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Absolute Rate Constants for the Addition of the 1‐( tert‐ Butoxy)carbonylethyl Radical onto Cyclic Alkenes in Solution
Author(s) -
Fischer Hanns,
Knühl Bernhard,
Marque Sylvain R. A.
Publication year - 2006
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200690216
Subject(s) - chemistry , electron paramagnetic resonance , enthalpy , reaction rate constant , alkyl , radical , medicinal chemistry , standard enthalpy change of formation , photochemistry , standard enthalpy of formation , organic chemistry , kinetics , nuclear magnetic resonance , thermodynamics , physics , quantum mechanics
Absolute rate constants are reported for the addition of the 1‐[( tert ‐butoxy)carbonyl]ethyl (= 2‐(1,1‐dimethylethoxy)‐1‐methyl‐2‐oxoethyl) radical . CHMeCO 2 ( t‐ Bu) to several cyclic and monosubstituted alkenes in MeCN as obtained by time‐resolved electron paramagnetic resonance (EPR). The activation energies for the addition of this alkyl radical are mainly governed by the addition enthalpy but are also substantially lowered by the ambiphilic effect and by relief of cyclic strain.