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<p>The interaction of mercaptoethanol with propargyl chloride leads to the formation of a mixture of products. After completion of the reaction (25–70&#xa0;°C, 3–18&#xa0;h), four main compounds were obtained: 6-methyl-2,3-dihydro-1,4-oxathiin (<b>3</b>) (up to 45%), (Z)-2,2’-(prop-1-ene-1,2-diylbis(sulfanediyl))bis(ethan-1-ol) (<b>4</b><i>Z</i>) (up to 36%), (E)-2,2’-(prop-1-ene-1,2-diylbis(sulfanediyl))bis(ethan-1-ol) (<b>4</b><i>E</i>) (up to 28%), 2,2’-(prop-2-ene-1,2-diylbis(sulfanediyl))bis(ethan-1-ol) (<b>5</b>) (up to 44%). Quantum chemical modeling of the mechanism of interaction between propargyl chloride and mercaptoethanol in the hydrazine hydrate-KOH system was carried out using the combined approach CCSD(T)/6–31 + G*//B3LYP/6-311 + + G**. It was shown that the initial step of the reaction is an attack by the hydroxyethanethiolate anion of the reagent molecule on the chlorine-substituted carbon atom of propargyl chloride. This is followed by isomerization of the acetylene product to a derivative with cumulated bonds, which then undergoes heterocyclization to 6-methyl-2,3-dihydro-1,4-oxathiine as a result of a nucleophilic attack by the hydroxyl group on the sp-hybridized carbon atom of the allene fragment. The formation of functionalized unsaturated acyclic diols occurs as a result of an attack by the thiolate anion of a second mercaptoethanol molecule on the carbon atom of the allene derivative.</p>

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Quantum chemical study of organic reaction mechanisms. xiv*1. interaction of propargyl chloride with mercaptoethanol in the system hydrazine hydrate-koh

  • 期刊论文

  • 发表日期：

    2026年3月3日

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  • Elena A. Chirkina,
  • Valentina A. Grabelnykh,
  • Nikolay A. Korchevin,
  • Alexandr I. Albanov,
  • Leonid B. Krivdin,
  • Igor B. Rozentsveig

摘要

The interaction of mercaptoethanol with propargyl chloride leads to the formation of a mixture of products. After completion of the reaction (25–70 °C, 3–18 h), four main compounds were obtained: 6-methyl-2,3-dihydro-1,4-oxathiin (3) (up to 45%), (Z)-2,2’-(prop-1-ene-1,2-diylbis(sulfanediyl))bis(ethan-1-ol) (4Z) (up to 36%), (E)-2,2’-(prop-1-ene-1,2-diylbis(sulfanediyl))bis(ethan-1-ol) (4E) (up to 28%), 2,2’-(prop-2-ene-1,2-diylbis(sulfanediyl))bis(ethan-1-ol) (5) (up to 44%). Quantum chemical modeling of the mechanism of interaction between propargyl chloride and mercaptoethanol in the hydrazine hydrate-KOH system was carried out using the combined approach CCSD(T)/6–31 + G*//B3LYP/6-311 + + G**. It was shown that the initial step of the reaction is an attack by the hydroxyethanethiolate anion of the reagent molecule on the chlorine-substituted carbon atom of propargyl chloride. This is followed by isomerization of the acetylene product to a derivative with cumulated bonds, which then undergoes heterocyclization to 6-methyl-2,3-dihydro-1,4-oxathiine as a result of a nucleophilic attack by the hydroxyl group on the sp-hybridized carbon atom of the allene fragment. The formation of functionalized unsaturated acyclic diols occurs as a result of an attack by the thiolate anion of a second mercaptoethanol molecule on the carbon atom of the allene derivative.