resorcinarene

In chemistry, a resorcinarene (also resorcarene or calix[4]resorcinarene) is a macrocycle, or a cyclic oligomer, based on the condensation of resorcinol (1,3-dihydroxybenzene) and an aldehyde. Resorcinarenes are a type of calixarene. Other types of resorcinarenes include the related pyrogallolarenes and octahydroxypyridines, derived from pyrogallol and 2,6-dihydroxypyridine, respectively. Resorcinarenes interact with other molecules forming a host–guest complex. Resorcinarenes and pyrogallolarenes self-assemble into larger supramolecular structures. Both in the crystalline state and in organic solvents, six resorcinarene molecules are known to form hexamers with an internal volume of around one cubic nanometer (nanocapsules) and shapes similar to the Archimedean solids. Hydrogen bonds appear to hold the assembly together. A number of solvent or other molecules reside inside. The resorcinarene is also the basic structural unit for other molecular recognition scaffolds, typically formed by bridging the phenolic oxygens with alkyl or aromatic spacers. A number of molecular structures are based on this macrocycle, namely cavitands and carcerands. Synthesis The resorcinarenes are typically prepared by condensation of resorcinol and an aldehyde in acid solution. This reaction was first described by Adolf von Baeyer who described the condensation of resorcinol and benzaldehyde but was unable to elucidate the nature of the product(s). The methods have since been refined. Recrystallization typically gives the desired isomer in quite pure form. However, for certain aldehydes, the reaction conditions lead to significant by-products. Alternative condensation conditions have been developed, including the use of Lewis acid catalysts. A green chemistry procedure uses solvent-free conditions: resorcinol, an aldehyde, and p-toluenesulfonic acid are ground together in a mortar and pestle at low temperature.