Reactivity of aminyl radicals in radical nucleophilic substitution reactions with diphenylphosphide anion

The photostimulated reactions of N-cyclopropyl-N-ethyl p-toluensulfonamide (4) with diphenylphosphide ions (2) in liquid ammonia gave 1,3-bis(diphenyl phosphinyl)-1-(N-ethyl)propylamine, isolated as the oxide 5, and 1,3-bis (d iphenylphosphinyl)-1-propanol, isolated as the oxide 6, all of them corresp onding to the aperture of the cyclopropylaminyl radical intermediate. The r eaction of 4 with 2 in excess and longer reaction times gave only 5 (73% yi eld). The photostimulated reactions of N-(n-butyl)-N-cyclobutyl p-toluensul fonamide (13) with 2 in liquid ammonia gave, after oxidation, N-(n-butyl)-N -cyclobutyl diphenylphosphonamide (14) in 94% yield. All these reactions oc cur by the radical nucleophilic substitution in which aminyl radicals are i ntermediates. The order of the magnitude of the rate constant for the coupl ing reaction of a dialkylaminyl radical with 2 could be intermediate betwee n those of the rearrangements of the cyclopropyl and cyclobutylaminyl radic als.