Electro-organic chemistry. Part 3. Transannular interaction and reactions of 5,13-disubstituted [2.2]metacyclophanes: substituent effects on carbon-13 n.m.r. spectra, cyclic voltammetric peak potentials, and anodic oxidation

Abstract

A series of 5,13-disubstituted [2.2]metacyclophanes have been prepared. Their proton and carbon-13 n.m.r. spectra have been measured. Cyclic voltammetry was conducted in acetonitrile. From these data the interaction of the substituent towards the opposing ring was estimated. The carbon-13 resonances of inner aryl carbon was found to be affected by the substituent in the other ring. Similarly the first anodic peak, E_P(O₁), and half-wave potential, E_1/2(1), were found to be dependent on the substituent in the other ring. Remarkable voltammogram changes were noted for methoxy-derivatives. Controlled-potential electrolysis at the potential of O₁ gave good yields of the corresponding 4,5,9,10-tetrahydropyrenes.