1-(4-butoxy-phenyl)-4-(2-pyridyl)-1,2,3-triazole | 1035272-85-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 1-(4-butoxy-phenyl)-4-(2-pyridyl)-1,2,3-triazole
• 英文别名: 2-[1-(4-Butoxyphenyl)triazol-4-yl]pyridine；2-[1-(4-butoxyphenyl)triazol-4-yl]pyridine
• CAS: 1035272-85-5
• 化学式: C₁₇H₁₈N₄O
• 分子量: 294.356
• InChiKey: VKZPWBKORBXVGN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  52.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  nickel(II) bromide trihydrate 、 1-(4-butoxy-phenyl)-4-(2-pyridyl)-1,2,3-triazole 以 甲醇 为溶剂， 反应 1.0h， 以70%的产率得到Ni(bromide)2(1-(4-butoxyphenyl)-4-(2-pyridyl)-1,2,3-triazole)2
  参考文献：
  名称：

  Nickel complexes with “click”-derived pyridyl-triazole ligands: weak intermolecular interactions and catalytic ethylene oligomerisation

  摘要：

  配体1-(环己基)-4-(2-吡啶基)-1,2,3-三唑（1）、1-(2,6-二异丙基苯基)-4-(2-吡啶基)-1,2,3-三唑（2）、1-(4-正丁氧基苯基)-4-(2-吡啶基)-1,2,3-三唑（3）和1-(甲基)-4-(2-吡啶基)-1,2,3-三唑（4）是通过铜(I)催化的“点击”反应，使用2-吡啶乙炔与相应的叠氮化物合成的。然后，将配体与NiBr2·3H2O反应，生成络合物(1)2NiBr2（1a）、(2)2NiBr2（2a）、(3)2NiBr2（3a）和(4)2NiBr2（4a）。1a的结构表征确认了围绕Ni(II)中心的单核和扭曲八面体环境，吡啶-三唑配体呈双螯合方式配位。在1,2,3-三唑环内的键长分析显示了一个短的NN双键，两侧有两个较长的C–N和N–N键，表明环内存在“偶氮”特性。高极性的五元1,2,3-三唑环使其C–H键呈酸性，这些键参与了与相邻分子Br基团之间的扩展弱分子间C–H···Br相互作用，形成了三维网络。这些“点击”配体的镍络合物作为乙烯聚合的前催化剂进行了测试，结果显示这些络合物在此反应中表现出适度的活性，并对C4寡聚物具有良好的选择性。

  DOI：

  10.1039/c2dt31805a
• 作为产物：
  描述：

  2-乙炔基吡啶 、 1-azido-4-butoxybenzene 在 copper(I) sulfate 、 copper(II) sulfate sodium ascorbate 作用下， 以 甲醇 、 水 、 叔丁醇 为溶剂， 反应 48.0h， 以270 mg的产率得到1-(4-butoxy-phenyl)-4-(2-pyridyl)-1,2,3-triazole
  参考文献：
  名称：

  1,3-Dipolar cycloaddition of alkynes to azides. Construction of operationally functional metal responsive fluorophores

  摘要：

  铜催化的4-丁氧基苯基重氮与2-、3-或4-乙炔基吡啶的1,3-偶极环加成反应生成1,4-二芳基三氮唑，这些化合物在加入金属阳离子后显示出荧光增强的特性。

  DOI：

  10.1039/b800284c

文献信息

• The redox series [Ru(bpy)₂(L)]ⁿ, n = +3, +2, +1, 0, with L = bipyridine, “click” derived pyridyl-triazole or bis-triazole: a combined structural, electrochemical, spectroelectrochemical and DFT investigation
  作者：Stephan Hohloch、David Schweinfurth、Michael G. Sommer、Fritz Weisser、Naina Deibel、Fabian Ehret、Biprajit Sarkar

  DOI：10.1039/c3dt52898g

  日期：——

  The compounds [Ru(bpy)2(L1)](ClO4)2 (1(ClO4)2), [Ru(bpy)2(L2)](ClO4)2 (2(ClO4)2), [Ru(bpy)2(L3)](ClO4)2 (3(ClO4)2), [Ru(bpy)2(L4)](ClO4)2 (4(ClO4)2), [Ru(bpy)2(L5)](ClO4)2 (5(ClO4)2), and [Ru(bpy)2(L6)](ClO4)26(ClO4)2 (bpy = 2,2′-bipyridine, L1 = 1-(4-isopropyl-phenyl)-4-(2-pyridyl)-1,2,3-triazole, L2 = 1-(4-butoxy-phenyl)-4-(2-pyridyl)-1,2,3-triazole, L3 = 1-(2-trifluoromethyl-phenyl)-4-(2-pyridyl)-1,2,3-triazole, L4 = 4,4′-bis-1-(2,6-diisopropyl-phenyl)}-1,2,3-triazole, L5 = 4,4′-bis-(1-phenyl)}-1,2,3-triazole, L6 = 4,4′-bis-1-(2-trifluoromethyl-phenyl)}-1,2,3-triazole) were synthesized from [Ru(bpy)2(EtOH)2](ClO4)2 and the corresponding “click”-derived pyridyl-triazole or bis-triazole ligands, and characterized by 1H-NMR spectroscopy, elemental analysis, mass spectrometry and X-ray crystallography. Structural analysis showed a distorted octahedral coordination environment about the Ru(II) centers, and shorter Ru–N(triazole) bond distances compared to Ru–N(pyridine) distances in complexes of mixed-donor ligands. All the complexes were subjected to cyclic voltammetric studies, and the results were compared to the well-known [Ru(bpy)3]2+ compound. The oxidation and reduction potentials were found to be largely uninfluenced by ligand changes, with all the investigated complexes showing their oxidation and reduction steps at rather similar potentials. A combined UV-vis-NIR and EPR spectroelectrochemical investigation, together with DFT calculations, was used to determine the site of electron transfer in these complexes. These results provided insights into their electronic structures in the various investigated redox states, showed subtle differences in the spectroscopic signatures of these complexes despite their similar electrochemical properties, and provided clues to the unperturbed redox potentials in these complexes with respect to ligand substitutions. The reduced forms of the complexes display structured absorption bands in the NIR region. Additionally, we also present new synthetic routes for the ligands presented here using Cu-abnormal carbene catalysts.

  化合物 [Ru(bpy)2(L1)](ClO4)2 (1(ClO4)2), [Ru(bpy)2(L2)](ClO4)2 (2(ClO4)2), [Ru(bpy)2(L3)](ClO4)2 (3(ClO4)2), [Ru(bpy)2(L4)](ClO4)2 (4(ClO4)2), [Ru(bpy)2(L5)](ClO4)2 (5(ClO4)2) 和 [Ru(bpy)2(L6)](ClO4)2 (6(ClO4)2)（bpy = 2,2′-联吡啶，L1 = 1-(4-异丙基-苯)-4-(2-吡啶基)-1,2,3-三唑，L2 = 1-(4-丁氧基-苯)-4-(2-吡啶基)-1,2,3-三唑，L3 = 1-(2-三氟甲基-苯)-4-(2-吡啶基)-1,2,3-三唑，L4 = 4,4′-双-1-(2,6-二异丙基-苯)}-1,2,3-三唑，L5 = 4,4′-双-(1-苯基)}-1,2,3-三唑，L6 = 4,4′-双-1-(2-三氟甲基-苯)}-1,2,3-三唑）是由 [Ru(bpy)2(EtOH)2](ClO4)2 与相应的“点击”衍生的吡啶-三唑或双三唑配体合成的，并通过 1H-NMR 光谱、元素分析、质谱和 X 射线晶体学进行表征。结构分析显示 Ru(II) 中心周围存在畸变的八面体配位环境，并且与混合供体配体的化合物相比，Ru–N(三唑) 键长较短而 Ru–N(吡啶) 键长较长。所有化合物都进行了循环伏安研究，并将结果与著名的 [Ru(bpy)3]2+ 化合物进行了比较。氧化和还原电位在很大程度上不受配体变化的影响，所有研究的化合物在相似的电位下表现出氧化和还原步骤。结合 UV-vis-NIR 和 EPR 光谱电化学研究，以及 DFT 计算，用于确定这些化合物中的电子转移位点。这些结果为它们在不同研究的氧化还原状态下的电子结构提供了见解，尽管这些化合物的电化学性质相似，但其光谱特征显示出微妙的差异，并为与配体替换有关的这些化合物中未受干扰的氧化还原电位提供了线索。化合物的还原形式在 NIR 区域表现出结构化的吸收带。此外，我们还展示了使用 Cu-不寻常的卡宾催化剂合成所呈现配体的新合成路线。
• 1,3-Dipolar cycloaddition of alkynes to azides. Construction of operationally functional metal responsive fluorophores
  作者：David Schweinfurth、Kenneth I. Hardcastle、Uwe H. F. Bunz

  DOI：10.1039/b800284c

  日期：——

  The copper catalyzed 1,3-dipolar cycloaddition of 4-butoxyphenylazide with 2-, 3- or 4-ethynylpyridine furnishes 1,4-diaryltriazoles, which display turn-on fluorescence upon addition of metal cations.

  铜催化的4-丁氧基苯基重氮与2-、3-或4-乙炔基吡啶的1,3-偶极环加成反应生成1,4-二芳基三氮唑，这些化合物在加入金属阳离子后显示出荧光增强的特性。
• Nickel complexes with “click”-derived pyridyl-triazole ligands: weak intermolecular interactions and catalytic ethylene oligomerisation
  作者：David Schweinfurth、Cheng-Yong Su、Shi-Chao Wei、Pierre Braunstein、Biprajit Sarkar

  DOI：10.1039/c2dt31805a

  日期：——

  The ligands 1-(cyclohexyl)-4-(2-pyridyl)-1,2,3-triazole (1), 1-(2,6-diisopropylphenyl)-4-(2-pyridyl)-1,2,3-triazole (2), 1-(4-butoxyphenyl)-4-(2-pyridyl)-1,2,3-triazole (3) and 1-(methyl)-4-(2-pyridyl)-1,2,3-triazole (4) were synthesized by the Cu(I) catalyzed “Click” reaction between 2-pyridylacetylene and the corresponding azides. The ligands were then reacted with NiBr2·3H2O to generate the complexes (1)2NiBr2 (1a), (2)2NiBr2 (2a), (3)2NiBr2 (3a) and (4)2NiBr2 (4a). Structural characterization of 1a confirmed the mononuclear and distorted octahedral environment around the Ni(II) center, with the pyridyl-triazole ligands coordinating in a bis-chelating fashion. Bond length analysis inside the 1,2,3-triazole ring shows a short NN double bond that is flanked by two longer C–N and N–N bonds pointing to the existence of “azo” character in the ring. The highly polar five-membered 1,2,3-triazole ring makes its C–H bond acidic, and these bonds participate in an extended weak intermolecular C–H⋯Br interactions with the Br-groups of neighboring molecules, resulting in a 3-D network. The nickel complexes with these “Click” ligands were tested as pre-catalysts for ethylene oligomerization, and the complexes showed moderate activity in that reaction with good selectivity towards C4 oligomers.

  配体1-(环己基)-4-(2-吡啶基)-1,2,3-三唑（1）、1-(2,6-二异丙基苯基)-4-(2-吡啶基)-1,2,3-三唑（2）、1-(4-正丁氧基苯基)-4-(2-吡啶基)-1,2,3-三唑（3）和1-(甲基)-4-(2-吡啶基)-1,2,3-三唑（4）是通过铜(I)催化的“点击”反应，使用2-吡啶乙炔与相应的叠氮化物合成的。然后，将配体与NiBr2·3H2O反应，生成络合物(1)2NiBr2（1a）、(2)2NiBr2（2a）、(3)2NiBr2（3a）和(4)2NiBr2（4a）。1a的结构表征确认了围绕Ni(II)中心的单核和扭曲八面体环境，吡啶-三唑配体呈双螯合方式配位。在1,2,3-三唑环内的键长分析显示了一个短的NN双键，两侧有两个较长的C–N和N–N键，表明环内存在“偶氮”特性。高极性的五元1,2,3-三唑环使其C–H键呈酸性，这些键参与了与相邻分子Br基团之间的扩展弱分子间C–H···Br相互作用，形成了三维网络。这些“点击”配体的镍络合物作为乙烯聚合的前催化剂进行了测试，结果显示这些络合物在此反应中表现出适度的活性，并对C4寡聚物具有良好的选择性。