2,6-Bis(2-cyanoethylsulfanyl)-3,7-bis(methylthio)tetrathiafulvalene | 160624-10-2

• 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: 2,6-Bis(2-cyanoethylsulfanyl)-3,7-bis(methylthio)tetrathiafulvalene
• 英文别名: 3-[[(2Z)-2-[4-(2-cyanoethylsulfanyl)-5-methylsulfanyl-1,3-dithiol-2-ylidene]-5-methylsulfanyl-1,3-dithiol-4-yl]sulfanyl]propanenitrile
• CAS: 160624-10-2
• 化学式: C₁₄H₁₄N₂S₈
• 分子量: 466.807
• InChiKey: LUSKPSQSYAKAFQ-YPKPFQOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  1,4-二氯-2-丁炔 、 2,6-Bis(2-cyanoethylsulfanyl)-3,7-bis(methylthio)tetrathiafulvalene 在 cesium hydroxide 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.0h， 以50%的产率得到(1Z,15Z)-4,13,18,27-tetrakis(methylsulfanyl)-3,6,11,14,17,20,25,28,29,30,31,32-dodecathiapentacyclo[24.2.1.12,5.112,15.116,19]dotriaconta-1,4,12,15,18,26-hexaen-8,22-diyne
  参考文献：
  名称：

  Convergent Synthesis of Rigid Macrocycles Containing One or Two Tetrathiafulvalene Units

  摘要：

  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。

  DOI：

  10.1055/s-1997-1363
• 作为产物：
  描述：

  4,5-双(2-氰乙基硫代)-1,3-二硫醇-2-硫酮 在 cesium hydroxide 、 mercury(II) diacetate 、 亚磷酸三乙酯 作用下， 以 甲醇 、 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.42h， 生成 2,6-Bis(2-cyanoethylsulfanyl)-3,7-bis(methylthio)tetrathiafulvalene
  参考文献：
  名称：

  Bis(1,3-dithiole-2-chalcogenones) and tetrathiafulvalenes in the synthesis of bridged tetrathiafulvalene-containing structures

  摘要：

  Bis(1,3-dithiole-2-chalcogenones) in which the 1,3-dithiole fragments are linked through various bridging groups were synthesized by different methods. Some of these compounds were converted into substituted tetrathiafulvalenes with bridged 1,3-dithiole rings. The same structures were synthesized from preliminarily prepared symmetric tetrathiafulvalenes containing 2-cyanoethylsulfanyl groups in both 1,3-dithiole rings. Similar spacers were used to bridge two tetrathiafulvalene fragments. Syntheses of the involved initial compounds were described.

  DOI：

  10.1134/s1070428007010186

文献信息

• Tetrathiafulvalene Crowns: Redox-Switchable Ligands
  作者：Franck Le Derf、Miloud Mazari、Nicolas Mercier、Eric Levillain、Gaëlle Trippé、Amédée Riou、Pascal Richomme、Jan Becher、Javier Garín、Jesus Orduna、Nuria Gallego-Planas、Alain Gorgues、Marc Sallé

  DOI：10.1002/1521-3765(20010119)7:2<447::aid-chem447>3.0.co;2-a

  日期：2001.1.19

  redox-responsive ligands that associate the electroactive tetrathiafulvalene core with polyether subunits of various lengths has been synthesized. X-ray structures are provided for each of the free ligands. The requisite structural criteria for reaching switchable ligands are satisfied for the largest macrocycles, that is, planarity of the 1,1',3,3'-tetrathiafulvalene (TTF) pi system and correctly oriented

  合成了一系列氧化还原反应性的配体，这些配体使电活性四硫富瓦烯核与各种长度的聚醚亚基缔合。为每个游离配体提供X射线结构。对于最大的大环，满足达到可转换配体的必要结构标准，即1,1'，3,3'-四硫富瓦烯（TTF）pi系统的平面性和正确取向的配位原子。这些配体根据腔尺寸识别各种金属阳离子的能力已通过各种技术（LSIMS，1H NMR和UV / Vis光谱，循环伏安法）进行了研究。这些系统在TTF冠醚之间显示出前所未有的高配位能力。通过循环伏安法已证实了其可切换的连接特性，金属阳离子的络合已通过三种相应的金属络合物（Pb2 +，Sr2 +和Ba2 +）的X射线结构进行了说明。这些复合物的固态结构显示出具有通道状排列的原始堆积模式。
• 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。
• Bis(1,3-dithiole-2-chalcogenones) and tetrathiafulvalenes in the synthesis of bridged tetrathiafulvalene-containing structures
  作者：G. G. Abashev、A. Yu. Bushueva、K. Yu. Lebedev、E. V. Shklyaeva

  DOI：10.1134/s1070428007010186

  日期：2007.1

  Bis(1,3-dithiole-2-chalcogenones) in which the 1,3-dithiole fragments are linked through various bridging groups were synthesized by different methods. Some of these compounds were converted into substituted tetrathiafulvalenes with bridged 1,3-dithiole rings. The same structures were synthesized from preliminarily prepared symmetric tetrathiafulvalenes containing 2-cyanoethylsulfanyl groups in both 1,3-dithiole rings. Similar spacers were used to bridge two tetrathiafulvalene fragments. Syntheses of the involved initial compounds were described.