Isotope effect in oxidative nucleophilic substitution of hydrogen in nitroarenes

Abstract

In a series of competitive experiments with labelled nitrobenzenes carried out in liquid ammonia at −70 °C it was shown that the rate of oxidative substitution of hydrogen with the carbanion of 2-phenylpropionitrile is ca. 9.8 times faster than the analogous substitution of deuterium in 4-D-nitrobenzene and perdeuterionitrobenzene. Thus Carom.-H bond breaking is the rate limiting step of the oxidative process.