2-formyl-9,10-bis(1,3-dithiol-4,5-ethylenedithio-2-ylidene)dihydroanthracene | 194299-40-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 2-formyl-9,10-bis(1,3-dithiol-4,5-ethylenedithio-2-ylidene)dihydroanthracene
• 英文别名: 9,10-Bis(5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)anthracene-2-carbaldehyde
• CAS: 194299-40-6
• 化学式: C₂₅H₁₆OS₈
• 分子量: 588.929
• InChiKey: UNIHLTCSOUSVQF-UHFFFAOYSA-N

物化性质

• 沸点：
  777.9±60.0 °C(predicted)
• 密度：
  1.70±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  34
• 可旋转键数：
  1
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  220
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2-formyl-9,10-bis(1,3-dithiol-4,5-ethylenedithio-2-ylidene)dihydroanthracene 以 甲苯 为溶剂， 反应 16.0h， 生成 2-(4-formyl-1,3-butadienyl)-9,10-bis(4,5-ethylenedithio-1,3-dithiol-2-ylidene)-9,10-dihydroanthracene
  参考文献：
  名称：

  π-扩展的四硫富瓦烯（TTFs）衍生的二阶非线性光学器件的推挽生色团的合成和性质

  摘要：

  通过π共轭低烯间隔基（14a – c – 16a – c）连接到对硝基苯基电子接受单元的新型π扩展四硫富瓦烯（exTTF）衍生物显示出良好的二阶光学非线性。寡烯间隔子的共轭长度和π共轭桥中噻吩环的存在（20a – c）已在理论上（PM3）和/或实验上（EFISH技术）进行了研究。已通过循环伏安法（CV）研究了新型化合物的氧化还原特性，并且CV数据显示了exTTF单元的良好供体能力。虽然这些化合物显示的分子内电荷转移（ICT）谱带的能量及其氧化还原电位对连接供体和受体部分的共轭间隔基的性质相当不敏感，但观察到其二阶非线性光学响应有所增加在增加共轭长度上。带有噻吩环的化合物20a – c具有出色的热稳定性，分解温度超过400°C。一系列新的D-π-A化合物（23a – c）还合成和研究了带有1，3-二硫醇-2-亚烷基供体单元的）。

  DOI：

  10.1016/s0040-4020(02)00803-7
• 作为产物：
  描述：

  2-羟甲基蒽醌 在 盐酸 、 正丁基锂 、 对甲苯磺酸 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 、 丙酮 、 甲苯 为溶剂， 反应 61.0h， 生成 2-formyl-9,10-bis(1,3-dithiol-4,5-ethylenedithio-2-ylidene)dihydroanthracene
  参考文献：
  名称：

  Synthesis and Properties of the First Highly Conjugated Tetrathiafulvalene Analogues Covalently Attached to [60]Fullerene

  摘要：

  The synthesis of the first C-60-based donor-acceptor (D-A) systems (12a-c) in which the C-60 core is covalently linked to strong, highly conjugated pi-electron donors derived of tetrathiafulvalene (TTF) with p-quinodimethane structure has been carried out by cyclization with azomethine ylides following Prate's procedure. The synthetic strategy requires the preparation of the novel formyl-substituted pi-extended donors which, in turn, are prepared in a multistep synthetic procedure by reaction of 2-formyl-9,10-anthraquinone (6) with the appropriately substituted phosphonate esters (8). Semiempirical PM3 calculations predict a geometry highly distorted from planarity for the donor fragment and a most stable conformation in which both 1,3-dithiole rings are far away from the [60]fullerene surface. The redox properties were determined by cyclic voltammetry in solution and reveal the presence of four cathodically shifted reduction waves, relative to C-60 and corresponding to the C-60 core, and a two-electron single oxidation wave to form stable dication species of the pi-extended donor units. Magnetic susceptibility measurements clearly indicate a paramagnetic behavior in the solid state, and a remarkable conductivity is observed for these single component organic compounds.

  DOI：

  10.1021/jo970320+

文献信息

• Synthesis and properties of π-extended triads (A2D) derived from tetrathiafulvalene (TTF) and tetracyano-p-quinodimethane (TCNQ)
  作者：M.Angeles Herranz、Susana González、Ignacio Pérez、Nazario Martı́n

  DOI：10.1016/s0040-4020(00)01058-9

  日期：2001.1

  A new series of electroactive triads (10a-c) has been prepared by Knoevenagel condensation of formyl-containing pi -extended TTFs (9a-c) to a suitably functionalized dimer (8) derived from the electron acceptor TCAQ. The electronic spectra of the triads (10a-c) show the presence of an intramolecular charge transfer (ICT) band from the donor pi -extended TTF unit to the conjugated carbonyl groups. Theoretical calculations at the semiempirical PM3 level predict different geometrical structures for the triads which rule out a through space electronic interaction between the donor (pi -extended TTF) and acceptor (TCAQs) moieties. Cyclic voltammetric measurements reveal the amphoteric behaviour of triads 10a-c and a negligible electronic interaction between the redox chromophores. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Synthesis and characterization of novel NLO-phores from π-extended tetrathiafulvalene (TTF) derivatives
  作者：MaAngeles Herranz、Nazario Martín、Luis Sánchez、Javier Garín、Jesús Orduna、Rafael Alcalá、Belén Villacampa、Carlos Sánchez

  DOI：10.1016/s0040-4020(98)00691-7

  日期：1998.9

  Donor-pi-Acceptor systems containing extended TTF derivatives with quinonoid structures have been synthesized and characterized. Their properties as second order NLO chromophores have been studied by experimental (EFISH) and theoretical methods. (C) 1998 Elsevier Science Ltd. All rights reserved.
• New π-extended tetrathiafulvalene-containing fulleropyrrolidine dyads endowed with vinyl spacers
  作者：M.A Herranz、N Martı́n、L Sánchez、C Seoane、D.M Guldi

  DOI：10.1016/s0022-328x(99)00595-1

  日期：2000.4

  The synthesis of novel C-60-donor dyads in which the fulleropyrrolidine moiety is covalently attached to an pi-extended tetrathiafulvalene analogue through an ethylenic spacer is described. The cyclic voltammetry confirms the redox reactivity of both donor and acceptor chromophores and the semiempirical PM3 theoretical calculations predict the existence of two conformational isomers. In the ground state, no evidence of charge transfer interaction was observed in solution. Upon excitation, the fullerene singlet excited state in C-60-donor dyads is subject to a solvent-dependent, rapid fluorescence quenching, suggesting an intramolecular electron transfer. (C) 2000 Elsevier Science S.A. All rights reserved.
• Synthesis and Properties of the First Highly Conjugated Tetrathiafulvalene Analogues Covalently Attached to [60]Fullerene
  作者：Nazario Martín、Ignacio Pérez、Luis Sánchez、Carlos Seoane

  DOI：10.1021/jo970320+

  日期：1997.8.1

  The synthesis of the first C-60-based donor-acceptor (D-A) systems (12a-c) in which the C-60 core is covalently linked to strong, highly conjugated pi-electron donors derived of tetrathiafulvalene (TTF) with p-quinodimethane structure has been carried out by cyclization with azomethine ylides following Prate's procedure. The synthetic strategy requires the preparation of the novel formyl-substituted pi-extended donors which, in turn, are prepared in a multistep synthetic procedure by reaction of 2-formyl-9,10-anthraquinone (6) with the appropriately substituted phosphonate esters (8). Semiempirical PM3 calculations predict a geometry highly distorted from planarity for the donor fragment and a most stable conformation in which both 1,3-dithiole rings are far away from the [60]fullerene surface. The redox properties were determined by cyclic voltammetry in solution and reveal the presence of four cathodically shifted reduction waves, relative to C-60 and corresponding to the C-60 core, and a two-electron single oxidation wave to form stable dication species of the pi-extended donor units. Magnetic susceptibility measurements clearly indicate a paramagnetic behavior in the solid state, and a remarkable conductivity is observed for these single component organic compounds.
• Synthesis and properties of push–pull chromophores for second-order nonlinear optics derived from π-extended tetrathiafulvalenes (TTFs)
  作者：Manuel Otero、Ma Ángeles Herranz、Carlos Seoane、Nazario Martı́n、Javier Garı́n、Jesús Orduna、Rafael Alcalá、Belén Villacampa

  DOI：10.1016/s0040-4020(02)00803-7

  日期：2002.9

  (EFISH technique) studied. The redox properties of the novel compounds have been investigated by cyclic voltammetry (CV) and the CV data reveal the good donor ability of the exTTF unit. Although the energy of the intramolecular charge-transfer (ICT) band displayed by these compounds and their redox potentials are fairly insensitive to the nature of the conjugated spacer linking the donor and the acceptor

  通过π共轭低烯间隔基（14a – c – 16a – c）连接到对硝基苯基电子接受单元的新型π扩展四硫富瓦烯（exTTF）衍生物显示出良好的二阶光学非线性。寡烯间隔子的共轭长度和π共轭桥中噻吩环的存在（20a – c）已在理论上（PM3）和/或实验上（EFISH技术）进行了研究。已通过循环伏安法（CV）研究了新型化合物的氧化还原特性，并且CV数据显示了exTTF单元的良好供体能力。虽然这些化合物显示的分子内电荷转移（ICT）谱带的能量及其氧化还原电位对连接供体和受体部分的共轭间隔基的性质相当不敏感，但观察到其二阶非线性光学响应有所增加在增加共轭长度上。带有噻吩环的化合物20a – c具有出色的热稳定性，分解温度超过400°C。一系列新的D-π-A化合物（23a – c）还合成和研究了带有1，3-二硫醇-2-亚烷基供体单元的）。