5-formyl-5'-(4-N,N-dimethylaminophenyl)-2,2'-bithiophene | 130840-97-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 双噻吩和低聚噻吩
• 英文名称: 5-formyl-5'-(4-N,N-dimethylaminophenyl)-2,2'-bithiophene
• 英文别名: 5-[5-[4-(Dimethylamino)phenyl]thiophen-2-yl]thiophene-2-carbaldehyde
• CAS: 130840-97-0
• 化学式: C₁₇H₁₅NOS₂
• 分子量: 313.444
• InChiKey: URIPLPVPBXHFNM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  76.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,3-二乙基-2-硫代巴比妥酸 、 5-formyl-5'-(4-N,N-dimethylaminophenyl)-2,2'-bithiophene 在 哌啶 作用下， 以 乙醇 为溶剂， 以89%的产率得到5-((5-(5-(4-(dimethylamino)phenyl)thiophen-2-yl)thiophen-2-yl)methylene)-1,3-diethyl-dihydro-2-thioxopyrimidine-4,6(1H,5H)-dione
  参考文献：
  名称：

  Fluorescence and two-photon absorption of push—pull aryl(bi)thiophenes: structure—property relationships

  摘要：

  本文介绍了一系列推拉芳基（双）噻吩发色团的光物理和 TPA 特性，这些发色团带有电子捐赠（D）和电子撤回（A）端基，其强度不断增加。所有化合物在可见光区域都显示出强烈的分子内电荷转移（ICT）吸收带。增加 D 和/或 A 的强度以及共轭路径的长度会引起吸收带的浴色和高色移，这与类似推挽多烯的情况相同。然而，与相应的推拉式多烯相比，荧光显著增加。特别是，由苯基-双噻吩共轭路径和带有强 D 和 A 端基的发色团被发现结合了非常大的单光子和双光子亮度，以及在红色/近红外区域的强发射。这些分子有望成为用于生物成像的双光子荧光探针。

  DOI：

  10.1039/c2pp25258a
• 作为产物：
  描述：

  bithienylzinc chloride 在 Pd(DBA),TPP 、 tetraphenylporphyrin 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 33.0h， 生成 5-formyl-5'-(4-N,N-dimethylaminophenyl)-2,2'-bithiophene
  参考文献：
  名称：

  Synthesis of new thiophene compounds with large second order optical non-linearitles

  摘要：

  DOI：

  10.1016/s0040-4039(00)97721-9

文献信息

• Synthesis and characterization of push-pull bithiophene and thieno[3,2-b]thiophene derivatives bearing an ethyne linker as sensitizers for dye-sensitized solar cells
  作者：Sara S.M. Fernandes、I. Mesquita、L. Andrade、A. Mendes、Licínia L.G. Justino、Hugh D. Burrows、M. Manuela M. Raposo

  DOI：10.1016/j.orgel.2017.06.048

  日期：2017.10

  ethynyl-thieno[3,2-b]thiophene spacers and cyanoacetic acid or rhodanine-3-acetic acid as anchoring group. The synthesis of the precursor aldehydes 4–5 was accomplished through a Sonogashira coupling, on the other hand, compound 8 was prepared by Suzuki coupling. Knoevenagel condensation of aldehydes 4, 5 and 8 with cyanoacetic acid or rhodamine-3-acetic acid afforded the final push-pull dyes 6, 7 and 9

  五推挽杂环染料4 - 7，和9被合成和表征为了研究在由结构修饰引起的光学，电子和光生伏打性质，即不同间隔单元和锚定基团的变化。最终推挽偶联染料6 - 7和9由形成N，N-用二噻吩，乙炔基二噻吩或乙炔基-噻吩并[3,2-缀合二甲基苯胺供体部分b ]噻吩间隔件和氰基乙酸或绕丹宁-3- -乙酸作为锚定基团。前体醛的合成4 - 5通过Sonogashira偶联来完成“合成”，另一方面，通过Suzuki偶联制备化合物8。醛的Knoevenagel缩合反应4，5和8与氰基乙酸或罗丹明-3-乙酸，得到最终推挽染料6，7和9。通过DFT和TDDFT计算获得有关构象，电子结构和电子分布的信息。这项有关染料的光学，氧化还原和光伏性质评估的跨学科研究表明，化合物7具有与氰乙酸锚定基团共轭的乙炔基-联噻吩间隔基的纳米晶TiO 2太阳能电池作为染料敏化剂的转化效率最高（3.51％）。共吸附研究还进行了对染料6 -
• Synthesis of 5-aryl-5′-formyl-2,2′-bithiophenes as new precursors for nonlinear optical (NLO) materials
  作者：Cyril Herbivo、Alain Comel、G. Kirsch、M. Manuela M. Raposo

  DOI：10.1016/j.tet.2008.12.078

  日期：2009.3

  A series of formyl-substituted 5-aryl-2,2′-bithiophenes 5 were synthesized using two different methods: Vilsmeier–Haack–Arnold reaction (VHA) or through Suzuki coupling. The synthesis of compounds 5 through the Vilsmeier–Haack–Arnold reaction, starting from inexpensive and easily available precursors such as acetophenones, gave the title compounds in low yields after four reaction steps. On the other

  使用两种不同的方法：Vilsmeier–Haack–Arnold反应（VHA）或通过Suzuki偶联合成了一系列被甲酰基取代的5-芳基-2,2'-联噻吩5。通过Vilsmeier-Haack-Arnold反应进行的化合物5的合成，是从廉价且容易获得的前体（如苯乙酮）开始的，经过四个反应步骤后，标题化合物的收率很低。另一方面，官能化的芳基硼酸7和5-溴-5'-甲酰基-2,2'-联噻吩6的Suzuki偶联仅一步就得到了高产率的化合物5。
• Theoretical and experimental studies of aryl-bithiophene based push-pull π-conjugated heterocyclic systems bearing cyanoacetic or rhodanine-3-acetic acid acceptors for SHG nonlinear optical applications
  作者：Sara S.M. Fernandes、Cyril Herbivo、João Aires-de-Sousa、Alain Comel、Michael Belsley、M. Manuela M. Raposo

  DOI：10.1016/j.dyepig.2017.10.001

  日期：2018.2

  understand how structural modifications influence the electronic, linear and nonlinear optical properties. The push-pull conjugated chromophores 2–3 bear a bithiophene spacer conjugated with a phenyl ring functionalized with N,N-dialkylamino electron-donor groups together with cyanoacetic or rhodanine-3-acetic acid acceptor groups. Theoretical (DFT calculations) and experimental studies were carried

  设计并合成了一系列基于推挽式芳基-联噻吩的系统2–3，以了解结构修饰如何影响电子，线性和非线性光学性质。推挽共轭生色团2-3带有联噻吩间隔基，该间隔基与被N，N-二烷基氨基电子给体基团以及氰基乙酸或Rhodanine-3-乙酸受体基团官能化的苯环共轭。进行了理论（DFT计算）和实验研究，以获取有关推挽联噻吩衍生物的构象，电子结构，电子分布，偶极矩和分子非线性响应的信息。这项多学科研究表明，发色团2e 由于N，N-二甲基氨基的强大的电子给体能力，乙炔连接基表现出最高的超极化率β（10440×10 -30 esu），并且乙炔连接基不仅延长了π-共轭路径，而且赋予了较小的畸变系统。
• Enhancing the temporal stability of DSSCs with novel vinylpyrimidine anchoring and accepting group
  作者：Isolda Duerto、Santiago Sarasa、Daniel Barrios、Jesús Orduna、Belén Villacampa、María-Jesús Blesa

  DOI：10.1016/j.dyepig.2022.110310

  日期：2022.7

  Three compounds based on aniline, thiophene and vinylpyrimidine as anchoring group have been prepared and studied as light harvesting units for dye-sensitized solar cells (DSSCs). They comprise thiophenyl π-spacer systems with one or two thiophenes (AT-Pyri, ATT-Pyri) and aniline as donor which is functionalized, in one case, with an hydroxyl group (HO-AT-Pyri). The bithiophene based dye (ATT-Pyri) shows

  已经制备并研究了三种基于苯胺、噻吩和乙烯基嘧啶作为锚定基团的化合物作为染料敏化太阳能电池 (DSSC) 的光收集单元。它们包含具有一个或两个噻吩（ AT-Pyri、ATT-Pyri）和苯胺作为供体的苯硫基 π-间隔系统，在一种情况下，用羟基（HO-AT-Pyri）官能化。基于二噻吩的染料 ( ATT-Pyri ) 具有更高的消光系数和更小的跃迁能，以及更宽的吸收光谱。因此，尽管染料吸收率较低，但与不含该基团的类似染料相比，基于一种噻吩并带有羟基 ( HO-AT-Pyri ) 的器件具有稍高的功率转换效率 (η) (AT-Pyri）。然而，当添加共吸附剂以避免染料聚集时，性能最佳的装置是基于具有二噻吩桥的染料 ( ATT-Pyri) 。基于这些乙烯基嘧啶染料的电池的光伏参数在 1000 小时内得到增强，特别是对于ATT-Pyri器件，其达到 η = 6.4%。
• Synthesis and characterization of novel, thermally stable 2-aryl-5-dicyanovinylthiophenes and 5-aryl-5′-dicyanovinyl-2,2′-bithiophenes as potentially promising non-linear optical materials
  作者：Cyril Herbivo、Alain Comel、G. Kirsch、A. Maurício C. Fonseca、M. Belsley、M. Manuela M. Raposo

  DOI：10.1016/j.dyepig.2010.01.006

  日期：2010.8

  Two series of dicyanovinyl-substituted compounds namely 2-aryl-5-dicyanovinylthiophenes and 5-aryl-5'-dicyanovinyl-2,2'-bithiophenes were synthesized through Knoevenagel condensation of the corresponding 2-aryl-5-formyl-thiophenes and 5-aryl-5'-formyl-2,2'-bithiophene precursors. In contrast, the 2-aryl-5-formyl-thiophenes precursor were prepared through the Vilsmeier Haack Arnold reaction starting from inexpensive and easily available precursors such as acetophenones; this method produced the title compounds in higher yield than that recently reported which involved the Suzuki coupling of functionalized aryl boronic acids with 5-bromo-2-formyl-thiophene. Electrochemical studies and characterization of both the linear and non-linear optical properties and thermal properties indicated that good non-linearity was complemented by exceptional thermal stability for some chromophores, making them potential candidates for several optoelectronic applications such as solvatochromic probes and non-linear optical materials. (C) 2010 Elsevier Ltd. All rights reserved.