Direct carboxylation of thiophene with CO2 in the solvent-free carboxylate-carbonate molten medium: Experimental and mechanistic insights

doi:10.1016/j.cjche.2022.09.003

中国化学工程学报 ›› 2022, Vol. 50 ›› Issue (10): 264-282.DOI: 10.1016/j.cjche.2022.09.003

• Catalysis, Kinetics and Reaction Engineering • 上一篇下一篇

Direct carboxylation of thiophene with CO₂ in the solvent-free carboxylate-carbonate molten medium: Experimental and mechanistic insights

Qingjun Zhang¹, Pengyuan Shi¹, Xigang Yuan^1,2, Youguang Ma^1,2, Aiwu Zeng^1,2

1 State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China;
2 Chemical Engineering Research Center, Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300350, China

收稿日期:2022-04-14 修回日期:2022-09-14 出版日期:2022-10-28 发布日期:2023-01-04
通讯作者: Aiwu Zeng,E-mail:awzeng@tju.edu.cn

Direct carboxylation of thiophene with CO₂ in the solvent-free carboxylate-carbonate molten medium: Experimental and mechanistic insights

Qingjun Zhang¹, Pengyuan Shi¹, Xigang Yuan^1,2, Youguang Ma^1,2, Aiwu Zeng^1,2

1 State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China;
2 Chemical Engineering Research Center, Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300350, China

Received:2022-04-14 Revised:2022-09-14 Online:2022-10-28 Published:2023-01-04
Contact: Aiwu Zeng,E-mail:awzeng@tju.edu.cn

摘要/Abstract

摘要： A feasible synthesis route is devised for realizing direct carboxylation of thiophene and CO₂ in a relatively mild solvent-free carboxylate-assisted carbonate (semi) molten medium. The effects of reaction factors on product yield are investigated, and the phase behavior analysis of the reaction medium is detected through the thermal characterization techniques. Product yield varies with the alternative carboxylate co-salts, which is attributed to the difference in deprotonation capacity caused by the base effect within the system. Besides, the detailed mechanism of this carbonate-promoted carboxylation reaction is studied, including two consecutive steps of the formation of carbanion through breaking the C—H bond(s) via the carbonate and the nucleophile attacking the weak electrophile CO₂ to form C—C bond(s). The activation energy barrier in C—H activation step is higher than the following CO₂ insertion step whether for the formation of the mono- and/or di-carboxylate, which is in good agreement with that of kinetic isotope effect (KIE) experiments, indicating that the C—H deprotonation is slow and the forming presumed carbanion reacts rapidly with CO₂. Both the activation energy barriers in deprotonation steps are the minimal for the cesium cluster system since there have the weak the cesium Cs-heteroatom S (thiophene) and Cs-the broken proton interactions compared to the K₂CO₃ system, which is likely to enhance the acidity of C—H bond, lowering the C—H activation barrier. Besides, these mechanistic insights are further assessed by investigating base and C—H substrate effects via replacing Cs₂CO₃ with K₂CO₃ and furoate (1a) with thiophene monocarboxylate (1b) or benzoate (1c).

关键词: Inert C—H bond, Carboxylation, Solvent-free medium, Base effect, Density functional theory (DFT) study

Abstract: A feasible synthesis route is devised for realizing direct carboxylation of thiophene and CO₂ in a relatively mild solvent-free carboxylate-assisted carbonate (semi) molten medium. The effects of reaction factors on product yield are investigated, and the phase behavior analysis of the reaction medium is detected through the thermal characterization techniques. Product yield varies with the alternative carboxylate co-salts, which is attributed to the difference in deprotonation capacity caused by the base effect within the system. Besides, the detailed mechanism of this carbonate-promoted carboxylation reaction is studied, including two consecutive steps of the formation of carbanion through breaking the C—H bond(s) via the carbonate and the nucleophile attacking the weak electrophile CO₂ to form C—C bond(s). The activation energy barrier in C—H activation step is higher than the following CO₂ insertion step whether for the formation of the mono- and/or di-carboxylate, which is in good agreement with that of kinetic isotope effect (KIE) experiments, indicating that the C—H deprotonation is slow and the forming presumed carbanion reacts rapidly with CO₂. Both the activation energy barriers in deprotonation steps are the minimal for the cesium cluster system since there have the weak the cesium Cs-heteroatom S (thiophene) and Cs-the broken proton interactions compared to the K₂CO₃ system, which is likely to enhance the acidity of C—H bond, lowering the C—H activation barrier. Besides, these mechanistic insights are further assessed by investigating base and C—H substrate effects via replacing Cs₂CO₃ with K₂CO₃ and furoate (1a) with thiophene monocarboxylate (1b) or benzoate (1c).

Key words: Inert C—H bond, Carboxylation, Solvent-free medium, Base effect, Density functional theory (DFT) study

Qingjun Zhang, Pengyuan Shi, Xigang Yuan, Youguang Ma, Aiwu Zeng. Direct carboxylation of thiophene with CO₂ in the solvent-free carboxylate-carbonate molten medium: Experimental and mechanistic insights[J]. 中国化学工程学报, 2022, 50(10): 264-282.

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Direct carboxylation of thiophene with CO₂ in the solvent-free carboxylate-carbonate molten medium: Experimental and mechanistic insights

Direct carboxylation of thiophene with CO₂ in the solvent-free carboxylate-carbonate molten medium: Experimental and mechanistic insights

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