39605-37-3Relevant articles and documents
Chemiluminescence of Dimethyldioxetanone. Unimolecular Generation of Excited Singlet and Triplet Acetone. Chemically Initiated Electron-Exchange Luminescence, the Primary Light Generating Reaction
Schmidt, Steven P.,Schuster, Gary B.
, p. 306 - 314 (1980)
Dimethyldioxetanone (2a) undergoes two distinct thermal reactions which generate electronically excited states.The unimolecular decomposition of 2a at 30.0 deg C produces excited singlet and triplet acetone, with efficiencies of 0.1 and 1.5percent, respectively.The composite activation energy for formation of singlet acetone is 3-4 kcal mol-1 greater than the activation energy for the thermal disappearance of 2a.This result is interpreted in terms of two parallel competitive pathways for dioxetanone decomposition, the more highly activated one of which leads to excited acetone.The addition of easily oxidized aromatic hydrocarbons or amines catalyzes the chemiluminescence of 2a.The magnitude of the catalytic rate constant and the efficiency of light production are correlated with the one electron oxidation potential of the hydrocarbon.Under these conditions, the chemiluminescence results from a chemically initiated electron-exchange luminescence path.
Synthesis of unstable cyclic peroxides for chemiluminescence studies
Bartoloni, Fernando H.,De Oliveira, Marcelo A.,Augusto, Felipe A.,Ciscato, Luiz Francisco M. L.,Bastos, Erick L.,Baader, Wilhelm J.
, p. 2093 - 2103 (2013/04/24)
Cyclic four-membered ring peroxides are important high-energy intermediates in a variety of chemi and bioluminescence transformations. Specifically, a-peroxylactones (1,2-dioxetanones) have been considered as model systems for efficient firefly bioluminescence. However, the preparation of such highly unstable compounds is extremely difficult and, therefore, only few research groups have been able to study the properties of these substances. In this study, the synthesis, purification and characterization of three 1,2-dioxetanones are reported and a detailed procedure for the known synthesis of diphenoyl peroxide, another important model compound for the chemical generation of electronically excited states, is provided. For most of these peroxides, the complete spectroscopic characterization is reported here for the first time.
