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Thermolysis and chemiluminescence of monocyclic 1,2,4-trioxan-5-ones

Authors
Jefford, Charles William
Josso, Martin C.
Vicente, Maria da Graça H.
Published in Helvetica Chimica Acta. 1994, vol. 77, no. 7, p. 1851-1860
Abstract The 3,6-substituted 1,2,4-trioxan-5-ones 11-14, on heating to 170-200°, underwent unimolecular thermolysis to generate electronically excited singlet ketones with an efficiency of ca. 0.2%. The chemiluminescence quantum yields (oSCL) depended on the nature of the 6-substitutents and increased linearly with temperature. The Arrhenius activation energies were obtained by measuring the rate of decay of luminescence and determined as 22.9, 30.4, 35.6, and 34.2 kcal/mol for 11-14, respectively. Step analysis of the chemiluminescence of 14 afforded an average activation energy of 44.3 kcal/mol. This latter result is explicable in terms of two decomposition paths, higher and lower in energy, leading to excited and dark products, respectively. The thermolysis of trioxanones 12-14 lacking a H-atom at the 6-position is interpreted as involving successive rupture of the peroxide bond, excision of ketone at the 3-substituted end, and loss of CO2, to finally produce ketone originating from the 6-position (see Scheme 4).
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Research group Groupe Bill
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JEFFORD, Charles William et al. Thermolysis and chemiluminescence of monocyclic 1,2,4-trioxan-5-ones. In: Helvetica Chimica Acta, 1994, vol. 77, n° 7, p. 1851-1860. https://archive-ouverte.unige.ch/unige:2888

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Deposited on : 2009-09-21

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