3-(5-{3-tert-Butyl-5-[5-(2-cyano-ethylsulfanyl)-4',5'-bis-methylsulfanyl-[2,2']bi[[1,3]dithiolylidene]-4-ylsulfanylmethyl]-benzylsulfanyl}-4',5'-bis-methylsulfanyl-[2,2']bi[[1,3]dithiolylidene]-4-ylsulfanyl)-propionitrile | 307310-83-4

• 分子结构分类: 有机化合物
• 英文名称: 3-(5-{3-tert-Butyl-5-[5-(2-cyano-ethylsulfanyl)-4',5'-bis-methylsulfanyl-[2,2']bi[[1,3]dithiolylidene]-4-ylsulfanylmethyl]-benzylsulfanyl}-4',5'-bis-methylsulfanyl-[2,2']bi[[1,3]dithiolylidene]-4-ylsulfanyl)-propionitrile
• 英文别名: 3-[[2-[4,5-bis(methylsulfanyl)-1,3-dithiol-2-ylidene]-5-[[3-[[2-[4,5-bis(methylsulfanyl)-1,3-dithiol-2-ylidene]-5-(2-cyanoethylsulfanyl)-1,3-dithiol-4-yl]sulfanylmethyl]-5-tert-butylphenyl]methylsulfanyl]-1,3-dithiol-4-yl]sulfanyl]propanenitrile
• CAS: 307310-83-4
• 化学式: C₃₄H₃₆N₂S₁₆
• 分子量: 985.729
• InChiKey: RPBGRVKHASBYLV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.88
• 重原子数：
  52.0
• 可旋转键数：
  16.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  47.58
• 氢给体数：
  0.0
• 氢受体数：
  18.0

反应信息

• 作为反应物：
  描述：

  2-碘乙醚 、 3-(5-{3-tert-Butyl-5-[5-(2-cyano-ethylsulfanyl)-4',5'-bis-methylsulfanyl-[2,2']bi[[1,3]dithiolylidene]-4-ylsulfanylmethyl]-benzylsulfanyl}-4',5'-bis-methylsulfanyl-[2,2']bi[[1,3]dithiolylidene]-4-ylsulfanyl)-propionitrile 在 cesium hydroxide 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 11.75h， 以84%的产率得到6,18-bis[4,5-bis(methylsulfanyl)-1,3-dithiol-2-ylidene]-25-tert-butyl-12-oxa-3,5,7,9,15,17,19,21-octathiatetracyclo[21.3.1.04,8.016,20]heptacosa-1(27),4(8),16(20),23,25-pentaene
  参考文献：
  名称：

  Multiple-Bridged Bis-Tetrathiafulvalenes:  New Synthetic Protocols and Spectroelectrochemical Investigations

  摘要：

  Synthetic strategies for preparing dimeric tetrathiafulvalenes (TTFs) linked by either one, two, or four bridges have been developed. In particular, we report efficient few-step protocols for the preparation of face-to-face overlapped quadruple-bridged bis-TTFs. The ready interconversion of cis and trans TTFs in the presence of catalytic amounts of acid was implemented in one synthetic protocol as a way to control the isomeric outcome. The compounds were characterized by NMR spectroscopy, mass spectrometry, and elemental analysis. Moreover, the X-ray crystal structure of the macrocycle 4b is presented and compared to semiempirical (PM3) geometry optimizations. Cyclic voltammetry and spectroelectrochemistry were used to describe the interactions established between two TTF units upon oxidation, that is, their ability to form mixed-valence complexes and pi-dimers either intra- or intermolecularly. The length, flexibility, and number of bridging units in a bis-TTF, as well as the specific TTF positions being connected, determine the extent of these interactions. Thus, rigid linkers enhance the formation of intermolecular mixed-valence complexes. For 4b, the absorption spectrum of this mixed-valence stale of TTF in solution has been recorded for the first time. Finally, preliminary complexation experiments with different electron-deficient molecules are described.

  DOI：

  10.1021/ja000537c
• 作为产物：
  描述：

  1,3-双(溴甲基)-5-叔丁基苯 、 2,3-bis(2-cyanoethylthio)-6,7-bis(methylthio)tetrathiafulvelene 在 cesium hydroxide 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 以81%的产率得到3-(5-{3-tert-Butyl-5-[5-(2-cyano-ethylsulfanyl)-4',5'-bis-methylsulfanyl-[2,2']bi[[1,3]dithiolylidene]-4-ylsulfanylmethyl]-benzylsulfanyl}-4',5'-bis-methylsulfanyl-[2,2']bi[[1,3]dithiolylidene]-4-ylsulfanyl)-propionitrile
  参考文献：
  名称：

  Multiple-Bridged Bis-Tetrathiafulvalenes:  New Synthetic Protocols and Spectroelectrochemical Investigations

  摘要：

  Synthetic strategies for preparing dimeric tetrathiafulvalenes (TTFs) linked by either one, two, or four bridges have been developed. In particular, we report efficient few-step protocols for the preparation of face-to-face overlapped quadruple-bridged bis-TTFs. The ready interconversion of cis and trans TTFs in the presence of catalytic amounts of acid was implemented in one synthetic protocol as a way to control the isomeric outcome. The compounds were characterized by NMR spectroscopy, mass spectrometry, and elemental analysis. Moreover, the X-ray crystal structure of the macrocycle 4b is presented and compared to semiempirical (PM3) geometry optimizations. Cyclic voltammetry and spectroelectrochemistry were used to describe the interactions established between two TTF units upon oxidation, that is, their ability to form mixed-valence complexes and pi-dimers either intra- or intermolecularly. The length, flexibility, and number of bridging units in a bis-TTF, as well as the specific TTF positions being connected, determine the extent of these interactions. Thus, rigid linkers enhance the formation of intermolecular mixed-valence complexes. For 4b, the absorption spectrum of this mixed-valence stale of TTF in solution has been recorded for the first time. Finally, preliminary complexation experiments with different electron-deficient molecules are described.

  DOI：

  10.1021/ja000537c