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The solvent effect on the reaction constants oftert-butyl radical addition to 2-substituted allyl chlorides

Authors
Journal
Tetrahedron
0040-4020
Publisher
Elsevier
Publication Date
Volume
61
Issue
18
Identifiers
DOI: 10.1016/j.tet.2005.02.083
Keywords
  • Solvent Effect
  • Free Radical Sh2′ Reaction
  • Tert-Butyl Radical Addition
  • 2-Substituted Allyl Chlorides
  • Wvalue
  • Hammett Reaction Constant

Abstract

Abstract The ρ values of free radical S H2′ reactions have been determined in various solvents. The correlation of Hammett ρ with Taft's π* gives a W value of 0.70. The W value is a measure of susceptibility of the reaction constant to change in solvent polarity. However, the W value is 2.64 in the dissociation reactions of substituted benzoic acids. The free radical reactions are less susceptible to the solvent effect than ionic reactions and this could be rationalized in terms of the partial charge formed in the transition state of free radical reaction is less than that of heterolytic reaction. The ρ values in S H2′ reactions might not reflect truly the partial charge separation at transition state, however, it might be a measure of the susceptibility of the reaction to the electronic effect of the substituents.

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