azobenzene-d₁₀ | 30504-49-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 偶氮苯
• 英文名称: azobenzene-d₁₀
• 英文别名: [D10]-azobenzene；Azobenzene-D10；bis(2,3,4,5,6-pentadeuteriophenyl)diazene
• CAS: 30504-49-5
• 化学式: C₁₂H₁₀N₂
• 分子量: 192.145
• InChiKey: DMLAVOWQYNRWNQ-LHNTUAQVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  azobenzene-d₁₀ 在 silver hexafluoroantimonate 、 dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 nitrosonium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以28.877%的产率得到
  参考文献：
  名称：

  Rhodium(III)-catalyzed regioselective C H nitrosation/annulation of unsymmetrical azobenzenes to synthesize benzotriazole N-oxides via a RhIII/RhIII redox-neutral pathway

  摘要：

  DOI：

  10.1016/j.tetlet.2021.153049
• 作为产物：
  描述：

  硝基苯-d5 在 silver(II) oxide 、 sodium hydroxide 、 锌 作用下， 生成 azobenzene-d₁₀
  参考文献：
  名称：

  A New Route to 4-Aminodiphenylamine via Nucleophilic Aromatic Substitution for Hydrogen: Reaction of Aniline and Azobenzene

  摘要：

  A new example of nucleophilic aromatic substitution for hydrogen is described which encompasses reacting aniline and azobenzene (1) in the presence of base under aerobic conditions to generate 4-(phenylazo)diphenylamine (2) in high yield. Monitoring the time course of the reaction under anaerobic conditions revealed that hydrazobenzene (9) was formed as an intermediate in the reaction in equal molar amounts as 2. However, under aerobic conditions 9 was shown not to persist in the reaction mixture. The kinetic effect of isotopic substitution on this reaction was probed by competition experiments utilizing equal molar mixtures azobenzene-d(10) and undeuterated material which gave a k(H)/k(D) of 4.6 +/- 0.1. It was concluded from these studies that azobenzene was functioning as both the electrophile and oxidant in this reaction. Catalytic hydrogenation of 2 generates 4-aminodiphenylamine (4-ADPA) (10) and aniline. These reactions form the basis of a novel synthetic route to 4-ADPA which does not utilize halogenated intermediates or reagents and ultimately relies on Oz as the terminal oxidant in the system.

  DOI：

  10.1021/jo00098a021

文献信息

• Rh(III)-catalyzed [4 + 1]-annulation of azobenzenes with α- carbonyl sulfoxonium ylides toward 3-acyl-(2H)-indazoles
  作者：Jiawei Zhu、Song Sun、Jiang Cheng

  DOI：10.1016/j.tetlet.2018.05.001

  日期：2018.6

  A Rh(III)-catalyzed [4 + 1]-annulation of azobenzenes with α- carbonyl sulfoxonium ylides was developed to access 2H-indazoles in moderate to excellent yields with good functional group compatibilities. It proceeded with the sequential insertion of the Rh(III) carbene to the C−H bond and cyclization steps, where sulfoxonium ylides served as efficient and stable carbene precursor.

  开发了Rh（III）催化的带有α-羰基亚砜基鎓盐的偶氮苯的[4 +1]环化反应，以中等到极好的收率获得了2 H-吲唑，并具有良好的官能团相容性。它先是将Rh（III）卡宾顺序插入到CH键中，然后进行环化步骤，其中sulf代亚砜作为有效且稳定的卡宾前体。
• Rh(III)-catalyzed annulation of azobenzenes and α-Cl ketones toward 3-acyl-2H-indazoles
  作者：Huan Li、Yuxuan Han、Zi Yang、Zhenyu Yao、Lianhui Wang、Xiuling Cui

  DOI：10.1016/j.cclet.2020.12.027

  日期：2021.5

  afforded in up to 97% yields for more than 30 examples. The obtained products are potentially valuable in organic synthesis and drug discovery. This protocol featured with high efficiency, extensive functional group tolerance and mild reaction conditions. The one-step efficient construction of an anti-inflammatory agent confirms the practicability of this procedure.

  已经开发了铑（III）与α- Cl酮催化的偶氮苯的[4 +1]环化反应。对于30多个实例，可以轻松以高达97％的收率获得3-Acyl-2 H-吲唑。所获得的产品在有机合成和药物开发中潜在有价值。该方案具有高效，广泛的官能团耐受性和温和的反应条件的特点。一步有效地构建抗炎剂，证实了该程序的实用性。
• One-pot Synthesis of Oxindoles through C−H Alkylation and Intramolecular Cyclization of Azobenzenes with Internal Olefins
  作者：Sang Hoon Han、Neeraj Kumar Mishra、Hyeim Jo、Yongguk Oh、Mijin Jeon、Saegun Kim、Woo Jung Kim、Jong Suk Lee、Hyung Sik Kim、In Su Kim

  DOI：10.1002/adsc.201700147

  日期：2017.7.17

  as maleimides, maleates and fumarates, followed by reductive intramolecular cyclization is described. A cationic rhodium catalyst in the presence of acetic acid additive in dichloroethane solvent was found to be the optimal catalytic system for the construction of ortho‐alkylated azobenzenes, which smoothly underwent the intramolecular cyclization leading to the formation of C3‐functionalized oxindoles

  描述了铑（III）催化的偶氮苯和内烯烃（例如马来酰亚胺，马来酸酯和富马酸酯）的位点CH烷基化反应，然后进行还原性分子内环化。发现在乙酸添加剂存在下于二氯乙烷溶剂中的阳离子铑催化剂是构建邻烷基化偶氮苯的最佳催化体系，该体系顺利进行了分子内环化反应，导致在存在下，形成C3官能化的吲哚。锌粉和乙酸。形成的羟吲哚支架可能是开发新型生物活性化合物的重要资产。
• Cobalt-Catalyzed Regioselective <i>para</i>-Amination of Azobenzenes via Nucleophilic Aromatic Substitution of Hydrogen
  作者：Yigao Tao、Rong Hu、Zeyu Xie、Ping Lin、Weiping Su

  DOI：10.1021/acs.joc.2c00026

  日期：2022.4.1

  The metal-catalyzed nucleophilic aromatic substitution of hydrogen (SNArH) via coordination of the substituent on the aromatic ring to the metal catalyst, in terms of reactivity, substrate type, and reaction selectivity, complements the transition metal-catalyzed C–H functionalization that proceeds via C–H metalation but remains an elusive target. Described herein is the development of an unprecedented

  通过芳环上的取代基与金属催化剂的配位，金属催化的氢的亲核芳族取代 (S N ArH) 在反应性、底物类型和反应选择性方面，补充了过渡金属催化的 C-H 官能化通过 C-H 金属化进行，但仍然是一个难以捉摸的目标。本文描述了一种前所未有的钴催化偶氮苯对位选择性胺化的发展，其本质上是由 Hammett 分析揭示的金属促进的 S N ArH 过程，从而说明了芳烃环上的取代基与金属催化剂可能导致芳烃环向 S N亲电活化氩气。这种钴催化的方案允许使用多种脂肪胺和苯胺作为胺化试剂，耐受偶氮苯的电子多样化取代基，并以良好的产率提供相应的产品，并对对胺化具有区域特异性选择性。
• Fusion of Aromatic Ring to Azoarenes: One-Pot Access to 5,6-Phenanthroliniums for Mitochondria-Targeted Far-Red/NIR Fluorescent Probes
  作者：Zheng Liu、Yonghua Xian、Jingbo Lan、Yuanyuan Luo、Weixin Ma、Jingsong You

  DOI：10.1021/acs.orglett.8b04072

  日期：2019.2.15

  Disclosed herein is a highly efficient strategy to fuse an aromatic ring to azoarenes for one-pot access to 5,6-phenanthrolinium skeletons via tandem ortho-C–H arylation and aryl quaternization. This protocol enables ortho-hindered azobenzenes to solely form 5-aryl-5,6-phenanthroliniums and ortho-unhindered azobenzenes to exclusively generate 5,7-diaryl-5,6-phenanthroliniums. The diarylated products

  本文公开了一种高效的策略，通过串联邻位-C-H芳基化和芳基季铵化作用，将芳族环与偶氮芳烃融合，从而可以一锅通地进入5,6-菲咯啉骨架。该方案使得邻位受阻的偶氮苯仅形成5-芳基-5,6-菲咯啉，邻位不受阻的偶氮苯仅产生5,7-二芳基-5,6-菲咯啉。二芳基化产物（5k - 5r）表现出远红至近红外发射（678-742 nm），斯托克斯位移大，可以特异性点亮活细胞中的线粒体，而且具有出色的光稳定性和低细胞毒性。