3-[[2-[4,5-Bis(pentylsulfanyl)-1,3-dithiol-2-ylidene]-5-methylsulfanyl-1,3-dithiol-4-yl]sulfanyl]propanenitrile | 177160-56-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二硫醇
• 英文名称: 3-[[2-[4,5-Bis(pentylsulfanyl)-1,3-dithiol-2-ylidene]-5-methylsulfanyl-1,3-dithiol-4-yl]sulfanyl]propanenitrile
• CAS: 177160-56-4
• 化学式: C₂₀H₂₉NS₈
• 分子量: 539.985
• InChiKey: HLXOKNZEDPNVTF-UHFFFAOYSA-N

物化性质

• 沸点：
  568.1±50.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  29
• 可旋转键数：
  14
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  226
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3-[[2-[4,5-Bis(pentylsulfanyl)-1,3-dithiol-2-ylidene]-5-methylsulfanyl-1,3-dithiol-4-yl]sulfanyl]propanenitrile 在 sodium hydroxide 、 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 19.5h， 生成 2-[4-(5-Methylsulfanyl-4',5'-bis-pentylsulfanyl-[2,2']bi[[1,3]dithiolylidene]-4-ylsulfanyl)-butoxy]-benzoic acid
  参考文献：
  名称：

  Synthesis of Novel Phthalocyanine−Tetrathiafulvalene Hybrids; Intramolecular Fluorescence Quenching Related to Molecular Geometry

  摘要：

  A number of silicon phthalocyanine bis-esters have been synthesized and characterized, with axial ligands containing one or more tetrathiafulvalene groups. Variations in the substitution positions around a central aromatic "hinge" within the ligands lead to different molecular geometries, and the fluorescence of the macrocyclic core is subsequently quenched to varying degrees by the electron-rich tetrathiafulvalene moiety, the magnitude of this effect being dependent upon both the relative separation of the two units and the flexibility of the linking group. Pc derivative 24, with a highly flexible linker group, and pc derivative 28, with a dendritic axial ligand, have the intensity of the macrocycle emission reduced by 99% and 96%, respectively, relative to a similar silicon pc reference compound lacking the TTF moieties. Molecular modeling studies of a series of such hybrids allow the degree of this fluorescence quenching to be related to the intramolecular spacing. Additionally, the potential for rapid electrochemical switching of the phthalocyanine fluorescence by oxidation of the appended tetrathiafulvalene units is explored.

  DOI：

  10.1021/jo020340y
• 作为产物：
  描述：

  4,5-bis(pentylthio)-1,3-dithiole-2-thione 在 cesium hydroxide 、 亚磷酸三乙酯 作用下， 以 甲苯 为溶剂， 反应 2.0h， 生成 3-[[2-[4,5-Bis(pentylsulfanyl)-1,3-dithiol-2-ylidene]-5-methylsulfanyl-1,3-dithiol-4-yl]sulfanyl]propanenitrile
  参考文献：
  名称：

  Sequential Functionalisation of Bis-Protected Tetrathiafulvalene-dithiolates

  摘要：

  据报道，2-氰乙基是 2-硫酮-1,3-二硫环戊-4,5-二硫酸盐和四硫富戊烯-硫酸盐的多功能保护基团。通过 4,5-双（2-氰乙基硫代）-1,3-二硫代-2-酮 5 与 1,3-二硫代-2-硫酮 2b-h 和 2j 在亚磷酸三乙酯中的交叉偶联，实现了双保护的 2-硫酮-1,3-二硫代-4,5-二硫酸盐和双保护的四噻吩富戊烯-2,3-二硫酸盐的单脱保护，产率非常高。在二甲基甲酰胺溶液中，使用一水合氢氧化铯在甲醇中进行选择性单脱保护，从双保护起始材料中生成单硫醇酯。随后用碘甲烷淬火，得到甲硫基取代的 1,3-二硫杂-2-硫酮 2i 和四硫杂戊烯 8，产量接近定量。报告了空气稳定的四硫富戊烯硫代铯 10 的 X 射线晶体结构。这是首次测定四硫富戊烯硫酸盐的单晶 X 射线晶体结构。

  DOI：

  10.1055/s-1996-4216

文献信息

• Through-space communication in a TTF–C₆₀–TTF triad
  作者：Frédéric Oswald、Stéphanie Chopin、Pilar de la Cruz、Jesús Orduna、Javier Garín、Atula S. D. Sandanayaka、Yasuyuki Araki、Osamu Ito、Juan Luis Delgado、Jack Cousseau、Fernando Langa

  DOI：10.1039/b613466a

  日期：——

  A 2-pyrazolino[60]fullerene-based triad, possessing two TTF units connected with flexible long linkages, has been prepared. Fluorescence quenching was observed in polar and non-polar solvents, suggesting the existence of a through-space photoinduced charge separation process with rates faster than 3.8 × 109 s−1 and with high efficiency (>0.85). The charge separated states were confirmed by transient absorption spectra in the visible and near-IR regions. The longest lifetime of the charge separated state was found to be 230 ns in CH2Cl2 solvent.

  我们制备出了一种基于 2-吡唑啉并[60]富勒烯的三聚体，它拥有两个以柔性长链连接的 TTF 单元。在极性和非极性溶剂中都观察到了荧光淬灭现象，这表明存在着一个通过空间光诱导的电荷分离过程，其速率快于 3.8 Ã 109 sâ1 ，效率高（>0.85）。可见光和近红外区域的瞬态吸收光谱证实了电荷分离态的存在。在 CH2Cl2 溶剂中，电荷分离态的最长寿命为 230 ns。
• Tetrathiafulvalene Thiolates: Important Synthetic Building Blocks for Macrocyclic and Supramolecular Chemistry
  作者：Klaus Simonsen、Jan Becher

  DOI：10.1055/s-1997-1001

  日期：1997.11

  The Preparation of rather complex molecular assemblies can now be accomplished by using a complete set of tetrathiafulvalene (TTF) based building blocks. The facile deprotection of the 2-cyanoethyl group, a versatile protecting group for 1,3-dithiolium-2-thione-4,5-dithiolaes and TTF-thiolates have proven to be a viable method for the incorporation of TTF units into macrocyclic and supramolecular compounds. Especially the stepwise protection-deprotection methodology have been used extensively by our group for the preparation of two and three dimensional macrocyclic (mono-, bis- and tricyclic) as well as TTF-based supramolecular systems. The generation, utilization and scope of the generated thiolates are illustrated by several examples: Dendrimeric and oligo-TTF's, three dimensional tetrathafulvalenophanes, TTF-containing catenanes and rotaxanes and donor acceptor systems based on TTF as the donating portion.

  现在，通过使用一整套基于四噻吩（TTF）的构建模块，可以制备相当复杂的分子组装体。2-Cyanoethyl 基团是 1,3-二硫代-2-硫酮-4,5-二硫环戊烯和 TTF-硫代酸酯的通用保护基团，对该基团进行简易脱保护已被证明是将 TTF 单元加入大环和超分子化合物的可行方法。特别是分步保护-保护方法已被我们小组广泛用于制备二维和三维大环（单环、双环和三环）以及基于 TTF 的超分子体系。我们通过几个实例来说明所生成的硫代化合物的生成、利用和应用范围：树枝状和低聚 TTF、三维四富戊烯烷、含 TTF 的卡替烷和轮烷以及以 TTF 为捐献部分的捐献受体系统。