N-(4-methoxy-3-methylphenyl)pyridin-2-amine | 1427730-90-2

• 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-methoxy-3-methylphenyl)pyridin-2-amine
• 英文别名: N-(4-Methoxy-3-methylphenyl)-2-pyridinamine
• CAS: 1427730-90-2
• 化学式: C₁₃H₁₄N₂O
• 分子量: 214.267
• InChiKey: BXRKUESRUJKWSO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  34.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(4-methoxy-3-methylphenyl)pyridin-2-amine 在 silver(I) nitrite 、 氧气 、 cobalt(II) diacetate tetrahydrate 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以71%的产率得到N-(4-methoxy-5-methyl-2-nitrophenyl)pyridin-2-amine
  参考文献：
  名称：

  通过质子耦合电子转移辅助钴催化的芳香族区域选择性邻位C（sp 2）-H键硝化

  摘要：

  钴的催化质子偶联电子转移（PCET）介导的芳香族C（sp 2）-H键使用螯合辅助可移动邻二胺导向基团的区域选择性邻位硝化。反应在温和条件下，在作为催化剂的Co（OAc）2 ·4H 2 O存在下，在O 2存在下，将AgNO 2用作硝基源以及末端氧化剂，进行了反应。作为外部氧化剂。此过程不需要外部碱或添加剂。通过DFT计算进行的对照实验和机理研究表明，该反应通过PCET促进的硝基官能团转移途径进行。而且，所产生的化合物是有价值的并且在药学上非常相关。

  DOI：

  10.1021/acs.joc.7b00808
• 作为产物：
  描述：

  2-碘吡啶 、 4-甲氧基-3-甲基苯胺 在 tris-(dibenzylideneacetone)dipalladium(0) 、 potassium tert-butylate 、 双(2-二苯基磷苯基)醚 作用下， 以 水 、 乙酸乙酯 、 甲苯 为溶剂， 以80%的产率得到N-(4-methoxy-3-methylphenyl)pyridin-2-amine
  参考文献：
  名称：

  Direct Ortho Arylation of 9-(Pyridin-2-yl)-9H-carbazoles Bearing a Removable Directing Group via Palladium(II)-Catalyzed C–H Bond Activation

  摘要：

  A one-pot synthesis of ortho-arylated 9-(pyridin-2-yl)-9H-carbazoles via C-H bond activation is presented. Silver nitrate and tert-butyl alcohol were found to be the best oxidant and solvent for the process, respectively. The product yields are from modest to excellent, and the reaction showed sufficient functional group tolerance. p-Benzoquinone served as an important ligand for the transmetalation and reductive elimination steps in the catalytic process. The key intermediate of the reaction, a 9-(pyridin-2-yl)-9H-carbazole palladacycle, was isolated, and its structure was unequivocally confirmed by X-ray crystallography. No kinetic isotope effect (k(H)/k(D) = 1.00 +/- 0.17) for the C-H bond activation step was observed. In addition, a Hammett experiment gave a negative rho value, -2.16 +/- 0.02. The directing group, pyridinyl, was demonstrated to be a removable functional group. Finally, a rational catalytic mechanism is presented on the basis of all experimental evidence.

  DOI：

  10.1021/om301071m

文献信息

• Palladium/Silver Synergistic Catalysis in Direct Aerobic Carbonylation of C(sp²)<i>−</i>H Bonds Using DMF as a Carbon Source: Synthesis of Pyrido-Fused Quinazolinones and Phenanthridinones
  作者：D. Nageswar Rao、Sk. Rasheed、Parthasarathi Das

  DOI：10.1021/acs.orglett.6b01292

  日期：2016.7.1

  An unprecedented Pd/Ag synergistic catalysis in the direct carbonylation of C(sp2)–H bonds utilizing DMF as the carbon source under oxygen is described and demonstrated in the synthesis of pyrido-fused quinazolinone and phenanthridinone scaffolds. Control experiments indicated that the “C” of the carbonyl group is derived from the methyl group of DMF and “O” originates from oxygen as in the case of

  在吡啶基-稠合的喹唑啉酮和菲啶酮支架的合成中，描述并证明了空前的Pd / Ag协同催化C（sp 2）-H键直接羰基化（利用DMF作为碳源）。对照实验表明，羰基的“ C”源自DMF的甲基，而“ O”源自氧，与Ge的最新研究一样。这种转变为“不含CO”的羰基化提供了另一种途径。
• Direct Ortho Arylation of 9-(Pyridin-2-yl)-9<i>H</i>-carbazoles Bearing a Removable Directing Group via Palladium(II)-Catalyzed C–H Bond Activation
  作者：Jean-Ho Chu、Chung-Chiu Wu、Deng-Hsiang Chang、Ya-Ming Lee、Ming-Jung Wu

  DOI：10.1021/om301071m

  日期：2013.1.14

  A one-pot synthesis of ortho-arylated 9-(pyridin-2-yl)-9H-carbazoles via C-H bond activation is presented. Silver nitrate and tert-butyl alcohol were found to be the best oxidant and solvent for the process, respectively. The product yields are from modest to excellent, and the reaction showed sufficient functional group tolerance. p-Benzoquinone served as an important ligand for the transmetalation and reductive elimination steps in the catalytic process. The key intermediate of the reaction, a 9-(pyridin-2-yl)-9H-carbazole palladacycle, was isolated, and its structure was unequivocally confirmed by X-ray crystallography. No kinetic isotope effect (k(H)/k(D) = 1.00 +/- 0.17) for the C-H bond activation step was observed. In addition, a Hammett experiment gave a negative rho value, -2.16 +/- 0.02. The directing group, pyridinyl, was demonstrated to be a removable functional group. Finally, a rational catalytic mechanism is presented on the basis of all experimental evidence.
• Cobalt-Catalyzed Regioselective Ortho C(sp²)-H Bond Nitration of Aromatics through Proton-Coupled Electron Transfer Assistance
  作者：Desaboini Nageswar Rao、Sk. Rasheed、Gaurav Raina、Qazi Naveed Ahmed、Chaitanya Kumar Jaladanki、Prasad V. Bharatam、Parthasarathi Das

  DOI：10.1021/acs.joc.7b00808

  日期：2017.7.21

  A cobalt-catalyzed proton-coupled electron transfer (PCET) mediated regioselective ortho-specific nitration of aromatic C(sp2)-H bonds using chelation-assisted removable vicinal diamine directing groups was developed. The reaction proceeded under mild conditions in the presence of Co(OAc)2·4H2O as the catalyst with AgNO2 utilized as the nitro source as well as terminal oxidant in the presence of O2

  钴的催化质子偶联电子转移（PCET）介导的芳香族C（sp 2）-H键使用螯合辅助可移动邻二胺导向基团的区域选择性邻位硝化。反应在温和条件下，在作为催化剂的Co（OAc）2 ·4H 2 O存在下，在O 2存在下，将AgNO 2用作硝基源以及末端氧化剂，进行了反应。作为外部氧化剂。此过程不需要外部碱或添加剂。通过DFT计算进行的对照实验和机理研究表明，该反应通过PCET促进的硝基官能团转移途径进行。而且，所产生的化合物是有价值的并且在药学上非常相关。