Catalysis by hydrogen halides in the gas phase. XI. Tertiary butyl ethyl ether and hydrogen chloride

Stimson, VR; Watson, EJ

doi:10.1071/ch9660401

Cited by 6 publications

(9 citation statements)

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“…Experimental activation energies found for these systems are about 130 kJ/mol [2, 4, 6], while computational results show an activation free energy around 136 kJ/mol using ωB97XD and 160 kJ/mol using the CCSD(T) correction. This suggests that, although there is a reasonable agreement between experimental and theoretical calculations, a subtle overestimation is obtained in the estimation of the activation free energy.…”

Section: Resultsmentioning

confidence: 99%

“…In the first stage, the HCl catalyzed gas-phase decomposition of t-butyl methyl ether (A), t-butyl ethyl ether (B), and t-butyl isopropyl ether (C) [2,4,6] was evaluated computationally following Scheme 1. Thermodynamic parameters estimated are reported in Table 1.…”

Section: Resultsmentioning

confidence: 99%

“…mechanism [2,3,7]. On the other hand, the hydrogen halide catalyzed reaction occurs in a homogeneous and molecular manner as suggested by kinetics studies [2].…”

mentioning

confidence: 92%

“…Reported reactions include the decomposition of butan‐2‐ol [1], acetaldehyde dimethyl acetal, 1,l‐dimethoxyethane [3], t‐ butyl isopropyl ether [4], 2,2‐dimethoxypropane [5], t‐ butyl methyl ether [6], t‐ butyl ethyl ether [2], and t‐ butylamine [7]. The uncatalyzed reaction of the latter compounds produces dehydrogenation, which is believed to occur through a radical chain mechanism [2, 3, 7]. On the other hand, the hydrogen halide catalyzed reaction occurs in a homogeneous and molecular manner as suggested by kinetics studies [2].…”

Section: Introductionmentioning

confidence: 99%

“…The uncatalyzed reaction of the latter compounds produces dehydrogenation, which is believed to occur through a radical chain mechanism [2, 3, 7]. On the other hand, the hydrogen halide catalyzed reaction occurs in a homogeneous and molecular manner as suggested by kinetics studies [2]. Previous studies [7] have indicated that the reaction rate for ethers is larger than that for alcohols due to the greater basicity of the ether oxygen compared to the alcohol group.…”

Section: Introductionmentioning

confidence: 99%

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Unveiling the structure‐reactivity relationship involved in the reaction mechanism of the HCl‐catalyzed alkyl t‐butyl ethers thermal decomposition. A computational study

Cuesta

Mora

Meneses

et al. 2022

Int J of Quantum Chemistry

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The gas‐phase thermal decomposition of a series of alkyl t‐butyl ethers catalyzed by hydrogen chloride is theoretically studied at the ωB97XD/6‐311++g(d)//CCSD(T)/6‐311++g(d) level. The experimental activation free energy for three known systems namely: t‐butyl methyl ether, t‐butyl ethyl ether, and t‐butyl isopropyl ether is used for validation of the proposed theoretical model as the transition state (TS). The chemical process was characterized using intrinsic reaction coordinate, reaction force, and reaction electronic flux profiles. The Cαδ+Oδ− polarization was identified as the determining factor in the rate‐limiting step. Upon functionalization on the Cα, 24 new compounds with different electron‐withdrawing and donating groups were studied. A good multiple‐linear correlation (R2 = 0.88) was found between the Ln(kX/kH) as the response variable and the Taft‐Topsom substituent parameters as attributes. This result supports the reliability and predictability of the proposed transition state model at this level of theory.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…mechanism [2,3,7]. On the other hand, the hydrogen halide catalyzed reaction occurs in a homogeneous and molecular manner as suggested by kinetics studies [2].…”

mentioning

confidence: 92%