dimethyl 4-[(4-aminophenyl)ethynyl]pyridine-2,6-dicarboxylate | 112776-85-9

• 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: dimethyl 4-[(4-aminophenyl)ethynyl]pyridine-2,6-dicarboxylate
• 英文别名: dimethyl 4-(phenylethynyl)-2,6-pyridinedicarboxylate；dimethyl 4-(phenylethynyl)pyridine-2,6-dicarboxylate；dimethyl 4-(2-phenylethynyl)pyridine-2,6-dicarboxylate
• CAS: 112776-85-9
• 化学式: C₁₇H₁₃NO₄
• 分子量: 295.295
• InChiKey: OPXCHNFKACZWQX-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：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  65.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl 4-[(4-aminophenyl)ethynyl]pyridine-2,6-dicarboxylate 在 碳酸氢钠 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 12.0h， 生成 dimethyl 4-[(4-[N'-[5-(methoxycarbonyl)pentyl]thioureido]phenyl)ethynyl]pyridine-2,6-dicarboxylate
  参考文献：
  名称：

  Self-Assembled Triple-Stranded Lanthanide Dimetallic Helicates with a Ditopic Ligand Derived from Bis(benzimidazole)pyridine and Featuring an (4-Isothiocyanatophenyl)ethynyl Substituent

  摘要：

  Bis(2-{6-(diethylcarbamoyl)-4-[(4-isothiocyanatophenyl)ethynyl]pyridin-2'-yl}-1-ethylbenzimidazol-5-yl)methane (L-G) reacts with trivalent lanthanide ions in acetonitrile to yield triple-stranded dimetallic helicates [Ln(2)(L-G)(3)](6+). H-1-NMR Data point to the helicates being the only species formed under stoichiometric conditions and having a time-averaged D-3 symmetry on the NMR time scale. The photophysical properties of L-G and its helicates are discussed with respect to the closely related ligands L-B, L-E, and their complexes, two ligands devoid of the isothiocyanatophenylethynyl substituent. ne quantum yield of the ligand fluorescence is three times smaller compared to L-E, while that of the Eu(III)centered luminescence (1.1%) is three times larger. On the other hand, the luminescence of Tb-III is not sensitized by L-G. This is explained in terms of energy differences between the singlet and triplet states on one hand, and between the 0-phonon transition of the triplet state and the excited metal ion states on the other. This work demonstrates that bulky substituents in the 4-position of the pyridine ring do not prevent the formation of triple-stranded helicates, opening the way for luminescent probes that can easily be coupled to biological materials.

  DOI：

  10.1002/1522-2675(200207)85:7<1915::aid-hlca1915>3.0.co;2-n
• 作为产物：
  描述：

  4-iodo-2,6-pyridinedicarboxylic acid dimethyl ester 、 苯乙炔 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 3.5h， 以48%的产率得到dimethyl 4-[(4-aminophenyl)ethynyl]pyridine-2,6-dicarboxylate
  参考文献：
  名称：

  质子和非质子溶剂中具有扩展 π 系统的凹面吡啶的碱度和溶剂致变色

  摘要：

  芳炔取代基与凹吡啶的 4 位相连，得到取代的凹吡啶 3，其紫外光谱在 300 nm 以上具有最大吸收。已经研究了它们的质子化和它们与极性溶剂的相互作用。首先，使用强酸会发生质子化，并确定相对碱度 (logKass)。远程芳环上的取代会影响吡啶的碱性，哈米特图显示 logKass 与远程芳环的电子密度之间存在线性关系。其次，凹形吡啶 3 能够“感知”其吡啶氮原子和醇之间的氢键。当加入一定量的酒精时，观察到吸收最大值向更长波长的移动。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany,

  DOI：

  10.1002/ejoc.200300053

文献信息

• Takalo, Harri; Kankare, Jouko, Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1987, vol. 41, # 3, p. 219 - 221
  作者：Takalo, Harri、Kankare, Jouko

  DOI：——

  日期：——
• TAKALO HARRI; KANKARE JOUKO, ACTA CHEM. SCAND., 41,(1987) N 3, 219-221
  作者：TAKALO HARRI、 KANKARE JOUKO

  DOI：——

  日期：——
• Basicity and Solvatochromism of Concave Pyridines with Extended π-Systems in Protic and Nonprotic Solvents
  作者：Ole Storm、Ulrich Lüning

  DOI：10.1002/ejoc.200300053

  日期：2003.8

  4-positions of concave pyridines to give substituted concave pyridines 3, which possess absorption maxima above 300 nm in their UV spectra. Their protonation and their interaction with polar solvents have been studied. Firstly, with strong acids, protonation occurs, and relative basicities (logKass) have been determined. Substitution at the remote aryl ring influences the basicity of the pyridine, and Hammett

  芳炔取代基与凹吡啶的 4 位相连，得到取代的凹吡啶 3，其紫外光谱在 300 nm 以上具有最大吸收。已经研究了它们的质子化和它们与极性溶剂的相互作用。首先，使用强酸会发生质子化，并确定相对碱度 (logKass)。远程芳环上的取代会影响吡啶的碱性，哈米特图显示 logKass 与远程芳环的电子密度之间存在线性关系。其次，凹形吡啶 3 能够“感知”其吡啶氮原子和醇之间的氢键。当加入一定量的酒精时，观察到吸收最大值向更长波长的移动。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany,
• Self-Assembled Triple-Stranded Lanthanide Dimetallic Helicates with a Ditopic Ligand Derived from Bis(benzimidazole)pyridine and Featuring an (4-Isothiocyanatophenyl)ethynyl Substituent
  作者：Raphaël Tripier、Marcel Hollenstein、Mourad Elhabiri、Anne-Sophie Chauvin、Gaël Zucchi、Claude Piguet、Jean-Claude G. Bünzli

  DOI：10.1002/1522-2675(200207)85:7<1915::aid-hlca1915>3.0.co;2-n

  日期：2002.7

  Bis(2-6-(diethylcarbamoyl)-4-[(4-isothiocyanatophenyl)ethynyl]pyridin-2'-yl}-1-ethylbenzimidazol-5-yl)methane (L-G) reacts with trivalent lanthanide ions in acetonitrile to yield triple-stranded dimetallic helicates [Ln(2)(L-G)(3)](6+). H-1-NMR Data point to the helicates being the only species formed under stoichiometric conditions and having a time-averaged D-3 symmetry on the NMR time scale. The photophysical properties of L-G and its helicates are discussed with respect to the closely related ligands L-B, L-E, and their complexes, two ligands devoid of the isothiocyanatophenylethynyl substituent. ne quantum yield of the ligand fluorescence is three times smaller compared to L-E, while that of the Eu(III)centered luminescence (1.1%) is three times larger. On the other hand, the luminescence of Tb-III is not sensitized by L-G. This is explained in terms of energy differences between the singlet and triplet states on one hand, and between the 0-phonon transition of the triplet state and the excited metal ion states on the other. This work demonstrates that bulky substituents in the 4-position of the pyridine ring do not prevent the formation of triple-stranded helicates, opening the way for luminescent probes that can easily be coupled to biological materials.