Kinetics and mechanism of acetone cyclic diperoxide (3,3,6,6-tetramethyl-1,2,4,5-tetraoxane) thermal decomposition in benzene solution

Abstract

mL of dry ra-pentane-diethyl ether (3:2 by volume) containing 2.0 mmol of n-heptane as internal standard was cooled to -23 °C under a blanket of argon and 4.0 mmol of t-BuLi as a solution in pentane was added via syringe over a 5-min period. The reaction mixture was stirred for 30 min -23 °C, the cooling bath was removed, and 10 mL of water was cautiously added. After warming to room temperature, the organic phase was separated, dried (MgSOJ, and analyzed by GLC on column A at 35 °C. The results are presented in Scheme II. Methylcyclopentane and 1-hexene were identified by comparison of their retention times and mass spectra obtained by GC/MS with those of authentic samples.Acknowledgment. This investigation was supported by a grant from the Humphrey Chemical Company, North Haven, CT, and we are gratefiil for their continued interest in our work. We acknowledge with thanks the help of Marvin Thompson in obtaining numerous high-resolution mass spectra. WFB thanks Professor Jack Baldwin of the Dyson Perrins Laboratory, Oxford, for his kind hospitality during the period when this paper was written.

Effect of ionic liquid on the thermal decomposition of cyclic organic peroxides

“…The kinetic data obtained in this work, and other results previously described by various authors for different cyclic peroxides (Cafferata et al, 1984;Cafferata et al, 1990;Cafferata et al, 1991;Eyler et al, 1994;Eyler et al, 2000;Barreto and Cañizo, 2004;Sheng et al, 2004;Cañizo, 2006;Iglesias et al, 2009), allowed to associate the rate constants with the unimolecular rupture process of one peroxidic bond as the rate-determining step of the decomposition route (Scheme 2).…”

Descomposicion termica del diperoxido de pinacolona (3,6-diterbutil-3,6-dimetil-1,2,4,5-tetraoxaciclohexano) en solución de 2-metoxietanol

“…1), para la reacción del DPP en 2-metoxietanol corresponden a un proceso simple representado por la ruptura homolítica 16 El birradical intermediario (ec. 2), puede experimentar posteriores reacciones que involucren rupturas de enlaces C-O, justificando la aparición de pinacolona con un rendimiento del 60 % (1,2 mol pinacolona/mol DPP descompuesto), o rupturas C-C dando lugar a radicales terbutilo y metilo, que luego reaccionan con el solvente extrayendo hidrógeno para formar metano (ec.…”

Crystal structures and photoreactivity of trans- and cis-valerophenone diperoxides

“…Photochemical or thermal decomposition of peroxidic compounds usually begins with cleavage of the weakest bond, i.e., a peroxide bond. Therefore, diperoxides trans-1 and cis-1 should decompose mainly from the O-O bond cleavage of path a in Scheme 3 [31][32][33][34]. It seems from the observation (i) that this mode of decomposition ends up with formation of 2 more than 3.…”