Calix[4]arenes with narrow rim 2-mercaptoethoxy substituents as potential precursor molecules for metallacages and sensors

The compound 5,11,17,23-tert-butyl-25,26,27,28-(2-mercaptoethoxy) calix[4]arene reacts with methylmercuric acetate to give 5,11,17,23-tert-butyl-25,26,27,28-(2-mercaptoethoxymercuriomethyl) calix[4]arene. Under vacuum this compound converts to bis-(5,11,17,23-tert-butyl-25,26,27-(2-mercaptoethoxymercuriomethyl)-28-(2-mercaptoethoxy))mercury calix[4]arene by loss of dimethylmercury. Additional loss of dimethylmercury gave a product that is intermediate between bis-(5,11,17,23-tert-butyl-25,26-(2-mercaptoethoxymercuriomethyl)-27,28-(2-mercaptoethoxy))dimercury calix[4]arene, bis-(5,11,17,23-tert-butyl-25-(2-mercaptoethoxymercuriomethyl)-26,27,28-(2-mercaptoethoxy))trimercury calix[4]arene, and the cluster bis-(5,11,17,23-tert-butyl-25,26,27,28-(2-mercaptoethoxy))tetramercury calix[4]arene (11). 5,11,17,23-Tert-butyl-25,26,27,28-(2-mercaptoethoxy) calix[4]arene reacts with 9-chloromethylanthracene to give 5,11,17,23-tert-butyl-25,26,27,28-(9-thiomethylanthracylethoxy) calix[4]arene.