O-(2,6-dimethylphenyl)hydroxylamine | 144181-59-9

• 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: O-(2,6-dimethylphenyl)hydroxylamine
• 英文别名: O-(2,6-Dimethyl-phenyl)-hydroxylamin
• CAS: 144181-59-9
• 化学式: C₈H₁₁NO
• 分子量: 137.181
• InChiKey: HCCIFYUIVCQULU-UHFFFAOYSA-N

物化性质

• 沸点：
  234.8±40.0 °C(Predicted)
• 密度：
  1.030±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  35.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  O-(2,6-dimethylphenyl)hydroxylamine 、 三氟乙酸酐 在 三氟乙酸 作用下， 生成 2,6-二甲基苯酚 、 2,6-二甲基-1,4-苯二酚 、 N-(3,5-dimethyl-4-hydroxyphenyl)trifluoroacetamide 、
  参考文献：
  名称：

  Acid-catalyzed amino-migration of O-phenylhydroxylamines

  摘要：

  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.

  DOI：

  10.1021/ja00051a012

文献信息

• PROTEASE INHIBITING SUCCINIC ACID DERIVATIVES
  申请人：BOEHRINGER INGELHEIM (CANADA) LTD.

  公开号：EP0827507B1

  公开（公告）日：1999-06-16
• FLAME RETARDANT POLY(ARYLENE ETHER)-POLYSILOXANE BLOCK COPOLYMER COMPOSITION AND ARTICLE
  申请人：SABIC Global Technologies B.V.

  公开号：EP2736976B1

  公开（公告）日：2017-07-26
• REINFORCED POLY(PHENYLENE ETHER) COMPOSITIONS, AND ARTICLES PREPARED THEREFROM
  申请人：SHPP Global Technologies B.V.

  公开号：EP3294809B1

  公开（公告）日：2021-08-11
• 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.