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Spin Trapping of Radical Intermediates Generated by the Oxidation of Substituted 4‐Methylphenols
Author(s) -
Majzlík Petr,
Omelka Ladislav,
Superatová Renata,
Holubcová Petra
Publication year - 2011
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.201000431
Subject(s) - chemistry , radical , adduct , nitroso , substituent , nitroso compounds , spin trapping , medicinal chemistry , photochemistry , phenol , organic chemistry
A series of substituted 4‐methylphenols 1 and 2 was oxidized with PbO 2 in the presence of nitroso compounds 3 – 10 . The formation of adducts of benzyl radicals with the nitroso spin traps in the reaction mixture was established, suggesting the abstraction of an H‐atom from the methyl substituent of 1 or 2 . In the consecutive steps, the adducts underwent a further rearrangement to the corresponding nitrones. When the starting phenol contained bulky t Bu groups in ortho ‐position (see 2,6‐di( tert ‐butyl)‐4‐methylphenol ( 1a )), the stable 2,6‐di( tert ‐butyl)‐4R‐phenoxy radicals (R=CHN + (O − )X) were detected as the final radical products. The indirect evidence of nitrones in the reaction mixture was performed in one case by the reaction with a RO $\rm{{_{2}^{{^\cdot} }}}$ radicals.