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Synthesis of organic carbonates over metal azolate frameworks via the carbonate interchange process using catechol carbonate and alcohols.

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Title: Synthesis of organic carbonates over metal azolate frameworks via the carbonate interchange process using catechol carbonate and alcohols.
Authors: Timofeeva, Maria N.1,2 (AUTHOR) timofeeva@catalysis.ru, Isaeva, Vera I.1,2 (AUTHOR) veraisaeva01@gmail.com, Arkhipov, Danil A.2 (AUTHOR), Prikhod'ko, Sergey A.1 (AUTHOR), Lukoyanov, Ivan A.1 (AUTHOR), Panchenko, Valentina N.1 (AUTHOR), Mel'gunova, Elena A.1 (AUTHOR), Jhung, Sung Hwa3 (AUTHOR)
Source: Applied Catalysis A: General. Oct2025, Vol. 706, pN.PAG-N.PAG. 1p.
Subjects: Microwave heating, Metal-organic frameworks, Chemical stability, Catalytic activity, Organic synthesis
Abstract: Metal-azolate frameworks (MAFs) is a promising sub-class of metal-organic frameworks (MOFs) due to their remarkable porosity, bifunctional acid-base character, and satisfactory thermal/chemical stability. Herein, synthesis of organic carbonates via the carbonate interchange reaction (CIR) using catechol carbonate (CC) and alcohols, namely cyclohexanol and hexanol-1 was demonstrated for the first time using MAF catalysts, such as MAF-4 (synonym ZIF-8), MAF-5, and MAF-6 obtained via synthesis under ambient conditions. CIR process was carried out at alcohol/CC molar ratio of 14.3, 10 wt% of MAFs (based on the weight of CC) and 60–110 °C under thermal heating and microwave (MW)-activation. The major CIR products were dicyclohexylcarbonate and dihexylcarbonate. Reaction rates depended on the strength of basic sites in the MAF materials and decreased in the order MAF-5 > MAF-6 > MAF-4. At the same time, reducing the channel size of MAF catalysts resulted in the decreased yields of organic carbonates in the following order MAF-6 > MAF-5 > MAF-4. The CIR process, assisted by microwave activation of the reaction mixture, offered several advantages over conventional thermal heating, including higher organic carbonate yields, shorter reaction times, and lower reaction temperatures. [Display omitted] • Organic carbonates were synthesized via carbonate interchange reaction. • Metal-azolate frameworks demonstrated good catalytic activity and selectivity. • Reaction rate depended on the strength of basic sites in the MAF materials. • The yield of organic carbonates was affected by a MAF's channel size. • MW-assisted synthesis showed superiority as compared with thermal heating. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
Description
Abstract:Metal-azolate frameworks (MAFs) is a promising sub-class of metal-organic frameworks (MOFs) due to their remarkable porosity, bifunctional acid-base character, and satisfactory thermal/chemical stability. Herein, synthesis of organic carbonates via the carbonate interchange reaction (CIR) using catechol carbonate (CC) and alcohols, namely cyclohexanol and hexanol-1 was demonstrated for the first time using MAF catalysts, such as MAF-4 (synonym ZIF-8), MAF-5, and MAF-6 obtained via synthesis under ambient conditions. CIR process was carried out at alcohol/CC molar ratio of 14.3, 10 wt% of MAFs (based on the weight of CC) and 60–110 °C under thermal heating and microwave (MW)-activation. The major CIR products were dicyclohexylcarbonate and dihexylcarbonate. Reaction rates depended on the strength of basic sites in the MAF materials and decreased in the order MAF-5 > MAF-6 > MAF-4. At the same time, reducing the channel size of MAF catalysts resulted in the decreased yields of organic carbonates in the following order MAF-6 > MAF-5 > MAF-4. The CIR process, assisted by microwave activation of the reaction mixture, offered several advantages over conventional thermal heating, including higher organic carbonate yields, shorter reaction times, and lower reaction temperatures. [Display omitted] • Organic carbonates were synthesized via carbonate interchange reaction. • Metal-azolate frameworks demonstrated good catalytic activity and selectivity. • Reaction rate depended on the strength of basic sites in the MAF materials. • The yield of organic carbonates was affected by a MAF's channel size. • MW-assisted synthesis showed superiority as compared with thermal heating. [ABSTRACT FROM AUTHOR]
ISSN:0926860X
DOI:10.1016/j.apcata.2025.120489