Calix[4]arenes bearing alpha-amino- or alpha-hydroxyphosphonic acid fragments at the upper rim

By the reaction of para-formylcalix[4]arenes 1-6 with trialkyl phosphites in the presence of dry hydrogen chloride calix[4]arenes 7-13 possessing dialkylphosphoryl-hydroxymethyl groupings at the upper rim were synthesized. Calix[4]arenes 18-23 functionalized with dialkylphosphoryl-alkyl(aryl)aminomethyl groups were obtained by sodium-promoted addition of dialkyl phosphites to C=N bonds of para-iminocalix[4]arenes 14-17. The consecutive treatment of alpha -hydroxy-or alpha -aminophosphonic acid dialkyl esters of calix[4]arenes 7, 10, 18, and 21 with bromotrimethylsilane and methanol gave dihydroxyphosphoryl derivatives of calix[4]arenes 24-27. It was shown that calix[4]arenes bearing at the macrocyclic upper rim hydroxymethylphosphonic fragments, as well as bis-hydroxymethyl(aminomethyl)phosphonic fragments, are able to undergo self-assembly with formation of dimeric OH . . .O=P hydrogen bonded associates. (C) 2001 John Wiley & Sons, Inc.