hexakis(4-hydroxyphenylthio)benzene | 113087-91-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: hexakis(4-hydroxyphenylthio)benzene
• 英文别名: 4-[2,3,4,5,6-Pentakis[(4-hydroxyphenyl)sulfanyl]phenyl]sulfanylphenol
• CAS: 113087-91-5
• 化学式: C₄₂H₃₀O₆S₆
• 分子量: 823.093
• InChiKey: MGBGLNHZHLGEGD-UHFFFAOYSA-N

物化性质

• 熔点：
  240 °C (decomp)
• 沸点：
  1068.9±65.0 °C(Predicted)
• 密度：
  1.62±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.2
• 重原子数：
  54
• 可旋转键数：
  12
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  273
• 氢给体数：
  6
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  hexakis(4-hydroxyphenylthio)benzene 在 吡啶 、 三氯氧磷 、 水 作用下， 反应 1.0h， 以82%的产率得到
  参考文献：
  名称：

  Synthesis and Properties of Water-Soluble Asterisk Molecules

  摘要：

  An asterisk is comprised of six semirigid arms projecting from a benzene nucleus. In the case at hand, asterisks were synthesized with one, two, or three aromatic rings (connected by sulfur atoms) in each of the six arms. A phosphomonoester at the termini of each arm solubilized the asterisks in water. The colloidal properties of these amphiphilic molecules were investigated by UV-vis and fluorescence spectroscopy, calorimetry, light scattering, surface tensiometry, and pulse-gradient spin-echo NMR. Solubility, solubilization, metal binding, and micelle "seeding" experiments were also carried out. Chain-conformation and supramolecular assembly into remarkable molecular "scrolls" were investigated by X-ray analysis and electron microscopy, respectively. One of the more interesting properties of the asterisks is that they remain monomeric in water despite having as many as 19 hydrophobic aromatic rings exposed to the water. The reasons for this behavior, and the possibility of exploiting it for constructing enzyme models free from aggregation equilibria, are discussed.

  DOI：

  10.1021/ja0206238
• 作为产物：
  描述：

  hexakis(4-methoxy-1-phenylthio)benzene 在 三溴化硼 作用下， 以86%的产率得到hexakis(4-hydroxyphenylthio)benzene
  参考文献：
  名称：

  多价PyBox星号配体

  摘要：

  研究了离散的多价PyBox配体。报告了一种有效的合成方法，其性质为1（紫外可见光，循环伏安法，NMR，MALDI-Tof）。它含有富硫的全硫化苯核，尽管有供体和可氧化的硫原子，但它与金属催化的反应相容。在模型反应中首次证明了使用全硫化芳族配体的金属催化：苯乙酮的Rh对映体选择性氢化硅烷化。有趣的特征是改变金属含量时的反应性和对映催化行为。这项工作为手性超分子组装体或用手性多价配体稳定的金属纳米粒子带来了新的思路。

  DOI：

  10.1016/j.tetlet.2008.06.075

文献信息

• Multivalent, Sulfur-Rich PyBox Asterisk Ligands in Asymmetric Metal Catalysis
  作者：Catherine Aubert、Carol Dallaire、Gérard Pèpe、E. Levillain、Guy Félix、Marc Gingras

  DOI：10.1002/ejoc.201200416

  日期：2012.11

  spectroscopy and cyclic voltammetry. PyBox ligands 1 and 2 were successfully used for Rh-catalyzed hydrosilylation of acetophenone, in spite of competitive bindings from six proximal sulfur atoms. The concept of multivalency and the presence of donating and oxidizable sulfur atoms in asymmetric metal catalysis were tested. The reactivities and the enantiocatalytic behavior of 1 and 2 with varying rhodium content

  报告了多价 PyBox 星号配体 1 和单价配体 2。1 中的创新特征是一个富含硫的过硫化苯核作为模板，将六个 PyBox 单元紧密连接在一起。C 6Cl 6 与对甲氧基苯硫醇的有效过硫化（95 %，每个 CS 键 > 99 %）和去保护导致六苯酚 4。 使用 Cl-PyBox 3 的 4 的六次 O-芳基化（94 %，每个 CO 键 >99 % ) 提供 1. 通过紫外/可见光谱和循环伏安法分析 1 和 2 的电子离域。尽管来自六个近端硫原子的竞争性结合，但 PyBox 配体 1 和 2 已成功用于 Rh 催化的苯乙酮氢化硅烷化。测试了多价的概念以及在不对称金属催化中存在的供体和可氧化的硫原子。测定了具有不同铑含量的 1 和 2 的反应性和对映催化行为。Rh 复合物在某些条件下的不稳定性通过与其他 PyBox 配体的一些交叉实验得到证实。借助分子模型 (GenMol™) 对 1 进行的构
• Reversible Switching between Phosphorescence and Fluorescence in a Unimolecular System Controlled by External Stimuli
  作者：Jing Xu、Hui Feng、Hao Teng、Guilin Chen、Saifei Pan、Jianrong Chen、Zhaosheng Qian

  DOI：10.1002/chem.201801739

  日期：2018.9.3

  aggregation‐induced phosphorescence characteristics, and demonstrates reversible switching among blue, green, and yellow phosphorescence by controlling molecular aggregation state or protonation state. Variation of solvent or pH value manipulates the interconversion between fluorescence and phosphorescence, while the change in protonation state in organic solvent switches two short‐lived emissions in a

  通过外部刺激操纵纯有机分子的发射特性是有吸引力的，但具有挑战性。在本文中，据报道具有基于双发射六硫代苯的分子具有明显的聚集诱导的磷光特性，并通过控制分子聚集状态或质子化状态证明了蓝色，绿色和黄色磷光之间的可逆转换。溶剂或pH值的变化控制了荧光和磷光之间的相互转换，而有机溶剂中质子状态的变化以可控的方式切换了两个短寿命的发射。通过将扭曲的结构与不同激发态之间能隙的适当布置相结合的合理设计，可以实现这种受控操纵。
• 一种用于生物体内铝离子检测与成像的探针的合成及应用
  申请人：浙江师范大学

  公开号：CN113024426B

  公开（公告）日：2022-06-10

  本发明提供了一种用于生物体内铝离子检测与成像的探针的合成及应用，属于检测技术领域。它解决了探针在水溶液中的低溶解度可能在成像过程中引起活细胞内自沉淀的错误信号，这将极大地影响生物系统中追踪Al3+的灵敏度和准确性。本发明设计并合成了一种新型磷光分子探针，通过在六硫代苯分子上修饰羧基，实现了铝离子特异性的检测，同时进一步在模型植物拟南芥中评估了活细胞中该探针对Al3+的成像性能。本发明通过在六(4‑羟基‑1‑苯硫基)苯(HHPB)分子中引入羧基设计并合成了一种铝离子特异性检测的新型磷光分子探针。利用独特的聚集诱导磷光(AIP)效应，开发了基于铝离子诱导的长寿命发射的时间门控发光检测方法。
• Polyvalent Interactions in Unnatural Recognition Processes
  作者：James N. Lowe、David A. Fulton、Sheng-Hsien Chiu、Arkadij M. Elizarov、Stuart J. Cantrill、Stuart J. Rowan、J. Fraser Stoddart

  DOI：10.1021/jo030283o

  日期：2004.6.1

  The synthesis of two cluster compounds, one containing six secondary dialkylammonium ion centers and the other possessing six benzo-m-phenylene[25]crown-8 (BMP25C8) macrocycles, both appended to hexakis(thiophenyl)benzene cores, is described. The binding of these clusters with complementary mono- and divalent ligands is investigated with NMR spectroscopy to probe polyvalency in these unnatural recognition systems. The ability of the two different families of clusters to bind complementary monovalent ligands is compared with that of the monovalent receptor pair, namely the dibenzylammonium ion and BMP25C8. This comparison is made possible by determining an average association constant (K-AVE) for the binding of each recognition site on the cluster with the corresponding monovalent ligand. We have found that the clustering of recognition sites together in one molecule is detrimental to their individual abilities to bind monovalent ligands. In the case of the polyvalent interaction between the hexakisBMP25C8 cluster and divalent dialkylammonium ions, an association constant, K-POLY, was calculated from the value of K-AVE determined for the complexation of the individual component recognition sites. This polyvalent interaction is significantly stronger than that associated with the averaged monovalent interactions.
• Subsite-differentiated analogs of biological [4Fe-4S]2+ clusters: synthesis, solution and solid-state structures, and subsite-specific reactions
  作者：T. D. P. Stack、R. H. Holm

  DOI：10.1021/ja00216a023

  日期：1988.4