Reactions of nitrophenide and halonitrophenide ions with acrylonitrile and alkyl acrylates in the gas phase: addition to the carbonyl group versus Michael addition

Gas‐phase reactions of isomeric nitrophenide ions and p‐halonitrophenide ions with acrylonitrile, methyl acrylate, and ethyl acrylate have been studied using mass spectrometry and computational methods. Depending on the structure of the α,β‐unsaturated compound, formation of adducts to the carbonyl group of the acrylate (for methyl acrylate and ethyl acrylate) and β‐adducts (adducts of p‐halonitrophenide ions to α,β‐unsaturated compounds in β position) was observed. Further transformations of these adducts lead to the products of elimination of an alcohol molecule and the anionic products of intramolecular substitution of a halogen atom, respectively. Copyright © 2012 John Wiley & Sons, Ltd.