Conformations of Bridged Diphenyls. VI. Substituent Effects and Internal Rotation in Triply Ortho-substituted Diphenyl Ethers

Abstract

Experimental evidence is presented to support the hypothesis that, in triply ortho-substituted diphenyl ethers, conformer interconversion involves both rings. The free energy barrier, measured by p.m.r., is sensitive to substituent effects arising in the ring having only one ortho substituent. The exceptionally high barrier found when an ortho iodine is present is consistent with the existence of a substituent-inside intermediate occurring during conformer conversion.