American Chemical Society
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Kinetics and Mechanisms of the Thermal Decomposition of 2‑Methyl-1,3-dioxolane, 2,2-Dimethyl-1,3-dioxolane, and Cyclopentanone Ethylene Ketal in the Gas Phase. Combined Experimental and DFT Study

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journal contribution
posted on 2012-09-20, 00:00 authored by Felix Rosas, Jesus Lezama, José R. Mora, Alexis Maldonado, Tania Cordova, Gabriel Chuchani
The kinetics of the gas-phase thermal decomposition of 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, and cyclopentanone ethylene ketal were determined in a static system and the reaction vessel deactivated with allyl bromide. The decomposition reactions, in the presence of the free radical suppressor propene, are homogeneous, are unimolecular, and follow first-order law kinetics. The products of these reactions are acetaldehyde and the corresponding ketone. The working temperature range was 459–490 °C, and the pressure range was 46–113 Torr. The rate coefficients are given by the following Arrhenius equations: for 2-methyl-1,3-dioxolane, log k = (13.61 ± 0.12) – (242.1 ± 1.0)­(2.303RT)−1, r = 0.9997; for 2,2-dimethyl-1,3-dioxolane, log k = (14.16 ± 0.14) – (253.7 ± 2.0)­(2.303RT)−1, r = 0.9998; for cyclopentanone ethylene ketal, log k = (14.16 ± 0.14) – (253.7 ± 2.0)­(2.303RT)−1, r = 0.9998. Electronic structure calculations using DFT methods B3LYP and MPW1PW91 with 6-31G­(d,p), and 6-31++G­(d,p) basis sets suggest that the decomposition of these substrates takes place through a stepwise mechanism. The rate-determining step proceeds through a concerted nonsynchronous four-centered cyclic transition state, and the elongation of the C–OCH3 bond in the direction Cαδ+...OCH3δ− is predominant. The intermediate products of these decompositions are unstable, at the working temperatures, decomposing rapidly through a concerted cyclic six-centered cyclic transition state type of mechanism.