Syntheses of p-nitrocalix[n]arenes were carried out under different reaction conditions by using nitrogen dioxide as nitration agent. It was found that only p-nitrocalix[4]arene, p-nitrocalix[6]arene and 25,26,27,28-tetramethoxy-5,11,17,23-tetranitrocalix[4]arene were obtained from the corresponding calix[4]- arene, calix[6]arene and 25,26,27,28-tetramethoxycalix[4]arene in yields of 90%, 70% and 40% respectively. Especially, the reaction of calix[4]arene with NO₂ could be finished in 20 min. The reaction mechanism based on resonance structures of phenoxy anion in calixarene is discussed.

Key words: nitration, nitrogen dioxide, calix[n]arene