3-((4,5-bis(dodecyloxy)-2-ethynylphenyl)ethynyl)pyridine | 1361114-12-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3-((4,5-bis(dodecyloxy)-2-ethynylphenyl)ethynyl)pyridine
• 英文别名: 3-[2-(4,5-Didodecoxy-2-ethynylphenyl)ethynyl]pyridine；3-[2-(4,5-didodecoxy-2-ethynylphenyl)ethynyl]pyridine
• CAS: 1361114-12-6
• 化学式: C₃₉H₅₇NO₂
• 分子量: 571.887
• InChiKey: UIDLSZYVEWPHKY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.2
• 重原子数：
  42
• 可旋转键数：
  27
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  31.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-((4,5-bis(dodecyloxy)-2-ethynylphenyl)ethynyl)pyridine 、 2,3-diiodopyrazine 在 copper(l) iodide 、 二(氰基苯)二氯化钯 、 三乙胺 、 2-二环己基磷-2,4,6-三异丙基联苯 作用下， 反应 24.0h， 以75%的产率得到2,3-bis((4,5-bis(dodecyloxy)-2-(pyridin-3-ylethynyl)phenyl)-ethynyl)pyrazine
  参考文献：
  名称：

  Evidence of Enhanced Conjugation in ortho-Arylene Ethynylenes with Transition Metal Coordination

  摘要：

  The effective conjugation of ortho and ortho-alt-para-arylene ethynylenes, with appropriately positioned pyridine and pyrazine heterocycles, increases upon binding to Ag(I) and Pd(II) cations. Significant bathochromic shifts in the electronic spectra, witnessed upon introduction of these metal bridges, are consistent with enhanced electron delocalization in the unsaturated backbone. Control studies suggest that this electronic behavior is attributable exclusively (in the case of Ag(I)) or partially (in the case of Pd(II)) to conformational restrictions of the conjugated backbones.

  DOI：

  10.1021/jo300034h
• 作为产物：
  描述：

  1,2-bis(dodecyloxy)-4-iodo-5-(trimethylsilyl)ethynylbenzene 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 生成 3-((4,5-bis(dodecyloxy)-2-ethynylphenyl)ethynyl)pyridine
  参考文献：
  名称：

  Evidence of Enhanced Conjugation in ortho-Arylene Ethynylenes with Transition Metal Coordination

  摘要：

  The effective conjugation of ortho and ortho-alt-para-arylene ethynylenes, with appropriately positioned pyridine and pyrazine heterocycles, increases upon binding to Ag(I) and Pd(II) cations. Significant bathochromic shifts in the electronic spectra, witnessed upon introduction of these metal bridges, are consistent with enhanced electron delocalization in the unsaturated backbone. Control studies suggest that this electronic behavior is attributable exclusively (in the case of Ag(I)) or partially (in the case of Pd(II)) to conformational restrictions of the conjugated backbones.

  DOI：

  10.1021/jo300034h

文献信息

• Molecular Turnstiles Featuring Bicyclic Rotators: Solution and Solid‐State Investigation of Steric and Electronic Concerns
  作者：Megan L. Rammer、Emily R. Gonnering、Zakarias L. Driscoll、Herh G. Vang、Eric Bosch、Nathan P. Bowling

  DOI：10.1002/ejoc.202300716

  日期：2023.9.21

  A molecular rotor is created when a 2,1,3‐benzothiadiazole rotator is incorporated into a rigid arylene ethynylene framework supported by pyridine coordination to a metal (Ag⁺ or PdCl₂) guest. Comparisons to a similarly sized naphthyl rotator via ¹H NMR spectroscopy provide insights into the movement of these bicyclic rotators relative to the rigid stator framework. Chemical shift increases of 0.3 ppm, or more, upon metal complexation are consistent with through‐space interaction of the central arene with a bound PdCl₂ guest. Further study via X‐ray crystallography illustrates that rotation of the 2,1,3‐benzothiadiazole unit in the solid state is likely hampered by relatively strong chalcogen bonding (N⋅⋅⋅S distance of 2.93 Å), forming 2S‐2N squares between benzothiadiazoles of neighboring complexes. Strong π–π interactions (3.29–3.36 Å) between neighboring complexes likewise restrict solid‐state rotation of the potential benzothiadiazole rotator. Modest changes to UV–vis spectra upon metal coordination suggest that electronic properties are mostly independent of stator configuration.

  摘要 当一个 2,1,3-苯并噻二唑转子通过吡啶配位与金属（Ag+ 或 PdCl2）客体结合到刚性芳基乙炔框架中时，分子转子就产生了。通过 1H NMR 光谱与类似大小的萘基旋转子进行比较，可以深入了解这些双环旋转子相对于刚性定子框架的运动情况。金属络合时，化学位移增加了 0.3 ppm 或更多，这与中心炔烃与结合的 PdCl2 客体的空间相互作用是一致的。通过 X 射线晶体学的进一步研究表明，2,1,3-苯并噻二唑单元在固态下的旋转可能受到相对较强的查尔根键（N⋅⋅S 间距为 2.93 Å）的阻碍，从而在相邻复合物的苯并噻二唑之间形成 2S-2N 平方。相邻复合物之间强烈的 π-π 相互作用（3.29-3.36 Å）同样限制了潜在苯并噻二唑旋转体的固态旋转。金属配位后紫外-可见光谱的微小变化表明，电子特性在很大程度上与定子构型无关。