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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
Author(s) -
Kerr J. Alistair,
Wright J. Paul
Publication year - 1984
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550161104
Subject(s) - chemistry , radical , thermochemistry , kinetics , alkyl , trifluoromethyl , decomposition , gas phase , medicinal chemistry , fluorine , photochemistry , organic chemistry , physics , quantum mechanics
Trifluoro‐ t ‐butoxy radicals have been generated by reacting fluorine with 2‐trifluoromethyl propan‐2‐ol:\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm \dot F} + {\rm CF}_3 {\rm C}({\rm OH})({\rm CH}_3)_2 \to {\rm HF} + {\rm CF}_3 {\rm C}({\rm \dot O})({\rm CH}_3)_2 $$\end{document}Over the temperature range 361‐600 K the trifluoro‐ t ‐butoxy radical decomposes exclusively by loss of the CF 3 group [reaction (−2)] rather than by loss of CH 3 group [reaction (−1)]:The limits of detectability of the product CF 3 COCH 3 , by gas‐chromatographic analysis, place a lower limit on the ratio k −2 / k −1 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.