(+)-N-(1-phenylethyl)-4-chloroaniline

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (+)-N-(1-phenylethyl)-4-chloroaniline
• 英文别名: (+)-N-(4-chlorophenyl)-1-phenylethylamine；4-chloro-N-(1-phenylethyl)aniline
• 化学式: C₁₄H₁₄ClN
• mdl: MFCD09839413
• 分子量: 231.725
• InChiKey: LURKEPOVOHKECE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.142
• 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-(1-phenylethyl)-4-chloroaniline 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：

  N-(1-phenylethylidene)-4-chloroaniline 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 2.0h， 生成 (+)-N-(1-phenylethyl)-4-chloroaniline
  参考文献：
  名称：

  铑（III）催化苯胺芳烃末端炔烃的加氢胺化

  摘要：

  在盐添加剂的存在下，双核Rh（III）物种[Cp * RhCl 2 ] 2催化芳族末端炔烃（ArCCH）与苯胺（Ar'NH 2）之间的加氢胺化反应，从而得到酮亚汀Ar' N═C（Me）（Ar）。已经基于实验和计算研究提出了反应途径。

  DOI：

  10.1021/om201134j

文献信息

• Fast Reductive Amination by Transfer Hydrogenation “on Water”
  作者：Qian Lei、Yawen Wei、Dinesh Talwar、Chao Wang、Dong Xue、Jianliang Xiao

  DOI：10.1002/chem.201204194

  日期：2013.3.18

  Reductive amination of various ketones and aldehydes by transfer hydrogenation under aqueous conditions has been developed, by using cyclometallated iridium complexes as catalysts and formate as hydrogen source. The pH value of the solution is shown to be critical for a high catalytic chemoselectivity and activity, with the best pH value being 4.8. In comparison with that in organic solvents, the reductive

  通过使用环金属化的铱络合物作为催化剂，甲酸盐作为氢源，开发了在水性条件下通过转移氢化进行各种酮和醛的还原胺化反应。溶液的pH值对于高催化化学选择性和活性至关重要，最佳pH值为4.8。与有机溶剂相比，水相中的还原胺化速度更快，并且底物与催化剂的摩尔比（S / C）可设置为高达1×10 5。，是还原胺化反应中报道的最高S / C值。该催化剂易于获得，反应操作简单，可以使各种酮和醛与各种胺高产率地反应。该方案为合成胺化合物提供了一种实用且环保的新方法。
• Chemoselective Reductive Amination of Aldehydes and Ketones by Dibutylchlorotin Hydride-HMPA Complex
  作者：Toshihiro Suwa、Erika Sugiyama、Ikuya Shibata、Akio Baba

  DOI：10.1055/s-2000-6273

  日期：——

  Reductive amination of various aldehydes and ketones has been performed effectively by pentacoordinate chloro-substituted tin hydride complex, Bu2SnClH-HMPA. The tin reagent worked particularly well for the case using weakly basic aromatic amines as starting substrates. Stoichiometric amounts of a substrate and a reducing agent were adequate for the reaction. The Sn-Cl bond in the complex plays an

  通过五配位氯取代的氢化锡络合物 Bu2SnClH-HMPA 可以有效地进行各种醛和酮的还原胺化。锡试剂在使用弱碱性芳香胺作为起始底物的情况下效果特别好。化学计量量的底物和还原剂足以进行反应。配合物中的 Sn-Cl 键在亚胺形成和随后的还原两个步骤中都起着重要作用。无论起始羰基和胺中的其他官能团如卤素、碳-碳双键和羟基如何，都可以实现羰基的高度化学选择性还原。
• Room-Temperature Copper-Catalyzed Carbon-Nitrogen Coupling of Aryl Iodides and Bromides Promoted by Organic Ionic Bases
  作者：Chu-Ting Yang、Yao Fu、Yao-Bing Huang、Jun Yi、Qing-Xiang Guo、Lei Liu

  DOI：10.1002/anie.200903158

  日期：2009.9.21

  solubility alone does not explain the performance of organic ionic bases in the room‐temperature coupling of aryl iodides and even bromides with aliphatic and aromatic amines and N‐heterocycles (NuH; see scheme). Conductivity measurements show that these organic ionic bases, which contain tetraalkylammonium or ‐phosphonium cations, are readily ionized in organic solvents.

  仅仅良好的溶解度并不能解释有机离子碱在芳基碘化物甚至溴化物与脂族和芳族胺以及N杂环的室温偶联中的性能（NuH；参见方案）。电导率测量表明，这些含有四烷基铵或阳离子的有机离子碱在有机溶剂中很容易被电离。
• Development of [3]ferrocenophane-derived N/B frustrated Lewis pairs for the metal-free catalytic hydrogenation of imines
  作者：Zhentao Pan、Hui Wang、Fei Ling、Lian Xiao、Dingguo Song、Weihui Zhong

  DOI：10.1080/00397911.2018.1555710

  日期：2019.2.16

  Abstract A series of novel [3]ferrocenophane-derived N/B frustrated Lewis pairs (FLPs) were synthesized and successfully applied to the catalytic hydrogenation of imines in 71-93% yields. This approach could be easily conducted on gram scale and provided versatile synthetic route for the key intermediate of sertraline hydrochloride without heavy metal residues. Graphical Abstract

  摘要 合成了一系列新型 [3] 二茂铁衍生的 N/B 受阻路易斯对 (FLPs) 并成功应用于亚胺的催化加氢，产率为 71-93%。这种方法可以很容易地在克规模上进行，并为盐酸舍曲林关键中间体的无重金属残留提供了通用的合成路线。图形概要
• Simple, efficient and reusable Pd–NHC catalysts for hydroamination
  作者：Qian Chen、Lanlan Lv、Meng Yu、Yanhui Shi、Yuling Li、Guangsheng Pang、Changsheng Cao

  DOI：10.1039/c3ra42990c

  日期：——

  series of chelating NHC–palladium complexes with different alkane-bridges of the type Pd[NHC–(CH2)n–NHC]X2 (X = Br or Cl, n = 2–4) were synthesized, where NHC is a triazolyl-N-heterocyclic carbene donor ligand. The bromide complexes with n = 2 and 3 were characterized by X-ray crystallography. The effects of the length of the bridge and halide ligand on the catalytic reactivity in the hydroamination reaction

  合成了一系列具有不同Pd [NHC–（CH 2）n –NHC] X 2（X = Br或Cl，n = 2–4）烷烃桥的螯合NHC-钯配合物。三唑基-N-杂环卡宾供体配体。X射线晶体学表征n = 2和3的溴化物配合物。研究了桥键和卤化物配体的长度对加氢胺化反应催化活性的影响。丙烯桥式Pd-NHC溴化物配合物2观察到最佳的催化性能。的加氢胺化苯乙炔 或者 4-甲基苯基乙炔用2催化的各种取代苯胺仅以良好的收率产生了马尔科夫尼科夫加成产物。有趣的是，这种均相催化剂可以重复使用三遍，而不会显着降低活性。