Conformational analysis of alkyl aryl ethers and alkyl aryl sulphides by photoelectron spectroscopy

Photoelectron spectroscopy shows that in t-butoxybenzenes, but not in methoxy-, ethoxy- or isopropoxybenzenes, there is a loss of p-π orbital overlap. A similar effect is observed in 2,6-dimethylalkoxybenzenes. In alkyl aryl sulphides two conformers predominate, the one with maximum p-π overlap and the other with reduced overlap. The importance of the less conjugated conformer increases monotonously through the series hydrogen, methyl, ethyl, isopropyl and t-butyl in alkyl phenyl sulphides.