Syntheses of Lower-Rim-1,3-Crowned Calix[6]Arenes and their Complexation Abilities Toward Cations

An approach to lower-rim-1,3-crowned calix6]arene and its derivatives in one-pot process has been accomplished. In the presence of very excess Na2C03 (27-150 equivalent per mole p-tert-butyleal ix6]arene 1) in acetonitrile, the lower-rim-1,3-bridged calix6]crown-3 (4), the bistosylethoxy-ethyl derivative of 4 (5), as well as the intermediate of 4, monotosylethoxyethyl p-tert-butylcalix6]arene 3, were obtained in rational yields, the distribution of the three compounds varied with the amount of the base used and other selected experimental conditions. 4 exhibits high selectivity towards Li⁺. 3 may be the first example of ionophore with high Et2NH2⁺ selectivity.