phenyl(methylthio)ketene | 144043-56-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: phenyl(methylthio)ketene
• CAS: 144043-56-1
• 化学式: C₉H₈OS
• 分子量: 164.228
• InChiKey: AXLUQVDZZSRIMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  phenyl(methylthio)ketene 在 sodium perchlorate 、 水 作用下， 生成 <α-(methylthio)>benzenacetic acid
  参考文献：
  名称：

  Correlation of rates of uncatalyzed and hydroxide-ion catalyzed ketene hydration. A mechanistic application and solvent isotope effects on the uncatalyzed reaction

  摘要：

  一些酮烯的水合速率在中性和碱性溶液中使用闪光光解技术进行了测量，确定了它们的非催化反应速率常数k_uc和羟基离子催化反应速率常数k_HO。这些结果以及来自文献的额外数据发现，提供了非常好的相关性log k_uc= -3.21 + 1.14 log k_HO，涵盖了10个数量级的反应性，并包括31个酮烯。这种良好的相关性意味着非催化和羟基离子催化的酮烯水合反应通过类似的反应机制发生，对于羟基离子催化的过程已知涉及对酮烯的羰基碳原子的亲核攻击。另一方面，苯羟基酮烯的速率常数不符合这种相关性，这表明这些速率常数所基于的机械分配可能不正确。这些非催化酮烯水合反应的溶剂同位素效应较弱；大多数小于k_H/k_D= 2。据认为，这些同位素效应在很大程度上，如果不是完全地是次要的性质，并且它们与既涉及单个水分子对酮烯羰基碳原子的亲核攻击产生带电中间体的反应机制一致，也与通过涉及几个水分子的环状过渡态而避免这种中间体的机制一致。关键词：酮烯水合，速率相关性，亲核攻击，溶剂同位素效应，苯羟基酮烯。

  DOI：

  10.1139/v00-032

文献信息

• Solvent isotope effect on the hydroxide-ion-catalyzed hydration of ketenes in aqueous solution
  作者：J. Andraos、Y. Chiang、S.J. Eustace、A.J. Kresge、S.W. Paine、V.V. Popik、K. Sung

  DOI：10.1139/cjc-77-4-459

  日期：——

  Five ketenes, phenyl(ethyl)ketene, phenyl(methylthio)ketene, diphenylketene, pentafluorophenylketene, and 1-naphthylketene, were generated flash photolytically and solvent isotope effects (H2O vs. D2O) on their hydroxide-ion-catalyzed hydration in aqueous solution were determined. The values obtained are all weakly inverse and closely similar (k(HO)/k(DO) = 0.76-0.97), as expected for these fast, hydroxide-ion-consuming reactions, known to proceed by nucleophilic attack of hydroxide on the ketene carbonyl group. The characteristic magnitude of these isotope effects should prove useful in identifying new examples of this reaction.
• Flash photolytic generation and reactivity of phenyl(methylthio)ketene in aqueous solution
  作者：J. Jones、A. J. Kresge

  DOI：10.1021/jo00050a019

  日期：1992.11

  Methyl phenyldiazothioacetate is found to undergo Wolff rearrangement to phenyl(methylthio)ketene upon flash photolysis in aqueous solution and not to add water forming an ester enol as is the case with its oxygen analog, methyl phenyldiazoacetate. Hydration of phenyl(methylthio)ketene to alpha-(methylthio)phenylacetic acid occurs by both uncatalyzed and hydroxide ion catalyzed processes, whose rate constants, when compared to those for phenylketene, show the methylthio group to be rate-retarding. This is different from the effect of a hydroxyl group in the same position, which previous work had shown to be rate accelerating; possible reasons for this difference are advanced.