Journal of Organic Chemistry p. 280 - 284 (1980)
Update date:2022-08-03
Topics:
Creary, Xavier
The effect of substituents on the thermal rearrangement of 2-aryl-3,3-dimethylmethylenecyclopropanes, 4, to 2-arylisopropylidenecyclopropanes, 5, has been determined.This has allowed an evaluation of substituent effects on a free-radical-like transition state devoid of polar character.In general, no correlation of all the data could be obtained with Hammett ? values.Electronegative meta substituents slightly decreased rates (ρ = -0.16).Conjugating substituents such as CN and CO2CH3 in the para position increased rates.The effect of the p-CF3 group was rate enhancing.The potential for C-F hyperconjugative stabilization is discussed as a radical-stabilizing feature.Thiomethyl and trimethylsilyl substituents in the para position increased rates.The possibility of radical-stabilizing interactions with vicinal ?* and ? orbitals is discussed. p-Methoxy substitution increased rates while p-fluoro substitution slowed rates.Resonance delocalization involving charge-separated forms 10a and 11 was suggested to be less favorable in the case of p-fluoro substitution.Delocalization involving an expanded octet accounted for increased rearrangement rates of p-Cl and p-Br-substituted 4.
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Doi:10.1139/v79-513
(1979)Doi:10.1021/acs.joc.9b01015
(2019)Doi:10.1021/jo0358877
(2004)Doi:10.1016/0008-6215(90)84083-7
(1990)Doi:10.1021/ja00520a025
(1979)Doi:10.1016/S0008-6215(00)85199-X
(1980)