Thermal Chemistry of Cyclopropyl Substituted Malonyl Peroxides. A New Chemiluminescent Reaction.
ILLINOIS UNIV AT URBANA ROGER ADAMS LAB
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This document investigates the thermal properties and chemiluminescent behavior of 4-cyclo-propyl-4-methyl-1,2-dioxolane-3,5-dione 2 and 4-spiro 2-spirocyclopropyl-cyclohexyl-1,2-dioxolane-3,5-dione. The gross chemical properties of these malonyl peroxides are analogous to other alkyl substituted examples. Thermolysis leads to rate limiting homolytic rupture of the oxygen-oxygen bond, loss of CO2 and then cyclization to an alpha-lactone. This sequence of reactions can be catalyzed by aromatic hydrocarbons through an apparent electron transfer process. Chemiluminescence from these peroxides can be observed in the presence of the aromatic hydrocarbons. The mechanism for light generation is postulated to be chemically initiated electron-exchange luminescence CIEEL proceeding through a cyclopropylcarbinyl to allylcarbinyl rearrangement.
- Organic Chemistry
- Physical Chemistry