9-Chloro-9H-fluorene-9-carboxylic acid dimethylamide | 210713-89-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9-Chloro-9H-fluorene-9-carboxylic acid dimethylamide
• 英文别名: 9-chloro-N,N-dimethylfluorene-9-carboxamide
• CAS: 210713-89-6
• 化学式: C₁₆H₁₄ClNO
• 分子量: 271.746
• InChiKey: ASCVJYHLZFNSBR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 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：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  乙醇 、 9-Chloro-9H-fluorene-9-carboxylic acid dimethylamide 生成 9-Ethoxy-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：

  N.N-Dimethyl-9-hydroxy-fluoren-carbonsaeureamid 在 氯化亚砜 、 sodium carbonate 作用下， 以 乙醚 为溶剂， 反应 96.0h， 以72%的产率得到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

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.