Thermal decomposition reaction of 3,3,6,6-tetramethyl- 1,2,4,5-tetroxane in 2-methoxy- ethanol solution

Abstract

The thermal decomposition study of 3,3,6,6-tetramethyl-1,2,4,5-tetroxane (acetone cyclic diperoxide) was carried out in 2-methoxyethanol solution in the 130-166ºC temperature range. The overall reaction follows a first-order kinetic law up to at least 75% diperoxide conversion. The activation parameters (∆H # = 22.5 ± 0.7 kcal⋅mol -1 and ∆S # = -25.6 ± 0.5 cal⋅mol -1 ⋅K -1 ) for the unimolecular rupture of the O-O bond in the diperoxide molecule were obtained by measuring the remnant diperoxide at different reaction times by the CG technique. Acetone was detected by GC as the major organic product of the reaction.

Some Recent Developments on the Synthesis, Chemical Reactivity, and Theoretical Studies of Tetroxanes

“…The synthesis and reactivity of cyclic peroxides have attracted the attention of many investigators (Schulz, 2000;Cafferatta et al, 1984Cafferatta et al, , 1986Cafferatta et al, , 1990Cafferatta et al, , 1991Cafferatta et al, , 1995Jorge et al, 1994Jorge et al, , 2000Jorge et al, , 2001Leiva et al, 1998Leiva et al, , 2001Castellanos et al, 2000;Romero & al, 2005;Gelancha et al, 2004;Oxley et al, 2002;Dubvikova et al, 2005;Hong & Lin, 1996), due to the particular reactivity of the O-O bond.…”

“…Several reaction of the decomposition (Cafferatta et al, 1984(Cafferatta et al, , 1986(Cafferatta et al, , 1990(Cafferatta et al, , 1991(Cafferatta et al, , 1995Jorge et al, 2000Eyler et al, 1993Eyler et al, , 1999Eyler et al, , 2000Eyler et al, , 2002, thermochemical (Eyler et al, 1999;Murray et al, 1966;Wulz et al, 1970) and quantum-chemical (Jorge et al, 1994(Jorge et al, , 2000(Jorge et al, , 2001Leiva et al, 1998Leiva et al, , 2001Castellanos et al, 2000;Diez & Jubert, 2000) data sets for 1,2,4-trioxanes and 1,2,4,5-tetroxanes are available. Solvent effects on the inversion barrier of 3,3,6,6,-tetramethyl-1,2,4,5-tetroxane (or dimeric acetone peroxide) have been studied (Brune et al, 1971) and a conformational analysis in the liquid phase suggested that the chair conformer is more stable than the twist form (Murray et al, 1966).…”