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Reactivity and reaction pathways of alkylalkoxybenzene radical cations. Part 2. Effects of 2‐alkyl substituents on the relative importance of deprotonation over de‐ tert ‐butylation of 2‐alkyl‐5‐ tert ‐butyl‐1,4‐dimethoxybenzene radical cations
Author(s) -
Zhao ChengXue,
Gong YueFa,
He HaiYing,
Jiang XiKui
Publication year - 1999
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199909)12:9<688::aid-poc184>3.0.co;2-c
Subject(s) - chemistry , deprotonation , alkyl , reactivity (psychology) , medicinal chemistry , electron paramagnetic resonance , photochemistry , organic chemistry , ion , medicine , physics , alternative medicine , pathology , nuclear magnetic resonance
The 2‐alkyl‐5‐ tert ‐butyl‐1,4‐dimethoxybenzene radical cations 1 +· a–e (2‐alkyl = Me, Et, i ‐Pr, c ‐PrCH 2 and PhCH 2 ) generated in one‐electron oxidation of their parent compounds 1a–e by pentafluorobenzoyl peroxide or cerium(IV) sulfate were characterized by EPR spectrometry. The product analysis shows that under certain conditions 1 +· a–e may collapse through two competitive pathways, i.e. deprotonation and de‐ tert ‐butylation. The deprotonation of 1 +· a–e is further assured by EPR observations of the corresponding benzyl radical intermediates. The relative importance of the two pathways is greatly dependent on the structure of the alkyl substituents, the nature of the solvents and the reaction temperature. For deprotonation, the reactivity order is found to be c ‐PrCH 2 >Me >PhCH 2 >Et ≫ i ‐Pr. Copyright © 1999 John Wiley & Sons, Ltd.