2,5-bis-[(thiophen-2-ylmethylene)-amino]-thiophene-3,4-dicarboxylic acid diethyl ester | 797803-71-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: 2,5-bis-[(thiophen-2-ylmethylene)-amino]-thiophene-3,4-dicarboxylic acid diethyl ester
• 英文别名: (2E, 5E)-Diethyl 2,5-bis((thiophen-2-yl)methyleneamino)thiophene-3, 4-dicarboxylate；diethyl 2,5-bis(thiophen-2-ylmethylideneamino)thiophene-3,4-dicarboxylate
• CAS: 797803-71-5
• 化学式: C₂₀H₁₈N₂O₄S₃
• 分子量: 446.572
• InChiKey: UYRRSYKZIBQRHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  162
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  5-硝基噻吩-2-甲醛 、 三乙烯二胺 、 2,5-bis-[(thiophen-2-ylmethylene)-amino]-thiophene-3,4-dicarboxylic acid diethyl ester 在 四氯化钛 氮气 作用下， 以 甲苯 为溶剂， 反应 6.0h， 生成 2-[(5-Nitro-thiophen-2-ylmethylene)-amino]-5-[(thiophen-2-ylmethylene)-amino]-thiophene-3,4-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  Conjugated thiophenes having conducting properties and synthesis of same

  摘要：

  本发明涉及含芳香硫吡咯核的共轭寡聚体和聚合物。这些共轭材料是通过芳香族二胺和芳香族二醛或含有醛和胺的双功能芳香族基团的简单高效缩合反应得到的。在各种溶剂中，在从室温到沸点温度的温度下，互补基团的缩合反应结果形成了共轭寡聚体和聚合物，随后可以将其铸造成薄膜。在温和的条件下进行寡聚和聚合反应，并通过去除产生的水副产物来促进共轭产物的生成。所得到的共轭化合物可以通过掺杂剂进行导电，从而获得p型或n型导体的电导材料。

  公开号：

  US08034895B2
• 作为产物：
  描述：

  2-噻吩甲醛 、 2,5-二氨基-3,4-噻吩二羧酸二乙酯 以 乙醇 为溶剂， 生成 2,5-bis-[(thiophen-2-ylmethylene)-amino]-thiophene-3,4-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  Conjugated thiophenoazomethines: electrochromic materials exhibiting visible-to-near-IR color changes

  摘要：

  制备了具有不同聚合度的共轭噻吩偶氮甲烷。分子量和多分散指数都与阶跃生长聚合反应一致，而不是预期的通过反式消解进行动态成分交换。研究发现，中性化合物的吸光度可根据其共轭程度在 450 至 630 纳米之间进行调节。此外，还发现氧化态的吸光度随结构的变化而在 490 纳米和 1111 纳米之间变化。在溶液中对共轭偶氮亚甲基的电致变色特性进行了评估。在环境条件下，电致变色装置可以实现从可见光到近红外的颜色切换。

  DOI：

  10.1039/c3tc30494a

文献信息

• Conjugated thiophenoazomethines: electrochromic materials exhibiting visible-to-near-IR color changes
  作者：Satyananda Barik、Daminda Navarathne、Maxence LeBorgne、W. G. Skene

  DOI：10.1039/c3tc30494a

  日期：——

  Conjugated thiophene azomethines with different degrees of polymerization were prepared. Both the molecular weights and polydispersity indices were consistent with step-growth polymerization instead of the expected dynamic component exchange by transimination. It was found that the absorbance of the neutral compounds could be tuned between 450 and 630 nm, contingent on their degree of conjugation. The absorbance of the oxidized state was also found to vary between 490 nm and 1111 nm as a function of structure. The electrochromic properties of the conjugated azomethines were assessed in solution. An electrochromic device was prepared from one of the polyazomethines and it was switched between blue and colorless states with a bias of ±2 V. Visible-to-NIR color switching of the electrochromic device was possible under ambient conditions.

  制备了具有不同聚合度的共轭噻吩偶氮甲烷。分子量和多分散指数都与阶跃生长聚合反应一致，而不是预期的通过反式消解进行动态成分交换。研究发现，中性化合物的吸光度可根据其共轭程度在 450 至 630 纳米之间进行调节。此外，还发现氧化态的吸光度随结构的变化而在 490 纳米和 1111 纳米之间变化。在溶液中对共轭偶氮亚甲基的电致变色特性进行了评估。在环境条件下，电致变色装置可以实现从可见光到近红外的颜色切换。
• Chemical doping of EDOT azomethine derivatives: insight into the oxidative and hydrolytic stability
  作者：Andréanne Bolduc、Stéphane Dufresne、W. G. Skene

  DOI：10.1039/c2jm14248a

  日期：——

  A series of EDOT (3,4-ethylenedioxythiophene) containing azomethines were prepared for investigating their opto-electronic properties. These properties were compared to those of their thiophene azomethine counterparts and it was found that incorporating the EDOT moiety resulted in a 30 nm bathochromic shift in the absorbance. Meanwhile, the oxidation potential (Epa) could be reduced by 100 mV by incorporating the electron rich moiety. Cyclic voltammetry revealed a one-electron oxidation process, resulting in a radical cation. This intermediate was stable when the azomethines contained amines in the 2,2′-positions, evidenced by the reversible oxidation in cyclic voltammetry. In contrast, the radical cation was irreversible when the 2,2′-positions were unsubstituted. It was found that the resulting radical cation was coupled by standard anodic polymerisation to form a polymer that was physisorbed onto the ITO electrode. The resulting polymer was mauve in colour with a λmax of 515 nm and a degree of polymerisation of ca. 5. This was spectroscopically determined relative to an EDOT polyazomethine derivative and a soluble thiophene polyazomethine. The stability of the EDOT azomethine derivatives towards electrochemical and chemical oxidation was also spectroscopically investigated. It was found that the resulting radical cation exhibited a ca. 100 nm bathochromic shift in absorbance relative to the neutral form and reversible colour switching between the neutral and oxidized states was possible. Chemical doping with FeCl3 generated a stable dication. High contrast colours between the neutral and oxidized states of the azomethines were observed. Multiple oxidation/neutralisation cycles were possible without detectable colour deterioration, demonstrating the chemical robustness of the conjugated azomethines towards oxidative decomposition and hydrolysis.

  研究人员制备了一系列含有 EDOT（3,4-亚乙二氧基噻吩）的偶氮甲烷，以研究它们的光电特性。结果发现，加入 EDOT 分子后，吸光度发生了 30 nm 的浴色偏移。同时，加入富电子分子后，氧化电位（Epa）可降低 100 mV。循环伏安法显示了一个单电子氧化过程，产生了一个自由基阳离子。当偶氮甲基在 2,2′-位含有胺时，这种中间体是稳定的，循环伏安法中的可逆氧化过程证明了这一点。相反，当 2,2′ 位未被取代时，自由基阳离子是不可逆的。研究发现，由此产生的自由基阳离子通过标准阳极聚合作用耦合成聚合物，并被物理吸附在 ITO 电极上。由此产生的聚合物呈淡紫色，λmax 为 515 纳米，聚合度约为 5。此外，还对 EDOT 偶氮亚甲基衍生物在电化学和化学氧化方面的稳定性进行了光谱研究。研究发现，由此产生的自由基阳离子的吸光度相对于中性形式会发生约 100 nm 的浴色偏移，并且可以在中性和氧化态之间进行可逆的颜色切换。通过化学方法掺入 FeCl3 生成了稳定的二阳离子。在偶氮金属的中性态和氧化态之间观察到了高对比度的颜色。在多次氧化/中和循环过程中都不会出现可检测到的颜色劣化现象，这表明共轭偶氮甲基胺对氧化分解和水解具有很强的化学稳定性。
• Conjugated Thiophenes Having Conducting Properties and Synthesis of Same
  申请人：Skene G. William

  公开号：US20070287842A1

  公开（公告）日：2007-12-13

  The present invention relates to conjugated oligomers and polymers comprising aromatic thiophene cores. The conjugated materials are obtained by simple and efficient condensation of an aryl diamine and an aryl dialdehyde or a bifunctional aryl moiety comprising both an aldehyde and an amine. Condensation of the complementary moieties at temperatures ranging from ambient to refluxing temperatures in various solvents resulted in conjugated oligomers and polymers that can subsequently be cast into thin films. Oligomerization and polymerization can be done under mild conditions with removal of the resulting water bi-product responsible for shifting the equilibrium in favour of the conjugated products. The resulting conjugated compounds can be made conducting with dopants affording electrically conducting materials of either p-type or n-type conductors depending on the dopant selected.

  本发明涉及含有芳香硫吡咯核的共轭寡聚物和聚合物。这些共轭材料是通过芳香族二胺和芳香族二醛或具有同时含有醛和胺的双官能团芳香族基团的简单而有效的缩合反应获得的。在各种溶剂中，在从常温到沸点温度的温度范围内缩合互补的官能团，得到了可以随后铸造成薄膜的共轭寡聚物和聚合物。在温和的条件下进行寡聚和聚合，去除产生的水副产物，有利于使平衡向共轭产物方向移动。所得的共轭化合物可以通过掺杂制成导电材料，根据所选择的掺杂剂，可以得到p型或n型导体的电导材料。
• Conjugated thiophenes having conducting properties and synthesis of same
  申请人：Université de Montréal

  公开号：US08034895B2

  公开（公告）日：2011-10-11

  The present invention relates to conjugated oligomers and polymers comprising aromatic thiophene cores. The conjugated materials are obtained by simple and efficient condensation of an aryl diamine and an aryl dialdehyde or a bifunctional aryl moiety comprising both an aldehyde and an amine. Condensation of the complementary moieties at temperatures ranging from ambient to refluxing temperatures in various solvents resulted in conjugated oligomers and polymers that can subsequently be cast into thin films. Oligomerization and polymerization can be done under mild conditions with removal of the resulting water bi-product responsible for shifting the equilibrium in favor of the conjugated products. The resulting conjugated compounds can be made conducting with dopants affording electrically conducting materials of either p-type or n-type conductors depending on the dopant selected.

  本发明涉及含芳香硫吡咯核的共轭寡聚体和聚合物。这些共轭材料是通过芳香族二胺和芳香族二醛或含有醛和胺的双功能芳香族基团的简单高效缩合反应得到的。在各种溶剂中，在从室温到沸点温度的温度下，互补基团的缩合反应结果形成了共轭寡聚体和聚合物，随后可以将其铸造成薄膜。在温和的条件下进行寡聚和聚合反应，并通过去除产生的水副产物来促进共轭产物的生成。所得到的共轭化合物可以通过掺杂剂进行导电，从而获得p型或n型导体的电导材料。
• Tuning of the photophysical and electrochemical properties of symmetric and asymmetric conjugated thiophenoazomethines
  作者：Shengzhen Liu、Ti Wu、Qi Zhu、Jialing Pu、Guangxue Chen、Weimin Zhang、Zhongxiao Li

  DOI：10.1039/c8ra00570b

  日期：——

  have a great effect on the electronic absorption and energy levels of the conjugated compounds, particularly the effect of terminal groups. The terminal withdrawing and donating groups of thiophenoazomethines led to the formation of an electronic push–pull, push–push and pull–pull system, which can perturb the electronic transitions between the ground and excited states. The flexible chain substituents

  通过容易获得的胺与各种醛的反应，实现了通往对称和不对称噻吩并亚甲基的合成路线。对该方法得到的一系列噻吩并亚甲基的研究表明，末端基团和共轭程度对共轭化合物的电子吸收和能级有很大影响，尤其是末端基团的影响。噻吩并亚甲基的末端撤离和供体基团导致形成电子推拉、推拉和拉拉系统，这可以扰乱基态和激发态之间的电子跃迁。噻吩单元上的柔性链取代基提高了其溶解度，也导致了红移吸收，但对能级的影响有限。