bis(1-methyl-2-methylbenzimidazolyl)benzylamine | 944777-99-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并咪唑类
• 英文名称: bis(1-methyl-2-methylbenzimidazolyl)benzylamine
• 英文别名: bis(N-methylbenzimidazol-2-ylmethyl)benzylamine；Benzyl-bis-(1-methyl-1h-benzoimidazol-2-ylmethyl)-amine；N,N-bis[(1-methylbenzimidazol-2-yl)methyl]-1-phenylmethanamine
• CAS: 944777-99-5
• 化学式: C₂₅H₂₅N₅
• 分子量: 395.507
• InChiKey: HBBBYCPPAGIAMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  38.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tetrakis(actonitrile)copper(I) hexafluorophosphate 、 bis(1-methyl-2-methylbenzimidazolyl)benzylamine 以 丙酮 、 乙腈 为溶剂， 以79%的产率得到[(bis(1-methyl-2-methylbenzimidazolyl)benzylamine)Cu(MeCN)]PF6
  参考文献：
  名称：

  Structural, spectroscopic, and electrochemical properties of tri- and tetradentate N3 and N3S copper complexes with mixed benzimidazole/thioether donors

  摘要：

  双(2-甲基苯并咪唑基)(2-甲基噻吩)胺(L1)、双(2-甲基苯并咪唑基)苄胺(L2)、双(2-甲基苯并咪唑基)(2,4-二甲基苯硫基乙基)胺(L3)的铜和亚铜络合物，双(1-甲基-2-甲基苯并咪唑基)苯甲胺 (Me2L2) 和双(1-甲基-2-甲基苯并咪唑基)(2,4-二甲基苯硫基乙基)胺 (Me2L3) 已进行光谱、结构和电化学表征。紫外-可见光谱和 X 射线晶体学证明，含硫醚的配体 L3 和 Me2L3 在溶液和固态下均可生成具有 Cu-S 键的络合物。根据 ESI 质谱数据，Cu2+ 络合物 [L1CuCl2] (1)、[L2CuCl2] (2) 和 [Me2L3CuCl]ClO4 (3Me,ClO4) 在溶液中以及固态下都是单体。它们的 Cu+ 类似物 [L1Cu]ClO4、[L2Cu]ClO4、[L3Cu]ClO4 (4–6)、[BOC2L1Cu(NCCH3)]ClO4 (4BOC)、[Me2L2Cu(NCCH3)2]PF6 (5Me) 和 [Me2L3Cu]2 (ClO4)2 (6Me) 在乙腈溶液中也是单体，正如 4BOC 和 5Me 的晶体学所证实的那样。相比之下，6Me 是固态二聚体，其中一个配体的硫醚基团与对称相关的 Cu+ 离子结合。循环伏安研究表明，双(2-甲基苯并咪唑基)胺-Cu2+/Cu+体系的半波电位范围为-0.16至-0.08 V（参考二茂铁-二茂铁电偶）；这些值比相关双(吡啶甲基)胺衍生配体报道的负值低近 0.23 V。基于这些观察，苯并咪唑衍生配体的 N3 或 N3S 供体组类似于之前报道的螯合系统，但它们提供的电子环境是独特的，并且可能与含组氨酸和蛋氨酸的金属酶有关。这也反映在 [Me2L2Cu(NCCH3)2]+ (5Me) 和 [Me2L3Cu]+ (6Me) 对分子氧的反应性上，这两种情况都会产生超氧阴离子。 6Me 中与硫醚结合的 Cu+ 中心似乎比 5Me 更有选择性地生成 O2˙−，这为硫醚配体在 Cu-O2 反应中的调节特性的假设提供了证据。

  DOI：

  10.1039/c2dt30756a
• 作为产物：
  描述：

  苄胺 在 sodium carbonate 作用下， 生成 bis(1-methyl-2-methylbenzimidazolyl)benzylamine
  参考文献：
  名称：

  Synthesis, crystal structure, DNA-binding properties, and antioxidant activity of a V-shaped ligand bis(N-methylbenzimidazol-2-ylmethyl)benzylamine and its zinc(II) complex

  摘要：

  A V-shaped ligand bis(N-methylbenzimidazol-2-ylmethyl)benzylamine (L) and its zinc(II) complex, [ZnL 2](pic)2?.?2CH3CN (pic?=?picrate), have been synthesized and characterized by physico-chemical and spectroscopic methods. Single-crystal X-ray crystallographic analysis revealed that the Zn(II) complex possesses a distorted trigonal bipyramidal geometry. Supramolecular interactions arising from various intra- or intermolecular p center dot center dot center dot p stacking interactions contributed to the form of the multidimensional configuration. Interactions of L and Zn(II) complex with DNA were monitored using spectrophotometric methods and viscosity measurements. The results suggest that L and Zn(II) complex both bind to DNA via intercalation and Zn(II) complex binds to DNA more strongly than L. Moreover, the Zn(II) complex also exhibited potential antioxidant properties in vitro.

  DOI：

  10.1080/00958972.2012.741229

文献信息

• Synthesis, structure, DNA-binding properties and antioxidant activity of silver(i) complexes containing V-shaped bis-benzimidazole ligands
  作者：Huilu Wu、Jingkun Yuan、Ying Bai、Guolong Pan、Hua Wang、Jin Kong、Xuyang Fan、Hongmei Liu

  DOI：10.1039/c2dt30512g

  日期：——

  A V-shaped ligand bis(2-benzimidazol-2-ylmethyl)benzylamine L1 with its two derivatives bis(N-methylbenzimidazol-2-ylmethyl)benzylamine L2 and bis(N-benzylbenzimidazol-2-ylmethyl)benzylamine L3 have been prepared. Reaction of these shape-specific designed ligands with Ag(pic) (pic = picrate) afforded three novel complexes, namely, [Ag2L12](pic)21, [Ag2L22](pic)2·2DMF 2 and [AgL3(pic)] 3. The ligands and complexes were characterized on the basis of elemental analysis, UV-Vis, IR, NMR spectroscopy and X-ray crystallography. Complex 1 is a dinuclear metallacycle with a 2-fold rotational symmetry in which two syn-conformational L1 ligands are connected by two linearly coordinated Ag(I) atoms. Due to the strong interaction between two adjacent Ag(I) atoms, the coordination mode of the central Ag(I) atom can be described as T-shaped. Complex 2 consists of a centrosymmetric dinuclear pore canal structure assembled from two nearly linearly coordinated Ag(I) atoms and two L2 ligands. The structure of complex 3 adopts a four-coordinate environment for AgN2O2, with the counterion participating in an eight-shaped geometry. In order to explore the relationship between the structure and biological properties, the DNA-binding properties have been investigated by viscosity measurements, electronic absorption, and fluorescence. The results suggest that the ligands and complexes bind to DNA in an intercalation mode, and their binding affinities for DNA are also different. Moreover, the three Ag(I) complexes also exhibited potential antioxidant properties in vitro studies.

  制备了一种V形配体双(2-苯并咪唑-2-基甲基)苄胺L1及其两种衍生物双(N-甲基苯并咪唑-2-基甲基)苄胺L2和双(N-苄基苯并咪唑-2-基甲基)苄胺L3。这些特定形状设计的配体与Ag(苦味酸根离子)(pic=苦味酸根离子)反应，得到了三种新型配合物，即[Ag2L12](pic)21、[Ag2L22](pic)2·2DMF 2和[AgL3(pic)] 3。根据元素分析、紫外-可见光谱、红外光谱、核磁共振波谱和X射线晶体学对配体和配合物进行了表征。配合物1是一种具有2重旋转变换对称性的双核金属环，其中两个顺式构象的L1配体通过两个线性配位的Ag(I)原子连接。由于两个相邻的Ag(I)原子之间存在较强的相互作用，中心Ag(I)原子的配位模式可以描述为T形。配合物2由两个近似线性配位的Ag(I)原子和两个L2配体组装成了一个中心对称的双核孔道结构。配合物3采用了AgN2O2的四配位环境，并且反离子参与了8字形几何构型。为了探究结构和生物活性之间的关系，通过粘度测定、电子吸收和荧光光谱法研究了其与DNA的结合特性。结果表明，配体和配合物均以插入方式结合DNA，并且它们对DNA的结合亲和力也不同。此外，三种Ag(I)配合物在体外研究中还表现出潜在的抗氧化性质。
• Structural, spectroscopic, and electrochemical properties of tri- and tetradentate N3 and N3S copper complexes with mixed benzimidazole/thioether donors
  作者：Ivan Castillo、Víctor M. Ugalde-Saldívar、Laura A. Rodríguez Solano、Brenda N. Sánchez Eguía、Erica Zeglio、Ebbe Nordlander

  DOI：10.1039/c2dt30756a

  日期：——

  Cupric and cuprous complexes of bis(2-methylbenzimidazolyl)(2-methylthiophene)amine (L1), bis(2-methylbenzimidazolyl)benzylamine (L2), bis(2-methylbenzimidazolyl)(2,4-dimethylphenylthioethyl)amine (L3), bis(1-methyl-2-methylbenzimidazolyl)benzylamine (Me2L2), and bis(1-methyl-2-methylbenzimidazolyl)(2,4-dimethylphenylthioethyl)amine (Me2L3) have been spectroscopically, structurally, and electrochemically characterised. The thioether-containing ligands L3 and Me2L3 give rise to complexes with Cu–S bonds in solution and in the solid state, as evidenced by UV-vis spectroscopy and X-ray crystallography. The Cu2+ complexes [L1CuCl2] (1), [L2CuCl2] (2) and [Me2L3CuCl]ClO4 (3Me,ClO4) are monomeric in solution according to ESI mass spectrometry data, as well as in the solid state. Their Cu+ analogues [L1Cu]ClO4, [L2Cu]ClO4, [L3Cu]ClO4 (4–6), [BOC2L1Cu(NCCH3)]ClO4 (4BOC), [Me2L2Cu(NCCH3)2]PF6 (5Me) and [Me2L3Cu]2(ClO4)2 (6Me) are also monomeric in acetonitrile solution, as confirmed crystallographically for 4BOC and 5Me. In contrast, 6Me is dimeric in the solid state, with the thioether group of one of the ligands bound to a symmetry-related Cu+ ion. Cyclic voltammetry studies revealed that the bis(2-methylbenzimidazolyl)amine-Cu2+/Cu+ systems possess half-wave potentials in the range −0.16 to −0.08 V (referenced to the ferrocenium–ferrocene couple); these values are nearly 0.23 V less negative than those reported for related bis(picolyl)amine-derived ligands. Based on these observations, the N3 or N3S donor set of the benzimidazole-derived ligands is analogous to previously reported chelating systems, but the electronic environment they provide is unique, and may have relevance to histidine and methionine-containing metalloenzymes. This is also reflected in the reactivity of [Me2L2Cu(NCCH3)2]+ (5Me) and [Me2L3Cu]+ (6Me) towards dioxygen, which results in the production of the superoxide anion in both cases. The thioether-bound Cu+ centre in 6Me appears to be more selective in the generation of O2˙− than 5Me, lending evidence to the hypothesis of the modulating properties of thioether ligands in Cu–O2 reactions.

  双(2-甲基苯并咪唑基)(2-甲基噻吩)胺(L1)、双(2-甲基苯并咪唑基)苄胺(L2)、双(2-甲基苯并咪唑基)(2,4-二甲基苯硫基乙基)胺(L3)的铜和亚铜络合物，双(1-甲基-2-甲基苯并咪唑基)苯甲胺 (Me2L2) 和双(1-甲基-2-甲基苯并咪唑基)(2,4-二甲基苯硫基乙基)胺 (Me2L3) 已进行光谱、结构和电化学表征。紫外-可见光谱和 X 射线晶体学证明，含硫醚的配体 L3 和 Me2L3 在溶液和固态下均可生成具有 Cu-S 键的络合物。根据 ESI 质谱数据，Cu2+ 络合物 [L1CuCl2] (1)、[L2CuCl2] (2) 和 [Me2L3CuCl]ClO4 (3Me,ClO4) 在溶液中以及固态下都是单体。它们的 Cu+ 类似物 [L1Cu]ClO4、[L2Cu]ClO4、[L3Cu]ClO4 (4–6)、[BOC2L1Cu(NCCH3)]ClO4 (4BOC)、[Me2L2Cu(NCCH3)2]PF6 (5Me) 和 [Me2L3Cu]2 (ClO4)2 (6Me) 在乙腈溶液中也是单体，正如 4BOC 和 5Me 的晶体学所证实的那样。相比之下，6Me 是固态二聚体，其中一个配体的硫醚基团与对称相关的 Cu+ 离子结合。循环伏安研究表明，双(2-甲基苯并咪唑基)胺-Cu2+/Cu+体系的半波电位范围为-0.16至-0.08 V（参考二茂铁-二茂铁电偶）；这些值比相关双(吡啶甲基)胺衍生配体报道的负值低近 0.23 V。基于这些观察，苯并咪唑衍生配体的 N3 或 N3S 供体组类似于之前报道的螯合系统，但它们提供的电子环境是独特的，并且可能与含组氨酸和蛋氨酸的金属酶有关。这也反映在 [Me2L2Cu(NCCH3)2]+ (5Me) 和 [Me2L3Cu]+ (6Me) 对分子氧的反应性上，这两种情况都会产生超氧阴离子。 6Me 中与硫醚结合的 Cu+ 中心似乎比 5Me 更有选择性地生成 O2˙−，这为硫醚配体在 Cu-O2 反应中的调节特性的假设提供了证据。
• Synthesis, crystal structure, DNA-binding properties, and antioxidant activity of a V-shaped ligand bis(<i>N</i>-methylbenzimidazol-2-ylmethyl)benzylamine and its zinc(II) complex
  作者：Huilu Wu、Jingkun Yuan、Ying Bai、Guolong Pan、Hua Wang、Juanhui Shao、Jiali Gao、Yaoyu Wang

  DOI：10.1080/00958972.2012.741229

  日期：2012.12.20

  A V-shaped ligand bis(N-methylbenzimidazol-2-ylmethyl)benzylamine (L) and its zinc(II) complex, [ZnL 2](pic)2?.?2CH3CN (pic?=?picrate), have been synthesized and characterized by physico-chemical and spectroscopic methods. Single-crystal X-ray crystallographic analysis revealed that the Zn(II) complex possesses a distorted trigonal bipyramidal geometry. Supramolecular interactions arising from various intra- or intermolecular p center dot center dot center dot p stacking interactions contributed to the form of the multidimensional configuration. Interactions of L and Zn(II) complex with DNA were monitored using spectrophotometric methods and viscosity measurements. The results suggest that L and Zn(II) complex both bind to DNA via intercalation and Zn(II) complex binds to DNA more strongly than L. Moreover, the Zn(II) complex also exhibited potential antioxidant properties in vitro.