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High-Temperature Batch and Continuous-Flow Transesterification of Alkyl and Enol Esters with Glycerol and Its Acetal Derivatives

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    Research Article

    High-Temperature Batch and Continuous-Flow Transesterification of Alkyl and Enol Esters with Glycerol and Its Acetal Derivatives
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    • Roberto Calmanti
      Roberto Calmanti
      Dipartimento di Scienze Molecolari e Nanosistemi dell’Università Ca’ Foscari Venezia, Via Torino 155, 30172 − Venezia Mestre, Italy
      More by Roberto Calmanti
    • Manuele Galvan
      Manuele Galvan
      Dipartimento di Scienze Molecolari e Nanosistemi dell’Università Ca’ Foscari Venezia, Via Torino 155, 30172 − Venezia Mestre, Italy
      More by Manuele Galvan
    • Emanuele Amadio
      Emanuele Amadio
      Dipartimento di Scienze Molecolari e Nanosistemi dell’Università Ca’ Foscari Venezia, Via Torino 155, 30172 − Venezia Mestre, Italy
      More by Emanuele Amadio
    • Alvise Perosa
      Alvise Perosa
      Dipartimento di Scienze Molecolari e Nanosistemi dell’Università Ca’ Foscari Venezia, Via Torino 155, 30172 − Venezia Mestre, Italy
      More by Alvise Perosa
      Orcidhttp://orcid.org/0000-0003-4544-8709
    • Maurizio Selva*
      Maurizio Selva
      Dipartimento di Scienze Molecolari e Nanosistemi dell’Università Ca’ Foscari Venezia, Via Torino 155, 30172 − Venezia Mestre, Italy
      *E-mail: [email protected]. Web: http://www.unive.it/persone/selva.
      More by Maurizio Selva
      Orcidhttp://orcid.org/0000-0002-9986-2393
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    ACS Sustainable Chemistry & Engineering

    Cite this: ACS Sustainable Chem. Eng. 2018, 6, 3, 3964–3973
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    https://doi.org/10.1021/acssuschemeng.7b04297
    Published January 15, 2018
    Copyright © 2018 American Chemical Society
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    Abstract

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    A new procedure for the transesterification of alkyl acetates and formates with model glycerol acetals (GAs: Solketal and glycerol formal) was explored in the absence of any catalysts at 180–275 °C. Highly selective transformations occurred in both batch and continuous-flow (CF) modes; particularly, the enol derivative isopropenyl acetate (iPAc) was the best performing reactant by which quantitative acetylation reactions were achieved with yields on GAs acetates >95%. An excess acylating agent was necessary (2–20 molar equivs), but the unconverted ester was fully recovered and could be reused. The reaction plausibly involved multiple mechanisms where either the electrophilic and the nucleophilic activation of reagents took place through both traces of acetic acid (formed in situ by the hydrolysis of esters) and the autoprotolysis of GAs. iPAc confirmed a superior performance than other esters also for the high-temperature conversion of glycerol; in this case, although acylation and acetalization processes were simultaneously possible, conditions were optimized to achieve the exhaustive transesterification of glycerol to triacetin, in both batch and CF modes. Triacetin was isolated in 99% yield.

    Copyright © 2018 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.7b04297.

    • Description of batch and continuous-flow apparatus and full spectral characterization (1H, 13C NMR, and MS) of compounds. (PDF)

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    Cited By

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    This article is cited by 26 publications.

    1. Davide Rigo, Daniele Polidoro, Lorenzo Marcuzzo, Alvise Perosa, Maurizio Selva. Isopropenyl Acetate for the Continuous-Flow Synthesis of Triacetin, Solketal Acetate, and Allyl Acetate from Pure or Crude Glycerol. ACS Sustainable Chemistry & Engineering 2023, 11 (34) , 12602-12613. https://doi.org/10.1021/acssuschemeng.3c02197
    2. Romaric Gérardy, Damien P. Debecker, Julien Estager, Patricia Luis, Jean-Christophe M. Monbaliu. Continuous Flow Upgrading of Selected C2–C6 Platform Chemicals Derived from Biomass. Chemical Reviews 2020, 120 (15) , 7219-7347. https://doi.org/10.1021/acs.chemrev.9b00846
    3. Shilpi Gupta, Smritilekha Bera, Dhananjoy Mondal. Nascent-HBr-Catalyzed Removal of Orthogonal Protecting Groups in Aqueous Surfactants. The Journal of Organic Chemistry 2020, 85 (4) , 2635-2645. https://doi.org/10.1021/acs.joc.9b02561
    4. Davide Rigo, Giulia Fiorani, Alvise Perosa, Maurizio Selva. Acid-Catalyzed Reactions of Isopropenyl Esters and Renewable Diols: A 100% Carbon Efficient Transesterification/Acetalization Tandem Sequence, from Batch to Continuous Flow. ACS Sustainable Chemistry & Engineering 2019, 7 (23) , 18810-18818. https://doi.org/10.1021/acssuschemeng.9b03359
    5. Lisa Cattelan, Giulia Fiorani, Alvise Perosa, Thomas Maschmeyer, Maurizio Selva. Two-Step Synthesis of Dialkyl Carbonates through Transcarbonation and Disproportionation Reactions Catalyzed by Calcined Hydrotalcites. ACS Sustainable Chemistry & Engineering 2018, 6 (7) , 9488-9497. https://doi.org/10.1021/acssuschemeng.8b02106
    6. Shiyu Guo, Jiawei Hua, Zhongxue Dai, Zhao Yang, Zheng Fang, Kai Guo. Two-Step Continuous Synthesis of Dicarbonyl Indoles via I2/DMSO-Promoted Oxidative Coupling: A Green and Practical Approach to Valuable Diketones from Aryl Acetaldehydes. ACS Sustainable Chemistry & Engineering 2018, 6 (6) , 7979-7988. https://doi.org/10.1021/acssuschemeng.8b01339
    7. Surachai Karnjanakom, Panya Maneechakr, Irwan Kurnia, Asep Bayu, Obie Farobie, Chanatip Samart, Suwadee Kongparakul, Guoqing Guan. Sustainable upgrading of crude glycerol via ultrasound-reinforced bio-refinery process with oxygen–nitrogen subsistence: Co-application of reusable heterogeneous catalyst. Energy Conversion and Management 2024, 310 , 118477. https://doi.org/10.1016/j.enconman.2024.118477
    8. Giulia Fiorani, Alvise Perosa, Maurizio Selva. Sustainable valorisation of renewables through dialkyl carbonates and isopropenyl esters. Green Chemistry 2023, 25 (13) , 4878-4911. https://doi.org/10.1039/D2GC04145F
    9. Gunjan, Radhika Singh, Subhalaxmi Pradhan. Valorization of Byproducts Produced During Extraction and Purification of Biodiesel. 2023, 333-366. https://doi.org/10.1002/9781119829522.ch12
    10. Davide Rigo, Anthony F. Masters, Thomas Maschmeyer, Maurizio Selva, Giulia Fiorani. Isopropenyl Esters (iPEs) in Green Organic Synthesis. Chemistry – A European Journal 2022, 28 (40) https://doi.org/10.1002/chem.202200431
    11. Manas Barik, Jyotiranjan Mishra, Shilpa Dabas, Eswaran Chinnaraja, Saravanan Subramanian, Palani S. Subramanian. Modified boehmite: a choice of catalyst for the selective conversion of glycerol to five-membered dioxolane. New Journal of Chemistry 2022, 46 (2) , 695-703. https://doi.org/10.1039/D1NJ04860K
    12. Yuanyuan Jiang, Ruru Zhou, Huaiyuan Zhao, Boyong Ye, Yihua Long, Zhengbao Wang, Zhaoyin Hou. A highly active and stable organic-inorganic combined solid acid for the transesterification of glycerol under mild conditions. Chinese Journal of Catalysis 2021, 42 (10) , 1772-1781. https://doi.org/10.1016/S1872-2067(21)63811-1
    13. Gitanjali Pradhan, Yogesh C. Sharma. A greener and cheaper approach towards synthesis of glycerol carbonate from bio waste glycerol using CaO–TiO2 Nanocatalysts. Journal of Cleaner Production 2021, 315 , 127860. https://doi.org/10.1016/j.jclepro.2021.127860
    14. 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
    15. Senri Hayashi, Yuya Tachibana, Naoto Tabata, Ken-ichi Kasuya. Chemically recyclable bio-based polyester composed of bifuran and glycerol acetal. European Polymer Journal 2021, 145 , 110242. https://doi.org/10.1016/j.eurpolymj.2020.110242
    16. Guido Gambacorta, James S Sharley, Ian R Baxendale. A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries. Beilstein Journal of Organic Chemistry 2021, 17 , 1181-1312. https://doi.org/10.3762/bjoc.17.90
    17. András Gy. Németh, Renáta Szabó, György Orsy, István M. Mándity, György M. Keserű, Péter Ábrányi-Balogh. Continuous-Flow Synthesis of Thioureas, Enabled by Aqueous Polysulfide Solution. Molecules 2021, 26 (2) , 303. https://doi.org/10.3390/molecules26020303
    18. Carlotta Campalani, Francesco Chioggia, Emanuele Amadio, Michele Gallo, Flavio Rizzolio, Maurizio Selva, Alvise Perosa. Supercritical CO2 extraction of natural antibacterials from low value weeds and agro-waste. Journal of CO2 Utilization 2020, 40 , 101198. https://doi.org/10.1016/j.jcou.2020.101198
    19. Davide Rigo, Roberto Calmanti, Alvise Perosa, Maurizio Selva. A transesterification–acetalization catalytic tandem process for the functionalization of glycerol: the pivotal role of isopropenyl acetate. Green Chemistry 2020, 22 (16) , 5487-5496. https://doi.org/10.1039/D0GC01775B
    20. Saurabh Kumar, Nagabhatla Viswanadham, Sandeep K. Saxena, Arumugam Selvamani, Jitendra Diwakar, Ala’a H. Al-Muhtaseb. Single-pot template-free synthesis of a glycerol-derived C–Si–Zr mesoporous composite catalyst for fuel additive production. New Journal of Chemistry 2020, 44 (20) , 8254-8263. https://doi.org/10.1039/D0NJ00523A
    21. Simone Cailotto, Matteo Negrato, Salvatore Daniele, Rafael Luque, Maurizio Selva, Emanuele Amadio, Alvise Perosa. Carbon dots as photocatalysts for organic synthesis: metal-free methylene–oxygen-bond photocleavage. Green Chemistry 2020, 22 (4) , 1145-1149. https://doi.org/10.1039/C9GC03811F
    22. Amadio Emanuele, Simone Cailotto, Carlotta Campalani, Lorenzo Branzi, Carlotta Raviola, Davide Ravelli, Elti Cattaruzza, Enrico Trave, Alvise Benedetti, Maurizio Selva, Alvise Perosa. Precursor-Dependent Photocatalytic Activity of Carbon Dots. Molecules 2020, 25 (1) , 101. https://doi.org/10.3390/molecules25010101
    23. Vanesa Domínguez-Barroso, Concepción Herrera, María Ángeles Larrubia, Rafael González-Gil, Marina Cortés-Reyes, Luis J. Alemany. Continuous-Flow Process for Glycerol Conversion to Solketal Using a Brönsted Acid Functionalized Carbon-Based Catalyst. Catalysts 2019, 9 (7) , 609. https://doi.org/10.3390/catal9070609
    24. Roberto Calmanti, Emanuele Amadio, Alvise Perosa, Maurizio Selva. Reaction of Glycerol with Trimethyl Orthoformate: Towards the Synthesis of New Glycerol Derivatives. Catalysts 2019, 9 (6) , 534. https://doi.org/10.3390/catal9060534
    25. Rajender S. Varma, Christophe Len. Glycerol valorization under continuous flow conditions-recent advances. Current Opinion in Green and Sustainable Chemistry 2019, 15 , 83-90. https://doi.org/10.1016/j.cogsc.2018.11.003
    26. Andrey A. Smirnov, Svetlana A. Selishcheva, Vadim A. Yakovlev. Acetalization Catalysts for Synthesis of Valuable Oxygenated Fuel Additives from Glycerol. Catalysts 2018, 8 (12) , 595. https://doi.org/10.3390/catal8120595
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    ACS Sustainable Chemistry & Engineering

    Cite this: ACS Sustainable Chem. Eng. 2018, 6, 3, 3964–3973
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acssuschemeng.7b04297
    Published January 15, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

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