2,2,2-trifluoro-N-(2-hydroxy-4-methylphenyl)acetamide | 39267-61-3

• 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-4-methylphenyl)acetamide
• 英文别名: N-(2-hydroxy-4-methylphenyl)trifluoroacetamide；N-(trifluoroacetyl)-2-hydroxy-4-methyl-aniline；2-Hydroxy-4-methyltrifluoracetanilid
• CAS: 39267-61-3
• 化学式: C₉H₈F₃NO₂
• mdl: MFCD24392241
• 分子量: 219.163
• InChiKey: ZKLKDCSHSSZHDI-UHFFFAOYSA-N

物化性质

• 熔点：
  194-194.5 °C
• 沸点：
  288.1±40.0 °C(Predicted)
• 密度：
  1.426±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.222
• 拓扑面积：
  49.3
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,2,2-trifluoro-N-(2-hydroxy-4-methylphenyl)acetamide 在 phosphorus pentoxide 作用下， 80.0~300.0 ℃ 、2.67 kPa 条件下， 以66%的产率得到6-Methyl-2-trifluoromethyl-benzooxazole
  参考文献：
  名称：

  Synthese de F-alkyl-2 benzoxazoles

  摘要：

  DOI：

  10.1016/s0022-1139(00)81483-9
• 作为产物：
  描述：

  2-氟-4-甲基苯胺 、 三氟乙酸 在 Oxone 作用下， 以 1,4-二氧六环 为溶剂， 以70%的产率得到2,2,2-trifluoro-N-(2-hydroxy-4-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.
• Direct C–N bond cleavage of N-vinyl or N-allyl arylamines: a metal-free strategy for N-devinylation and N-deallylation
  作者：Shilpi Balgotra、Vunnam Venkateswarlu、Ram A. Vishwakarma、Sanghapal D. Sawant

  DOI：10.1016/j.tetlet.2015.05.042

  日期：2015.7

  A simple and convenient N-devinylation and N-deallylation strategy for N-vinyl and N-allyl arylamines in the presence of TFA/oxone is presented with the formation of selective ortho-hydroxylated and N-triflu-oroacylated arylamine product in good yields. This method is important for protection/deprotection of arylamines in organic synthesis and useful as a medicinal chemistry tool at late stage modifications in drug discovery programs. (c) 2015 Elsevier Ltd. All rights reserved.
• Acid-promoted aromatic substitution processes in photochemical and thermal decompositions of aryl azides
  作者：Richard J. Sundberg、Kenneth B. Sloan

  DOI：10.1021/jo00951a018

  日期：1973.6
• The relationship between the structures and absorption spectra of cyan color indoaniline dyes
  作者：Masafumi Adachi、Yukichi Murata、Shinichiro Nakamura

  DOI：10.1021/jo00071a038

  日期：1993.9

  The absorption spectra of 23 indoaniline dyes were calculated on the AM1-optimized structures by means of the INDO/S method. The observed and calculated absorption wavelengths showed good correlation for the main (longest wavelength) absorption bands (observed at 560-670 nm), and there was fair correlation between the observed molar extinction coefficients and the calculated oscillator strengths. The observed absorption wavelengths could be reproduced by the calculation for the subabsorption bands near the visible region (observed at 320-380 nm). A qualitative correlation of the solvatochromic shift with the difference between ground and excited state dipole moments was obtained.