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Two-Step Synthesis of Dialkyl Carbonates through Transcarbonation and Disproportionation Reactions Catalyzed by Calcined Hydrotalcites

Cite this: ACS Sustainable Chem. Eng. 2018, 6, 7, 9488–9497
Publication Date (Web):May 30, 2018
https://doi.org/10.1021/acssuschemeng.8b02106
Copyright © 2018 American Chemical Society

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    Abstract

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    A two-step methodology was implemented to prepare dialkyl carbonates from both primary and secondary alcohols, including glycerol acetals, tetrahydrofurfuryl alcohol, and cyclohexanol. Accordingly, alcohols were initially subjected to a batch transcarbonation (carbonate interchange) reaction with the nontoxic dimethyl carbonate, providing the corresponding asymmetrical methyl alkyl carbonates (ROCO2Me). These compounds were then used as reactants for a continuous-flow (CF) disproportionation reaction, producing the corresponding symmetrical dialkyl carbonates (ROCO2R). Although transcarbonation and dismutation took place at different operating temperatures (90 and 180–275 °C, respectively), both reactions were catalyzed by the same heterogeneous Mg/Al mixed oxides catalyst, obtained upon calcination of commercially available hydrotalcites (HTs). Yields and selectivities for methyl alkyl carbonates were excellent, in the range of 93–96% and 95–98%, respectively. CF-disproportionation reactions were strongly affected by the nature/structure of reactants; nevertheless, they provided the corresponding dialkyl carbonates with selectivities and productivities up to 92% and 164 mgprod·(gcat·min)−1, respectively. Overall, the reported methodology displays attractive sustainability features, including a straightforward upgrade of biomass derivatives, development of a continuous-flow intensified process, and improved catalyst recycle and products’ purification, while disclosing stimulating perspectives for further investigations on the reaction mechanism and on the role of HTs as catalyst precursors for the synthesis of organic carbonates.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.8b02106.

    • Detailed description of batch and continuous-flow apparatus and full spectral characterization (1H, 13C NMR, and MS) of the synthesized compounds (PDF)

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    Cited By

    This article is cited by 4 publications.

    1. Maurizio Selva, Alvise Perosa, Daily Rodríguez-Padrón, Rafael Luque. Applications of Dimethyl Carbonate for the Chemical Upgrading of Biosourced Platform Chemicals. ACS Sustainable Chemistry & Engineering 2019, 7 (7) , 6471-6479. https://doi.org/10.1021/acssuschemeng.9b00464
    2. Davide Rigo, Roberto Calmanti, Alvise Perosa, Maurizio Selva, Giulia Fiorani. Diethylene Glycol/NaBr Catalyzed CO 2 Insertion into Terminal Epoxides: From Batch to Continuous Flow. ChemCatChem 2021, 13 (8) , 2005-2016. https://doi.org/10.1002/cctc.202002010
    3. Tiefeng Wang, Xu Li, Xiaosheng Zhang, Jinxiang Dong. Rapid Synthesis of Asymmetric Methyl-Alkyl Carbonates Catalyzed by α-KMgPO4 in a Sealed-Vessel Reactor Monowave 50. Catalysts 2021, 11 (4) , 499. https://doi.org/10.3390/catal11040499
    4. Giulia Fiorani, Claudia Crestini, Maurizio Selva, Alvise Perosa. Advancements and Complexities in the Conversion of Lignocellulose Into Chemicals and Materials. Frontiers in Chemistry 2020, 8 https://doi.org/10.3389/fchem.2020.00797

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