N-(4-chlorophenyl)-9H-fluoren-9-amine | 62453-34-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: N-(4-chlorophenyl)-9H-fluoren-9-amine
• 英文别名: (4-chloro-phenyl)-fluoren-9-yl-amine；(4-Chlor-phenyl)-fluoren-9-yl-amin
• CAS: 62453-34-3
• 化学式: C₁₉H₁₄ClN
• 分子量: 291.78
• InChiKey: HPLPOQMMLZWVCL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(4-chlorophenyl)-9H-fluoren-9-amine 在 potassium hydride 作用下， 以 乙腈 为溶剂， 反应 0.33h， 生成
  参考文献：
  名称：

  Hydride, Hydrogen, Proton, and Electron Affinities of Imines and Their Reaction Intermediates in Acetonitrile and Construction of Thermodynamic Characteristic Graphs (TCGs) of Imines as a “Molecule ID Card”

  摘要：

  A series of 61 imines with various typical structures were synthesized, and the thermodynamic affinities (defined as enthalpy changes or redox potentials in this work) of the imines to abstract hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the imines to abstract hydrogen atoms and protons, and the thermodynamic affinities of the hydrogen adducts of the imines to abstract electrons in acetonitrile were determined by using titration calorimetry and electrochemical methods. The pure heterolytic and homolytic dissociation energies of the C = N pi-bond in the imines were estimated. The polarity of the C = N double bond in the imines was examined using a linear free-energy relationship. The idea of a thermodynamic characteristic graph (TCG) of imines as an efficient "Molecule ID Card" was introduced. The TCG can be used to quantitatively diagnose and predict the characteristic chemical properties of imines and their various reaction intermediates as well as the reduction mechanism of the imines. The information disclosed in this work could not only supply a gap of thermodynamics for the chemistry of imines but also strongly promote the fast development of the applications of imines.

  DOI：

  10.1021/jo902332n
• 作为产物：
  描述：

  2'-bromo-[1,1'-biphenyl]-2-carbaldehyde 在 copper acetylacetonate 、 sodium carbonate 作用下， 以 乙醇 、 甘油 为溶剂， 反应 15.0h， 生成 N-(4-chlorophenyl)-9H-fluoren-9-amine
  参考文献：
  名称：

  N-甲苯磺酰hydr与胺的铜催化偶联：芴衍生物的合成

  摘要：

  已经开发了在同一羧基中心上一个C–N键和一个C–C键的原始结构。该方法涉及2'-溴-联芳基-N-甲苯磺酰基hydr与不同的胺之间的铜催化的交叉偶联反应，从而产生9 H-芴-9-胺衍生物。该反应在温和的条件下在甘油（一种廉价且对环境友好的溶剂）中进行，而无需添加任何外部配体。

  DOI：

  10.1021/cs5014877

文献信息

• Intramolecular addition of aryl radicals to carbon-nitrogen double bonds
  作者：Milena Gioanola、Rino Leardini、Daniele Nanni、Patrizia Pareschi、Giuseppe Zanardi

  DOI：10.1016/0040-4020(94)01068-b

  日期：1995.2

  5-exo cyclisation regiospecifically. A competitive 1,5-hydrogen shift leading to imidoyl radicals was noticed. An analogous behaviour is also exhibited by vinyl radicals when allowed to add to carbon-nitrogen double bonds.

  自由基6a，b的环化对5-exo过程具有高度区域选择性；6-内环闭环是次要路线，它们的比例取决于取代基。没有观察到五元自由基中间体7a，b的环膨胀。自由基27a，27b特异性地引起5-exo环化。注意到竞争性的1，5-氢转移导致亚氨基自由基。当被允许加成碳氮双键时，乙烯基基团也表现出类似的行为。
• Energetics of Multistep versus One-step Hydride Transfer Reactions of Reduced Nicotinamide Adenine Dinucleotide (NADH) Models with Organic Cations and <i>p</i>-Quinones
  作者：Jin-Pei Cheng、Yun Lu、Xiaoqing Zhu、Linjing Mu

  DOI：10.1021/jo9715985

  日期：1998.9.1

  Free energy changes of each elementary step involved in the formal hydride transfer (H(-)(T)) reactions (including the so-called "one-step" H(-)(T) and "multistep" H(-)(T) mechanisms) of the reduced nicotinamide adenine dinucleotide (NADH) models with various cations and quinones (17) were investigated either by direct thermodynamic measurements or by calculations from thermochemical cycles. Based

  正式的氢化物转移（H（-）（T））反应（包括所谓的“一步” H（-）（T）和“多步” H（-）（通过直接热力学测量或通过热化学循环计算，研究了具有各种阳离子和醌的还原烟酰胺腺嘌呤二核苷酸（NADH）模型的机理（T）。基于由此得出的能量数据，结合动力学观察结果（尤其是动力学同位素效应），系统分析了NADH介导的还原反应的力学特征。这些分析得出的实用指南表明，如果初始电子转移的能隙是多步机制（e（-）-H（*）或e（-）-H（+）-e（-）） NADH模型化合物和还原性底物之间的[DeltaG（e（-）（T））]远小于吸热e（-）（T）的1.0 V的经验临界极限。相反，如果DeltaG（e（-）（T））远大于1.0 V，则可能会发生协调的单步H（-）（T）。该指南还建议，如果DeltaG（e（-）（T））处于不确定状态，则可能采用“混合”机制。
• Reduction of Schiff Bases. II. Benzhydrylamines and Structurally Related Compounds^1a,b
  作者：JOHN H. BILLMAN、KWANG M. TAI

  DOI：10.1021/jo01098a009

  日期：1958.4
• Hydride, Hydrogen, Proton, and Electron Affinities of Imines and Their Reaction Intermediates in Acetonitrile and Construction of Thermodynamic Characteristic Graphs (TCGs) of Imines as a “Molecule ID Card”
  作者：Xiao-Qing Zhu、Qiao-Yun Liu、Qiang Chen、Lian-Rui Mei

  DOI：10.1021/jo902332n

  日期：2010.2.5

  A series of 61 imines with various typical structures were synthesized, and the thermodynamic affinities (defined as enthalpy changes or redox potentials in this work) of the imines to abstract hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the imines to abstract hydrogen atoms and protons, and the thermodynamic affinities of the hydrogen adducts of the imines to abstract electrons in acetonitrile were determined by using titration calorimetry and electrochemical methods. The pure heterolytic and homolytic dissociation energies of the C = N pi-bond in the imines were estimated. The polarity of the C = N double bond in the imines was examined using a linear free-energy relationship. The idea of a thermodynamic characteristic graph (TCG) of imines as an efficient "Molecule ID Card" was introduced. The TCG can be used to quantitatively diagnose and predict the characteristic chemical properties of imines and their various reaction intermediates as well as the reduction mechanism of the imines. The information disclosed in this work could not only supply a gap of thermodynamics for the chemistry of imines but also strongly promote the fast development of the applications of imines.
• Copper-Catalyzed Coupling of <i>N</i>-Tosylhydrazones with Amines: Synthesis of Fluorene Derivatives
  作者：Jessy Aziz、Gilles Frison、Montserrat Gómez、Jean-Daniel Brion、Abdallah Hamze、Mouad Alami

  DOI：10.1021/cs5014877

  日期：2014.12.5

  An original formation of one C–N bond and one C–C bond on the same carbenic center has been developed. This approach involves a copper-catalyzed cross-coupling reaction between 2′-bromo-biaryl-N-tosylhydrazones and different amines leading to 9H-fluoren-9-amine derivatives. This reaction proceeds under mild conditions in glycerol, an inexpensive and environmentally friendly solvent, without adding any

  已经开发了在同一羧基中心上一个C–N键和一个C–C键的原始结构。该方法涉及2'-溴-联芳基-N-甲苯磺酰基hydr与不同的胺之间的铜催化的交叉偶联反应，从而产生9 H-芴-9-胺衍生物。该反应在温和的条件下在甘油（一种廉价且对环境友好的溶剂）中进行，而无需添加任何外部配体。