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The kinetics of the addition of alkyl radicals to carbonyl groups. I. The kinetics of the gas phase decomposition reactions of the trifluoro-t-butoxy radical

✍ Scribed by J. Alistair Kerr; J. Paul Wright

Publisher: John Wiley and Sons
Year: 1984
Tongue: English
Weight: 268 KB
Volume: 16
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550161104

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✦ Synopsis

Trifluoro-t-butoxy radicals have been generated by reacting fluorine with 2-trifluoromethyl propan-2-01:

Over the temperature range 361-600 K the trifluoro-t-butoxy radical decomposes exclusively by loss of the -CF, group [reaction ( -2)] rather than by loss of -CH, group [reaction ( -111:

The limits of detectability of the product CF,COCH, , by gas-chromatographic analysis, place a lower limit on the ratio k _ , / k -, of ca. 75. The implications of these results in relation to the reverse radical addition reactions to the carbonyl group are discussed along with the thermochemistry of the reactions.

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