FREE-RADICAL ALKYLATIONS OF 2-HYDROXY-1,4-NAPHTHOQUINONE

2-Hydroxy-1,4-naphthoquinone (I) canbe alkylated in the 3 position by reaction of I with a hydrocarbon and t-butyl peroxide. A free-radical chain reaction consisting of the addition of an alkyl radical to the quinoneat the 3 position yielding an -hydroxyalkyl radical that transfers a hydrogen atom to the peroxide is proposed for these reactions. The hydrogen atom transfer reaction yields the keto form of the alklation product, t-butyl alcohol, and a chain-carrying t-butoxyl radical that abstracts a hydrogen atom from the hydrocarbon producing the alkyl free radical that adds to I. Kinetic studies of the reaction indicate that the peroxide undergoes an induced decomposition supporting the mechanism proposed for these reactions. © 1968, American Chemical Society. All rights reserved.