[show abstract][hide abstract] ABSTRACT: Theoretical calculations of the gas-phase thermal decomposition kinetics of 2-thiomethyl-1-chloroethane and 4-thiomethyl-1-chlorobutane have been carried out by using Density Functional Theory (DFT), composite CBS-Q3, and Møller-Plesset second-order (MP2) methods in order to elucidate a reasonable reaction mechanism of these compounds. The enhanced reactivities of these two substrates, when compared with their parent compounds, attributed to neighboring group participation (NGP) or anquimeric assistance in the literature, were investigated. For 2-thiomethyl-1-chloroethane two dehydrochlorinaton pathways, with and without NGP were studied. The results of quantum chemical estimations of 2-thiomethyl-1-chloroethane in the gas phase show good agreement with experimental values at B3LYP/6-31++G(2d,p) level, and suggest the 1,2-elimination through non-synchronous four-membered cyclic transition state is the preferred mechanism. For 4-thiomethyl-1-chlorobutane, the significant increase in rate compared to 2-thiomethyl-1-chloroethane, together with the formation of a cyclic product tetrahydrothiophene suggest the anchimeric assistance by the CH3S group in the transition state. Best calculated parameters were obtained with CAM-B3LYP/6-31G++(2d,p). Results support the NGP of the thiomethyl group, through cyclic ion-pair type of intermediate. The bond polarization of the C – Cl, in the direction of Cδ…Clδ, appears to be the rate determining step of these decompositions.
Computational and Theoretical Chemistry 01/2013; · 1.14 Impact Factor
[show abstract][hide abstract] ABSTRACT: 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-OCH(3) bond in the direction C(α)(δ+)...OCH(3)(δ-) 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.
The Journal of Physical Chemistry A 08/2012; 116(37):9228-37. · 2.77 Impact Factor
[show abstract][hide abstract] ABSTRACT: The gas-phase thermal elimination of 2,2-diethoxypropane was found to give ethanol, acetone, and ethylene, while 1,1-diethoxycyclohexane yielded 1-ethoxycyclohexene and ethanol. The kinetics determinations were carried out, with the reaction vessels deactivated with allyl bromide, and the presence of the free radical suppressor cyclohexene and toluene. Temperature and pressure ranges were 240.1-358.3 °C and 38-102 Torr. The elimination reactions are homogeneous, unimolecular, and follow a first-order rate law. The rate coefficients are given by the following Arrhenius equations: for 2,2-diethoxypropane, log k(1) (s(-1)) = (13.04 ± 0.07) - (186.6 ± 0.8) kJ mol(-1) (2.303RT)(-1); for the intermediate 2-ethoxypropene, log k(1) (s(-1)) = (13.36 ± 0.33) - (188.8 ± 3.4) kJ mol(-1) (2.303RT)(-1); and for 1,1-diethoxycyclohexane, log k = (14.02 ± 0.11) - (176.6 ± 1.1) kJ mol(-1) (2.303RT)(-1). Theoretical calculations of these reactions using DFT methods B3LYP, MPW1PW91, and PBEPBE, with 6-31G(d,p) and 6-31++G(d,p) basis set, demonstrated that the elimination of 2,2-diethoxypropane and 1,1-diethoxycyclohexane proceeds through a concerted nonsynchronous four-membered cyclic transition state type of mechanism. The rate-determining factor in these reactions is the elongation of the C-O bond. The intermediate product of 2,2-diethoxypropane elimination, that is, 2-ethoxypropene, further decomposes through a concerted cyclic six-membered cyclic transition state mechanism.
The Journal of Physical Chemistry A 12/2011; 116(2):846-54. · 2.77 Impact Factor
[show abstract][hide abstract] ABSTRACT: The kinetics of the thermal decomposition of the title compounds in the gas phase have been studied at the B3LYP/6-31G(d,p), B3LYP/6-31++G(d,p), MPW91PW91/6-31G(d,p), MPW91PW91/6-31++G(d,p), PBEPBE/6-31G(d,p), and PBEPBE/6-31++G(d,p) levels of theory. These halide substrates produce the corresponding cyclohexadiene and hydrogen chloride. The DFT calculations suggest a non-synchronous four-membered cyclic transition state type of mechanism. The elongation and subsequent polarization of the C–Cl bond, in the direction of Cδ+…Clδ−, is rate determining step in these elimination reactions. Differences in reactivity in these substrates are discussed in terms of the transition state structure and electron distribution.
Journal of Molecular Structure-theochem - J MOL STRUC-THEOCHEM. 01/2009; 916(1):17-22.