S-methyl phenyldiazothioacetate | 144043-54-9

• 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: S-methyl phenyldiazothioacetate
• 英文别名: methyl phenyldiazothioacetate；S-methyl 2-diazo-2-phenylethanethioate
• CAS: 144043-54-9
• 化学式: C₉H₈N₂OS
• 分子量: 192.241
• InChiKey: YZZZZFBQUDIFLN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  44.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  S-methyl phenyldiazothioacetate 在 高氯酸 、 sodium perchlorate 作用下， 生成 <α-(methylthio)>benzenacetic acid
  参考文献：
  名称：

  Flash photolytic generation and reactivity of phenyl(methylthio)ketene in aqueous solution

  摘要：

  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.

  DOI：

  10.1021/jo00050a019
• 作为产物：
  描述：

  S-methyl 2-phenylethanethioate 在 4-二甲氨基吡啶 、 对甲苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙醚 为溶剂， 反应 60.0h， 生成 S-methyl phenyldiazothioacetate
  参考文献：
  名称：

  Flash photolytic generation and reactivity of phenyl(methylthio)ketene in aqueous solution

  摘要：

  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.

  DOI：

  10.1021/jo00050a019

文献信息

• Methylthio group migration in the acid-catalyzed hydrolysis of S-methyl phenyldiazothioacetate. Kinetics and mechanism of the reaction
  作者：J. Jones、A. J. Kresge

  DOI：10.1021/jo00062a005

  日期：1993.5

  The acid-catalyzed hydrolysis of S-methyl phenyldiazothioacetate, C6H5C(=N2)COSCH3, in aqueous solution at 25-degrees-C was found to occur with the hydronium ion isotope effect k(H)+/k(D)+ = 3.08 and to give a Bronsted relation, based on carboxylic acid catalysts, whose exponent is alpha = 0.70. This is taken to mean that the reaction occurs by rate-determining proton transfer to the diazo carbon atom. The principal product of the reaction, however, is alpha-(methylthio)-alpha-phenylacetic acid, C6H5CH(SCH3)-CO2H, which must be formed by 1,2-shift of the methylthio group. An argument is presented which suggests that this shift is accompanied by a rate acceleration and that it consequently must take place in the rate-determining step of the 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.