Accession Number : ADA114393
Title : Thermal Chemistry of Cyclopropyl Substituted Malonyl Peroxides. A New Chemiluminescent Reaction.
Descriptive Note : Technical rept.,
Corporate Author : ILLINOIS UNIV AT URBANA ROGER ADAMS LAB
Personal Author(s) : Darmon,Michael J ; Schuster,Gary B
PDF Url : ADA114393
Report Date : 26 Apr 1982
Pagination or Media Count : 36
Abstract : 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.
Descriptors : *Thermochemistry, *Substitution reactions, *Chemiluminescence, Electron transfer, Peroxides, Reaction kinetics, Cyclic compounds, Thermal properties, Aromatic compounds, Hydrocarbons, Methyl radicals, Propyl radicals
Subject Categories : Organic Chemistry
Distribution Statement : APPROVED FOR PUBLIC RELEASE