Synthesis of divinyl sulfide via addition of the hydrogen sulfide anion to acetylene in an alkaline metal hydroxide/DMSO superbasic system: A quantum-chemical insight

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• 作者：Nadezhda M. Vitkovskaya^a ; Vladimir B. Kobychev^a ; Anna D. Skitnevskaya^a ; Vladimir B. Orel^a ; Alexander S. Bobkov^a ; Andrey A. Zubarev^a ; Boris A. Trofimov^b ; ^{boris_trofimov@irioch.irk.ru}
• 关键词：Divinyl sulfide ; Acetylene ; Vinylation ; KOH/DMSO superbasic system ; Quantum chemical study
• 刊名：Tetrahedron Letters
• 出版年：2017
• 出版时间：4 January 2017
• 年：2017
• 卷：58
• 期：1
• 页码：92-96
• 全文大小：673 K
• 卷排序：58

文摘

Hydrosulfide addition to acetylene to give enthiolate is the rate-determining step. High S-nucleophilicity of enthiolate causes the selective formation of DVS. In the calculations, the NaOH·4DMSO and KOH·5DMSO models of the superbasic reaction center were employed. The H2S interaction with a superbase center instantly leads to the NaSH (KSH)·nDMSO complex. The rate-determining activation energies are close for both sodium and potassium hydrosulfides.