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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]
Copyright of Applied Catalysis A: General is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Label: Title
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  Data: Synthesis of organic carbonates over metal azolate frameworks via the carbonate interchange process using catechol carbonate and alcohols.
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  Data: <searchLink fieldCode="AR" term="%22Timofeeva%2C+Maria+N%2E%22">Timofeeva, Maria N.</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<i> timofeeva@catalysis.ru</i><br /><searchLink fieldCode="AR" term="%22Isaeva%2C+Vera+I%2E%22">Isaeva, Vera I.</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<i> veraisaeva01@gmail.com</i><br /><searchLink fieldCode="AR" term="%22Arkhipov%2C+Danil+A%2E%22">Arkhipov, Danil A.</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Prikhod'ko%2C+Sergey+A%2E%22">Prikhod'ko, Sergey A.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Lukoyanov%2C+Ivan+A%2E%22">Lukoyanov, Ivan A.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Panchenko%2C+Valentina+N%2E%22">Panchenko, Valentina N.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Mel'gunova%2C+Elena+A%2E%22">Mel'gunova, Elena A.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Jhung%2C+Sung+Hwa%22">Jhung, Sung Hwa</searchLink><relatesTo>3</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22Applied+Catalysis+A%3A+General%22">Applied Catalysis A: General</searchLink>. Oct2025, Vol. 706, pN.PAG-N.PAG. 1p.
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  Data: <searchLink fieldCode="DE" term="%22Microwave+heating%22">Microwave heating</searchLink><br /><searchLink fieldCode="DE" term="%22Metal-organic+frameworks%22">Metal-organic frameworks</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+stability%22">Chemical stability</searchLink><br /><searchLink fieldCode="DE" term="%22Catalytic+activity%22">Catalytic activity</searchLink><br /><searchLink fieldCode="DE" term="%22Organic+synthesis%22">Organic synthesis</searchLink>
– Name: Abstract
  Label: Abstract
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  Data: 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]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Applied Catalysis A: General is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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      – Type: doi
        Value: 10.1016/j.apcata.2025.120489
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      – Code: eng
        Text: English
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        Type: general
      – SubjectFull: Metal-organic frameworks
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      – SubjectFull: Chemical stability
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      – SubjectFull: Catalytic activity
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      – SubjectFull: Organic synthesis
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      – TitleFull: Synthesis of organic carbonates over metal azolate frameworks via the carbonate interchange process using catechol carbonate and alcohols.
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              Text: Oct2025
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