SECONDARY DEUTERIUM ISOTOPE EFFECTS IN RADICAL-FORMING REACTIONS .4. CONCERTED PERESTER DECOMPOSITIONS

The secondary deuterium isotope effects on the rates of decomposition of t-butyl peresters of phenyl-acetic (1), hydratropic (2), α,α-dimethylphenylacetic (3), and pivalic acids have been determined by infrared, galvinoxyl, and double-labeling methods. The α effects for 1 and 2 are 1.03-1.06 per deuterium. The (β effects for the series are 1.014-1.020 per deuterium. The implications of these effects with respect to the detailed mechanisms of the reactions are discussed. © 1969, American Chemical Society. All rights reserved.