(5-{[5-(Hydroxy-pentafluorophenyl-methyl)-1H-pyrrol-2-yl]-phenyl-methyl}-1H-pyrrol-2-yl)-pentafluorophenyl-methanol | 1027977-96-3

• 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: (5-{[5-(Hydroxy-pentafluorophenyl-methyl)-1H-pyrrol-2-yl]-phenyl-methyl}-1H-pyrrol-2-yl)-pentafluorophenyl-methanol
• 英文别名: [5-[[5-[hydroxy-(2,3,4,5,6-pentafluorophenyl)methyl]-1H-pyrrol-2-yl]-phenylmethyl]-1H-pyrrol-2-yl]-(2,3,4,5,6-pentafluorophenyl)methanol
• CAS: 1027977-96-3
• 化学式: C₂₉H₁₆F₁₀N₂O₂
• 分子量: 614.442
• InChiKey: QJDAAXVJEIXJQP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  43
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  72
• 氢给体数：
  4
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  (5-{[5-(Hydroxy-pentafluorophenyl-methyl)-1H-pyrrol-2-yl]-phenyl-methyl}-1H-pyrrol-2-yl)-pentafluorophenyl-methanol 在 indium(III) chloride 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 5,15-bis(pentafluorophenyl)-10-phenylporphyrin
  参考文献：
  名称：

  Synthesis of phenylethyne-linked porphyrin dyads

  摘要：

  Four new porphyrin dyads have been prepared for studies in artificial photosynthesis. The two porphyrins are joined at the meso positions via a phenylethyne linker and are present in zinc/zinc or zinc/free base metalation states. The porphyrin bearing the ethynyl unit incorporates zero, one, or two pentafluorophenyl groups at non-linking meso positions for tuning the porphyrin redox potentials. The synthetic approach entailed Pd-mediated coupling of porphyrin building blocks that bear a single ethynylphenyl or bromo/iodo substituent. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.01.003
• 作为产物：
  描述：

  五氟苯甲酰氯 在 sodium tetrahydroborate 、 乙基溴化镁 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 1.34h， 生成 (5-{[5-(Hydroxy-pentafluorophenyl-methyl)-1H-pyrrol-2-yl]-phenyl-methyl}-1H-pyrrol-2-yl)-pentafluorophenyl-methanol
  参考文献：
  名称：

  带有多达四个不同内消旋取代基的卟啉的合理合成。

  摘要：

  带有特定取代基图案的卟啉是仿生和材料化学中至关重要的组成部分。我们已开发出避免统计反应的方法，采用最少的色谱法，并提供最多克量的区域异构纯卟啉，带有多达四个不同内消旋取代基的预先指定图案。该方法基于几克数量的二吡咯甲烷的可用性。使用EtMgBr和酰氯对二吡咯甲烷进行二酰化的方法已经完善。已经开发出一种新的制备不对称二酰基二吡咯甲烷的方法，该方法涉及（1）用EtMgBr和吡啶硫基吡啶酯单酰化，然后（2）在与EtMgBr和酰氯反应时引入第二个酰基单元。通过制备多克量的带有各种取代基的二酰基二吡咯甲烷，已经检验了这些酰化方法的范围。用NaBH（4）在甲醇THF中将二酰基二吡咯甲烷还原为相应的二吡咯甲烷-二甲醇。卟啉的形成涉及二吡咯甲烷-二甲醇和二吡咯甲烷的酸催化缩合，然后用DDQ氧化。通过检查各种反应参数（溶剂，温度，酸，浓度，时间），可以确定最佳的缩合条件。确定的条件（2.5 mM反应物在室温下含有30

  DOI：

  10.1021/jo000882k

文献信息

• Design and synthesis of light-harvesting rods for intrinsic rectification of the migration of excited-state energy and ground-state holesElectronic supplementary information (ESI) available: 1H and 13C NMR spectra for all new porphyrin precursors; 1H NMR and LD-MS spectra for all new porphyrins and porphyrin arrays (LD-MS only for deprotected arrays 12′ and 14′, and pentad 18); analytical SEC data for all porphyrin arrays. See http://www.rsc.org/suppdata/jm/b1/b108168c/
  作者：Robert S. Loewe、Robin K. Lammi、James R. Diers、Christine Kirmaier、David F. Bocian、Dewey Holten、Jonathan S. Lindsey

  DOI：10.1039/b108168c

  日期：2002.4.17

  We present the design of molecular materials for ultimate use in solid-state solar cells. The molecular materials are semi-rigid oligomeric rods of defined length with metalloporphyrins in the backbone and a carboxy group at one end for attachment to a surface. The rods are designed to absorb visible light, and then undergo excited-state energy transfer and ground-state hole transfer in opposite directions along the length of the rod. The rational synthesis of the multiporphyrin arrays relies on joining porphyrin building blocks in an efficient and controlled manner. Several porphyrin building blocks have been synthesized that bear bromophenyl, iodophenyl, trimethylsilylethynylphenyl and/or ethynylphenyl substituents for use in a copper-free Sonogashira reaction using Pd2(dba)3 and P(o-tol)3. Competition experiments performed on equimolar quantities of an iodo-porphyrin and a bromo-porphyrin with an ethynyl-porphyrin show iodo + ethyne coupling with a low amount (35 °C) or undetectable amount (22 °C) of bromo + ethyne coupling. Efficient coupling of bromo-porphyrins with ethynyl-porphyrins was achieved using the same copper-free Sonogashira reaction conditions at higher temperature (50 °C or 80 °C). These findings allow successive coupling reactions to be achieved using substrates bearing iodo and bromo synthetic handles. Thus, a porphyrin-based tetrad (or pentad) was synthesized with a final convergent coupling of a bromo-substituted dyad (or triad) and an ethynyl-substituted dyad. A porphyrin triad was prepared by sequential iodo + ethyne coupling reactions. The triad, tetrad, and pentad each are comprised of a terminal magnesium porphyrin bearing one carboxy group (for surface attachment) and two pentafluorophenyl groups; the remaining porphyrins in each array are present as the zinc chelate. Electrochemical characterization of benchmark porphyrins indicates the presence of the desired electrochemical gradient for hole hopping in the arrays. Static absorption data indicate that the arrays are weakly coupled, while static fluorescence data indicate that the excited-state energy flows in high yield to the terminal magnesium porphyrin. Time-resolved spectroscopic analysis leads to rate constants in THF of (9 ps)−1, (15 ps)−1, and (30 ps)−1 for ZnMg dyad 20, Zn2Mg triad 13, and Zn3Mg tetrad 15, respectively, and quantum efficiencies ≥99% for energy flow to the magnesium porphyrin in each case. These design and synthesis strategies should be useful for the construction of materials for molecular-based solar cells.

  我们介绍了用于固态太阳能电池的终极应用的分子材料的设计。这些分子材料是具有特定长度的半刚性寡聚棒，其骨架中含有金属卟啉，一端带有羧基以附着于表面。这些棒设计用于吸收可见光，然后在棒的长度上沿着相反方向进行激发态能量传递和基态空穴传递。多卟啉阵列的合理合成依赖于以高效且受控的方式连接卟啉构建块。已经合成了几种带有溴苯基、碘苯基、三甲基硅乙炔基苯基和/或乙炔基苯基的卟啉构建块，用于在无铜Sonogashira反应中使用Pd2(dba)3和P(o-tol)3。在等摩尔量的碘卟啉和溴卟啉与乙炔基卟啉的竞争实验中，碘+乙炔偶联在低量（35°C）或无法检测量（22°C）下，而溴+乙炔偶联未发生。在更高温度（50°C或80°C）下，使用相同的无铜Sonogashira反应条件实现了溴卟啉与乙炔基卟啉的高效偶联。这些发现允许使用带有碘和溴合成柄的底物实现连续偶联反应。因此，通过最终的汇聚偶联反应合成具有溴取代的双体（或三体）和乙炔基取代的双体的基于卟啉的四体（或五体）。通过连续的碘+乙炔偶联反应制备了卟啉三体。三体、四体和五体各自由一个末端带有羧基（用于表面附着）和两个五氟苯基的镁卟啉组成；每个阵列中的其余卟啉作为锌螯合物存在。基准卟啉的电化学表征显示了阵列中空穴跳跃所需的电化学梯度的存在。静态吸收数据显示阵列是弱耦合的，而静态荧光数据显示激发态能量高效流向末端镁卟啉。时间分辨光谱分析得出了THF中的速率常数，分别为ZnMg双体20的(9 ps)−1、Zn2Mg三体13的(15 ps)−1和Zn3Mg四体15的(30 ps)−1，且每次能量流向镁卟啉的量子效率≥99%。这些设计和合成策略应有助于构建基于分子的太阳能电池材料。
• Rational Syntheses of Porphyrins Bearing up to Four Different Meso Substituents
  作者：Polisetti Dharma Rao、Savithri Dhanalekshmi、Benjamin J. Littler、Jonathan S. Lindsey

  DOI：10.1021/jo000882k

  日期：2000.11.1

  using EtMgBr and an acid chloride has been refined. A new procedure for the preparation of unsymmetrical diacyl dipyrromethanes has been developed that involves (1) monoacylation with EtMgBr and a pyridyl benzothioate followed by (2) introduction of the second acyl unit upon reaction with EtMgBr and an acid chloride. The scope of these acylation methods has been examined by preparing multigram quantities

  带有特定取代基图案的卟啉是仿生和材料化学中至关重要的组成部分。我们已开发出避免统计反应的方法，采用最少的色谱法，并提供最多克量的区域异构纯卟啉，带有多达四个不同内消旋取代基的预先指定图案。该方法基于几克数量的二吡咯甲烷的可用性。使用EtMgBr和酰氯对二吡咯甲烷进行二酰化的方法已经完善。已经开发出一种新的制备不对称二酰基二吡咯甲烷的方法，该方法涉及（1）用EtMgBr和吡啶硫基吡啶酯单酰化，然后（2）在与EtMgBr和酰氯反应时引入第二个酰基单元。通过制备多克量的带有各种取代基的二酰基二吡咯甲烷，已经检验了这些酰化方法的范围。用NaBH（4）在甲醇THF中将二酰基二吡咯甲烷还原为相应的二吡咯甲烷-二甲醇。卟啉的形成涉及二吡咯甲烷-二甲醇和二吡咯甲烷的酸催化缩合，然后用DDQ氧化。通过检查各种反应参数（溶剂，温度，酸，浓度，时间），可以确定最佳的缩合条件。确定的条件（2.5 mM反应物在室温下含有30
• Synthesis of phenylethyne-linked porphyrin dyads
  作者：Kin-ya Tomizaki、Andrey B Lysenko、Masahiko Taniguchi、Jonathan S Lindsey

  DOI：10.1016/j.tet.2004.01.003

  日期：2004.2

  Four new porphyrin dyads have been prepared for studies in artificial photosynthesis. The two porphyrins are joined at the meso positions via a phenylethyne linker and are present in zinc/zinc or zinc/free base metalation states. The porphyrin bearing the ethynyl unit incorporates zero, one, or two pentafluorophenyl groups at non-linking meso positions for tuning the porphyrin redox potentials. The synthetic approach entailed Pd-mediated coupling of porphyrin building blocks that bear a single ethynylphenyl or bromo/iodo substituent. (C) 2004 Elsevier Ltd. All rights reserved.