[5-[[5-[hydroxy-(4-methylphenyl)methyl]-1H-pyrrol-2-yl]-[4-(2-trimethylsilylethynyl)phenyl]methyl]-1H-pyrrol-2-yl]-(4-methylphenyl)methanol | 250695-23-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: [5-[[5-[hydroxy-(4-methylphenyl)methyl]-1H-pyrrol-2-yl]-[4-(2-trimethylsilylethynyl)phenyl]methyl]-1H-pyrrol-2-yl]-(4-methylphenyl)methanol
• CAS: 250695-23-9
• 化学式: C₃₆H₃₈N₂O₂Si
• 分子量: 558.795
• InChiKey: VWYQDOJJDXDMLF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.53
• 重原子数：
  41
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  72
• 氢给体数：
  4
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5-(4-iodophenyl)dipyrromethane 、 [5-[[5-[hydroxy-(4-methylphenyl)methyl]-1H-pyrrol-2-yl]-[4-(2-trimethylsilylethynyl)phenyl]methyl]-1H-pyrrol-2-yl]-(4-methylphenyl)methanol 在 三氟乙酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 乙腈 为溶剂， 反应 1.08h， 以0.34 g的产率得到5-(4-iodophenyl)-15-[4-(2-(trimethylsilyl)ethynyl)phenyl]-10,20-di(p-tolyl)porphyrin
  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
• 作为产物：
  描述：

  4-三甲基硅乙炔基苯甲醛 在 甲醇 、 sodium tetrahydroborate 、 乙基溴化镁 、 三氟乙酸 作用下， 以 四氢呋喃 为溶剂， 反应 3.25h， 生成 [5-[[5-[hydroxy-(4-methylphenyl)methyl]-1H-pyrrol-2-yl]-[4-(2-trimethylsilylethynyl)phenyl]methyl]-1H-pyrrol-2-yl]-(4-methylphenyl)methanol
  参考文献：
  名称：

  Rational Synthesis of Trans-Substituted Porphyrin Building Blocks Containing One Sulfur or Oxygen Atom in Place of Nitrogen at a Designated Site

  摘要：

  The use of heteroatom-substituted porphyrins in bioorganic and materials chemistry requires the ability to position a variety of substituents in a controlled manner about the porphyrin periphery. We describe a rational route to trans-AB(2)C-type porphyrins bearing one oxygen atom (N3O) or one sulfur atom (NBS) in a designated location in the porphyrin core. The synthesis involved four stages: (1) Acid-catalyzed condensation of a furyl- or thienylcarbinol in excess pyrrole afforded the aryl-substituted furyl- or thienylpyrromethane in high yield. (2) Treatment of the furyl- or thienylpyrromethane with an acid chloride catalyzed by SnCl4 or AlCl3 afforded the corresponding diketo product. (3) Reduction with NaBH4 in alcoholic solvents gave the furyl- or thienylpyrromethanediols. (4) Reaction of a furylpyrromethanediol, thienylpyrromethanediol, or dipyrromethanediol with a dipyrromethane in a one-flask process of condensation followed by oxidation gave the corresponding porphyrin. Reaction conditions previously identified to minimize scrambling in a dipyrromethane-aldehyde condensation were found to be effective in this application. Thus, reaction with 10 mM reactants in acetonitrile at 0 degrees C containing BF3 . Et2O and NH4Cl followed by oxidation with DDQ resulted in the desired porphyrin(10-20% yields) without acidolysis. In this manner, N3O-, N3S-, or Na-porphyrins bearing 5-(p-iodophenyl), 15-[4-(2-(trimethylsilyl)ethynyl)phenyl], and 10,20-di-p-tolyl groups have been made. This set of trans-substituted porphyrin building blacks is expected to be useful in the synthesis of biomimetic energy transduction systems.

  DOI：

  10.1021/jo9909305

文献信息

• Synthesis of Thiol-Derivatized Europium Porphyrinic Triple-Decker Sandwich Complexes for Multibit Molecular Information Storage
  作者：Junzhong Li、Dorota Gryko、Rajeev B. Dabke、James R. Diers、David F. Bocian、Werner G. Kuhr、Jonathan S. Lindsey

  DOI：10.1021/jo000490d

  日期：2000.11.1

  Lanthanide triple-decker sandwich molecules employing porphyrins and phthalocyanines afford four cationic states and are very attractive for molecular information storage applications. Five triple-decker building blocks have been prepared of the type (phthalocyanine)Eu(phthalocyanine)Eu(porphyrin), each bearing one iodo, one ethyne, or one iodo and one ethyne group attached to the porphyrin unit. Two

  在分子水平上存储多个信息位需要具有大量不同氧化态的分子。使用卟啉和酞菁的镧系元素三层三明治分子具有四个阳离子态，对于分子信息存储应用非常有吸引力。已经制备了五种三层结构的砌块，其类型为（酞菁）Eu（酞菁）Eu（卟啉），每个带有一个连接到卟啉单元上的碘，一个乙炔或一个碘和一个乙炔基团。用S-乙酰基硫代苯基单元衍生化具有不同氧化电位的两个三层积木，以附着到电活性表面上。为了探索由三层结构组成的阵列的准备工作，这可能导致存储更多的位，制备了两种类型的三层组的二元组。通过重复的Sonogashira偶联制备带有一个S-乙酰基硫代苯基单元的三层乙炔连接的二联体，并通过改进的Glaser偶联制备丁二炔连接的二联体。通过吸收光谱法，激光解吸质谱法和（1）1 H NMR光谱法表征三层。硫醇衍生的三层化合物通过原位裂解硫醇保护基团在金上形成自组装单分子层（SAMs）。每个阵列的SAM具有电化学稳定性，并表现
• 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
• Rational Synthesis of Trans-Substituted Porphyrin Building Blocks Containing One Sulfur or Oxygen Atom in Place of Nitrogen at a Designated Site
  作者：Won-Seob Cho、Han-Je Kim、Benjamin J. Littler、Mark A. Miller、Chang-Hee Lee、Jonathan S. Lindsey

  DOI：10.1021/jo9909305

  日期：1999.10.1

  The use of heteroatom-substituted porphyrins in bioorganic and materials chemistry requires the ability to position a variety of substituents in a controlled manner about the porphyrin periphery. We describe a rational route to trans-AB(2)C-type porphyrins bearing one oxygen atom (N3O) or one sulfur atom (NBS) in a designated location in the porphyrin core. The synthesis involved four stages: (1) Acid-catalyzed condensation of a furyl- or thienylcarbinol in excess pyrrole afforded the aryl-substituted furyl- or thienylpyrromethane in high yield. (2) Treatment of the furyl- or thienylpyrromethane with an acid chloride catalyzed by SnCl4 or AlCl3 afforded the corresponding diketo product. (3) Reduction with NaBH4 in alcoholic solvents gave the furyl- or thienylpyrromethanediols. (4) Reaction of a furylpyrromethanediol, thienylpyrromethanediol, or dipyrromethanediol with a dipyrromethane in a one-flask process of condensation followed by oxidation gave the corresponding porphyrin. Reaction conditions previously identified to minimize scrambling in a dipyrromethane-aldehyde condensation were found to be effective in this application. Thus, reaction with 10 mM reactants in acetonitrile at 0 degrees C containing BF3 . Et2O and NH4Cl followed by oxidation with DDQ resulted in the desired porphyrin(10-20% yields) without acidolysis. In this manner, N3O-, N3S-, or Na-porphyrins bearing 5-(p-iodophenyl), 15-[4-(2-(trimethylsilyl)ethynyl)phenyl], and 10,20-di-p-tolyl groups have been made. This set of trans-substituted porphyrin building blacks is expected to be useful in the synthesis of biomimetic energy transduction systems.