2-[α-hydroxy-α-(4-iodophenyl)]methylthiophene | 250695-03-5

• 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: 2-[α-hydroxy-α-(4-iodophenyl)]methylthiophene
• 英文别名: (4-Iodophenyl)-thiophen-2-ylmethanol
• CAS: 250695-03-5
• 化学式: C₁₁H₉IOS
• 分子量: 316.162
• InChiKey: BCGYBYLJQKRRBY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  48.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[α-hydroxy-α-(4-iodophenyl)]methylthiophene 在 甲醇 、 sodium tetrahydroborate 、 三氟化硼乙醚 作用下， 以 四氢呋喃 为溶剂， 反应 11.17h， 生成 [5-[[5-[hydroxy-(4-methylphenyl)methyl]thiophen-2-yl]-(4-iodophenyl)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
• 作为产物：
  描述：

  2-(4-iodobenzoyl)thiophene 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 0.17h， 以99%的产率得到2-[α-hydroxy-α-(4-iodophenyl)]methylthiophene
  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 Functionalized Unsymmetrical Thiophene Diols and Their Use in the Synthesis of<i>cis</i>-21-Monothia- and<i>cis</i>-21,23-Dithiaporphyrin Building Blocks with Two Different Functional Groups
  作者：Mangalampalli Ravikanth、Sokkalingam Punidha

  DOI：10.1055/s-2005-872245

  日期：——

  A series of functionalized unsymmetrical thiophene ­diols were synthesized and used for the synthesis of cis-21-monothia and cis-21,23-dithiaporphyrin building blocks having two ­different functional groups at meso-positions. To show the use of the cis-thiaporphyrin building blocks with two different functional groups, a porphyrin trimer comprised of N4, N3S and N2S2 por­phyrin sub-units was synthesized by using both covalent and non-covalent interactions.

  一系列功能化的非对称噻吩二醇被合成出来，并被用于合成具有两个不同官能团的中位点的顺式-21-单硫杂和顺式-21,23-二硫杂卟啉结构单元。为了展示具有两个不同官能团的顺式噻啉结构单元的使用，使用共价和非共价相互作用合成了由N4、N3S和N2S2卟啉亚基组成的卟啉三聚体。