Chemiluminescence of secondary peroxyesters

Article abstract of DOI:10.1021/ja00401a026

The thermolysis of 1-phenylethyl peroxyacetate and a series of substituted 1-phenylethyl peroxybenzoates was investigated. Thermolysis in benzene gives acetophenone and the corresponding carboxylic acid. The study of the reaction kinetics and kinetic isotope effect indicates that the unimolecular thermolysis proceeds by homolysis of the oxygen-oxygen bond. Electronically excited states are formed in the thermolyses of these peroxyesters. These are detected by their characteristic direct chemiluminescence or by indirect chemiluminescence. In the presence of easily oxidized catalysts these peroxyesters give excited states by the chemically initiated electron-exchange luminescence (CIEEL) path. The mechanism of these luminescent reactions was investigated.