Investigation into reactions of methyl methacrylate and ethyl acrylate with chlorine atom.

Reactions between chlorine and unsaturated esters in gas phase are examined in a slow-flow reaction tube inside the laboratory-built photoionization mass spectrometer at the energy range of 8-11 eV. 248 nm laser radiation is used to initiate the reaction. Products are distinguished, CHOCl for addition, and CHO, CHOCl and CHOCl for abstraction. The direct or indirect products are detected, indicating secondary reactions. And experimental ionization potentials are procured for direct adducts of methyl methacrylate to be 8.30 eV and for that of ethyl acrylate to be 9.95 eV which are well consistent with theoretical ionization potentials of likely isomers. Theoretical reaction channels are also accounted for, optimized under M06-2X/6-31 + G(d,p) level and ionization potentials of products are calculated under M06-2X/6-31 + G(d,p) level also. Differences between experimental and theoretical details are discussed.