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Unexpected Acid Catalysis in Reactions of Peroxyl Radicals with Phenols
Author(s) -
Valgimigli Luca,
Amorati Riccardo,
Petrucci Silvia,
Pedulli Gian Franco,
Hu Di,
Hanthorn Jason J.,
Pratt Derek A.
Publication year - 2009
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200903360
Subject(s) - chemistry , radical , reactivity (psychology) , catalysis , phenols , photochemistry , phenol , counterintuitive , organic chemistry , medicine , alternative medicine , pathology , philosophy , epistemology
Weak organic acids in millimolar concentrations increase the reactivity of peroxyl radicals with common phenolic antioxidants dramatically. This counterintuitive phenomenon relies on a substantially different reaction mechanism from that in the absence of an acid: rate‐determining electron transfer occurs from the hydrogen‐bonded phenol to the hydroperoxide cation radical present in equilibrium with the peroxyl radical under these conditions (see scheme).