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,ß-unsaturated compound, formation of adducts to the carbonyl group of the acrylate (for methyl acrylate and ethyl acrylate) and ß-adducts (adducts of p-halonitrophenide ions to α,ß-unsaturated compounds in ß 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.