2,2,2-trifluoro-N-(2-hydroxy-6-methylphenyl)acetamide

• 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: 2,2,2-trifluoro-N-(2-hydroxy-6-methylphenyl)acetamide
• 英文别名: N-(2-hydroxy-6-methylphenyl)trifluoroacetamide
• 化学式: C₉H₈F₃NO₂
• 分子量: 219.163
• InChiKey: IQCLEPIXHVZSOJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  49.3
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  2-氟-6-甲基苯胺 、 三氟乙酸 在 Oxone 作用下， 以 1,4-二氧六环 为溶剂， 以68%的产率得到2,2,2-trifluoro-N-(2-hydroxy-6-methylphenyl)acetamide
  参考文献：
  名称：

  Metal-Free Chemoselective ortho-C(sp2)–F Bond Hydroxylation and N-Trifluoroacylation of Fluoroarylamines for Domino Synthesis of 2-(N-Trifluoroacyl)aminophenols

  摘要：

  A novel chemoselective reaction for the formation of C-O bonds by C(sp(2))-F bond cleavage and concomitant N-trifluoroacylation of fluoroanilines using trifluoroacetic acid and Oxone((R)) is presented. This domino reaction gives o-hydroxy-N-trifluoroacetanilides in good yields under metal-free conditions in a single step. Selective ortho-directed monohydroxylation and N-trifluoroacylation of 2- and 6-fluoro- or 2,6-difluoro-substituted anilines takes place in this transformation.

  DOI：

  10.1055/s-0034-1379905

文献信息

• CH Oxygenation and<i>N</i>-Trifluoroacylation of Arylamines Under Metal-Free Conditions: A Convenient Approach to 2-Aminophenols and<i>N</i>-Trifluoroacyl-<i>ortho</i>-aminophenols
  作者：Vunnam Venkateswarlu、K. A. Aravinda Kumar、Shilpi Balgotra、G. Lakshma Reddy、M. Srinivas、Ram A. Vishwakarma、Sanghapal D. Sawant

  DOI：10.1002/chem.201402411

  日期：2014.5.26

  Direct ortho‐hydroxylation through CH oxygenation and N‐trifluoroacylation of anilines was achieved in a single step under metal‐free conditions by using a combination of TFA and oxone. The method allowed the formation of functionalised amino phenolic compounds such as ortho‐hydroxy‐N‐trifluoroacetanilides in good yields with broad substrate scope.

  通过在无金属条件下，通过使用TFA和过硫酸氢钾的组合，一步实现苯胺的CH 3 H氧化和N-三氟酰化直接邻羟基化。该方法可以形成功能化的氨基酚类化合物，例如邻-羟基-N-三氟乙酰苯胺，收率高，具有广泛的底物范围。
• Acid-catalyzed amino-migration of O-phenylhydroxylamines
  作者：Naoki Haga、Yasuyuki Endo、Kenichiro Kataoka、Kentaro Yamaguchi、Koichi Shudo

  DOI：10.1021/ja00051a012

  日期：1992.12

  The mechanism of amino-migration of O-phenylhydroxylamine (1a) was studied. It was found that 1 rearranges to give 2-aminophenol (50%) and 4-aminophenol (7%) in trifluoroacetic acid (TFA). The predominance of the ortho rearrangement of 1 clearly distinguishes this process from the Bamberger rearrangement. From cross-coupling experiments employing stable isotopes, it was clarified that the ortho rearrangement proceeds intramolecularly and the para rearrangement involves both intra- and intermolecular processes. Good first-order kinetics were obtained for the rearrangement. The Hammett plot (sigma+) with a large negative slope (rho = -7.8) indicates that initial heterolytic N-O bond cleavage of 1 occurs and generates a positive charge on the oxygen atom with considerable delocalization into the aromatic ring. An ion-molecule pair involving a phenoxenium ion and an ammonia molecule as an intermediate rationalizes all of the results. In this pair, intramolecular combination to the ortho position proceeds preferentially over that to the para position. Formation of catechol and hydroquinone can be explained in terms of nucleophilic attack of TFA on the phenoxenium ion in a solvent-separated pair.
• Metal-Free Chemoselective ortho-C(sp2)–F Bond Hydroxylation and N-Trifluoroacylation of Fluoroarylamines for Domino Synthesis of 2-(N-Trifluoroacyl)aminophenols
  作者：Sanghapal Sawant、Vunnam Venkateswarlu、Shilpi Balgotra、K. Aravinda Kumar、Ram Vishwakarma

  DOI：10.1055/s-0034-1379905

  日期：——

  A novel chemoselective reaction for the formation of C-O bonds by C(sp(2))-F bond cleavage and concomitant N-trifluoroacylation of fluoroanilines using trifluoroacetic acid and Oxone((R)) is presented. This domino reaction gives o-hydroxy-N-trifluoroacetanilides in good yields under metal-free conditions in a single step. Selective ortho-directed monohydroxylation and N-trifluoroacylation of 2- and 6-fluoro- or 2,6-difluoro-substituted anilines takes place in this transformation.