Facile synthesis of p-tert-butylthiacalix[4]arene by the reaction of p-tert-butylphenol with elemental sulfur in the presence of a base

Thiacalix[4]arenes with Triple Bonds at the Lower Rim: Synthesis and Structure

“…Calix [4]arenes 3 and 4 were synthesized according to the known procedures, [13,14] accordingly. 25,26,27,8,14, [4]arene, 3b-d. A mixture of thiacalix [4]arene 3 (1 g, 2 mmol), propargyl bromide (3.808 g, 0.032 mol), cesium/potassium carbonate (0.04 mol) was kept at boiling in acetone (100 ml) with continuous stirring for 50 hours.…”

Monocyanomethylated thiacalix[4]arenes: synthesis and lower rim modification

“…The introduction of a heteroatom as a bridge provides an additional opportunity to tune the ring size, conformational and binding properties of a macrocycle. Since the starting p-R-thiacalix [4]arenes (1, R = tert-butyl, tert-octyl, 1-adamantyl or phenyl) [2][3][4][5] are accessible now in multi-gram scale, these macrocycles have sparked a great deal of interest as building blocks in the synthesis of more complicated systems. The regioselective alkylation and acylation of the lower rim hydroxyls of the classical calix [4]arenes have become important synthetic tools for the construction of a great variety of synthetic receptors.…”

Syntheses of Tetrasulfonylcalix[4]biscrown-6 and Crystal Structures

“…Since Kumakai et al 1 reported viable synthetic routes on p-tert-butylthiacalixarenes in 1997, this class of macrocyclic ligand has attracted considerable interest as an alternative to 'classic' calixarenes 2 by providing sites for functionalization not only on the aromatic rings but also on the bridging sulfur atoms. Thiacalixarenes possess additional coordination sites and the cavity dimensions are increased compared with analogous calixarenes.…”

“…3 For this concern, syntheses of several 1,3-thiacalix[4]biscrown derivatives, the first representatives of crown ether-bridged compounds in the thiacalixarene series were reported. Our synthesis began with para-tert-butylphenol which was cyclized with sulfur molecule (S 8 ) to give a para-tertbutylthiacalix[4]arene (1) 3 as shown in Scheme 1. Dealkylation using AlCl 3 in phenol provided a thiacalix[4]arene (2) in moderate yield.…”