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Skeletal rearrangement for water loss from molecular protonated ions of t ‐butoxycyclohexane
Author(s) -
Diakiw Vladimir,
Gordon Patrick M.,
Kingston Eric E.,
Shan James S.,
Lacey Michael J.
Publication year - 1989
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210240817
Subject(s) - chemistry , protonation , stereospecificity , stereochemistry , ring (chemistry) , ion , catalysis , biochemistry , organic chemistry
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 (83%) involves migration of the t ‐butyl group to the 2‐(6‐) position of the cyclohexyl ring with reciprocal hydrogen transfer. A second reaction pathway (12%) 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 (5%) 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.