Linear free energy relationships in radical reactions. II. hydrogen abstraction from substituted toluenes by Tert‐Butyl, Tert‐Butoxyl and Tert‐Butylperoxyl radicals

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Abstract

Calculations were carried out to study the validity of σ‐scales for hydrogen abstraction from substituted toluenes by tert‐butyl, tert‐butoxyl and tert‐butylperoxyl radicals. Rate constants were compiled and evaluated from the literature for meta‐ and/or para‐substituted toluenes. The substituents were characterized by factored ionic sigmas (σI, σR, σ R+), ionic scales (σ, σ+) and various radical sigmas (σσ). The dependence of log k values on these substituent descriptors was investigated using ‘stepwise linear regression’ and ‘all possible regression’ methods. The following predictive equations can be recommended: for tert‐butyl radicals, at 321 K: (Formula Presented.) for tert‐butoxyl radicals, at 313 K: (Formula Presented.) and for tert‐butylperoxyl radicals, at 303 K: (Formula Presented.) The results suggest that there is no unversal radical scale for hydrogen abstraction reactions, that the rate is primarily influenced by polar factors (inductive, resonance) and that only two radical scales (σĊ and σ α·) are appropriate, showing a small, yet significant, role of radical stabilization.

Original languageEnglish
Pages (from-to)244-250
Number of pages7
JournalJournal of Physical Organic Chemistry
Volume7
Issue number5
DOIs
Publication statusPublished - 1994

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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