tetrakis-(1,3-benzodithiol-2-ylidene)cyclopentanone | 112373-02-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: tetrakis-(1,3-benzodithiol-2-ylidene)cyclopentanone
• 英文别名: tetrakis(1,3-benzodithiol-2-ylidene)cyclopentanone；2,3,4,5-Tetrakis(1,3-benzodithiol-2-ylidene)cyclopentan-1-one
• CAS: 112373-02-1
• 化学式: C₃₃H₁₆OS₈
• 分子量: 685.017
• InChiKey: JJSYBFZOLGHKFC-UHFFFAOYSA-N

物化性质

• 熔点：
  298 °C
• 密度：
  1.683±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10
• 重原子数：
  42
• 可旋转键数：
  0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  tetrakis-(1,3-benzodithiol-2-ylidene)cyclopentanone 在 四氟硼酸-二乙醚络合物 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 乙醚 、 苯 为溶剂， 反应 4.0h， 生成 tetrakis(1,3-benzodithiol-2-ylidene)cyclopentylium tetrafluoroborate
  参考文献：
  名称：

  Novel redox behavior of [5]radialenes substituted with 1,3-dithiol groups

  摘要：

  Only one pair of reversible waves involving a net four-electron transfer has been observed in the redox process of pentakis(1,3-benzodithiol-2-ylidene)cyclopentane (1a), a potent electron-donating molecule. This is the first case of a single-wave four-electron transfer with only one macroscopic redox site in organic redox systems. Normal explicit difference digital simulation analysis assuming Nemstian response has been carried out to elucidate the detailed redox process of la. Our studies have shown that la mainly follows a two-step two-electron transfer and is converted to the tetracation (1a4+) via the dication (1a2+). The estimated redox potentials for the 1a/1a2+ and 1a2+/1a4+ couples are 0.394 +/- 0.003 and 0.386 +/- 0.003 V vs SCE, respectively. Thus three electrons are transferred at virtually no cost in energy after the first electron is transferred. The C-13 NMR study has revealed that 1a4+ has a unique electronic structure of cyclopentadienide substituted with five 1,3-dithiolylium groups. Two factors play important roles in the unusual multiple electron transfer with enhanced interaction: (1) preferential twist of all five 1,3-dithiolylium moieties from the central five-membered ring so as to decrease the intramolecular Coulomb repulsion and steric hindrance; (2) the aromatic stabilization arising from the contribution of the cyclopentadienide structure in 1a4+.

  DOI：

  10.1021/j100052a042
• 作为产物：
  描述：

  2,2'-(1,2-dibromo-ethanediylidene)bis(1,3-benzodithiole) 、 一氧化碳 在 四(三苯基膦)镍 铜 、 锌 作用下， 50.0 ℃ 、101.32 kPa 条件下， 以84%的产率得到tetrakis-(1,3-benzodithiol-2-ylidene)cyclopentanone
  参考文献：
  名称：

  Tetrakis(1,3-dithiol-2-ylidene)cyclopentanone: a new electron donor with remarkably low oxidation potential

  摘要：

  DOI：

  10.1021/ja00210a069

文献信息

• Molecular and Crystal Structures of Dicationic Tetrakis(1,3-benzodithiol-2-ylidene)cyclopentanone
  作者：Masafumi Ueda、Akimi Tahara、Takashi Shirahata、Yohji Misaki

  DOI：10.1246/bcsj.20160271

  日期：2016.12.15

  Molecular and crystal structures of dicationic tetrakis(1,3-benzodithiol-2-ylidene)cyclopentanone (1b), (1b2+)2(ReO4−)4(CH3CN)3(H2O)0.7, were successfully determined by X-ray single-crystal diffraction. It was suggested that two 1,3-dithiol-2-ylidenes adjacent to the carbonyl group were effectively conjugated with each other. The remaining two 1,3-dithiol-2-ylidenes, where two positive charges were

  双阳离子四(1,3-苯二硫醇-2-亚基)环戊酮(1b)、(1b2+)2(ReO4-)4(CH3CN)3(H2O)0.7的分子和晶体结构通过X射线单-晶体衍射。这表明与羰基相邻的两个 1,3-dithiol-2-ylidenes 彼此有效共轭。剩下的两个 1,3-二硫醇-2-亚基，主要分布有两个正电荷，从中央五元环明显扭曲。
• Sugimoto, Toyonari; Misaki, Yohji; Yoshida, Zen-Ichi, Molecular Crystals and Liquid Crystals (1969-1991), 1989, vol. 176, p. 259 - 270
  作者：Sugimoto, Toyonari、Misaki, Yohji、Yoshida, Zen-Ichi、Yamauchi, Jun

  DOI：——

  日期：——
• SUGIMOTO, TOYONARI;MISAKI, YOHJI;ARAI, YOSHIHISA;YAMAMOTO, YUKISHI;YOSHID+, J. AMER. CHEM. SOC., 110,(1988) N 2, 628-629
  作者：SUGIMOTO, TOYONARI、MISAKI, YOHJI、ARAI, YOSHIHISA、YAMAMOTO, YUKISHI、YOSHID+

  DOI：——

  日期：——