Calixradialenes: Calixarene Derivatives with Exocyclic Double Bonds

Reaction of dioxocalix[4]­arene 7 with MeLi followed by 2-fold elimination of water yielded calixarene 8 possessing exocyclic double bonds at two adjacent bridges. Calixarene 8 exists in tetrachloroethane-d2 solution at rt, as a 2.3:1 mixture of the 1,3-alternate and partial cone conformers. Keto­[n]­calixarenes (n = 5, 6) were prepared via hydrolysis of the bromocalixarenes 11 and 12, followed by CrO3 oxidation of the respective hydroxymethylene derivatives. Addition of MeLi to the ketocalix­[n]­arenes (n = 4, 5 and 6) followed by elimination of water yielded the corresponding calix­[n]­radialenes. Calix[5]- and calix[6]­radialenes adopt in the crystal irregular alternate (i.e., noncone) conformations.