14][14]Metaparacyclophane: first example of an [m][n]metaparacyclophane

The synthesis of 14]14]metaparacyclophane, the first m]n]metaparacyclophane ever known, is described. The reaction sequence began with the bis-chloromethylation of 14]paracyclophane in refluxing CS(2), which yielded a nonseparable mixture of 16,19- and 16,20-bis(chloromethyl)14]paracyclophane in an 8:1 ratio. Acetolysis of these dichlorides gave the corresponding diacetate mixture from which the minor component 16,20-bis(acetoxymethyl)14]paracyclophane was isolated and elaborated into the desired cyclophane via the disulfone of 2,15-dithia16]14]metaparacyclophane and subsequent sulfur dioxide extrusion by a one-flask Ramberg-B?cklund reaction procedure followed by hydrogenation.