4-Fluoro-N,N-dimethylaniline N-oxide | 130445-20-4

• 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: 4-Fluoro-N,N-dimethylaniline N-oxide
• 英文别名: 4-Fluoro-N,N-dimethylbenzen-1-amine N-oxide；4-fluoro-N,N-dimethylbenzeneamine oxide
• CAS: 130445-20-4
• 化学式: C₈H₁₀FNO
• 分子量: 155.172
• InChiKey: HJHICKRDRNIGPS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  11
• 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：
  18.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-Fluoro-N,N-dimethylaniline N-oxide 在 二溴亚砜 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 4.75h， 以26%的产率得到2-bromo-4-fluoro-N,N-dimethylaniline
  参考文献：
  名称：

  亚硫酰卤处理N，N-二烷基苯胺N-氧化物合成卤代苯胺

  摘要：

  N，N-二烷基苯胺N-氧化物的特殊反应性使得可以方便实用地获得富含电子的芳基卤化物。一对互补的反应协议允许用于选择性对-bromination或邻位的-chlorination N，N- -dialkylanilines在高达69％的分离收率。通过将N，N-二烷基苯胺暂时氧化为相应的N，N-二烷基苯胺N-氧化物并去除生成的弱N – O ，可以生成各种卤化苯胺 通过在低温下用亚硫酰溴或亚硫酰氯处理可实现键合。

  DOI：

  10.1021/acs.joc.8b01590
• 作为产物：
  描述：

  氟代二甲基苯胺 在 甲基三氧化铼(VII) 双氧水 作用下， 以 甲醇 为溶剂， 以85%的产率得到4-Fluoro-N,N-dimethylaniline N-oxide
  参考文献：
  名称：

  Kinetics and Mechanism of Oxidation of Anilines by Hydrogen Peroxide As Catalyzed by Methylrhenium Trioxide

  摘要：

  The oxidation of anilines by hydrogen peroxide in methanol is catalyzed by methylrhenium trioxide, CH3ReO3. The major product of the oxidation of aniline at room temperature is nitrosobenzene. For 4-substituted N,N-dimethylanilines, the N-oxide is the only product. The rate constants for the oxidation of 4-substituted N,N-dimethylanilines follow a linear Hammett relationship with rho = -1.19. The rate constants for the reaction between CH3Re(O)(2)(O-2), referred to as A, and 4-XC(6)H(5)NMe(2) are as follows: 4-Me, 24.5; 4-H, 18.4; 4-F, 12.7; 4-Br, 8.7; and 4-NO2, 1.9 L mol(-1) s(-1). This shows that electron-withdrawing substituents inhibit the reaction. The corresponding rate constant for the oxidation of aniline is 2.04 +/- 0.11 L mol(-1) s(-1), whereas it is 178 +/- 11 L mol(-1) s(-1) for the oxidation of N-phenylhydroxylamine to nitrosobenzene. A mechanism has been assigned on the basis of the kinetics and product yields. The data are consistent with the attack of the nucleophilic nitrogen atom on one of the peroxidic oxygen atom of A. The kinetics of the reaction of CH3ReO3 and hydrogen peroxide in methanol were also investigated. The formation of the 1:1 peroxide compound A is characterized by an equilibrium constant K-1 = 261 +/- 6 L mol(-1) The equilibration occurs rapidly: k(1) = 1150 +/- 60 L mol(-1) s(-1) and k(-1)= 4.4 +/- 0.4 s(-1) at 25.0 degrees C. The bisperoxide compound, CH3Re(O)(O-2)(2)(H2O), B, forms more slowly. The rate constant is k(2) = 308 +/- 16 L mol(-1) s(-1), and the equilibrium constant is K-2 = 814 +/- 14 L mol(-1) at 25.0 degrees C in methanol. B reacts with the anilines, but much more slowly than A.

  DOI：

  10.1021/jo00110a042

文献信息

• Metal‐Free Deoxygenation of Amine <i>N</i> ‐Oxides: Synthetic and Mechanistic Studies
  作者：William Lecroq、Jules Schleinitz、Mallaury Billoue、Anna Perfetto、Annie‐Claude Gaumont、Jacques Lalevée、Ilaria Ciofini、Laurence Grimaud、Sami Lakhdar

  DOI：10.1002/cphc.202100108

  日期：2021.6.16

  unprecedented combination of light and P(III)/P(V) redox cycling for the efficient deoxygenation of aromatic amine N-oxides. Moreover, we discovered that a large variety of aliphatic amine N-oxides can easily be deoxygenated by using only phenylsilane. These practically simple approaches proceed well under metal-free conditions, tolerate many functionalities and are highly chemoselective. Combined experimental

  我们在此报告了一种前所未有的光和 P(III)/P(V) 氧化还原循环的组合，用于芳香胺N-氧化物的有效脱氧。此外，我们发现仅使用苯基硅烷就可以轻松地对多种脂肪胺N-氧化物进行脱氧。这些实际上简单的方法在无金属条件下可以很好地进行，耐受许多功能并且具有高度的化学选择性。结合实验和计算研究，能够深入了解控制芳香族和脂肪族胺N-氧化物反应性的因素。
• Organotin(IV) complexes of some N,N-dimethylaniline N-oxide derivatives
  作者：Talal A.K. Al-Allaf、Maher A.M. Al-Tayy

  DOI：10.1016/0022-328x(90)80154-r

  日期：1990.7
• Kinetics and Mechanism of Oxidation of Anilines by Hydrogen Peroxide As Catalyzed by Methylrhenium Trioxide
  作者：Zuolin Zhu、James H. Espenson

  DOI：10.1021/jo00110a042

  日期：1995.3

  The oxidation of anilines by hydrogen peroxide in methanol is catalyzed by methylrhenium trioxide, CH3ReO3. The major product of the oxidation of aniline at room temperature is nitrosobenzene. For 4-substituted N,N-dimethylanilines, the N-oxide is the only product. The rate constants for the oxidation of 4-substituted N,N-dimethylanilines follow a linear Hammett relationship with rho = -1.19. The rate constants for the reaction between CH3Re(O)(2)(O-2), referred to as A, and 4-XC(6)H(5)NMe(2) are as follows: 4-Me, 24.5; 4-H, 18.4; 4-F, 12.7; 4-Br, 8.7; and 4-NO2, 1.9 L mol(-1) s(-1). This shows that electron-withdrawing substituents inhibit the reaction. The corresponding rate constant for the oxidation of aniline is 2.04 +/- 0.11 L mol(-1) s(-1), whereas it is 178 +/- 11 L mol(-1) s(-1) for the oxidation of N-phenylhydroxylamine to nitrosobenzene. A mechanism has been assigned on the basis of the kinetics and product yields. The data are consistent with the attack of the nucleophilic nitrogen atom on one of the peroxidic oxygen atom of A. The kinetics of the reaction of CH3ReO3 and hydrogen peroxide in methanol were also investigated. The formation of the 1:1 peroxide compound A is characterized by an equilibrium constant K-1 = 261 +/- 6 L mol(-1) The equilibration occurs rapidly: k(1) = 1150 +/- 60 L mol(-1) s(-1) and k(-1)= 4.4 +/- 0.4 s(-1) at 25.0 degrees C. The bisperoxide compound, CH3Re(O)(O-2)(2)(H2O), B, forms more slowly. The rate constant is k(2) = 308 +/- 16 L mol(-1) s(-1), and the equilibrium constant is K-2 = 814 +/- 14 L mol(-1) at 25.0 degrees C in methanol. B reacts with the anilines, but much more slowly than A.
• Synthesis of Halogenated Anilines by Treatment of <i>N</i>,<i>N</i>-Dialkylaniline <i>N</i>-Oxides with Thionyl Halides
  作者：Hayley Reed、Tyler R. Paul、William J. Chain

  DOI：10.1021/acs.joc.8b01590

  日期：2018.9.21

  The special reactivity of N,N-dialkylaniline N-oxides allows practical and convenient access to electron-rich aryl halides. A complementary pair of reaction protocols allow for the selective para-bromination or ortho-chlorination of N,N-dialkylanilines in up to 69% isolated yield. The generation of a diverse array of halogenated anilines is made possible by a temporary oxidation level increase of N

  N，N-二烷基苯胺N-氧化物的特殊反应性使得可以方便实用地获得富含电子的芳基卤化物。一对互补的反应协议允许用于选择性对-bromination或邻位的-chlorination N，N- -dialkylanilines在高达69％的分离收率。通过将N，N-二烷基苯胺暂时氧化为相应的N，N-二烷基苯胺N-氧化物并去除生成的弱N – O ，可以生成各种卤化苯胺 通过在低温下用亚硫酰溴或亚硫酰氯处理可实现键合。
• Metal-Free Functionalization of <i>N</i>,<i>N</i>-Dialkylanilines via Temporary Oxidation to <i>N</i>,<i>N</i>-Dialkylaniline <i>N</i>-Oxides and Group Transfer
  作者：Robert S. Lewis、Michael F. Wisthoff、J. Grissmerson、William J. Chain

  DOI：10.1021/ol501813s

  日期：2014.7.18

  A simple set of protocols for the controlled elaboration of anilines is reported allowing access to a diverse array of aminophenols, aminoarylsulfonates, alkylated anilines, and aminoanilines in 29-95% yield in a single laboratory operation from easily isolable, bench-stable N,N-dialkylaniline N-oxides. The introduction of new C-O, C-C, and C-N bonds on the aromatic ring is made possible by a temporary increase in oxidation level and excision of a weak N-O bond.