Skeletal Rearrangement for Water Loss from Molecular Protonated Ions of t-Butoxycyclohexane

Article abstract of DOI:10.1002/oms.1210240817

Isotopic labelling and chemical substitution support the proposition that the skeletal rearrangement for water loss from molecular protonated ions of t-butoxycyclohexane involves competition between three reaction pathways.The principal reaction pathway (83percent) involves migration of the t-butyl group to the 2-(6-) position of the cyclohexyl ring with reciprocal hydrogen transfer.A second reaction pathway (12percent) involves ring contraction followed by reciprocal exchange of the t-butyl group with the 2-(5-) hydrogen atom of the nascent cyclopentyl ring.The third reaction pathway (5percent) involves rearrangement of a proton-bound complex to permit ipso attack by isobutene.Stereospecific substitutions indicate that the principal reaction pathway is susceptible to 1,3-diaxial interactions.