4-[4-(N,N-diphenylamino)phenylethynyl]phenylboronic acid | 1332869-79-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-[4-(N,N-diphenylamino)phenylethynyl]phenylboronic acid
• 英文别名: [4-[2-[4-(N-phenylanilino)phenyl]ethynyl]phenyl]boronic acid
• CAS: 1332869-79-0
• 化学式: C₂₆H₂₀BNO₂
• 分子量: 389.261
• InChiKey: OWAOFEYOBWDAHZ-UHFFFAOYSA-N

物化性质

• 沸点：
  598.6±60.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.24
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  43.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-[4-(N,N-diphenylamino)phenylethynyl]phenylboronic acid 在 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 22.0h， 生成 4,6-bis[4-((4-(diphenylamino)phenyl)ethynyl)phenyl]dibenzo[b,d]thiophene
  参考文献：
  名称：

  Double-coupling of dibromo arenes with aryltriolborates for synthesis of diaryl-substituted planar frameworks

  摘要：

  A new method for simple and practical synthesis of diaryl-substituted arenes using potassium aryltriolborates was developed. Double-cross-coupling of dibromo arenes with aryltriolborates was carried out in the presence of a palladium catalyst, such as Pd(OAc)(2), Pd(PPh3)(4) or Pd(OAc)(2)/BIPHEP. The use of CuCl (40 mol %) with a palladium catalyst was found to be highly effective to give diaryl-substituted aromatic compounds in good yields. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.06.083
• 作为产物：
  描述：

  N-{4-[2-(4-bromophenyl)ethynyl]phenyl}diphenylamine 在 正丁基锂 、 硼酸三甲酯 、 盐酸 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以78%的产率得到4-[4-(N,N-diphenylamino)phenylethynyl]phenylboronic acid
  参考文献：
  名称：

  Double-coupling of dibromo arenes with aryltriolborates for synthesis of diaryl-substituted planar frameworks

  摘要：

  A new method for simple and practical synthesis of diaryl-substituted arenes using potassium aryltriolborates was developed. Double-cross-coupling of dibromo arenes with aryltriolborates was carried out in the presence of a palladium catalyst, such as Pd(OAc)(2), Pd(PPh3)(4) or Pd(OAc)(2)/BIPHEP. The use of CuCl (40 mol %) with a palladium catalyst was found to be highly effective to give diaryl-substituted aromatic compounds in good yields. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.06.083

文献信息

• Synthesis and Photophysical Properties of a Series of Pyrazine-Based Push-Pull Chromophores
  作者：Kellyn Hoffert、Raphaël J. Durand、Sébastien Gauthier、Françoise Robin-le Guen、Sylvain Achelle

  DOI：10.1002/ejoc.201601204

  日期：2017.1.18

  were obtained by Knoevenagel condensation and palladium-catalyzed cross-coupling reactions starting from commercially available 2-methyl- or 2-chloropyrazine. The optical absorption and emission properties of these chromophores were studied in different solvents. Some proved to be highly emissive and exhibit strong emission solvatochromism, which suggests a highly polar emitting state, characteristic

  描述了十八种推拉吡嗪荧光团。甲氧基、二甲氨基和二苯氨基用作给电子基团 (EDG)，并使用由多个键和 1,4-亚苯基部分组成的六个 π 共轭系统将 EDG 连接到吡嗪核心。发色团是通过 Knoevenagel 缩合和钯催化的交叉偶联反应获得的，起始于市售的 2-甲基-或 2-氯吡嗪。在不同溶剂中研究了这些发色团的光吸收和发射特性。一些被证明具有高发射性并表现出强烈的发射溶剂化变色，这表明具有高度极性的发射状态，这是经历分子内电荷转移 (ICT) 的化合物的特征。
• A Benzophosphole <i>P</i>-Oxide with an Electron-Donating Group at 3-Position: Enhanced Fluorescence in Polar Solvents
  作者：Eriko Yamaguchi、Aiko Fukazawa、Youhei Kosaka、Daisuke Yokogawa、Stephan Irle、Shigehiro Yamaguchi

  DOI：10.1246/bcsj.20150238

  日期：2015.11.15

  Fluorophores with intramolecular charge-transfer (ICT) character in the excited state exhibit significant solvatochromism of their fluorescence. Here, we report an example for such compounds, a benzophosphole P-oxide bearing an electron-donating p-(diphenylamino)phenyl group at the 3-position. While this compound shows only subtle dependence of the absorption maximum on the solvent polarity (λmax = 383–392 nm), its emission maximum is significantly red-shifted upon increasing the solvent polarity (cyclohexane: λem = 457 nm; DMF: λem = 598 nm). Most notably, the fluorescence quantum yields gradually increase with increased Stokes shifts, ultimately reaching ΦF = 0.28 in DMF. This trend is fundamentally different from that observed for the corresponding 2-(diphenylamino)phenyl-substituted benzophosphole congener, for which applications as a fluorescent bioimaging probe were previously demonstrated. In this study, the origins of this striking difference are examined by a combined experimental and theoretical approach. Our results suggest that the observed difference arises from a significant contribution of quinoidal resonance forms in the ICT excited state, which suppresses nonradiative decay and hence increases the quantum yield in polar solvents.

  在激发态具有分子内电荷转移（ICT）特性的荧光团，其荧光具有显著的溶解变色特性。在此，我们报告了此类化合物的一个实例，即在 3 位上带有一个电子捐献对（二苯基氨基）苯基的苯并膦唑 P-氧化物。虽然这种化合物的吸收最大值与溶剂极性（λmax = 383-392 nm）只有微妙的关系，但当溶剂极性增加时，其发射最大值会发生明显的红移（环己烷：λem = 457 nm；DMF：λem = 598 nm）。最值得注意的是，荧光量子产率随着斯托克斯位移的增加而逐渐增大，最终在 DMF 中达到 ΦF = 0.28。这种趋势与相应的 2-（二苯基氨基）苯基取代的苯并膦烯同系物的趋势截然不同，后者以前曾被证明可用作荧光生物成像探针。本研究采用实验和理论相结合的方法，对这一显著差异的根源进行了研究。我们的研究结果表明，所观察到的差异是由 ICT 激发态中的醌类共振形式造成的，它抑制了非辐射衰变，从而提高了极性溶剂中的量子产率。