5H,17H-6,10:18,22-Diepiazenobis[1,3]dithiolo[4,5-b:4',5'-m][1,4,12,15]tetrathiacyclodocosine-2,14-dithione | 126522-13-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 5H,17H-6,10:18,22-Diepiazenobis[1,3]dithiolo[4,5-b:4',5'-m][1,4,12,15]tetrathiacyclodocosine-2,14-dithione
• 英文别名: 3,5,7,9,17,19,21,23-octathia-29,30-diazapentacyclo[23.3.1.111,15.04,8.018,22]triaconta-1(29),4(8),11(30),12,14,18(22),25,27-octaene-6,20-dithione
• CAS: 126522-13-2
• 化学式: C₂₀H₁₄N₂S₁₀
• 分子量: 603.005
• InChiKey: YDZZZIXNBGLFEL-UHFFFAOYSA-N

物化性质

• 沸点：
  778.2±70.0 °C(Predicted)
• 密度：
  1.72±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  32
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  292
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  5H,17H-6,10:18,22-Diepiazenobis[1,3]dithiolo[4,5-b:4',5'-m][1,4,12,15]tetrathiacyclodocosine-2,14-dithione 在 亚磷酸三乙酯 作用下， 以 xylene 为溶剂， 反应 5.0h， 以20%的产率得到1,4,5,6-Tetrahydro-2,7:3,6-bis(2',6'-pyridylenebismethylene)-1,4,5,8-tetrathiafulvalene
  参考文献：
  名称：

  Crown ether annelated tetrathiafulvalenes. 2

  摘要：

  A synthetic procedure leading to derivatives of tetrathiafulvalene (TTF) incorporating polyether chains of various lengths, some nitrogen analogs, and a 2,6-bis(methylene)pyridine analog has been developed. These compounds possess cage-type structures which were confirmed by X-ray crystallography in four cases, two of which are reported herein for the first time. Structural and electronic features of these cage molecules were correlated to oxidation potentials by the use of semiempirical methods (MNDO-PM3). An investigation of the alkali metal ion affinity using PDMS revealed that these compounds are poor ligands. Finally, in one case, protonation of the core TTF was studied by NMR.

  DOI：

  10.1021/jo00058a013
• 作为产物：
  描述：

  2,6-双(溴甲基)吡啶 、 4,5-双(苯甲酰硫基)-1,3-二硫杂环戊烯-2-硫酮 在 sodium 作用下， 生成 5H,17H-6,10:18,22-Diepiazenobis[1,3]dithiolo[4,5-b:4',5'-m][1,4,12,15]tetrathiacyclodocosine-2,14-dithione
  参考文献：
  名称：

  Crown ether annelated tetrathiafulvalenes. 2

  摘要：

  A synthetic procedure leading to derivatives of tetrathiafulvalene (TTF) incorporating polyether chains of various lengths, some nitrogen analogs, and a 2,6-bis(methylene)pyridine analog has been developed. These compounds possess cage-type structures which were confirmed by X-ray crystallography in four cases, two of which are reported herein for the first time. Structural and electronic features of these cage molecules were correlated to oxidation potentials by the use of semiempirical methods (MNDO-PM3). An investigation of the alkali metal ion affinity using PDMS revealed that these compounds are poor ligands. Finally, in one case, protonation of the core TTF was studied by NMR.

  DOI：

  10.1021/jo00058a013

文献信息

• Preparation, characterisation and complexation of a redox-active, soft-donor macrocycle
  作者：Hilary J. Hartigan、Georg Seeber、Andrew R. Mount、Lesley J. Yellowlees、Neil Robertson

  DOI：10.1039/b309317d

  日期：——

  Two new redox-active macrocycles 2 and 3 have been prepared based on an 18-membered S4N2–donor ring conjugated to one or two CpCo(dithiolene) redox/chromophore units respectively. Cyclic voltammetry for 2 showed one reversible reduction process at −0.29 V and EPR spectroscopy of the reduced form indicated a significant degree of delocalisation of the unpaired electron. The compound 2 showed an intense low-energy absorption at 675 nm (in CH2Cl2) that was shown to shift to higher energy during electrochemical reduction. Interaction of 2 with guest Ag(I) ions was followed by monitoring changes in the electrochemical and spectroscopic behaviour with sequential additions of the guest metal ion and by electrochemistry at a silver electrode. UV/Vis spectroscopic results indicated a strong interaction of Ag(I) with 2 involving large changes in the electronic nature of the macrocycle chromophore. Cyclic voltammetry also indicated interaction between 2 and Ag(I) and suggested the involvement of a film containing 2 on the electrode surface.

  基于18元S4N2供体环与一个或两个CpCo(二硫烯)氧化还原/发色团单元分别共轭，制备了两种新的氧化还原活性大环化合物2和3。循环伏安法对化合物2的测试显示，在−0.29 V处有一个可逆的还原过程，而其还原形式的电子顺磁共振光谱表明未成对电子有明显的离域化程度。化合物2在675 nm（在CH2Cl2中）处显示出强烈的低能量吸收，这一吸收在电化学还原过程中显示出向更高能量的位移。通过监测客体Ag(I)离子逐次添加时电化学和光谱行为的改变，以及在银电极上的电化学行为，追踪了化合物2与客体Ag(I)离子的相互作用。紫外/可见光谱结果表明，Ag(I)与化合物2之间存在强烈的相互作用，涉及大环发色团电子性质的显著变化。循环伏安法也表明化合物2与Ag(I)之间存在相互作用，并暗示电极表面可能涉及含有化合物2的薄膜。
• A novel macrocycle containing the 4,5-dithio-1,3-dithiole-2-thione unit and a related macrocycle incorporating the tetrathiafulvalene moiety
  作者：B. Girmay、J. D. Kilburn、A. E. Underhill、K. S. Varma、M. B. Hursthouse、M. E. Harman、J. Becher、G. Bojesen

  DOI：10.1039/c39890001406

  日期：——

  A novel macrocycle (3) incorporating the 4,5-dithio-1,3-dithiole-2-thione unit has been prepared from 2,6-bis(bromomethyl)pyridine and 4,5-bis(benzoylthio)-1,3-dithiole-2-thione: intramolecular triethylphosphite coupling of (3) leads to a novel macrocyclic π-donor (4) incorporating a non-planar tetrathiafulvalene moiety; the crystal structures of (3) and (4) are reported.

  由2，6-双（溴甲基）吡啶和4，5-双（苯甲酰硫基）-1，3制备了结合有4，5-二硫-1，3-二硫基-2-硫酮单元的新型大环（3）。 -二硫代-2-硫酮：（3）的分子内亚磷酸三乙酯偶联导致引入了非平面四硫富瓦烯部分的新型大环π-供体（4）；报告了（3）和（4）的晶体结构。