Pyrolysis Reactions of 3-Oxetanone

Wright, Emily M.; Warner, Brian J.; Foreman, Hannah E.; McCunn, Laura R.; Urness, Kimberly N.

doi:10.1021/acs.jpca.5b04565

Cited by 7 publications

(18 citation statements)

References 45 publications

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“…At all energies, ketene pathway was less preferred over CO + ethylene oxide/CH 2 OCH 2 formation. This is an important finding given the fact that previous studies 16,17 have considered the ketene channel as the predominant dissociation pathway for 3oxetanone molecule. Also, different minor pathways emerged with increase in available energy.…”

Section: ■ Summary and Conclusionmentioning

confidence: 62%

“…The dissociation products CH 2 CO + HCHO have been observed in earlier pyrolysis experiments. 17 The fraction of trajectories showing this pathway is small given the low-energy barrier. Subsequent dissociation of the reaction products did not happen in the 150 and 200 kcal/mol simulations.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…14,15 Several studies have been reported in the literature on the decomposition reactions of small heterocyclic molecules and their substituted variants. For the thermal decomposition of 3oxetanone, two different dissociation patterns 16,17 can be considered as shown in Figure 1. The first one involves the formation of ketene (CH 2 CO) + formaldehyde (HCHO), and the second one leads to ethylene oxide (oxirane, c-C 2 H 4 O) + carbon monoxide (CO).…”

Section: ■ Introductionmentioning

confidence: 99%

“…Recently, matrix-isolation Fourier transform infrared spectroscopy and photoionization mass spectrometry techniques were used to investigate the pyrolysis products of 3-oxetanone in the gas phase. 17 Reaction products identified were ketene, formaldehyde, ethylene oxide, and carbon monoxide along with other species such as ethylene and methyl radical. In these experiments, determining the branching ratio between the two primary dissociation pathways and the quantification of reaction products such as CO were not possible.…”

Section: ■ Introductionmentioning

confidence: 99%

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Dissociation Chemistry of 3-Oxetanone in the Gas Phase

2017

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3-Oxetanone is a strained cyclic molecule which plays an important role in synthetic chemistry. A few studies exist in the literature about the equilibrium properties of this molecule and the dissociation patterns of substituted 3-oxetanones. For the unsubstituted 3-oxetanone, formation of ketene (CHCO) and formaldehyde (HCHO) was considered to be the major dissociation pathway. In a recent work, pyrolysis products of 3-oxetanone molecule in the gas phase were investigated by Fourier transform infrared spectroscopy and photoionization mass spectrometry. In this study, an additional dissociation channel forming ethylene oxide (c-CHO) and carbon monoxide CO was reported. In the present work, gas phase dissociation chemistry of 3-oxetanone was investigated by electronic structure theory, ab initio classical chemical dynamics simulations, and Rice-Ramsperger-Kassel-Marcus (RRKM) rate constant calculations. The barrier height for the ethylene oxide channel was found to be much higher than the ketene pathway. The dynamics simulations were performed at three different total energies, viz., 150, 200, and 300 kcal/mol, and multiple reaction pathways and varying branching ratios observed. A new dissociation channel involving a ring-opened isomer of ethylene oxide was identified in the simulations. This pathway has a lower energy barrier and was dominant in our dynamics simulations.

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Section: ■ Summary and Conclusionmentioning

confidence: 62%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Dissociation Chemistry of 3-Oxetanone in the Gas Phase

2017

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“…McCunn and co-workers studied the pyrolysis reactions of OXT in the gas phase experimentally [14]. Their results reveal that the major products are formaldehyde, ketene, carbon monoxide, ethylene oxide, ethylene and methyl radical at temperatures from 600 to 1200 °C.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Kinetics and Mechanism of the Thermal Decomposition of 3-Oxetanone in the Gas Phase

Khavani

Karimi

2017

Progress in Reaction Kinetics and Mechanism

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The kinetics and mechanism of the thermal decomposition reaction of 3-oxetanone in the gas phase were studied using quantum chemical calculations. The major products of this reaction are formaldehyde, ketene, carbon monoxide, ethylene oxide, ethylene and methyl radical. Formaldehyde, ketene, carbon monoxide and ethylene oxide are the initial decomposition products and other species are the products of ethylene oxide decomposition. The results of B3LYP and QCISD(T) calculations reveal that thermal decomposition of 3-oxetanone to ethylene oxide and carbon monoxide is more probable than to formaldehyde and ketene from an energy viewpoint. Moreover, quantum theory of atoms in molecules and natural bond orbital analysis indicate that 3-oxetanone decomposition to formaldehyde, ketene, carbon monoxide and ethylene occurs via a concerted mechanism and bonds that are involved in the transition states have a covalent character. Moreover, the calculated changes in bond lengths in the transition states reveal that bond breaking and new bond formation occur asynchronously in a concerted mechanism.

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Oxetanes and Oxetenes: Monocyclic

Rojas

Bull

2022

Comprehensive Heterocyclic Chemistry IV

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Pyrolysis Reactions of 3-Oxetanone

Cited by 7 publications

References 45 publications

Dissociation Chemistry of 3-Oxetanone in the Gas Phase

Dissociation Chemistry of 3-Oxetanone in the Gas Phase

Theoretical Study of the Kinetics and Mechanism of the Thermal Decomposition of 3-Oxetanone in the Gas Phase

Oxetanes and Oxetenes: Monocyclic

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