N-(4-chlorobenzyl)-4-nitroaniline

• 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-(4-chlorobenzyl)-4-nitroaniline
• 英文别名: N-[(4-chlorophenyl)methyl]-4-nitroaniline
• 化学式: C₁₃H₁₁ClN₂O₂
• mdl: MFCD11124534
• 分子量: 262.696
• InChiKey: JUDCNWPXYMSGHM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.076
• 拓扑面积：
  57.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1-(4-氯苯基)-N-(4-硝基苯基)甲亚胺 在 polymethylhydrosiloxane 作用下， 以 二氯甲烷 为溶剂， 生成 N-(4-chlorobenzyl)-4-nitroaniline
  参考文献：
  名称：

  Polymethylhydrosiloxane (PMHS)/trifluoroacetic acid (TFA): a novel system for reductive amination reactions

  摘要：

  Polymethylhydrosiloxine (PMHS)/trifluoroacetic acid (TFA) was discovered as a novel metal-free system for reductive amination reactions. A variety of(het)aryl amines as well as a representative carbamate and urea were successfully alkylated by benzaldehyde in the presence of PMHS and TFA in dichloromethane at room temperature in moderate to excellent yields (28-87%). Furthermore, this reaction protocol was Successfully applied to the alkylation of p-nitroaniline with a wide range of aldehydes, ketones, and a representative acetal to obtain the alkylated products in yields ranging from 40% to 92%. The current work represents one of the very few examples of PMHS being activated by a Bronsted acid. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2009.08.048

文献信息

• Copper-catalyzed direct amination of benzylic hydrocarbons and inactive aliphatic alkanes with arylamines
  作者：Hua Yao、Bo Xie、Xiaoyang Zhong、Shengzhou Jin、Sen Lin、Zhaohua Yan

  DOI：10.1039/d0ob00491j

  日期：——

  A new synthetic method toward direct C-N bond formation through saturated C-H amination of benzylic hydrocarbons and inactive aliphatic alkanes with primary aromatic amines under an inexpensive catalyst/oxidant (Cu/DTBP) system has been developed. Both aminopyridines and anilines could react smoothly with primary and secondary benzylic C-H substrates or cyclohexane to form the corresponding aromatic

  在廉价的催化剂/氧化剂（Cu / DTBP）系统下，已经开发出一种新的合成方法，该方法可通过苄基烃和惰性脂肪族烷烃与伯芳族胺的饱和CH胺化直接形成CN键。氨基吡啶和苯胺均可与伯和仲苄基CH底物或环己烷顺利反应，以中等至良好的收率形成相应的芳族仲胺。该协议的优点是宽泛的官能团耐受性和使用现成的原料。
• Competitive Reaction Pathways in the Nucleophilic Substitution Reactions of Aryl Benzenesulfonates with Benzylamines in Acetonitrile
  作者：Jin Heui Choi、Byung Choon Lee、Hai Whang Lee、Ikchoon Lee

  DOI：10.1021/jo0161835

  日期：2002.2.1

  The reactions of aryl benzenesulfonates (YC6H4SO2OC6H4Z) with benzylamines (XC6H4CH2NH2) in acetonitrile at 65.0 degrees C have been studied. The reactions proceed competitively by S-O (kS-O) and C-O (kC-O) bond scission, but the former provides the major reaction pathway. On the basis of analyses of the Hammett and Brönsted coefficients together with the cross-interaction constants rho(XY), rho(YZ)

  研究了芳基苯磺酸盐（YC6H4SO2OC6H4Z）与苄胺（XC6H4CH2NH2）在乙腈中于65.0摄氏度下的反应。反应通过SO（kS-O）和CO（kC-O）键分裂而竞争地进行，但前者提供了主要的反应途径。在分析Hammett和Brönsted系数以及交叉相互作用常数rho（XY），rho（YZ）和rho（XZ）的基础上，提出了通过限速形成SO键裂解的逐步机理三角-双锥体五元（TBP-5C）中间体，而CO键断裂则是通过限速从Meisenheimer型络合物中排出磺酸根阴离子（YC6H4SO3-）来进行的。
• A binuclear Cu(<scp>ii</scp>) complex as an efficient photocatalyst for <i>N</i>-alkylation of aromatic amines
  作者：Rishi Ranjan、Argha Chakraborty、Reena Kyarikwal、Rakesh Ganguly、Suman Mukhopadhyay

  DOI：10.1039/d2dt01771g

  日期：——

  Visible-light driven photoreactions using transition metal complexes as catalysts are currently a research hotspot in developing environmentally friendly sustainable processes. To develop a potential copper-based photocatalyst, a binuclear Cu(II) complex has been synthesized using a Mannich base ligand viz. 2,4-dichloro-6-((4-(2-hydroxyethyl)piperazin-1-yl)methyl)phenol (H2L). The photocatalyst has

  使用过渡金属配合物作为催化剂的可见光驱动光反应目前是开发环保可持续工艺的研究热点。为了开发一种潜在的铜基光催化剂，使用曼尼希碱配体即合成了双核 Cu( II ) 配合物。2,4-二氯-6-((4-(2-羟乙基)哌嗪-1-基)甲基)苯酚( H 2 L )。已使用 ESI-MS 和单晶 X 射线衍射对光催化剂进行了表征。在可见光照射下，该催化剂可催化氢在N中的自转移-烷基化胺形成和苯甲醇氧化反应，转化率极好。通过 ESI-MS 光谱、UV-Vis 光谱和计算研究探索了催化反应的合理机制途径。
• N-coordinated Ru(II) Catalyzed Solvent Free N-alkylation of Primary Amines with Alcohols through Borrowing Hydrogen Strategy
  作者：Bhavya Patel、Rishi Ranjan、Nimesh R. Chauhan、Suman Mukhopadhyay、Angshuman Roychoudhury、Komal M Vyas

  DOI：10.1039/d3nj00210a

  日期：——

  conditions. This drastic variation in catalytic performance was observed due to the co-operative effect of –NH2 in [Ru-1] and [Ru-3]. Metal–ligand cooperation (MLC) in both the complexes stabilizes the intermediate transition state and also the electron deficient Ru(II) center in [Ru-1] has very good binding affinity towards the substrate, which leads to superior catalytic conversion with [Ru-1] compared to

  借用氢化 (BH) 是一种强大的方法，广泛用于使用均相分子催化剂将胺与醇进行N-烷基化。为了探索化学性质，本文介绍了两种新型单体 Ru( II ) 配合物 [(η 6 - p -cymene)Ru(L1)Cl 2 ] [Ru-1]，带有 4-三氟甲氧基苯胺 (L1) 和 [(η 6 - p - cymene)Ru(L2)Cl] [Ru-2]合成了奎哪酸 (L2)，并利用 FTIR、1 H 和13等分析和光谱方法揭示了它们的结构特征C NMR、ESI-MS 和元素分析。[Ru-1]和[Ru-2]的晶格结构均通过单晶 XRD (SC-XRD) 阐明。此外，根据文献合成了基于苯胺的络合物[Ru-3]并用于比较。[ Ru-(1–3) ]的催化功效在良性和无溶剂条件下使用醇作为烷化剂对胺进行N-烷基化进行了检查。通过 GC-MS 和 HPLC 分析监测催化性能。基于伯胺 (L1) 的络合物[Ru-1]表现出令人印象深刻的
• Highly active primary amine ligated Ru(II)-arene complexes as selective catalysts for solvent-free N-alkylation of Anilines
  作者：Bhaskarjyoti Sarma、Rishi Ranjan、Nimesh R. Chauhan、Suman Mukhopadhyay、Angshuman Roy Choudhury、Komal M. Vyas

  DOI：10.1016/j.mcat.2023.113440

  日期：2023.9

  conversion of primary amine to secondary amine using alcohols under milder and solvent-free conditions and compared with the reported aniline-based Ru(II)-arene complex [Ru-3]. Among them, [Ru-1] could achieve 100% selectivity towards mono N-alkylated amines with > 99% conversion without formation of any imine derivatives. The results suggested that the lone pair of electrons of benzyl alcohol binds easily

  合成了具有取代苯胺基配体的高效Ru(II)催化剂，其化学式为[Ru(η 6 -对伞花烃)Cl 2 (L1)] [Ru-1]和[Ru(η 6 -对伞花烃)Cl 2 (L2)] [Ru-2]（其中，L1 = 3,5-双（三氟甲基）苯胺且 L2 = 3,4,5-三甲氧基苯胺）。两种配合物的结构特征均通过 ESI-MS、1 H 和13 C NMR、FT-IR、元素分析和单晶 X 射线衍射研究进行了验证。[Ru-1]和[Ru-2]的催化性能研究了在较温和且无溶剂的条件下使用醇将伯胺转化为仲胺的情况，并与报道的苯胺基 Ru(II)-芳烃络合物[Ru-3]进行比较。其中，[Ru-1]对单N-烷基化胺具有100%的选择性，转化率>99%，且不形成任何亚胺衍生物。结果表明，苯甲醇的孤对电子很容易与[Ru-1]催化剂的缺电子Ru(II)中心结合，使其比富电子的[Ru-2]和[Ru-3]更有效]催化剂。[Ru-1]的催化性能证明它是最活跃的伯胺连接