Photochemical α Cleavage of Ketones in Solution. VI. Substituent Effects on the Photochemical α Cleavage of Deoxybenzoin

F. D. Lewis*, C. H. Hoyle, J. G. Magyar, H. G. Heine, W. Hartmann

*Corresponding author for this work

Research output: Contribution to journalArticle

35 Scopus citations

Abstract

The effects of aromatic substituents which are not conjugated with the carbonyl on the photochemical behavior of deoxybenzoin have been investigated. Photochemical α cleavage is the exclusive primary photoprocess observed in benzene solution. Room temperature phosphorescence is observed for several deoxybenzoins and provides a convenient method of measuring triplet lifetimes. Substituents affect the rate constant for α cleavage without altering the triplet energy or radiative lifetime. The rate constants for α cleavage fit the Hammett equation with the use of σ+ (ρ = -1.1). It is concluded that the transition state for α cleavage lies early on the reaction coordinate and has moderate ionic character.

Original languageEnglish (US)
Pages (from-to)488-492
Number of pages5
JournalJournal of Organic Chemistry
Volume40
Issue number4
DOIs
StatePublished - Feb 1 1975

ASJC Scopus subject areas

  • Organic Chemistry

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