The p-tert-butylthiacalix[4]arene (1) was firstly alkylated with methyl iodide to obtain thiacalix[4]arene (2), which was reacted with 1,2-dibromoethane and 1,3-dibromopropane to give thiacalix[4]arene derivatives 3 and 4 in the presence of potassium carbonate, respectively. A series of p-tert-butylthiacalix[4]arene derivatives 5a, 5b, 6a and 6b which append 1,3,4-thiadiazol-2-ylthio groups at the lower rims were easily synthesized in good yields by the reaction of di(bromoalkoxy)calix[4]arene intermediates 3 or 4 with 2-mercapto-1,3,4-thiadiazole derivatives in the presence of sodium hydroxide. All novel compounds were characterized by ¹H NMR, ¹³C NMR, IR, MS and elemental analysis. Meanwhile, the structures of thiacalix[4]arene derivatives 3 and 5a were identified by X-ray diffraction analysis.

Key words: thiacalix[4]arene, thiadiazole, synthesis, crystal structure