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The addition of methyl radicals to hexafluoroacetone

✍ Scribed by L. Batt; S. I. Mowat

Publisher: John Wiley and Sons
Year: 1984
Tongue: English
Weight: 558 KB
Volume: 16
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550160509

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✦ Synopsis

The reaction of methyl radicals (Me) with hexafluoroacetone (HFA), generated from ditertiary butyl peroxide (dtBP), was studied over the temperature range of 402-433 K and the pressure range of 38-111 torr. The reaction resulted in the following displacement process taking place:

where TFA refers to trifluoroacetone. The trifluoromethyl radicals that were generated abstract a hydrogen atom from the peroxide:

such that k,, is given by: log k,.(M-' . s-') = 8.2 ? 0.7 -8.9 t-1.3/0 where 8 = 2.303RT kcal/mol. The interaction of methyl and trifluoromethyl radicals results in the following steps:

Product analysis shows that k,,/k::2k:i2 = 2.0 ? 0.2 such that k,, = 1 0 ' 0 4 z 0 5 M ~1 .

s-'. The rate constant k , is given by:

It is concluded that the preexponential factor for the addition of methyl radicals to ketones is lower than that for the addition of methyl radicals to olefins.

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