N-[1-(2-Methoxy-phenyl)-meth-(E)-ylidene]-benzene-1,2-diamine | 7191-91-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: N-[1-(2-Methoxy-phenyl)-meth-(E)-ylidene]-benzene-1,2-diamine
• 英文别名: 2-[(2-methoxyphenyl)methylideneamino]aniline
• CAS: 7191-91-5
• 化学式: C₁₄H₁₄N₂O
• 分子量: 226.278
• InChiKey: GODHNGYMZKCKAP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.03
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  47.61
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  N-[1-(2-Methoxy-phenyl)-meth-(E)-ylidene]-benzene-1,2-diamine 在 sodium tetrahydroborate 作用下， 以 2,2,2-三氟乙醇 为溶剂， 反应 0.5h， 以0.35 g的产率得到(2-aminophenyl)-[(2-methoxyphenyl)methyl]amine
  参考文献：
  名称：

  Hydrogen-Bond-Driven Electrophilic Activation for Selectivity Control: Scope and Limitations of Fluorous Alcohol-Promoted Selective Formation of 1,2-Disubstituted Benzimidazoles and Mechanistic Insight for Rationale of Selectivity

  摘要：

  Hydrogen-bond-driven electrophilic activation for selectivity control during competitive formation of 1,2-disubstituted and 2-substituted benzimidazoles from o-phenylenediamine and aldehydes is reported. The fluorous alcohols trifluoroethanol and hexafluoro-2-propanol efficiently promote the cyclocondensation of o-phenylenediamine with aldehydes to afford selectively the 1,2-disubstituted benzimidazoles at rt in short times. A mechanistic insight is invoked by NMR, mass spectrometry, and chemical studies to rationalize the selectivity. The ability of the fluorous alcohols in promoting the reaction and controlling the selectivity can be envisaged from their better hydrogen bond donor (HBD) abilities compared to that of the other organic solvents as well as of water. Due to the better HBD values, the fluorous alcohols efficiently promote the initial bisimine formation by electrophilic activation of the aldehyde carbonyl. Subsequently the hydrogen-bond-mediated activation of the in situ-formed bisimine triggers the rearrangement via 1,3-hydride shift to form the 1,2-disubstituted benzimidazoles.

  DOI：

  10.1021/jo301793z
• 作为产物：
  描述：

  邻苯二胺 、 邻甲氧基苯甲醛 以 2,2,2-三氟乙醇 为溶剂， 反应 0.08h， 生成 N-[1-(2-Methoxy-phenyl)-meth-(E)-ylidene]-benzene-1,2-diamine
  参考文献：
  名称：

  Hydrogen-Bond-Driven Electrophilic Activation for Selectivity Control: Scope and Limitations of Fluorous Alcohol-Promoted Selective Formation of 1,2-Disubstituted Benzimidazoles and Mechanistic Insight for Rationale of Selectivity

  摘要：

  Hydrogen-bond-driven electrophilic activation for selectivity control during competitive formation of 1,2-disubstituted and 2-substituted benzimidazoles from o-phenylenediamine and aldehydes is reported. The fluorous alcohols trifluoroethanol and hexafluoro-2-propanol efficiently promote the cyclocondensation of o-phenylenediamine with aldehydes to afford selectively the 1,2-disubstituted benzimidazoles at rt in short times. A mechanistic insight is invoked by NMR, mass spectrometry, and chemical studies to rationalize the selectivity. The ability of the fluorous alcohols in promoting the reaction and controlling the selectivity can be envisaged from their better hydrogen bond donor (HBD) abilities compared to that of the other organic solvents as well as of water. Due to the better HBD values, the fluorous alcohols efficiently promote the initial bisimine formation by electrophilic activation of the aldehyde carbonyl. Subsequently the hydrogen-bond-mediated activation of the in situ-formed bisimine triggers the rearrangement via 1,3-hydride shift to form the 1,2-disubstituted benzimidazoles.

  DOI：

  10.1021/jo301793z

文献信息

• A highly diastereoselective [5+1] annulation to 2,2,3-trisubstituted tetrahydroquinoxalines <i>via</i> intramolecular Mannich-type trapping of ammonium ylides
  作者：Xiao-Yu Guan、Min Tang、Zhang-Qin Liu、WenHao Hu

  DOI：10.1039/c9cc04890a

  日期：——

  A novel tandem intermolecular ammonium ylide formation/intramolecular Mannich-type [5+1] cyclization reaction of aryl diazoacetates and ortho-aminophenyl imine derivatives was developed. The reaction provides an efficient methodology for direct synthesis of diverse trisubstituted tetrahydroquinoxalines bearing a quaternary stereogenic carbon center in moderate to good yields with excellent diastereoselectivity

  开发了一种新型的串联分子间铵盐形成/分子内曼尼希型[5 + 1]芳基重氮乙酸酯和邻氨基苯基亚胺衍生物的环化反应。该反应提供了一种有效的方法学，可直接合成具有中等立体构型碳中心的多种三取代四氢喹喔啉，并具有良好的非对映选择性，并具有良好的收率。该方法具有效率高，反应条件温和和立体选择性高的特点。
• Cyclodehydrogenation of N-benzylidene-o-phenylenediamines to 2,2'-diaryl-1,1'-bibenzimidazoles with dioxygen catalyzed by copper(I) chloride in pyridine. A structural study of 2,2'-bis(3,4,5-trimethoxyphenyl)-1,1'-bibenzimidazole
  作者：Gabor Speier、Laszlo Parkanyi

  DOI：10.1021/jo00352a016

  日期：1986.1
• Hydrogen-Bond-Driven Electrophilic Activation for Selectivity Control: Scope and Limitations of Fluorous Alcohol-Promoted Selective Formation of 1,2-Disubstituted Benzimidazoles and Mechanistic Insight for Rationale of Selectivity
  作者：Rajesh Chebolu、Damodara N. Kommi、Dinesh Kumar、Narendra Bollineni、Asit K. Chakraborti

  DOI：10.1021/jo301793z

  日期：2012.11.16

  Hydrogen-bond-driven electrophilic activation for selectivity control during competitive formation of 1,2-disubstituted and 2-substituted benzimidazoles from o-phenylenediamine and aldehydes is reported. The fluorous alcohols trifluoroethanol and hexafluoro-2-propanol efficiently promote the cyclocondensation of o-phenylenediamine with aldehydes to afford selectively the 1,2-disubstituted benzimidazoles at rt in short times. A mechanistic insight is invoked by NMR, mass spectrometry, and chemical studies to rationalize the selectivity. The ability of the fluorous alcohols in promoting the reaction and controlling the selectivity can be envisaged from their better hydrogen bond donor (HBD) abilities compared to that of the other organic solvents as well as of water. Due to the better HBD values, the fluorous alcohols efficiently promote the initial bisimine formation by electrophilic activation of the aldehyde carbonyl. Subsequently the hydrogen-bond-mediated activation of the in situ-formed bisimine triggers the rearrangement via 1,3-hydride shift to form the 1,2-disubstituted benzimidazoles.
• Synthesis of 2-Aminoquinoxalines via One-Pot Cyanide-Based Sequential Reaction under Aerobic Oxidation Conditions
  作者：Yeon-Ho Cho、Kyung-Hee Kim、Cheol-Hong Cheon

  DOI：10.1021/jo4021908

  日期：2014.2.7

  A highly efficient synthesis of 2-aminoquinoxalines has been developed via the one-pot two-step cyanide-mediated sequential reactions of ortho-phenylenediamines with aldehydes under aerobic oxidation conditions. A variety of substrates, including aliphatic aldehydes bearing acidic a-protons, are applicable to this protocol and afford the desired 2-aminoquinoxalines in high yields.