4-Methoxy-1-[4-methoxy-2-[5-methoxy-2-(4-methoxyphenyl)phenyl]phenyl]-2-[5-methoxy-2-(4-methoxyphenyl)phenyl]benzene | 1244642-45-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-Methoxy-1-[4-methoxy-2-[5-methoxy-2-(4-methoxyphenyl)phenyl]phenyl]-2-[5-methoxy-2-(4-methoxyphenyl)phenyl]benzene
• 英文别名: 4-methoxy-1-[4-methoxy-2-[5-methoxy-2-(4-methoxyphenyl)phenyl]phenyl]-2-[5-methoxy-2-(4-methoxyphenyl)phenyl]benzene
• CAS: 1244642-45-2
• 化学式: C₄₂H₃₈O₆
• 分子量: 638.76
• InChiKey: NSQZWDBKIJWRBV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.9
• 重原子数：
  48
• 可旋转键数：
  11
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-Methoxy-1-[4-methoxy-2-[5-methoxy-2-(4-methoxyphenyl)phenyl]phenyl]-2-[5-methoxy-2-(4-methoxyphenyl)phenyl]benzene 在 三溴化硼 、 水 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以82%的产率得到3-[5-Hydroxy-2-[4-hydroxy-2-[5-hydroxy-2-(4-hydroxyphenyl)phenyl]phenyl]phenyl]-4-(4-hydroxyphenyl)phenol
  参考文献：
  名称：

  Enhanced Helical Folding of ortho-Phenylenes through the Control of Aromatic Stacking Interactions

  摘要：

  The ortho-phenylenes are a simple class of foldamers, with the formation of helices driven by offset aromatic stacking interactions parallel to the helical axis. For the majority of reported o-phenylene oligomers, the perfectly folded conformer comprises perhaps 5075% of the total population. Given the hundreds or thousands of possible conformers for even short oligomers, this distribution represents a substantial bias toward the folded state. However, next-generation o-phenylenes with better folding properties are needed if these structures are to be exploited as functional units within more complex architectures. Here, we report several new series of o-phenylene oligomers, varying both the nature and orientation of the substituents on every repeat unit. The conformational behavior was probed using a combination of NMR spectroscopy, DFT calculations, and X-ray crystallography. We find that increasing the electron-withdrawing character of the substituents gives oligomers with substantially improved folding properties. With moderately electron-withdrawing groups (acetoxy), we observe >90% of the perfectly folded conformer, and stronger electron withdrawing groups (triflate, cyano) give oligomers for which misfolded states are undetectable by NMR. The folding of these oligomers is only weakly solvent-dependent. General guidelines for the assessment of o-phenylene folding by NMR and UVvis spectroscopy are also discussed.

  DOI：

  10.1021/ja509902m
• 作为产物：
  描述：

  C₃₆H₃₁F₃O₈S 、 4-甲氧基苯硼酸 在 2-双环己基膦-2',6'-二甲氧基联苯 、 potassium phosphate 、 palladium diacetate 作用下， 以 四氢呋喃 、 水 为溶剂， 以75%的产率得到4-Methoxy-1-[4-methoxy-2-[5-methoxy-2-(4-methoxyphenyl)phenyl]phenyl]-2-[5-methoxy-2-(4-methoxyphenyl)phenyl]benzene
  参考文献：
  名称：

  邻亚苯基：不寻常的共轭低聚物，具有惊人的长有效共轭长度

  摘要：

  邻亚苯基代表了一类基本但相对未开发的共轭分子结构。我们已经开发出一种强大的单分散邻亚苯基低聚物的合成方法，我们已经通过合成高达十二聚体的同源系列来证明这一点。邻亚苯基表现出复杂的构象行为，但偏向于特定的 2 重对称构象，我们认为该构象对应于堆叠螺旋。令人惊讶的是，该系列表现出远距离离域，这是通过紫外/可见光谱中的红移来测量的。尽管转变的总体幅度不大（但与其他一些共轭材料类别相当），但该系列的有效共轭长度约为 8 个重复单元。随着长度的增加，低聚物的荧光光谱也表现出不寻常的低色移。这些趋势的起源在该系列前沿分子轨道的构象分析和 DFT 计算的背景下进行了讨论。

  DOI：

  10.1021/ja106050s

文献信息

• Enhanced Helical Folding of <i>ortho</i>-Phenylenes through the Control of Aromatic Stacking Interactions
  作者：Sanyo Mathew、Laura A. Crandall、Christopher J. Ziegler、C. Scott Hartley

  DOI：10.1021/ja509902m

  日期：2014.11.26

  The ortho-phenylenes are a simple class of foldamers, with the formation of helices driven by offset aromatic stacking interactions parallel to the helical axis. For the majority of reported o-phenylene oligomers, the perfectly folded conformer comprises perhaps 5075% of the total population. Given the hundreds or thousands of possible conformers for even short oligomers, this distribution represents a substantial bias toward the folded state. However, next-generation o-phenylenes with better folding properties are needed if these structures are to be exploited as functional units within more complex architectures. Here, we report several new series of o-phenylene oligomers, varying both the nature and orientation of the substituents on every repeat unit. The conformational behavior was probed using a combination of NMR spectroscopy, DFT calculations, and X-ray crystallography. We find that increasing the electron-withdrawing character of the substituents gives oligomers with substantially improved folding properties. With moderately electron-withdrawing groups (acetoxy), we observe >90% of the perfectly folded conformer, and stronger electron withdrawing groups (triflate, cyano) give oligomers for which misfolded states are undetectable by NMR. The folding of these oligomers is only weakly solvent-dependent. General guidelines for the assessment of o-phenylene folding by NMR and UVvis spectroscopy are also discussed.
• <i>ortho</i>-Phenylenes: Unusual Conjugated Oligomers with a Surprisingly Long Effective Conjugation Length
  作者：Jian He、Jason L. Crase、Shriya H. Wadumethrige、Khushabu Thakur、Lin Dai、Shouzhong Zou、Rajendra Rathore、C. Scott Hartley

  DOI：10.1021/ja106050s

  日期：2010.10.6

  oligomers which we have demonstrated by synthesizing a homologous series up to the dodecamer. The o-phenylenes exhibit complex conformational behavior but are biased toward a specific 2-fold-symmetric conformation which we believe corresponds to a stacked helix. Surprisingly, the series exhibits long-range delocalization, as measured by bathochromic shifts in UV/vis spectra. Although the overall magnitude of

  邻亚苯基代表了一类基本但相对未开发的共轭分子结构。我们已经开发出一种强大的单分散邻亚苯基低聚物的合成方法，我们已经通过合成高达十二聚体的同源系列来证明这一点。邻亚苯基表现出复杂的构象行为，但偏向于特定的 2 重对称构象，我们认为该构象对应于堆叠螺旋。令人惊讶的是，该系列表现出远距离离域，这是通过紫外/可见光谱中的红移来测量的。尽管转变的总体幅度不大（但与其他一些共轭材料类别相当），但该系列的有效共轭长度约为 8 个重复单元。随着长度的增加，低聚物的荧光光谱也表现出不寻常的低色移。这些趋势的起源在该系列前沿分子轨道的构象分析和 DFT 计算的背景下进行了讨论。