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A mechanism of alkali metal carbonates catalysing the synthesis of β-hydroxyethyl sulfide with mercaptan and ethylene carbonate

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Abstract

The reaction of β-hydroxyethylation is essential to the current practice of organic chemistry. Here, we proposed a new and green route to synthesize 2-hydroxyethyl n-alkyl sulfide with n-alkyl mercaptan and ethylene carbonate (EC) in the presence of alkali carbonates as catalysts and revealed the mechanism by experiments and theoretical calculations. The reaction reported proceeds rapidly with high yields when it is performed at 120 °C and the catalytic loading is ∼1 mol%. This protocol is applicable to other mercaptans to synthesize the corresponding β-hydroxyethyl sulfide. Density functional theory-based calculations show the energy profile for the reaction pathway. The rate-determining step is the ring-opening of EC. A negatively charged O atom of alkali carbonates approaches the S atom of –SH under the influence of hydrogen bonds. An activated S atom that carries more negative charge serves as a nucleophilic reagent and assists in the ring-opening of EC by reducing the Mayer bond orders of the C1–O1 bond in EC. Alkali cations also contribute to the C1–O1 bond cleavage. The energy barrier for the ring-opening of EC decreases with the decrease of electronegativity of alkali cations. Subsequent transference of a H atom leads to the formation of β-hydroxyethyl sulfide, the dissociation of CO2 and the reduction of K2CO3.

Graphical abstract: A mechanism of alkali metal carbonates catalysing the synthesis of β-hydroxyethyl sulfide with mercaptan and ethylene carbonate

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Publication details

The article was received on 21 Aug 2019, accepted on 07 Oct 2019 and first published on 10 Oct 2019


Article type: Paper
DOI: 10.1039/C9OB01816F
Org. Biomol. Chem., 2019, Advance Article

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    A mechanism of alkali metal carbonates catalysing the synthesis of β-hydroxyethyl sulfide with mercaptan and ethylene carbonate

    D. Liu, T. Thomas, H. Gong, F. Li, Q. Li, L. Song, T. Azhagan, H. Jiang and M. Yang, Org. Biomol. Chem., 2019, Advance Article , DOI: 10.1039/C9OB01816F

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