Design of Bowl-shaped Molecules and Their Application to the Stabilization of Highly Reactive Species

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In this study bowl-shaped molecules with calix [6] arene and cyclophane skeletons were designed and synthesized. First, the synthesis of some new bicyclic cyclophanes having some functional groups were carried out using an orcinol benzyl ether unit as a central bridge and a diphenylmethane unit as a peripheral ring. The structures of these cyclophanes were studied by NMR and X-ray crystallography to show that the diameter of their cavity is about 14@90. The thermolysis of a compound having a sulfoxide functionality in the cavity gave the first stable arenesulfenic acid. Second, bowl-shaped molecules having a calix [6] arene skeleton were synthesized using calix [6] arenes and 2,6-bis (bromomethyl) benzene derivatives with azide and t-butylthio substituents in the cavity and their structures were studied by NMR and X-ray crystallography. Here again, a stable arenesulfenic acid was synthesized by thermolysis of a sulfoxide. Both bromo and sulfenic acid derivatives were shown to have 1,2,3-alternate conformations. The photolysis of an azide derivative afforded unusual products derived from insertion of the intermediary nitrene into calixarene ring.