Synthesis of novel macrocyclic compounds containing sulphur or oxygen in the ring: thia- and oxa-cyclophanes. Mass spectral and other studies

Abstract

The synthesis of a number of large-ring heterocyclic compounds containing two or four sulphur atoms in the ring is described. The compounds include 2,2′-bridged biphenyls having 7–11 -membered heterocyclic rings; and 7-, 8-, 9-, 14-, 16-, 18-, and 24-membered heterocyclic systems containing o-xylylene bridges. Oxygen analogues of the former series are also described. The ¹H n.m.r. and mass spectra of the compounds are discussed.

Most of the sulphur macrocycles are derivatives of o-xylene-αα′-dithiol (Ia) or biphenyl-2,2′-dithiol; improved syntheses of the latter compounds are described, together with certain reactions of their simple derivatives including complex formation with palladium (II) and platinum (II) bromides.

Biphenyl-2,2′-bisdialkylsulphonium di(methyl sulphates) when heated undergo a novel reaction to give dibenzo-thiophen.