DFT Research on Benzothiophene Pyrolysis Reaction Mechanism

Li, Tianshuang; Li, Jie; Hong-liang, Zhang; Sun, Kai; Xiao, Jin

doi:10.1021/acs.jpca.8b09882

Cited by 29 publications

(16 citation statements)

References 33 publications

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“…C 2,3 -carbene/F-C 2,3 -carbene, also known as α-carbene, is the IM formed through the 2,3-H transfer. In the preceding study, − we have found that the H transfer along the carbon skeleton generally has a low energy barrier. Prior to the illustration of α-carbene cracking, the conversion of α-carbene to other carbenes needs to be manifested.…”

Section: Resultsmentioning

confidence: 88%

Unimolecular Pyrolysis Mechanism of Thiophene and Furan: An Ab Initio Comparative Study

Hong-liang

et al. 2021

Energy Fuels

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Thiophene sulfur is the most stable and abundant organic sulfur species in petroleum. In this work, the unimolecular pyrolysis mechanism of thiophene was investigated using high-level ab initio methods. As a contrast, similar reactions of furan were computed using the same methods. It was found that the most likely initiation reactions for thiophene unimolecular pyrolysis are 2,3-H and 3,2-H transfers. The 3,2-H shift forms buta-2,3-dienethial, which subsequently decomposes to CS + CH 3 C 2 H and HC 2 CH 2 radical (*) + HCS*, whereas the 2,3-H migration corresponds to α-carbene and ultimately leads to C

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Section: Resultsmentioning

confidence: 88%

Unimolecular Pyrolysis Mechanism of Thiophene and Furan: An Ab Initio Comparative Study

Hong-liang

et al. 2021

Energy Fuels

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“…The average energy deviation of 54 IMs between B3LYP/6-311G++(d,p) and CBS-QB3 is 0.46 kcal/mol. These data can be found in ref Supporting Information Part D. It is believed that the data calculated using UB3LYP/6-311G++(d,p) is credible.…”

Section: Computational Detailsmentioning

confidence: 83%

“…In this work, we adopted a density functional theory (DFT) method to study the pyrolysis mechanism of DBT. This method has been successfully applied in our study of BT and thiophene pyrolysis . The aim of this study is to identify the primary pyrolysis products and the dominating pyrolysis reaction pathway of DBT.…”

Section: Introductionmentioning

confidence: 99%

DFT Study on the Dibenzothiophene Pyrolysis Mechanism in Petroleum

Hong-liang

et al. 2019

Energy Fuels

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Dibenzothiophene sulfur (DBTs), the most stable sulfur species, is present in remarkable concentration in petroleum. Removal of DBTs is with profound significance in environmental protection. In this work, a density functional theory method was adopted to investigate the pyrolysis mechanism of DBT. It was found that the pyrolysis of DBT is possibly started by H-migration or S–C bond rupture. Three main reaction pathways were found. Two dominating pyrolysis pathways are through thiol intermediate pyrolysis and another is through DBT carbene direct dissociation. The dominating products are sulfur-free atoms, 2-ethynyl-benzothiophene, 3-ethynyl-benzothiophene, ethyne, biphenylene, and 1,8-dihydrocyclopentaindene, with a certain amount of benzothiophene and SH radicals. For DBT, BT, and thiophene, the most difficult step is the initial step. The highest energy barrier of DBT is about 17 kcal/mol higher than BT and thiophene, indicating that pyrolysis of DBT needs more intense reaction conditions. Thiophenes can be stable in extreme conditions, which is possibly caused by the high energy barrier of the initial reaction step. After the initial reaction steps, BT and DBT can be desulfurized more easily through thiol intermediates. Searching the catalyst that could lower the energy barrier of the initial step and the reagent that could convert thiophenes directly into thiols may be a potential desulfurization approach for thiophenes.

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“…On the other hand, the reaction mechanism of benzothiophene pyrolysis also has been extensively studied in the desulfurization of petroleum coke, which will not be discussed here. [46]…”

Section: Pyrolysismentioning

confidence: 99%

Organic Transformation of Benzothiophenes by C−S Bond Cleavage Beyond Reductive Desulfurization

Huang

2021

Eur J Org Chem

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As the analogues of indole bicyclic system, benzothiophenes are often overlooked in organic transformation, and synthetic methods developed mostly rely on the acidic protons at C2 or C3 position, known as CÀ H functionalization. Complementary to the structural modification of benzothiophenes, CÀ S bond cleavage can realize the skeleton reconstruction. Reduction of benzothiophenes always involves the CÀ S bond cleavage, especially in the hydrodesulfurization (HDS) of petroleum products. Beyond reductive desulfurization, although CÀ S bond cleavage of benzothiophenes has been achieved by diverse methodologies, there is no systematic review on such topic. Herein, transformation of benzothiophenes via CÀ S bond cleavage in organic synthesis will be presented along with briefly delineated mechanism.

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DFT Research on Benzothiophene Pyrolysis Reaction Mechanism

Cited by 29 publications

References 33 publications

Unimolecular Pyrolysis Mechanism of Thiophene and Furan: An Ab Initio Comparative Study

Unimolecular Pyrolysis Mechanism of Thiophene and Furan: An Ab Initio Comparative Study

DFT Study on the Dibenzothiophene Pyrolysis Mechanism in Petroleum

Organic Transformation of Benzothiophenes by C−S Bond Cleavage Beyond Reductive Desulfurization

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