Hydrogen atom abstraction from substituted toluenes by tert-butoxy radical

Abstract

The relative rates of abstraction of benzylic hydrogen from substituted toluenes by tert-butoxy radicals generated from tert-butyl hypochlorite have been reexamined. Abstraction from para-methylanisole was shown to occur at the ether methyl as well as at the benzylic methyl group. For this reason the compound was excluded from an analysis of the polar effect. A slightly better Hammett correlation was obtained using sigma rather than sigma-plus values.

Is there a photochemical Hammond postulate?

“…6 ). 18 If the HLP is valid in the excited state, we should see a trend which follows these electronic effects.…”