Investigation of the Mechanism of the Unimolecular and The Electron Donor Catalyzed Thermal Fragmentation of Secondary Peroxy Esters. Chemiluminescence of 1-Phenylethyl Peroxyacetate.

摘要

The mechanism of the thermolysis of 1-phenylethyl peroxyacetate was studied. In the absence of easily oxidized substrates this perester undergoes thermal fragmentation to yield quantitatively acetophenone and acetic acid. These products are formed by initial oxygen-oxygen bond homolysis followed by in cage hydrogen atom transfer. A small fraction of the so formed acetophenone is generated in an electronically excited state. In the presence of easily oxidized substrates the reaction of the perester is catalyzed and generates excited states by the chemically initiated electron-exchange luminescence (CIEEL) mechanism. An analogy with the catalyzed reaction is drawn to the excitation step of bacterio-luminescence. (Author)