Kinetics and Mechanism of the Reactions of Aromatic Nitroso Oxides with Tetracyanoethylene

Abstract

The kinetics of reaction of phenylnitroso oxide and a number of its para-substituted analogues (R = Me2N, MeO, Me, and Br) with tetracyanoethylene in acetonitrile at room temperature was studied using flash photolysis. It was established that nitroso oxides exhibited nucleophilic properties in this reaction, and the rate constants for the trans forms of these species in the above series changed by seven orders of magnitude. In the presence of a strong electron-donating substituent (Me2N or MeO), the cis form, which is usually inert toward organic substrates, also reacted with the olefin along with the trans form. The reaction mechanism was studied using the density functional theory.