Peroxyl Radical Clocks

Authors

Bill Roschek, Vanderbilt University
Keri A. Tallman, Vanderbilt University
Christopher L. Rector, Vanderbilt University
Jason G. GillmoreFollow
Derek A. Pratt, Vanderbilt University
Carlo Punta, Vanderbilt University
Ned A. Porter, Vanderbilt University

Document Type

Article

Publication Date

4-28-2006

Publication Source

Journal of Organic Chemistry

Volume Number

71

Issue Number

9

First Page

3527

Last Page

3532

Publisher

American Chemical Society

ISSN

0022-3263

Comments

This article was published while author Jason G. Gillmore was at the Center in Mo lecular Toxicology, Vanderbilt University.

Abstract

A series of peroxyl radical clocks has been developed and calibrated based on the competition between the unimolecular β-fragmentation (kβ) of a peroxyl radical and its bimolecular reaction with a hydrogen atom donor (kH). These clocks are based on either methyl linoleate or allylbenzene and were calibrated directly with α-tocopherol or methyl linoleate, which have well-established rate constants for reaction with peroxyl radicals (kH-tocopherol = 3.5 × 106 M-1 s-1, kH-linoleate = 62 M-1 s-1). This peroxyl radical clock methodology has been successfully applied to determine inhibition and propagation rate constants ranging from 100 to 107 M-1 s-1.

Recommended Citation

Repository citation: Roschek, Bill; Tallman, Keri A.; Rector, Christopher L.; Gillmore, Jason G.; Pratt, Derek A.; Punta, Carlo; and Porter, Ned A., "Peroxyl Radical Clocks" (2006). Faculty Publications. Paper 1040.
https://digitalcommons.hope.edu/faculty_publications/1040

Published in: Journal of Organic Chemistry, Volume 71, Issue 9, April 28, 2006, pages 3527-3532. Copyright © 2006 American Chemical Society, Washington, D.C..