ChemInform Abstract: REAKTIVITAET POLYFLUORIERTER UNGESAETTIGTER VERBINDUNGEN GEGENUEBER METHYLRADIKALEN

Sass, V. P.; Nadervel, T. A.; Rondarev, D. S.; Bresler, L.S.; Sokolov, S. V.

doi:10.1002/chin.197318161

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1997

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“…The methods were simple and allowed the detection of abstraction besides addition reactions. Hence, they were also applied by others to obtain additional methyl affinities , and extended to additions of the ethyl, the n -propyl, the cyclopropyl, and the trifluoromethyl 1a,d,7-11 radicals.…”

Section: Introductionmentioning

confidence: 99%

Absolute Rate Constants and Arrhenius Parameters for the Addition of the Methyl Radical to Unsaturated Compounds: The Methyl Affinities Revisited

and

Fischer

1997

J. Am. Chem. Soc.

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Absolute rate constants and their Arrhenius parameters are reported for the addition of the methyl radical to 21 monosubstituted and 1,1-disubstituted alkenes and to 6 benzenes in 1,1,2-trifluoro-1,2,2-trichloroethane solution. They are used to convert relative reaction rates known as methyl affinities from the work of M. Szwarc and others for about 250 additional unsaturated compounds to the absolute scale. An analysis shows that the addition rates depend on the reaction enthalpy but also indicates a moderate nucleophilic polar effect for the liquid-phase reactions. It is pointed out that this polar effect may be smaller in the gas phase.

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