Theoretical study of the ozonolysis of allyl acetate: mechanism and kinetics

The potential energy surface (PES) and mechanism of the reaction of allyl acetate (AAC) with O₃ are investigated by using density functional theory (DFT) and ab initio (MP2 and CCSD(T)) methods. The kinetics and main product branching ratios over the temperature range of (200–2,000 K) and at various pressures are obtained by employing multichannel Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The results show that the main products are 2-oxoethyl acetate and formaldehyde. Two channels are found for the decomposition of primary ozonides: one path is corresponding to the 2-oxoethyl acetate + CH₂OO formation (R1); the other channel products formaldehyde + CH₃C(O)OCH₂CHOO (R2). In the whole temperature range, R1 is calculated to be preferable and its product yield accounts for 60–77% of the total while R2 is found to contribute 20–40% to the total product yield. The overall rate constants show pressure independence and strong positive temperature dependence.