First synthesis of adamantylated thiacalix[4]arenes

p-(1-Adamantyl)thiacalix[4]arene was synthesized both by condensation of p-(1-adamantyl)phenol with sulfur in the presence of NaOH and by alkylation of p-H-thiacalix[4]arene with 1-adamantanol in trifluoroacetic acid. Using the latter method, the first thiacalix[4]arene carboxylated at the upper rim was obtained from p-H-thiacalix[4]arene and 3-carboxy-1-adamantanol. The X-ray structural analysis revealed that p-(1-adamantyl)thiacalix[4]arene adopts a cone conformation leading to an inclusion complex with chloroform under the conditions of crystallization.