CALIXARENES .32. REACTIONS OF CALIX[4]QUINONES

Calix[4]quinones are readily accessible by direct oxidation of p-tert-butylcalix[4]arenes as mono-, di-, tri- or tetraquinones depending on the number of free phenolic rings in the calixarene. The mono- and diquinones are shown to be useful synthesis intermediates in the following processes: (a) 1,2-carbonyl additions with malononitrile in the presence of secondary amines to yield p-[1-(dialkylamino)-2,2-dicyanovinyl] calixarenes (11) or with malononitrile in the absence of amines to yield p-(1,2,2-tricyanovinyl)calixarenes (9); (b) 1,2-carbonyl addition with pyrrolidine to yield a p-pyrrolidinocalix[4]arene (14); (c) 1,4-conjugate additions with a variety of nucleophiles, including sodio diethyl malonate, acetate, thiourea, p-thiocresol, and mercaptoacetic acid to give the chiral calixarenes 16-2 1.