2,2'-dibromo-4,4'-dimethoxydiphenylamine | 540464-01-5

• 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: 2,2'-dibromo-4,4'-dimethoxydiphenylamine
• 英文别名: 2-bromo-N-(2-bromo-4-methoxyphenyl)-4-methoxyaniline
• CAS: 540464-01-5
• 化学式: C₁₄H₁₃Br₂NO₂
• 分子量: 387.071
• InChiKey: ABXDCKFLMZLIIK-UHFFFAOYSA-N

物化性质

• 沸点：
  403.3±45.0 °C(Predicted)
• 密度：
  1.641±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  30.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,2'-dibromo-4,4'-dimethoxydiphenylamine 在 正丁基锂 、 六甲基二硅氮烷 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 氘代苯 为溶剂， 反应 21.08h， 生成
  参考文献：
  名称：

  Comparison of the Electronic Properties of Diarylamido-Based PNZ Pincer Ligands: Redox Activity at the Ligand and Donor Ability Toward the Metal

  摘要：

  This paper presents the synthesis and characterization of a series of pincer ligands and their Ni, Pd, Pt, and Rh complexes. The ligands under examination are based on a diarylamine which is modified either by two phosphino (-PR2) substituents in the ortho-positions (PNP ligands) or by a cornbination of a phosphino and an iminyl (-CH=NX) substituent (PNN ligands). The ligands can be broken down into three groups: (a) C-2v-symmetric PNP ligands with identical side -PR2 donors, (b) C-2-Symmetric PNP' ligands with different-PR2 side donors, and (c) PNN ligands containing a -PPr2 side donor. All of the ligands under study readily formed square-planar complexes of the types (PNZ)PdCl, (pNZ)Pd(OAc), and (PNZ)RhCO, where PNZ is the corresponding anionic tridentate pincer ligand. For select PNP ligands, (PNP)NiCl and (PNP)PtCl were also studied. The (PNZ)MCl complexes (M = Ni, Pd, Pt) underwent quasireversible oxidation in cyclic voltammetry experiments, Based on the close similarity of formal potentials for Pd, and Pt analogs, and based on the previous literature evidence, these oxidation events are ascribed primarily to the PNZ ligand, and the E-1/2 values can be used to compare the ease of oxidation of different ligands. A (PNP)PdCl complex containing methoxy substituents para- to the central nitrogen underwent two quasireversible oxidations. Two mono-oxidized complexes were isolated and structurally characterized in comparison to their neutral analog, revealing minimal changes in the bond distances and angles. Several other neutral complexes were also structurally characterized. The carbonyl stretching frequency in (PN-Z)RhCO complexes was used to gauge the donating ability of the various pincer ligands toward the metal. Comparison of E-1/2 values for (PNZ)PdCl and v(CO) values for (PNZ)RhCO revealed that the two are not consistently correlated across all the studied ligands and can be tuned to different degrees through judicious ligand alteration.

  DOI：

  10.1021/ic503062w
• 作为产物：
  描述：

  4-溴苯甲醚 在 1,1'-双(二苯基膦)二茂铁 、 N-溴代丁二酰亚胺(NBS) 、 palladium diacetate 、 sodium tert-pentoxide 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 60.0h， 生成 2,2'-dibromo-4,4'-dimethoxydiphenylamine
  参考文献：
  名称：

  Comparison of the Electronic Properties of Diarylamido-Based PNZ Pincer Ligands: Redox Activity at the Ligand and Donor Ability Toward the Metal

  摘要：

  This paper presents the synthesis and characterization of a series of pincer ligands and their Ni, Pd, Pt, and Rh complexes. The ligands under examination are based on a diarylamine which is modified either by two phosphino (-PR2) substituents in the ortho-positions (PNP ligands) or by a cornbination of a phosphino and an iminyl (-CH=NX) substituent (PNN ligands). The ligands can be broken down into three groups: (a) C-2v-symmetric PNP ligands with identical side -PR2 donors, (b) C-2-Symmetric PNP' ligands with different-PR2 side donors, and (c) PNN ligands containing a -PPr2 side donor. All of the ligands under study readily formed square-planar complexes of the types (PNZ)PdCl, (pNZ)Pd(OAc), and (PNZ)RhCO, where PNZ is the corresponding anionic tridentate pincer ligand. For select PNP ligands, (PNP)NiCl and (PNP)PtCl were also studied. The (PNZ)MCl complexes (M = Ni, Pd, Pt) underwent quasireversible oxidation in cyclic voltammetry experiments, Based on the close similarity of formal potentials for Pd, and Pt analogs, and based on the previous literature evidence, these oxidation events are ascribed primarily to the PNZ ligand, and the E-1/2 values can be used to compare the ease of oxidation of different ligands. A (PNP)PdCl complex containing methoxy substituents para- to the central nitrogen underwent two quasireversible oxidations. Two mono-oxidized complexes were isolated and structurally characterized in comparison to their neutral analog, revealing minimal changes in the bond distances and angles. Several other neutral complexes were also structurally characterized. The carbonyl stretching frequency in (PN-Z)RhCO complexes was used to gauge the donating ability of the various pincer ligands toward the metal. Comparison of E-1/2 values for (PNZ)PdCl and v(CO) values for (PNZ)RhCO revealed that the two are not consistently correlated across all the studied ligands and can be tuned to different degrees through judicious ligand alteration.

  DOI：

  10.1021/ic503062w

文献信息

• para-Phenylene-Bridged Spirobi(triarylamine) Dimer with Four Perpendicularly Linked Redox-Active π Systems
  作者：Akihiro Ito、Kazuhira Hata、Kensuke Kawamoto、Yasukazu Hirao、Kazuyoshi Tanaka、Motoo Shiro、Ko Furukawa、Tatsuhisa Kato

  DOI：10.1002/chem.201000848

  日期：2010.9.17

  para‐Phenylene‐bridged spirobi(triarylamine) dimer 2, in which π conjugation through four redox‐active triarylamine subunits is partially segregated by the unique perpendicular conformation, was prepared and characterized by structural, electrochemical, and spectroscopic methods. Quantum chemical calculations (DFT and CASSCF) predicted that the frontier molecular orbitals of 2 are virtually fourfold

  制备了对苯撑桥联的螺双（三芳基胺）二聚体2，其中通过四个氧化还原活性三芳基胺亚基的π共轭通过独特的垂直构象部分隔离，并通过结构，电化学和光谱方法进行了表征。量子化学计算（DFT和CASSCF）预测2的前沿分子轨道实际上退化了四倍，因此2的氧化态可提供有趣的电子和磁性。实际上，自由基阳离子2。+的连续波ESR光谱。结果表明，未成对的电子被困在内部两个氧化还原活性的二苯胺基亚基中，而且在它们的上方已完全离域。可以通过用SbCl 5处理制备的2的分离盐的磁化率测量和脉冲ESR光谱显示，生成的四阳离子2 4+主要分解为1）分解的四（自由基阳离子）的混合物，该混合物由ab组成。三（自由基阳离子）部分和trianisylamine自由基阳离子部分（≈75％）和2）在tetraanisyl-抗磁醌型双阳离子p-苯二胺部分和两个三茴香胺自由基阳离子部分（约25％）。此外，发现分解的四（自由基）阳离子中三（
• A Spiro-Fused Triarylaminium Radical Cation with a Triplet Ground State
  作者：Akihiro Ito、Masashi Urabe、Kazuyoshi Tanaka

  DOI：10.1002/anie.200390244

  日期：2003.2.24