Three mono-substituted p-tert-calix[6]arenes (2a～2c) with terminal halogen groups have been synthesized by treating p-tert-calix[6]arene with Br(CH₂)₄Br, Br(CH₂)₆Br or ClCH₂C≡CCH₂Cl in THF using K₂CO₃ as base in moderate yield, respec-tively. 2a and 2b could be further converted to 3a and 3b in high yields by MeOTs. Their structures and conformations were characterized by ¹H NMR and MS spectra. It was concluded that 2a～2c and 3b existed in cone conformation at room temperature, but no confined conformation of 3a was observed.

Key words: methylation, conformation, mono-functionalization, p-tert-calix[6]arene