N-(+/-)-α-methylbenzyl-N-2,4,6-trichlorobenzylamine

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-(+/-)-α-methylbenzyl-N-2,4,6-trichlorobenzylamine
• 英文别名: 2,4,6-trichloro-N-(1-phenylethyl)aniline
• 化学式: C₁₄H₁₂Cl₃N
• mdl: MFCD11195726
• 分子量: 300.615
• InChiKey: JTVQOEOOMUSHQU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  18
• 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

• 作为产物：
  描述：

  2,4,6-三氯苯胺 在 二叔丁基过氧化物 、 [Cl2NN]Cu-OtBu 作用下， 以 正戊烷 为溶剂， 反应 24.08h， 生成 N-(+/-)-α-methylbenzyl-N-2,4,6-trichlorobenzylamine
  参考文献：
  名称：

  Copper(II) Anilides in sp³ C-H Amination

  摘要：

  We report a series of novel beta-diketiminato copper(II) anilides [Cl2NN]Cu-NHAr that participate in C-H amination. Reaction of H2NAr (Ar = 2,4,6-Cl3C6H2 (Ar-Cl3), 3,5-(CF3)(2)C6H3 (Ar-F6), or 2-py) with the copper(II) t-butoxide complex [Cl2NN]-Cu-(OBu)-O-t yields the corresponding copper(II) anilides [Cl2NN]-Cu-NHAr. X-ray diffraction of these species reveal three different bonding modes for the anilido moiety: kappa(1)-N in the trigonal [Cl2NN]Cu-NHArCl3 to dinuclear bridging in {[Cl2NN]Cu}(2)(mu-NHArF6)(2) and kappa(2)-N,N in the square planar [Cl2NN]Cu(kappa(2)-NH-2-py). Magnetic data reveal a weak antiferromagnetic interaction through a pi-stacking arrangement of [Cl2NN]Cu-NHArCl3; solution EPR data are consistent with monomeric species. Reaction of [Cl2NN]Cu-NHAr with hydrocarbons R-H (R-H = ethylbenzene and cyclohexane) reveals inefficient stoichiometric C-H amination with these copper(II) anilides. More rapid C-H amination takes place, however, when (BuOOBu)-Bu-t-Bu-t is used, which allows for HAA of R-H to occur from the (BuO center dot)-Bu-t radical generated by reaction of [Cl2NN]Cu and (BuOOBu)-Bu-t-Bu-t. The principal role of these copper(II) anilides [Cl2NN]Cu-NHAr is to capture the radical R-center dot generated from HAA by (BuO center dot)-Bu-t to give functionalized aniline R-NHAr, resulting in a novel amino variant of the Kharasch-Sosnovsky reaction.

  DOI：

  10.1021/ja5026547

文献信息

• Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations
  申请人：The University of Chicago

  公开号：US10647733B2

  公开（公告）日：2020-05-12

  Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

  基于以氮为供体的有机桥联配体，包括基于1,3-二酮亚胺（NacNac）、联吡啶和柳酸亚胺的金属-有机框架（MOFs）组成物被合成，然后用金属前驱体如第一行过渡金属的络合物进行后合成金属化。有机桥联配体的金属络合物也可以直接并入MOFs中。MOFs提供了一个多功能的、可回收和可重复使用的单点固体催化剂家族，用于催化各种不对称有机转化。这些固体催化剂也可以集成到流动反应器或超临界流体反应器中。
• Palladium-Catalyzed SN1 Reactions of Secondary Benzylic Alcohols: Etherification, Amination, and Thioetherification
  作者：Kimberly J. Miller、Mahdi M. Abu-Omar

  DOI：10.1002/ejoc.200390185

  日期：2003.3

  The reaction of various secondary benzylic alcohols in the presence of PdII catalysts provides ethers in good to high yields. Unsymmetric ethers could also be obtained with good selectivity by coupling two different alcohols. Direct amination is observed with electron-deficient anilines, and thioethers are prepared conveniently in high yields by the direct action of thiols on sec-phenylethyl alcohol

  各种仲苄醇在 PdII 催化剂存在下的反应以良好到高产率提供醚。不对称醚也可以通过偶联两种不同的醇以良好的选择性获得。用缺电子苯胺观察到直接胺化，硫醚通过硫醇对仲苯乙醇的直接作用以高产率方便地制备。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Catalytic CH Amination with Aromatic Amines
  作者：Raymond T. Gephart、Daria L. Huang、Mae Joanne B. Aguila、Graham Schmidt、Andi Shahu、Timothy H. Warren

  DOI：10.1002/anie.201201921

  日期：2012.6.25

  A β‐diketiminato copper(I) catalyst enables CH amination of anilines employing low catalyst loadings to preclude oxidation to the diazene ArNNAr (see scheme). Electron‐poor anilines are particularly resistant towards diazene formation and participate in the amination of strong and unactivated CH bonds. N‐alkyl anilines also take part in CH amination.

  苯胺加入俱乐部：一个β-二酮亚胺基铜（I）催化剂使C  ħ使用低催化剂载量，以排除氧化成氮烯ArNNAr苯胺的胺化（参见方案）。贫电子苯胺特别抗重氮形成，并参与强和未活化的CH键的胺化。N-烷基苯胺也参与CH胺化反应。
• 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。
• METAL-ORGANIC FRAMEWORKS CONTAINING NITROGEN-DONOR LIGANDS FOR EFFICIENT CATALYTIC ORGANIC TRANSFORMATIONS
  申请人：The University of Chicago

  公开号：US20170182486A1

  公开（公告）日：2017-06-29

  Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.