Thermolysis of 4-Methyl-4-(1-propenyl)malonyl Peroxide: Mechanistic Limits to Chemiluminescence Efficiency

摘要

The preparation and thermal chemistry of 4-methyl-4-(1-propenyl)malonyl peroxide (3) is described. Thermolysis in acetonitrile at 84 C gives 2,4-dimethylbut-2-ene-4-olide in 45% yield and oligomeric ester derived from an intermediate alpha-lactone in 55% yield. The reaction of 3 can be catalyzed by aromatic hydrocarbons such as perylene. Under these conditions weak chemiluminescence results. The mechanism for light generation is identified as chemically initiated electron-exchange luminescence (CIEEL). Application of the CIEEL mechanism to 3 reveals an important limitation to light generation by this path.