(4-iodophenyl)[5-(p-toluoyl)thien-2-yl][5-(p-toluoyl)pyrrol-2-yl]methane | 250695-16-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4-iodophenyl)[5-(p-toluoyl)thien-2-yl][5-(p-toluoyl)pyrrol-2-yl]methane
• 英文别名: [5-[(4-iodophenyl)-[5-(4-methylbenzoyl)thiophen-2-yl]methyl]-1H-pyrrol-2-yl]-(4-methylphenyl)methanone
• CAS: 250695-16-0
• 化学式: C₃₁H₂₄INO₂S
• 分子量: 601.508
• InChiKey: XDAWJIOQLSAQPJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  36
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  78.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4-iodophenyl)[5-(p-toluoyl)thien-2-yl][5-(p-toluoyl)pyrrol-2-yl]methane 在 甲醇 、 sodium tetrahydroborate 、 三氟化硼乙醚 、 氯化铵 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 1.97h， 生成 5-(4-iodophenyl)-15-[4-(2-(trimethylsilyl)ethynyl)phenyl]-10,20-di(p-tolyl)-23H-21-thiaporphyrin
  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：

  4-碘苯甲醛 在 正丁基锂 、 四甲基乙二胺 、 三氟化硼乙醚 作用下， 以 正己烷 为溶剂， 反应 11.0h， 生成 (4-iodophenyl)[5-(p-toluoyl)thien-2-yl][5-(p-toluoyl)pyrrol-2-yl]methane
  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