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
      Physical Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE