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Absolute Rate Constants for Iminyl Radical Reactions.

Marie-Helene Le Tadic-Biadatti1, Anne-Claude Callier-Dublanchet, John H. Horner

  • 1Department of Chemistry, Wayne State University, Detroit, Michigan 48202, Laboratoire de Synthèse Organique Associé au CNRS, Ecole Polytechnique, F-91128 Palaiseau, France, and Institue de Chimie des Substances Naturelles, CNRS, F-91198 Gif-Sur-Yvette, France.

The Journal of Organic Chemistry
|February 7, 1997
PubMed
Summary

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The cyclization and trapping reactions of iminyl radicals were studied. These iminyl radicals exhibit slower reaction kinetics compared to typical alkyl radicals, impacting their chemical behavior.

Area of Science:

  • Organic Chemistry
  • Physical Chemistry
  • Reaction Kinetics

Background:

  • Iminyl radicals are reactive intermediates in organic synthesis.
  • Understanding their reaction kinetics is crucial for controlling chemical transformations.

Purpose of the Study:

  • To determine the rate constants for the cyclization of a specific iminyl radical.
  • To measure the trapping kinetics of this iminyl radical with different thiophenols.
  • To compare the reactivity of iminyl radicals with alkyl radicals.

Main Methods:

  • Laser flash photolysis was employed to study cyclization kinetics.
  • Indirect methods, utilizing unimolecular rate constants, were used for trapping kinetics.
  • Experiments were conducted over a range of temperatures (0-83°C).

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Main Results:

  • The iminyl radical (3) cyclizes at a rate constant of 2.2 x 10^6 s^-1 at 25°C.
  • Trapping rate constants with thiophenol and p-chlorothiophenol were 0.6 x 10^7 M^-1 s^-1 and 1.4 x 10^7 M^-1 s^-1, respectively.
  • Iminyl radical reactions were found to be slower than analogous alkyl radical reactions.

Conclusions:

  • The study quantifies the cyclization and trapping rates of iminyl radical 3.
  • The findings highlight the distinct reactivity of iminyl radicals compared to alkyl radicals.
  • This kinetic data provides valuable insights for synthetic strategies involving iminyl radicals.