diethyl 3,4-bis-(3-pyridyl)-thieno[2,3-b]thiophene-2,5-dicarboxylate | 851539-58-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: diethyl 3,4-bis-(3-pyridyl)-thieno[2,3-b]thiophene-2,5-dicarboxylate
• 英文别名: Diethyl 3,4-dipyridin-3-ylthieno[2,3-b]thiophene-2,5-dicarboxylate
• CAS: 851539-58-7
• 化学式: C₂₂H₁₈N₂O₄S₂
• 分子量: 438.528
• InChiKey: WBULPLBLCBGDRR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  135
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  diethyl 3,4-bis-(3-pyridyl)-thieno[2,3-b]thiophene-2,5-dicarboxylate 在 氢氧化钾 作用下， 以 水 、 二甲基亚砜 为溶剂， 反应 2.0h， 以85%的产率得到3,4-Di-pyridin-3-yl-thieno[2,3-b]thiophene-2,5-dicarboxylic acid
  参考文献：
  名称：

  Dipyridyl/pyridinium thieno[2,3-b]thiophenes as new atropisomeric systems. Synthesis, conformational analysis and energy minimization

  摘要：

  Synthesis of a new class of cofacially oriented dipyridyl(pyridinium)lthieno[2,3-b]thiophenes with or without -CO2Et and -COMe substituents at C2, and C5 positions of thieno[2,3-b]thiophene ring was readily accomplished using a double Dieckman cyclization protocol as the key step. While C2/C5 substituted dipyfidylthieno[2,3-b]thiophenes exhibited syn/anti atropisomerism at least up to 70 degrees C with Arrhenius energy of activation (Delta G(not equal)) in the range of 17-18 kcal/mol, on the other hand unsubstituted dipyfidylthieno[2,3-b]thiophene and its bis-N-quaternized salt were found to show free conformational rotation with an estimated Delta G(not equal) of lower than 10 kcal/mol. Conformational energy minimization using AMI protocol revealed a slight preference for the anti over syn isomers. Compared to the unsubstituted dipyfidylthieno[2,3-b]thiophenes, higher energy barriers to rotation (3.7-5.1 kcal/mol) in substituted dipyridylthieno[2,3-b]thiophenes can be attributed to steric encumbrance resulting from -CO2Et and -COMe substituents located on the non-rotating thienothiophene platform. (c) 2005 Elsevier Ltd. All fights reserved.

  DOI：

  10.1016/j.tet.2005.01.123
• 作为产物：
  描述：

  二硫化碳 、 1,3-二吡啶-3-基丙烷-1,3-二酮 、 溴乙酸乙酯 在 potassium fluoride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 30.0h， 以28%的产率得到diethyl 3,4-bis-(3-pyridyl)-thieno[2,3-b]thiophene-2,5-dicarboxylate
  参考文献：
  名称：

  Dipyridyl/pyridinium thieno[2,3-b]thiophenes as new atropisomeric systems. Synthesis, conformational analysis and energy minimization

  摘要：

  Synthesis of a new class of cofacially oriented dipyridyl(pyridinium)lthieno[2,3-b]thiophenes with or without -CO2Et and -COMe substituents at C2, and C5 positions of thieno[2,3-b]thiophene ring was readily accomplished using a double Dieckman cyclization protocol as the key step. While C2/C5 substituted dipyfidylthieno[2,3-b]thiophenes exhibited syn/anti atropisomerism at least up to 70 degrees C with Arrhenius energy of activation (Delta G(not equal)) in the range of 17-18 kcal/mol, on the other hand unsubstituted dipyfidylthieno[2,3-b]thiophene and its bis-N-quaternized salt were found to show free conformational rotation with an estimated Delta G(not equal) of lower than 10 kcal/mol. Conformational energy minimization using AMI protocol revealed a slight preference for the anti over syn isomers. Compared to the unsubstituted dipyfidylthieno[2,3-b]thiophenes, higher energy barriers to rotation (3.7-5.1 kcal/mol) in substituted dipyridylthieno[2,3-b]thiophenes can be attributed to steric encumbrance resulting from -CO2Et and -COMe substituents located on the non-rotating thienothiophene platform. (c) 2005 Elsevier Ltd. All fights reserved.

  DOI：

  10.1016/j.tet.2005.01.123