Calixarenes with nitrogen or phosphorus substituents on the lower rim

Calixn]arenes (n=4,6) with diphenylphosphinite groups appended to their lower rim have been synthesized by reaction first with base, followed by chlorodiphenylphosphine. The reaction has also been carried out with the partially methoxylated calixn]arenes. Calix6]arenes with phosphate groups selectively bridging adjacent pairs of oxygens have been synthesized by reaction first with base, followed by ethyl dichlorophosphate. Calixn]arenes (n=4,6) with 2-aminoethyloxy groups appended to the lower rim have been synthesized both by the reduction of an amide or nitrile group. Calixarenes with 2-hydroxyethyloxy and 2-bromoxyethyloxy groups appended to the lower rim have also been prepared. A route to preparing calixarene-functionalized polymers by the alkylation of polyethyleneimine is also described.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.