39605-37-3Relevant academic research and scientific papers
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.
Steric and stereoelectronic control of the mode selectivity as a function of alkene structure in the reaction with dimethyl α-peroxy lactone: Cycloadducts and ene products versus epoxides
Adam, Waldemar,Blancafort, Lluis
, p. 4778 - 4787 (2007/10/03)
The oxidation of di-, tri-, and tetrasubstituted alkenes 2 by dimethyl α-peroxy lactone (1) affords the cycloaddition, ene, and epoxidation products 3-6. In the presence of methanol, additionally the trapping products 7 are obtained. The observed dichotomy in the product distribution requires two different paths for this reaction, namely a path via an open, stretched 1,6 dipole and another path for epoxidation. Both paths arise from an SN2 attack of the double bond of the alkene 2 on the peroxide bond of the α-peroxy lactone 1, the first unsymmetrical (end-on attack), leading to the 1,6 dipole A, and the second symmetrical (central attack) with respect to the approach of the double bond, leading to epoxidation. The 1,6 dipole is postulated to afford the cycloadducts, of which the thermodynamically favored diastereomers are obtained, and the ene products. In the epoxidation, the α-lactone released after oxygen transfer oligomerizes to the polyester 8 or in the presence of methanol is trapped as α-methoxy acid 9. The reaction is regioselective both with respect to the attacked oxygen atom of the α-peroxy lactone 1, as revealed by the trapping products 7, as well as with respect to the attacking carbon atom for unsymmetrical alkenes 2c,d, as displayed by the ene products 5 and 6. The former regioselectivity is dictated by the inherent polarization of the peroxide bond through the carbonyl group which makes the alkoxy oxygen the more electrophilic one toward nucleophilic attack, while for the latter the incipient positive charge of the open 1,6 dipole is better stabilized by the more substituted carbon atom of the end-on attacking unsymmetrical alkene. The preferred reaction mode has been found to be sensitive to the structure of the alkene and the difference in reactivity has been explained in terms of steric and stereoelectronic factors. Thus, for the sterically less hindered cis-di- and trisubstitued alkenes the path along the open 1,6 dipole is favored (stereoelectronic control), while the more sterically demanding trans-di- and tetrasubstituted alkenes react by the epoxidation mode (steric control).
