N-(1-phenylethyl)-4-(trifluoromethyl)aniline

• 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: N-(1-phenylethyl)-4-(trifluoromethyl)aniline
• 化学式: C₁₅H₁₄F₃N
• 分子量: 265.278
• InChiKey: ZUVFMKSIZABDSP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-(1-phenylethyl)-4-(trifluoromethyl)aniline 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：

  1-phenyl-N-(4-(trifluoromethyl)phenyl)ethan-1-imine 在 苯硅烷 、 C₁₂H₃₇CoP₄⁽¹⁺⁾ 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以98%的产率得到N-(1-phenylethyl)-4-(trifluoromethyl)aniline
  参考文献：
  名称：

  甲硅烷基二氢化钴络合物作为亚胺氢化硅烷化的有用催化剂的意义

  摘要：

  在这里，我们描述了甲硅烷基钴 (III) 二氢化物配合物的形成和使用，作为从低价明确定义的钴 (I) 配合物开始的各种亚胺氢化硅烷化的强大催化剂。该反应在低催化剂负载下是有效的，具有各种带有各种保护基团的亚胺，以及脂肪族酮亚胺和喹啉。动力学、DFT 计算、NMR 光谱研究、氘化实验和 X 射线衍射分析使我们能够提出基于甲硅烷基二氢钴 (III) 配合物进行氢化钴的催化循环。

  DOI：

  10.1021/acscatal.1c03886

文献信息

• Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds
  申请人：Yale University

  公开号：US06384282B2

  公开（公告）日：2002-05-07

  The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.

  本发明涉及一种将胺添加到底物中的碳-碳双键的过程，包括：在存在过渡金属催化剂的条件下，将胺与至少含有一个碳-碳双键的化合物反应，以形成产物，其中胺与前述碳-碳双键的碳原子之间形成共价键。过渡金属催化剂包括第8族金属和含有一个或多个2电子给体原子的配体。本发明还涉及胺化合物与含有碳-碳双键的化合物的对映选择性反应，以及用于评估这些反应中潜在催化剂的热量测定分析。
• Enantioselective Organocatalytic Reductive Amination
  作者：R. Ian Storer、Diane E. Carrera、Yike Ni、David W. C. MacMillan

  DOI：10.1021/ja057222n

  日期：2006.1.1

  The first enantioselective organocatalytic reductive amination reaction has been accomplished. The development of a new chiral phosphoric acid catalyst has provided a convenient strategy for the enantioselective construction of protected primary amines and provided a highly stereoselective method for the reductive amination of heterocyclic amines. A diverse spectrum of ketone and amine substrates can

  第一个对映选择性有机催化还原胺化反应已经完成。新型手性磷酸催化剂的开发为受保护伯胺的对映选择性构建提供了一种方便的策略，并为杂环胺的还原胺化提供了一种高度立体选择性的方法。可以以高产率和出色的对映选择性容纳各种不同的酮和胺底物。这种新协议实现了还原胺化与亚胺还原的关键优势，因为从烷基-烷基酮衍生的酮亚胺对分离不稳定，使用这种直接有机催化还原胺化可以全面绕过这一基本限制。
• An Effective [Fe^III(TF₄DMAP)Cl] Catalyst for C–H Bond Amination with Aryl and Alkyl Azides
  作者：Yi-Dan Du、Zhen-Jiang Xu、Cong-Ying Zhou、Chi-Ming Che

  DOI：10.1021/acs.orglett.8b03765

  日期：2019.2.15

  [FeIII(TF4DMAP)Cl] can efficiently catalyze intermolecular sp3 C–H amination using aryl azides and intramolecular sp3 C–H amination of alkyl azides in moderate-to-high product yields. At catalyst loading down to 1 mol %, the reactions display high chemo- and regioselectivity with broad substrate scope and are effective for late-stage functionalization of complex natural/bioactive molecules.

  的[Fe III（TF 4 DMAP）CL]可以有效地催化分子间的SP 3 C-H使用芳基叠氮化和分子内藻胺化3烷基叠氮化物的C-H的胺化在中度到高的产物收率。在低至1 mol％的催化剂负载量下，反应显示出高的化学选择性和区域选择性以及广泛的底物范围，并且对于复杂的天然/生物活性分子的后期功能化有效。
• New cyclopentadienyl, indenyl or fluorenyl substituted phosphine compounds and their use in catalytic reactions
  申请人：Evonik Degussa GmbH

  公开号：EP1894938A1

  公开（公告）日：2008-03-05

  The invention is directed to a phosphine compound represented by general formula (1) wherein R' and R" independently are selected from alkyl, cycloalkyl and 2-furyl radicals, or R' and R" are joined together to form with the phosphorous atom a carbon-phosphorous monocycle comprising at least 3 carbon atoms or a carbon-phosphorous bicycle; the alkyl radicals, cycloalkyl radicals, and carbon-phosphorous monocycle being unsubstituted or substituted by at least one radical selected from the group of alkyl, cycloalkyl, aryl, alkoxy, and aryloxy radicals; Cps is a partially substituted or completely substituted cyclopentadien-1-yl group, including substitutions resulting in a fused ring system, and wherein a substitution at the 1-position of the cyclopentadien-1-yl group is mandatory when the cyclopentadien-1-yl group is not part of a fused ring system or is part of an indenyl group. Also claimed is the use of these phosphines as ligands in catalytic reactions and the preparation of these phosphines.

  该发明涉及一种由通式（1）表示的膦化合物 其中 R'和R"独立地选自烷基、环烷基和2-呋喃基，或者R'和R"结合在一起与磷原子形成至少含有3个碳原子的碳-磷单环或碳-磷双环；所述烷基基团、环烷基基团和碳-磷单环未取代或取代，所述取代包括来自烷基、环烷基、芳基、烷氧基和芳氧基基团中至少一个基团的选择； Cps是部分取代或完全取代的环戊二烯-1-基团，包括导致融合环系统的取代，当环戊二烯-1-基团不是融合环系统的一部分或是茚基团的一部分时，环戊二烯-1-基团的1-位取代是强制的。还声明了这些膦化合物作为催化反应中的配体以及这些膦化合物的制备的用途。
• Enantioselective Hydrogenation of Acyclic Aromatic <i>N</i>-Aryl Imines Catalyzed by an Iridium Complex of (<i>S,S</i>)-1,2-Bis(<i>tert</i>-butylmethylphosphino)ethane
  作者：Tsuneo Imamoto、Noriyuki Iwadate、Kazuhiro Yoshida

  DOI：10.1021/ol060546b

  日期：2006.5.1

  [reaction: see text] An iridium(I) complex of (S,S)-1,2-bis(tert-butylmethylphosphino)ethane with tetrakis(3,5-bis(trifluoromethyl)phenyl)borate as the counterion catalyzes the hydrogenation of acyclic aromatic N-aryl imines under 1 atm of hydrogen pressure at room temperature to give the corresponding optically active secondary amines with up to 99% ee.

  [反应：参见正文]（S，S）-1,2-双（叔丁基甲基膦基）乙烷与四（3,5-双（三氟甲基）苯基）硼酸酯的铱（I）络合物作为抗衡离子催化加氢反应在室温下，在1个大气压的氢气压力下，在室温下制备无环芳族N-芳基亚胺，得到相应的旋光仲胺，其ee高达99％。