2-(N,N-diethylcarbamoyl)-6-(1'-ethyl-1H-benzimidazol-2'-yl)pyridine | 252739-47-2

• 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: 2-(N,N-diethylcarbamoyl)-6-(1'-ethyl-1H-benzimidazol-2'-yl)pyridine
• 英文别名: N,N-diethyl-6-(1-ethylbenzimidazol-2-yl)pyridine-2-carboxamide
• CAS: 252739-47-2
• 化学式: C₁₉H₂₂N₄O
• 分子量: 322.41
• InChiKey: YIEIQVYLKKSWNJ-UHFFFAOYSA-N

物化性质

• 沸点：
  552.8±60.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  51
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(N,N-diethylcarbamoyl)-6-(1'-ethyl-1H-benzimidazol-2'-yl)pyridine 在 氢氧化钾 作用下， 以 乙醇 为溶剂， 反应 12.0h， 以92%的产率得到6-(1'-ethylbenzimidazol-2'-yl)pyridine-2-carboxylic acid
  参考文献：
  名称：

  Lanthanide Helicates Self-Assembled in Water:  A New Class of Highly Stable and Luminescent Dimetallic Carboxylates

  摘要：

  The segmental ligand bis{1-ethyl-2-[6'-carboxy)pyridin-2'-yl]benzimidazol-5-yl}methane (L-C) reacts with the entire series of Ln(III) ions to yield a new class of neutral lanthanide carboxylates, the triple-stranded dimetallic helicates [Ln(2)(L-C-2H)(3)], which are stable in water in the pH range 4-13. A competitive titration with 1,4,7,10-tetraazacyclododecane-N,N',N",N'''-tetraacetic acid (dota) shows the Eu-III helicate to have a stability comparable to that of [Eu(dota)](-). According to the X-ray structures of isotypical [Ln(2)(L-C-2H)(3)].20.5H(2)O (Ln = Eu, Tb) (C(93)H(72)Ln(2)N(18)O(12).20.5H(2)O, monoclinic, P2(1)/c, Z = 8), the helicates are comprised of two types of slightly different molecules (A, B) within the asymmetric unit. The three ligand strands are helically wrapped around the two nine-coordinate Ln(III) ions, leading to pseudo-D-3 symmetries around the metals. The Ln(III) distances lie in the ranges 8.81--8.83 Angstrom for molecules A and 9.04-9.07 Angstrom for molecules B, while the helical pitch amounts to 23.7--23.8 Angstrom (A) and 24.5-24.7 Angstrom (B). In solution, the helicates retain time-averaged D-3 symmetries along the entire Ln(III) series, as shown by H-1 and C-13 NMR. The derivation of equations adapted to heterodimetallic complexes allows the separation of contact and dipolar contributions to the isotropic paramagnetic shift. Somewhat different structures are evidenced between larger (Ln = Ce-Tb) and smaller (Ln = Er--Yb) Ln(III) ions, attributed to a lengthening of the helix on going toward heavier lanthanides. The photophysical properties of the helicates depend on the nature of the Ln(III) ion, and LC is revealed to be a good sensitizer of Eu-III. The flexible route used to synthesize LC opens interesting perspectives for the fine-tuning of the chemical and photophysical properties of lanthanide-containing homodimetallic helicates with potential applications in labeling and sensing technologies.

  DOI：

  10.1021/ja991854q
• 作为产物：
  描述：

  2,6-吡啶二羧酸单甲酯 在 氢氧化钾 、 氯化亚砜 、 双氧水 、 edetate disodium 、 三乙胺 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 6.67h， 生成 2-(N,N-diethylcarbamoyl)-6-(1'-ethyl-1H-benzimidazol-2'-yl)pyridine
  参考文献：
  名称：

  Lanthanide Helicates Self-Assembled in Water:  A New Class of Highly Stable and Luminescent Dimetallic Carboxylates

  摘要：

  The segmental ligand bis{1-ethyl-2-[6'-carboxy)pyridin-2'-yl]benzimidazol-5-yl}methane (L-C) reacts with the entire series of Ln(III) ions to yield a new class of neutral lanthanide carboxylates, the triple-stranded dimetallic helicates [Ln(2)(L-C-2H)(3)], which are stable in water in the pH range 4-13. A competitive titration with 1,4,7,10-tetraazacyclododecane-N,N',N",N'''-tetraacetic acid (dota) shows the Eu-III helicate to have a stability comparable to that of [Eu(dota)](-). According to the X-ray structures of isotypical [Ln(2)(L-C-2H)(3)].20.5H(2)O (Ln = Eu, Tb) (C(93)H(72)Ln(2)N(18)O(12).20.5H(2)O, monoclinic, P2(1)/c, Z = 8), the helicates are comprised of two types of slightly different molecules (A, B) within the asymmetric unit. The three ligand strands are helically wrapped around the two nine-coordinate Ln(III) ions, leading to pseudo-D-3 symmetries around the metals. The Ln(III) distances lie in the ranges 8.81--8.83 Angstrom for molecules A and 9.04-9.07 Angstrom for molecules B, while the helical pitch amounts to 23.7--23.8 Angstrom (A) and 24.5-24.7 Angstrom (B). In solution, the helicates retain time-averaged D-3 symmetries along the entire Ln(III) series, as shown by H-1 and C-13 NMR. The derivation of equations adapted to heterodimetallic complexes allows the separation of contact and dipolar contributions to the isotropic paramagnetic shift. Somewhat different structures are evidenced between larger (Ln = Ce-Tb) and smaller (Ln = Er--Yb) Ln(III) ions, attributed to a lengthening of the helix on going toward heavier lanthanides. The photophysical properties of the helicates depend on the nature of the Ln(III) ion, and LC is revealed to be a good sensitizer of Eu-III. The flexible route used to synthesize LC opens interesting perspectives for the fine-tuning of the chemical and photophysical properties of lanthanide-containing homodimetallic helicates with potential applications in labeling and sensing technologies.

  DOI：

  10.1021/ja991854q

文献信息

• In search for tuneable intramolecular intermetallic interactions in polynuclear lanthanide complexes
  作者：Natalia Dalla Favera、Laure Guénée、Gérald Bernardinelli、Claude Piguet

  DOI：10.1039/b905131g

  日期：——

  helical conformations of its central diphenylmethane spacer in its uncoordinated form (amphiverse helix) and in its complexed form in [Eu2(L5)(NO3)6(H2O)2] (regular helix), which puts the two metals at a contact distance of 8.564(1) Å. In solution, fast rearrangements yield an average planar extended conformation of the spacer, which increases the intramolecular intermetallic contact distance by 30%

  不对称三齿2-苯并咪唑基-6-羧酰胺基吡啶结合单元在分子中的反应 配体 具有中性Ln（NO 3）3（Ln是三价镧系元素）的L4 b和L5给出单核[Ln（L4 b）（NO 3）3（溶剂）]和双核[Ln 2（L5）（NO 3）6（溶剂）2 ]配合物。的晶体结构L4 b和[铕（L4 b）（NO 3）3（CH 3 CN）]解开三齿结合其协调需要对金属，负责在改变一个处理单元的构象变化电子吸收光谱 和在 1 H NMR谱记录在乙腈溶液中。在固态，双三齿配体 L5以[Eu 2（L5）（NO 3）6（H 2 O）2 ]（规则螺旋）的形式显示其中心二苯甲烷间隔基的可变螺旋构象，呈无配位形式（双螺旋）和呈络合物形式。两种金属的接触距离为8.564（1）Å。在溶液中，快速重排产生间隔基的平均平面延伸构象，从而使[Ln 2（L5）（NO 3）6（H 2 O）2]中的分子内金属间接触距离增加30％]。出乎意料的是
• Borgne, Thierry Le; Altmann, Peter; Andre, Nicolas, Dalton Transactions
  作者：Borgne, Thierry Le、Altmann, Peter、Andre, Nicolas、Buenzli, Jean-Claude G.、Bernardinelli, Gerald、et al.

  DOI：——

  日期：——