6103-08-8Relevant articles and documents
Interception of deaminatively generated benzyl carbenium ions by acetone
Song, Fenhong,Darbeau, Ron W.,White, Emil H.
, p. 1825 - 1829 (2007/10/03)
Essentially free benzyl carbenium ions were generated via protonation of phenyldiazomethane with benzoic acid in acetone. Interestingly, no proton transfer occurred below -20 °C. After protonation and dediazoniation of the diazoalkane at -20 °C, the solvent was found to intercept the deaminatively generated carbocations to yield initially the corresponding O-benzyl oxonium ion and benzyl benzoate. The onium ion, however, was labile under the reaction conditions, and decomposed into a cascade of products whose concentrations as a function of time were used to trace the reaction pathway. Thus, the O-benzyl oxonium ion reacted with benzoate ion to yield (2- benzyloxy)isopropyl benzoate; subsequent decomposition of this O-benzyl-O- benzoyl ketal produced 2,2-dibenzyloxypropane (a dibenzyl ketal), 2- benzyloxypropene, and benzyl alcohol. In a related study, benzyl cations were generated via thermolyses of N-benzyl-N-nitroso-O-benzoyl hydroxylamine at 0 and -70 °C. The product distributions were found to be temperature-dependent and different from that in the PhCHN2 + PhCO2H case.
