The thermal decomposition reaction of 3,6-dibutanal-1,2,4,5-tetroxane (DPG) in acetonitrile, at the temperatures range of 403-439 K and initial concentration 2.85 × 10-2 mol L-1, follows a pseudo-first order kinetic law. Glutaraldehyde is the main organic product obtained. The activation parameter values of the initial step of the reaction (ΔH# = 123.54 ± 0.9 kJ mol-1; ΔS# = -19.13 ± 0.8 J mol-1 K-1; Ea = 126.97 ± 0.9 kJ mol-1) support a reaction mechanism which includes a homolytic rupture of one peroxidic bond of the DPG molecule with participation of the solvent and involving a biradical intermediate. Other organic reaction products obtained (butanal methanoate, tert-butyl acetate and 2,2-dimetoxypropane) support the stepwise reaction mechanism.
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