Journal of Organic Chemistry p. 1555 - 1559 (1987)
Update date:2022-08-11
Topics:
Mahiou, Belaid
Gleicher, Gerald Jay
The relative rates of hydrogen atom abstraction from a series of 13 homoaryl- and heteroarylmethanes by the tert-butoxy radical were determined at 70 deg C.The attacking radical was photochemically generated from di-tert-butyl peroxide.A relatively small range of relative rates (factor of 7) has been found among the compounds studied; however, significant position variation among isomers is noted.The relative reactivities of the homoaryl- and heteroarylmethanes can be correlated with various calculated energy differences obtained from both HMO and standard semiempirical SCF-MO methods.Fairly good correlations were obtained by use of a carbocation model for the transition state (correlation coefficient 0.92).Much poorer correlations were obtained when a radical model was used for the transition state with either the HMO or SCF-MO approach (maximum correlation coefficient 0.49).This suggests that considerable charge development must be associated with the transition state of this reaction.
View MoreDoi:10.1016/j.ejmech.2016.12.008
(2017)Doi:10.1021/jp014088u
(2002)Doi:10.1039/b211099g
(2003)Doi:10.1021/ja01310a047
(1935)Doi:10.1002/chem.200500158
(2005)Doi:10.1021/ja01373a053
(1930)