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Nucleophilic character of the tert-butyl radical. Absolute rate constants for the reactions with substituted toluenes

✍ Scribed by H. R. Dütsch; H. Fischer

Publisher
John Wiley and Sons
Year
1982
Tongue
English
Weight
254 KB
Volume
14
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The decay of photochemically generated tert‐butyl radicals is studied at 48°C in 11 m‐ and p‐substituted toluenes by time‐resolved electron spin resonance spectroscopy. It is governed by the second‐order self‐termination perturbed by a pseudo‐first‐order reaction of the radical with the toluenes. The first‐order lifetimes yield the rate constants k~A~ for hydrogen transfer from toluenes to tert‐butyl. Substituent effects on the rate constants confirm the nucleophilic character of the radical.

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