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Reaction Mechanisms in the Direct Carboxylation of Alcohols for the Synthesis of Acyclic Carbonates

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Abstract

Dialkylcarbonates, (RO)2CO, can be prepared from alcohols and CO2. Such reaction is clean (water is the co-product) but thermodynamically disfavored. In principle, the reaction mechanism of formation of carbonates requires the acid–base activation of alcohols. Existing data support that the first step is the formation of the alkoxo group RO− that reacts with CO2 to give the hemicarbonate moiety ROC(O)O−. The latter converts into the relevant carbonate (RO)2CO following different pathways depending on the catalyst used. DFT calculations have been used in a few cases to support the reaction mechanism. Transition states relevant to various mechanistic scenarios have been identified. The results indicated that the relative energies of these transition states depend on the nature of the alkyl group and the molecularity of the reactive step. Organic catalysts, homogeneous-, heterogenized- and heterogeneous-metal systems are discussed in this paper and the known relevant mechanisms compared. Water represents a serious limitation to equilibrium shift to the right and can affect the catalysts. Techniques used to remove water are also discussed.

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Acknowledgments

One of us (AA) thanks TOTAL for a partial financial support to part of the present work.

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Authors and Affiliations

  1. CIRCC, Via Celso Ulpiani 27, 70126, Bari, Italy

    Michele Aresta, Angela Dibenedetto & Antonella Angelini

  2. Department of Chemistry, University of Bari, Via Orabona 4, 70125, Bari, Italy

    Angela Dibenedetto & Antonella Angelini

  3. Research Center for Natural Sciences, HAS, Magyar Tudosok Korutja 2, Budapest, H-1117, Hungary

    Imre Pápai

Authors
  1. Michele Aresta
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  2. Angela Dibenedetto
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  3. Antonella Angelini
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  4. Imre Pápai
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Correspondence to Michele Aresta.

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Aresta, M., Dibenedetto, A., Angelini, A. et al. Reaction Mechanisms in the Direct Carboxylation of Alcohols for the Synthesis of Acyclic Carbonates. Top Catal 58, 2–14 (2015). https://doi.org/10.1007/s11244-014-0342-0

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