3,4,11,12-Tetrathia-tricyclo[12.2.2.2^6,9]icosa-1(17),6(20),7,9(19),14(18),15-hexaene | 58074-35-4

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 3,4,11,12-Tetrathia-tricyclo[12.2.2.2^6,9]icosa-1(17),6(20),7,9(19),14(18),15-hexaene
• 英文别名: 3,4,11,12-Tetrathiatricyclo[12.2.2.26,9]icosa-1(17),6,8,14(18),15,19-hexaene
• CAS: 58074-35-4
• 化学式: C₁₆H₁₆S₄
• 分子量: 336.567
• InChiKey: XNSKIMIFFFMHGO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  101
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1,4-二(溴甲基)苯 在 benzyltriethylammonium tetrathiomolybdate 作用下， 反应 0.5h， 以52%的产率得到3,4,11,12-Tetrathia-tricyclo[12.2.2.2^6,9]icosa-1(17),6(20),7,9(19),14(18),15-hexaene
  参考文献：
  名称：

  A facile entry to macrocyclic disulfides: an efficient synthesis of redox-switched crown ethers

  摘要：

  An interesting sulfur transfer reaction with benzyltriethylammonium tetrathiomolybdate has been used efficiently for the synthesis of macrocyclic disulfides. This methodology has been extended to a high-yield synthesis of ''redox-switched'' crown ethers which have potential application for selective ion transport across liquid membranes.

  DOI：

  10.1021/jo00085a025

文献信息

• SYNTHESIS OF CYCLOPHANES FROM A SELF-ASSEMBLY REACTION
  申请人：University of Oregon

  公开号：US20160137598A1

  公开（公告）日：2016-05-19

  Disclosed herein is a novel method for preparing cyclophanes, comprising forming a disulfide cyclophane by contacting a linker moiety which includes two or more thiol groups, with a metal salt and an oxidant. The disulfide cyclophane is then desulfurized to form a thiacyclophane comprising thioether bridges. This thiacyclophane optionally may be further desulfurized to form an unsaturated hydrocarbon cyclophane, which can then be reduced to form a saturated hydrocarbon cyclophane. The various cyclophanes can be synthesized in a ring form, such as a dimer, trimer or tetramer etc., or they can be synthesized in a tetrahedral or larger structure. Also disclosed are novel cyclophanes formed by the disclosed method.

  本文揭示了一种制备环戊烷的新方法，包括通过将含有两个或更多硫醚基团的连接剂与金属盐和氧化剂接触来形成二硫化环戊烷。然后对二硫化环戊烷进行脱硫作用，形成含有硫醚桥的硫代环戊烷。这种硫代环戊烷可以选择性地进一步脱硫，形成不饱和碳氢化合物环戊烷，然后可以还原为饱和碳氢化合物环戊烷。这些不同的环戊烷可以以环形形式合成，如二聚体、三聚体或四聚体等，或者它们可以以四面体或更大的结构合成。此外，还披露了通过上述方法形成的新型环戊烷。
• Copper(<scp>ii</scp>) serves as an efficient additive for metal-directed self-assembly of over 20 thiacyclophanes
  作者：Ngoc-Minh Phan、Lev N. Zakharov、Darren W. Johnson

  DOI：10.1039/c8cc08095j

  日期：——

  Cu2+ salts are presented as an alternative to previously reported pnictogen additives in the self-assembly of 23 different thiacyclophanes. This process allows for further tuning of library equilibrium mixtures: for instance, by altering additive types and concentrations, trimeric macrocycles are amplified. These trimeric disulfides can then be covalently trapped to form 2 novel thioethers, highlighting

  在23种不同的噻唑烷酮的自组装过程中，Cu 2+盐可作为以前报道的光气添加剂的替代品。该过程允许进一步调节文库平衡混合物：例如，通过改变添加剂类型和浓度，可扩增三聚体大环化合物。然后可以将这些三聚体二硫键共价捕获以形成2个新的硫醚，突出显示了接近这些新的萘桥联环芳基的简便途径。
• Coupling Metaloid-Directed Self-Assembly and Dynamic Covalent Systems as a Route to Large Organic Cages and Cyclophanes
  作者：Mary S. Collins、Ngoc-Minh Phan、Lev N. Zakharov、Darren W. Johnson

  DOI：10.1021/acs.inorgchem.7b02716

  日期：2018.4.2

  including 3D cages. Traditional cyclization reactions carried out under kinetic control are generally low-yielding, which often results in the formation of insoluble oligomers and polymers as unwanted side products. The prospect of self-assembling organic structures efficiently under thermodynamic control adds an attractive tool for the synthesis of cyclophanes and other large cage compounds. This method

  大的环状和笼状二硫键结构的合成是通过自组装的光生硫氰酸盐配合物开始的光生助碘氧化而实现的。光子原的定向行为使得能够在竞争的低聚物/聚合物上快速且选择性地合成许多离散的二硫键组件，范围从小且应变的结构到大而多面的结构（包括3D笼）。在动力学控制下进行的传统环化反应通常产率低，这通常导致形成不溶性低聚物和聚合物，这是不希望的副产物。在热力学控制下有效地自组装有机结构的前景为合成环烷和其他大笼化合物提供了诱人的工具。这种在动态共价系统中由类金属定向的自组装方法可以快速，判别性地实现二硫化物环烷素的自组装，而不会出现传统环烷素合成中有时会出现的后果，例如收率低，反应时间长，闭环选择性低，和广泛的净化。本文提供了这种方法的概述，探讨了光原添加剂和溶剂在此反应中的作用，开始测试该策略在复杂3D分子形成中的局限性，并将我们的策略扩展到包括不包含在内的一锅法合成需要使用光气添加剂。该观点还包括扩展的介绍，
• Pnictogen-directed synthesis of discrete disulfide macrocycles
  作者：Mary S. Collins、Matthew E. Carnes、Aaron C. Sather、Orion B. Berryman、Lev N. Zakharov、Simon J. Teat、Darren W. Johnson

  DOI：10.1039/c3cc43524e

  日期：——

  Cyclic disulfide macrocycles were rapidly synthesized cleanly and selectively from rigid dithiols via oxidation with iodine when activated by pnictogen additives (As and Sb). Macrocycles were confirmed by 1H-NMR spectroscopy and X-ray crystallography. A p-xylyl-based disulfide trimer and tetramer crystallized in hollow, stacked columns stabilized by intermolecular, sulfur⋯sulfur close contacts.

  当通过pnictogen添加剂（As和Sb）活化后，通过碘氧化，可以从刚性二硫醇中快速、选择性地合成出环状二硫键大环。大环通过1H-NMR光谱和X射线晶体学得到证实。以对二甲苯为基的二硫键三聚体和四聚体结晶为中空堆叠柱状，通过分子间硫……硫的紧密接触而稳定。
• Ramesha A. R., Chandrasekaran Srinivasan, J. Org. Chem, 59 (1994) N 6, S 1354-1357
  作者：Ramesha A. R., Chandrasekaran Srinivasan

  DOI：——

  日期：——