(6E)-4-butyl-6-(4-butyl-4,5-dihydrocyclopenta[b]thiophen-6-ylidene)-4,5-dihydrocyclopenta[b]thiophene | 877378-60-4

• 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: (6E)-4-butyl-6-(4-butyl-4,5-dihydrocyclopenta[b]thiophen-6-ylidene)-4,5-dihydrocyclopenta[b]thiophene
• CAS: 877378-60-4
• 化学式: C₂₂H₂₈S₂
• 分子量: 356.596
• InChiKey: LWLKTHCUGJJDBA-FMQUCBEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N,N-二甲基甲酰胺 、 (6E)-4-butyl-6-(4-butyl-4,5-dihydrocyclopenta[b]thiophen-6-ylidene)-4,5-dihydrocyclopenta[b]thiophene 在 三氯氧磷 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 18.0h， 以85%的产率得到(E)-2-formyl-6,6'-bis(4-n-butyl-4,5-dihydro-6H-cyclopenta[b]thienylidene)
  参考文献：
  名称：

  通过共价桥接微调线性pi共轭低聚物的电子性能。

  摘要：

  已经通过多步合成方法构建了一系列的低聚噻吩亚乙烯基，即通过连接在共轭主链的不同位置的乙烯桥而刚性化的π-共轭低聚物。电子吸收光谱显示，与开链参考化合物的光谱相比，共轭体系的刚性产生最大吸收的红移和HOMO-LUMO能隙的缩小。所有低聚物的循环伏安图显示，这些化合物可被可逆地氧化成其阳离子自由基和阳离子，而刚性化作用则使第一氧化电位产生较大的负移，这表明HOMO含量显着增加。电化学数据证实，共价桥接强烈影响HOMO和LUMO的水平，这些数据表明，在pi共轭骨架上的桥固定位点对阳离子自由基和离子的相对稳定性起决定性作用。根据理论计算检查这些各种结果表明，除了局部控制键长交替以及HOMO-LUMO间隙外，共价桥固定在π共轭体系的选定位置还限制了变形。 π共轭结构在氧化成带电态时的结构。

  DOI：

  10.1002/chem.200500853
• 作为产物：
  描述：

  1-(3-噻吩基)-1-戊酮 在 sodium hydroxide 、 sodium amalgam 、 正丁基锂 、 三氯化铝 、 氯化亚砜 、 四氯化钛 、 锌 作用下， 以 四氢呋喃 、 二硫化碳 、 乙醚 、 乙醇 、 水 为溶剂， 反应 57.5h， 生成 (6E)-4-butyl-6-(4-butyl-4,5-dihydrocyclopenta[b]thiophen-6-ylidene)-4,5-dihydrocyclopenta[b]thiophene
  参考文献：
  名称：

  Bridged Dithienylethylenes as Precursors of Small Bandgap Electrogenerated Conjugated Polymers

  摘要：

  Bridged dithienylethylenes (DTEs) bearing solubilizing alkyl chains at various positions (2-5) have been synthesized by McMurry dimerization of cyclopenta[b]thiophen-6-ones. In order to introduce alkyl substituents at different positions of the DTE molecule, the precursor ketones have been prepared by different strategies based on a combination of Mannich or Wittig-Horner reaction and Friedel-Craft intramolecular cyclization. The position and the length of the alkyl substituents exert a strong effect on the ability of the precursor to undergo electrochemical polymerization. Thus, whereas substitution at the alpha-position of the ethylene linkage (3) results in a rapid inhibition of electropolymerization, introduction of alkyl chains at the beta-position (4, 5) greatly improves the efficiency of the polymerization process. The analysis of the electrochemical and optical properties of the polymers shows that rigidification of the DTE molecule leads to a significant decrease of the oxidation potential and bandgap. A comparative analysis of DTE and its bridged analogues by means of X-ray diffraction reveals, in agreement with experimental and theoretical results, that the observed reduction of both the HOMO-LUMO gap of the precursor and the bandgap of the corresponding polymers are related to a relaxation of bond length alternation in the DTE moiety.

  DOI：

  10.1021/jo9623447

文献信息

• Bridged Dithienylethylenes as Precursors of Small Bandgap Electrogenerated Conjugated Polymers
  作者：Philippe Blanchard、Hugues Brisset、Bertrand Illien、Amédée Riou、Jean Roncali

  DOI：10.1021/jo9623447

  日期：1997.4.1

  Bridged dithienylethylenes (DTEs) bearing solubilizing alkyl chains at various positions (2-5) have been synthesized by McMurry dimerization of cyclopenta[b]thiophen-6-ones. In order to introduce alkyl substituents at different positions of the DTE molecule, the precursor ketones have been prepared by different strategies based on a combination of Mannich or Wittig-Horner reaction and Friedel-Craft intramolecular cyclization. The position and the length of the alkyl substituents exert a strong effect on the ability of the precursor to undergo electrochemical polymerization. Thus, whereas substitution at the alpha-position of the ethylene linkage (3) results in a rapid inhibition of electropolymerization, introduction of alkyl chains at the beta-position (4, 5) greatly improves the efficiency of the polymerization process. The analysis of the electrochemical and optical properties of the polymers shows that rigidification of the DTE molecule leads to a significant decrease of the oxidation potential and bandgap. A comparative analysis of DTE and its bridged analogues by means of X-ray diffraction reveals, in agreement with experimental and theoretical results, that the observed reduction of both the HOMO-LUMO gap of the precursor and the bandgap of the corresponding polymers are related to a relaxation of bond length alternation in the DTE moiety.
• Fine Tuning of the Electronic Properties of Linear π-Conjugated Oligomers by Covalent Bridging
  作者：Philippe Blanchard、Patrick Verlhac、Laurent Michaux、Pierre Frère、Jean Roncali

  DOI：10.1002/chem.200500853

  日期：2006.1.23

  that the sites of fixation of the bridges on the pi-conjugated backbone exert a determining effect on the relative stability of the cation radical and dication. Examination of these various results in the light of theoretical calculations shows that in addition to a local control of bond length alternation, and hence of the HOMO-LUMO gap, the fixation of covalent bridges at selected positions of the pi-conjugated

  已经通过多步合成方法构建了一系列的低聚噻吩亚乙烯基，即通过连接在共轭主链的不同位置的乙烯桥而刚性化的π-共轭低聚物。电子吸收光谱显示，与开链参考化合物的光谱相比，共轭体系的刚性产生最大吸收的红移和HOMO-LUMO能隙的缩小。所有低聚物的循环伏安图显示，这些化合物可被可逆地氧化成其阳离子自由基和阳离子，而刚性化作用则使第一氧化电位产生较大的负移，这表明HOMO含量显着增加。电化学数据证实，共价桥接强烈影响HOMO和LUMO的水平，这些数据表明，在pi共轭骨架上的桥固定位点对阳离子自由基和离子的相对稳定性起决定性作用。根据理论计算检查这些各种结果表明，除了局部控制键长交替以及HOMO-LUMO间隙外，共价桥固定在π共轭体系的选定位置还限制了变形。 π共轭结构在氧化成带电态时的结构。