Journal of Physical Chemistry p. 9304 - 9310 (1992)
Update date:2022-08-11
Topics:
Bogan, Denis J.
Lee, Dong-Heon
Chemically activated tetramethyl-1,2-dioxetane has been prepared by the reaction of O2(1Δg) with 2,3-dimethyl-2-butene at temperatures of 450 to 775 K and a pressure of 0.25 Torr.The observed product of the reaction was excited 1n?*(S1) acetone, which was identified by chemiluminescence spectra of the acetone (S1 -> S0) transition.Neither acetone (Ti) nor any other excited states were observed under the above conditions.The temperature dependence of the chemiluminescence gave an activation energy for the cycloaddition reaction of 8610 +/- 200 (1?) cal/mol.The quantum yield for acetone (S1) was 4 * 10-3 per reactive collision; its (1?) error is estimated as +/- a factor of 3.Chemiluminescence spectra taken at O2(3Σ1g) partial pressures greater than 2 Torr showed formaldehyde (S1 -> S0) bands.This is attributed to the well-known hydrocarbon "cool flame" mechanism, due to the presence of methyl radical formed by the thermal decomposition, in two steps, of 2,3-dimethyl-3-hydroperoxy-1-butene, another product path for the title reaction.This is the first report on the chemically activated decomposition of tetramethyl-1,2-dioxetane.
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