Phenol-Catalyzed Thione-Thiol Rearrangement of Xanthates and Modified Intermediate Neglect of Differential Overlap (MINDO/3) Analysis of the Reaction Mechanism

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概要

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• S-Alkyl dithiocarbonates (xanthates) of alkanols containing strained σ bonds underwent rearrangement to S, S-dialkyl dithiocarbonates, catalyzed by phenolic compounds. The reaction followed first-order kinetics and the rates were affected by the acidity of the phenols. The rate contants are proportional to the square of the concentration of phenol.The modified intermediate neglect of differential overlap (MINDO/3) geometry optimization indicates that S, S-dialkyl dithiocarbonate is ca. 9 kcal/mol more stable than O, S-dialkyl xanthate. The thione-thiol rearrangement and sulfide formation reactions were analyzed by MO simulations. The experimental results can be well reproduced by the MINDO/3 method rather than the modified neglect of diatomic overlap (MNDO) method. Based on these data, the reaction mechanism is discussed.

• 公益社団法人日本薬学会の論文
• 1992-10-25

著者

• 原野 一誠

  Faculty of Pharmaceutical Sciences, Kumamoto University

• 久野 拓造

  Faculty Of Pharmaceutical Sciences Kumamoto University

• 原野 一誠

  熊本大学 薬

• 原野 一誠

  熊本大学薬学部

• 久野 拓三

  熊本大学薬学部

• 清永 秀雄

  Faculty of Pharmaceutical Sciences, Kumamoto University

• 清永 秀雄

  Faculty Of Pharmaceutical Sciences Kumamoto University

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