Reaction of tert-Alkoxyl and Radicals with Styrene Studied by the Nitroxide Radical-Trapping Technique

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Nakamura, T
Busfield, WK
Jenkins, ID
Rizzardo, E
Thang, SH
Suyama, S
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1997
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Abstract

The reactions of tert-alkyl peroxypivalates 1 (R = methyl, ethyl, and n-propyl) with styrene in the presence of the free-radical scavenger (1,1,3,3-tetramethyl-2,3-dihydro-1H-isoindol-2-yl)oxyl (2) have been studied at 60 °C. tert-Butyl and tert-alkoxyl radicals (tert-butoxyl, tert-pentyloxyl, and tert-hexyloxyl radicals) were generated from the thermolysis of 1, and the derivative alkyl radicals (methyl, ethyl, n-propyl, and 4-hydroxy-4-methylpentyl radicals) were formed by subsequent unimolecular reactions (β-scission and 1,5-H shift) of the corresponding tert-alkoxyl radicals. The extent of the unimolecular reactions of the tert-alkoxyl radicals (versus addition to styrene) and the relative reactivity of alkyl radicals toward addition to styrene were obtained from the competitive addition/trapping reactions. The absolute rate constants for the addition of tert-butyl, ethyl, methyl, and n-propyl radicals to styrene at 60 °C were estimated to be (7.4, 4.7, 5, and 5.4) × 105 M-1 s-1, respectively.

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Journal of Organic Chemistry
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This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Organic Chemistry, copyright 1997 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see 10.1021/jo9707489
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Medicinal and biomolecular chemistry
Organic chemistry
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