Mannich reaction between calix[4]arenes and diaza-18-crown-6

An upper rim calixdiazacrown is synthesized by reaction of calix[4]arene wi th formaldehyde and diaza-18-crown-6 according to an 1,2 addition. This add ition has been proved by bidimensional H-1 NMR experiments. The calixdiazac rown can be converted to the corresponding quaternary salt, which, by treat ment with two equivalents of a nucleophile yields a 5,11 disubstituted cali x[4]arene. With the 4, 5, 17 trimethylcalixarene, the intramolecular 1,3 ad dition is not observed. The reaction gives a compound made of two calix[4]a renes moieties connected in para position by one diaza-18-crown-6 moiety.