(5-{[5-(Hydroxy-p-tolyl-methyl)-1H-pyrrol-2-yl]-p-tolyl-methyl}-furan-2-yl)-p-tolyl-methanol | 250695-24-0

• 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-p-tolyl-methyl)-1H-pyrrol-2-yl]-p-tolyl-methyl}-furan-2-yl)-p-tolyl-methanol
• 英文别名: [5-[[5-[hydroxy-(4-methylphenyl)methyl]furan-2-yl]-(4-methylphenyl)methyl]-1H-pyrrol-2-yl]-(4-methylphenyl)methanol
• CAS: 250695-24-0
• 化学式: C₃₂H₃₁NO₃
• 分子量: 477.603
• InChiKey: KXJYKMAFRQABGG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  36
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  69.4
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5-[4-(trimethylsilylethynyl)phenyl]dipyrromethane 、 (5-{[5-(Hydroxy-p-tolyl-methyl)-1H-pyrrol-2-yl]-p-tolyl-methyl}-furan-2-yl)-p-tolyl-methanol 在 三氟化硼乙醚 、 氯化铵 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 乙腈 、 甲苯 为溶剂， 反应 1.17h， 以25 mg的产率得到5,10,20-tri(p-tolyl)-15-[4-(2-(trimethylsilyl)ethynyl)phenyl]-23H-21-oxaporphyrin
  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
• 作为产物：
  描述：

  (p-tolyl)(furan-2-yl)(pyrrol-2-yl)methane 在 甲醇 、 sodium tetrahydroborate 、 三氯化铝 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.67h， 生成 (5-{[5-(Hydroxy-p-tolyl-methyl)-1H-pyrrol-2-yl]-p-tolyl-methyl}-furan-2-yl)-p-tolyl-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

• Customized, core-modified corroles from [2+2] condensation of dipyrromethanes
  作者：Won-Seob Cho、Chang-Hee Lee

  DOI：10.1016/s0040-4039(99)02142-5

  日期：2000.1

  Corroles and core-modified corroles were synthesized by acid-catalyzed condensation under low-scrambling conditions. The synthesis utilized [2+2] condensation of two different dipyrromethanes. The condensation afforded different corroles bearing heteroatoms in a predesignated location depending on the starting dipyrromethanes. Selective α–α′ linkage was achieved by positioning a linking carbon unit

  在低加扰条件下，通过酸催化的缩合反应合成了硬酚和核修饰的硬酚。该合成利用了两种不同的二吡咯甲烷的[2 + 2]缩合反应。根据起始的二吡咯甲烷，缩合反应在预定的位置上提供了带有杂原子的不同杂种。选择性α–α'键是通过将连接碳单元置于二吡咯甲烷的不同位置来实现的。
• 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.