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ESR spin‐trap study of radicals present during the thermolysis of some di‐ tert ‐alkyl peroxides
Author(s) -
Mekarbane Pierre G.,
Tabner Brian J.
Publication year - 1998
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/(sici)1097-458x(1998110)36:11<826::aid-omr377>3.0.co;2-1
Subject(s) - chemistry , radical , peroxide , hydrogen atom abstraction , thermal decomposition , electron paramagnetic resonance , hydrogen peroxide , photochemistry , spin trapping , toluene , alkyl , medicinal chemistry , decomposition , organic chemistry , nuclear magnetic resonance , physics
The thermolysis mechanism of di‐ tert ‐butyl anddi‐ tert ‐amyl peroxide was investigated in a variety of solventsemploying electron spin resonance in collaboration with thespin‐trapping technique. The tert ‐amyloxyl radical was trappedfor the first time during the thermolysis of di‐ tert ‐amylperoxide. The relative ease of β‐scission of the tert ‐amyloxyl radical to give propan‐2‐one and butan‐2‐one wasestablished as 32:1 at 382 K. In addition, competition reactionsindicate that radicals derived from di‐ tert ‐butyl peroxide are ca . 5.5 times more reactive than those derived fromdi‐ tert ‐amyl peroxide towards hydrogen atom abstraction fromtoluene at 382 K. © 1998 John Wiley & Sons, Ltd.