9-hydroxy-N,N-dimethylfluorene-9-carbothioamide | 181644-24-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9-hydroxy-N,N-dimethylfluorene-9-carbothioamide
• CAS: 181644-24-6
• 化学式: C₁₆H₁₅NOS
• 分子量: 269.367
• InChiKey: IJCOITVFPJPLCX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  55.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  9-hydroxy-N,N-dimethylfluorene-9-carbothioamide 在 氯化亚砜 、 sodium carbonate 、 臭氧 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 96.0h， 生成 9-Chloro-9H-fluorene-9-carboxylic acid dimethylamide
  参考文献：
  名称：

  Reaction of Benzylic α-Hydroxythioamides with Thionyl Chloride

  摘要：

  9-Hydroxy-9-(N,N-dimethylthiocarbamyl)fluorene,4, reacts very rapidly with 1 equiv of thionyl chloride to give the corresponding alpha-chlorothioamide derivative, 2. However reaction of 4 with 2 equiv of thionyl chloride gives the desulfurized product 9-chloro-9-(N,N-dimethylcarbamyl)fluorene 6. This unusual desulfurization reaction, which is neither completely general nor completely understood at the present time, occurs less readily than initial formation of the alpha-chlorothioamide. The a-chlorothioamide 2 is highly reactive in hydroxylic solvents. The substantially less reactive alpha-chloroamide 6 undergoes reaction in hydroxylic solvents via the intermediacy of the 9-(N,N-dimethylcarbamyl)-9-fluorenyl cation, 15, at rates comparable to those of the or-H analogue, 9-chlorofluorene, 14. Computational studies indicate that the cl-carbonyl cation 15 prefers a conformation in which the carbonyl group is rotated 90 degrees with respect to the fluorenyl system. The relatively rapid rate of solvolysis of 6 is attributed to relief of ground-state strain as the cation 15 forms, as well as delocalization involving the fluorene system. Carbonyl conjugation as a cation-stabilizing feature does not appear to operate in the alpha-carbonyl cation 15.

  DOI：

  10.1021/jo971590v
• 作为产物：
  描述：

  9-芴酮 、 N,N-二甲基硫代甲酰胺 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以79%的产率得到9-hydroxy-N,N-dimethylfluorene-9-carbothioamide
  参考文献：
  名称：

  Characterization and Reactivity of the [N,N-Dimethyl(thioformamidyl)]-9-fluorenyl Cation¹

  摘要：

  The 9-[N,N-dimethyl(thioformamidyl)]-9-fluorenyl cation was generated under stable ion conditions and characterized by UV/visible and NMR spectroscopy and methanol trapping reactions. The same cation was generated by laser excitation of the appropriate chloride precursor in 2,2,2-trifluoroethanol, and rate constants for nucleophilic quenching by alcohols and several anions were measured. The quenching data for this and other 9-fluorenyl cations demonstrate that the reactivity decreases for 9-substituents in the order H > carbomethoxy > N,N-dimethyl(thioformamidyl), demonstrating that the thioamidyl group imparts substantial kinetic stabilization to an adjacent cationic center. Both steric and electronic factors are suggested to be important in determining this reactivity order.

  DOI：

  10.1021/jo941685m

文献信息

• Reaction of Benzylic α-Hydroxythioamides with Thionyl Chloride
  作者：Xavier Creary、Jennifer Tricker

  DOI：10.1021/jo971590v

  日期：1998.7.1

  9-Hydroxy-9-(N,N-dimethylthiocarbamyl)fluorene,4, reacts very rapidly with 1 equiv of thionyl chloride to give the corresponding alpha-chlorothioamide derivative, 2. However reaction of 4 with 2 equiv of thionyl chloride gives the desulfurized product 9-chloro-9-(N,N-dimethylcarbamyl)fluorene 6. This unusual desulfurization reaction, which is neither completely general nor completely understood at the present time, occurs less readily than initial formation of the alpha-chlorothioamide. The a-chlorothioamide 2 is highly reactive in hydroxylic solvents. The substantially less reactive alpha-chloroamide 6 undergoes reaction in hydroxylic solvents via the intermediacy of the 9-(N,N-dimethylcarbamyl)-9-fluorenyl cation, 15, at rates comparable to those of the or-H analogue, 9-chlorofluorene, 14. Computational studies indicate that the cl-carbonyl cation 15 prefers a conformation in which the carbonyl group is rotated 90 degrees with respect to the fluorenyl system. The relatively rapid rate of solvolysis of 6 is attributed to relief of ground-state strain as the cation 15 forms, as well as delocalization involving the fluorene system. Carbonyl conjugation as a cation-stabilizing feature does not appear to operate in the alpha-carbonyl cation 15.
• Characterization and Reactivity of the [<i>N</i>,<i>N</i>-Dimethyl(thioformamidyl)]-9-fluorenyl Cation¹
  作者：Calvin S. Q. Lew、David F. Wong、Linda J. Johnston、Michael Bertone、C. Hopkinson、Edward Lee-Ruff

  DOI：10.1021/jo941685m

  日期：1996.1.1

  The 9-[N,N-dimethyl(thioformamidyl)]-9-fluorenyl cation was generated under stable ion conditions and characterized by UV/visible and NMR spectroscopy and methanol trapping reactions. The same cation was generated by laser excitation of the appropriate chloride precursor in 2,2,2-trifluoroethanol, and rate constants for nucleophilic quenching by alcohols and several anions were measured. The quenching data for this and other 9-fluorenyl cations demonstrate that the reactivity decreases for 9-substituents in the order H > carbomethoxy > N,N-dimethyl(thioformamidyl), demonstrating that the thioamidyl group imparts substantial kinetic stabilization to an adjacent cationic center. Both steric and electronic factors are suggested to be important in determining this reactivity order.