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On the reactivity of amines toward tert-butoxy radicals

✍ Scribed by M. V. Encina; E. A. Lissi

Publisher: John Wiley and Sons
Year: 1978
Tongue: English
Weight: 223 KB
Volume: 10
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550100611

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✦ Synopsis

Jayanty, Simonaitis and Heicklen [l] have found that amines delay the conversion of NO t~ NO2 when mixtures of C3H6, NO, NOz, and 0 2 were irradiated. The inhibition was assumed to be due to the trapping of some of the free radicals that carry out the oxidation process, but the different inhibiting strength of the added amines was difficult to understand. In order to establish if the relative inhibiting strengths are determined by the amine reactivity or by the secondary reactions of the products, quantitative data on the reactivity of amines toward different free radicals are needed. Unfortunately this type of data are almost nonexistent. In the present work we have measured the reactivity of several amines toward tert-butoxy radicals.

Tert-butoxy radicals were generated in the thermal decomposition of di-tert-butyl peroxide at 115 "C in diluted benzene solution. The primary reaction products (tert -butanol and acetone) were analyzed by gas-liquid chromatography.

The results obtained were interpreted in terms of the following reaction scheme:

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