzed cyclocondensation of 2,2^′-thiobis[4-tert-butylphenol] with formaldehyde. The present method also afforded the first isolation of the analogues with six and eight phenol units, 3₆ (10%) and 3₈ (5%), respectively. Solvent extraction showed that 3₄ had high selectivity toward Cu²⁺ ion at pH 5.5 by coordination of the bridging sulfur with cooperative donation of the adjacent phenolate oxygens.