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Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Thermal decomposition reaction of acetone triperoxide in toluene solution
1Laboratorio de Quimica, Facultad de Ingenieria, Universidad Nacional del Centro de la Provincia de Buenos Aires, Olavarria, Republica Argentina. neyler@fio.unicen.edu.ar
Abstract:
The thermal decomposition reaction of acetone cyclic triperoxide (3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxacyclononane, ACTP) in the temperature range of 130.0-166.0 degrees C and an initial concentration of 0.021 M has been studied in toluene solution. The thermolysis follows first-order kinetic laws up to at least ca. 78% acetone triperoxide conversion. Under the experimental conditions, a radical-induced decomposition reaction as a competing mechanism may be dismissed, so the activation parameters correspond to the unimolecular thermal decomposition reaction of the ACTP molecule [delta H++ = 41.8 (+/- 1.6) kcal mol-1 and delta S++ = 18.5 (+/- 3.8) cal mol-1K-1]. Analysis of the reaction products are not enough to elucidate the real mechanism for the thermolysis of the acetone triperoxide in toluene solution.
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