4',5'-bis(2-cyanoethylthio)-4,5-bis(pentylthio)-2,2'-bis-1,3-dithiole | 177160-48-4

• 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: 4',5'-bis(2-cyanoethylthio)-4,5-bis(pentylthio)-2,2'-bis-1,3-dithiole
• 英文别名: 2,3-bis(2-cyanoethylthio)-6,7-bis(n-pentylthio)tetrathiafulvalene；2,3-bis(2-cyanoethylthio)-6,7-bis(pentylthio)tetrathiafulvalene；3-[[2-[4,5-Bis(pentylsulfanyl)-1,3-dithiol-2-ylidene]-5-(2-cyanoethylsulfanyl)-1,3-dithiol-4-yl]sulfanyl]propanenitrile
• CAS: 177160-48-4
• 化学式: C₂₂H₃₀N₂S₈
• 分子量: 579.022
• InChiKey: AFJGENLFZQBQMZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.4
• 重原子数：
  32
• 可旋转键数：
  16
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  250
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  4',5'-bis(2-cyanoethylthio)-4,5-bis(pentylthio)-2,2'-bis-1,3-dithiole 在 sodium 作用下， 以 乙醇 为溶剂， 反应 4.0h， 生成
  参考文献：
  名称：

  TTF‐Modified DNA

  摘要：

  DOI：

  10.1002/chem.200800505
• 作为产物：
  描述：

  1-溴戊烷 在 亚磷酸三乙酯 作用下， 以 乙腈 为溶剂， 反应 8.0h， 生成 4',5'-bis(2-cyanoethylthio)-4,5-bis(pentylthio)-2,2'-bis-1,3-dithiole
  参考文献：
  名称：

  具有戊硫基和己硫基的不对称有机金属金 (III)-二噻吩配合物表现出独特的热结构相变

  摘要：

  合成了两种含有戊硫基和己硫基的金 (III)-二硫烯络合物，以开发具有热结构相变的分子材料。戊硫基络合物的熔点仅为 198 °C。己硫基络合物在两个结晶相和各向同性液体之间表现出多重相变。高温区的晶体以缓慢的结晶速率生长。

  DOI：

  10.1002/ejic.202300017

文献信息

• Convergent Synthesis of Rigid Macrocycles Containing One or Two Tetrathiafulvalene Units
  作者：Klaus B. Simonsen、Niels Thorup、Jan Becher

  DOI：10.1055/s-1997-1363

  日期：1997.12

  The synthesis of rigid tetrathiafulvalenenophanes containing one or two tetrathiafulvalene units is presented, together with a stepwise convergent synthesis of macrocyclic bis-tetrathiafulvalenes via several open dimeric tetrathiafulvalenes. These systems were investigated by cyclic voltammetry, which revealed that intramolecular interaction between the electroactive units only took place if the units were fixed in a rigid conformation. The X-ray structure of 10a confirmed the cis configuration of a concave molecule, which is packed in antiparallel stacks.

  介绍了包含一个或两个四硫富瓦烯单元的刚性四硫富瓦烯衍生物的合成，并逐步通过几种开链二聚四硫富瓦烯合成了大环双四硫富瓦烯。通过循环伏安法研究了这些系统，结果表明，只有在电活性单元固定在刚性构象中时，才会发生单元间的分子内相互作用。10a的X射线结构证实了其凹面分子的顺式构型，该分子以反平行堆叠方式排列。
• Sequential Functionalisation of Bis-Protected Tetrathiafulvalene-dithiolates
  作者：Klaus B. Simonsen、Niels Svenstrup、Jesper Lau、Ole Simonsen、Pernille Mørk、Gitte J. Kristensen、Jan Becher

  DOI：10.1055/s-1996-4216

  日期：1996.3

  The utilisation of the 2-cyanoethyl group as a versatile protecting group for 2-thioxo-1,3-dithiole-4,5-dithiolates and tetrathiafulvalene-thiolates is reported. Mono deprotection of bis-protected 2-thioxo-1,3-dithiole-4,5-dithiolate and of bis-protected tetrathiafulvalene-2,3-dithiolates [obtained by cross coupling of 4,5-bis(2-cyanoethylthio)-1,3-dithio-2-one 5 and the 1,3-dithiole-2-thiones 2b-h and 2j in triethyl phosphite] was achieved in very high yields. The monothiolates were generated from the bis-protected starting materials by selective mono deprotection in dimethylformamide solution using one equivalent of caesium hydroxide monohydrate in methanol. Subsequent quenching with iodomethane gave the resulting methylthio-substituted 1,3-dithiole-2-thione 2i and tetrathiafulvalenes 8 in near quantitative yield. The X-ray crystal structure of the air-stable caesium tetrathiafulvalene-thiolate 10 is reported. This is the first single crystal X-ray structure determination of a tetrathiafulvalene-thiolate.

  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。
• Bis(trisubstituted tetrathiafulvalenyl) disulfides: Disulfide-bridged TTF dimers
  作者：Philippe Leriche、Michel Giffard、Amédée Riou、Jean-Philippe Majani、Jack Cousseau、Michel Jubault、Alain Gorgues、Jan Becher

  DOI：10.1016/0040-4039(96)01063-5

  日期：1996.7

  The title compounds are synthesized, using the oxidative coupling of TTF thiolates. The disulfide linkage induces approximate orthogonality between the two TTF units, while maintaining virtually unchanged their electrochemical properties.

  使用TTF硫醇盐的氧化偶联合成标题化合物。二硫键在两个TTF单元之间产生近似正交的关系，而实际上保持它们的电化学性质不变。
• New materials derivatives of tetrathiapentalene functionalized by amide groups: Synthesis, characterization, and electrical study
  作者：Meriam Boumedjout、Amel Bendjeddou、Tahar Abbaz、Lakhmici Kaboub、Abdelkrim Gouasmia、Didier Villemin

  DOI：10.1080/10426507.2015.1114485

  日期：2016.6.2

  GRAPHICAL ABSTRACT ABSTRACT A new series of bis-fused tetrathiafulvalene containing functional groups was synthesized. The synthesis was carried out by using routes involving cross coupling, reduction, and oxidation reactions. The identity of these new donors is confirmed by 1 H NMR spectroscopy, mass spectrometry, and elemental analysis. We have used the cyclic voltammetry in order to determine the

  图形摘要摘要合成了一系列新的含有官能团的双稠合四硫富瓦烯。通过使用涉及交叉偶联、还原和氧化反应的路线进行合成。这些新供体的身份通过 1 H NMR 光谱、质谱和元素分析得到证实。我们使用循环伏安法来确定这些分子的特征 π 供体并验证所涉及的氧化还原过程的可逆性。分子轨道图已使用密度泛函计算进行计算。与四氰基醌二甲烷 (TNQ) 的电荷转移配合物是通过化学氧化还原反应制备的。
• 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。