Conformational control of photochemical behavior. Competitive α cleavage and γ-hydrogen abstraction of alkyl phenyl ketones

Frederick D. Lewis*, Richard W. Johnson, Douglas E. Johnson

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

76 Scopus citations

Abstract

The photochemical α cleavage and γ-hydrogen abstraction reactions of several acyclic and cycloalkyl phenyl ketones have been investigated. Photochemical reactions of cyclohexyl phenyl ketones are more rapid than ring inversion. As a consequence, product compositions are determined by ground state conformational populations. In contrast, pseudorotation in cyclopentyl phenyl ketones and bond rotations in acyclic ketones are more rapid than photochemical reactions. The Curtin-Hammett principle applies to the reactions of these ketones. Product compositions are determined by relative rates of the competitive primary photoprocesses rather that conformational populations. For cyclohexyl phenyl ketone isoenergetic energy transfer from the long-lived equatorial excited state to the highly reactive axial conformer is observed to occur with a rate constant of 1.2 × 108 M-1 sec-1.

Original languageEnglish (US)
Pages (from-to)6090-6099
Number of pages10
JournalJournal of the American Chemical Society
Volume96
Issue number19
DOIs
StatePublished - Jan 1 1974

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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