2,4-己二炔-1,6-二基 双(4-甲基苯磺酸酯) | 32527-15-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2,4-己二炔-1,6-二基 双(4-甲基苯磺酸酯)
• 中文别名: 2,4-己二炔-1,6-二基双(4-甲基苯磺酸酯)；2,4-己二炔-1,6-二基双(对甲苯磺酸酯)
• 英文名称: 1,6-bis(p-toluenesulfonyloxy)-2,4-hexadiyne
• 英文别名: 2,4-hexadiyne-1,6-diol bis(p-toluenesulfonate)；2,4-Hexadiyne-1,6-diol, bis(4-methylbenzenesulfonate)；6-(4-methylphenyl)sulfonyloxyhexa-2,4-diynyl 4-methylbenzenesulfonate
• CAS: 32527-15-4
• 化学式: C₂₀H₁₈O₆S₂
• 分子量: 418.491
• InChiKey: DXMVSZQXZAMXJA-UHFFFAOYSA-N

物化性质

• 熔点：
  91-95 °C(Solv: acetone (67-64-1); hexane (110-54-3))
• 沸点：
  506.24°C (rough estimate)
• 密度：
  1.3472 (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  6

安全信息

• 海关编码：
  2905290000

反应信息

• 作为反应物：
  描述：

  2,4-己二炔-1,6-二基 双(4-甲基苯磺酸酯) 在 乙醇 、 氯仿 、 sodium iodide 作用下， 生成 1,6-dioiiodo-2,4-hexadiyne
  参考文献：
  名称：

  371.炔类化合物的研究。第XXXV部分。炔丙基取代基对联乙炔的紫外线吸收的影响

  摘要：

  DOI：

  10.1039/jr9520002005
• 作为产物：
  描述：

  对甲苯磺酸丙炔酯 在 四甲基乙二胺 、 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate 、 copper(l) chloride 作用下， 反应 6.5h， 以85%的产率得到2,4-己二炔-1,6-二基 双(4-甲基苯磺酸酯)
  参考文献：
  名称：

  Glaser oxidative coupling in ionic liquids: an improved synthesis of conjugated 1,3-diynes

  摘要：

  Terminal alkynes undergo oxidative-coupling smoothly in the presence of the CuCl-TMEDA catalytic system in hydrophobic [bmim]PF6 ionic liquid under aerobic conditions to produce 1,3-diynes in excellent yields under mild conditions. The substrates, alkynes, show enhanced reactivity and selectivity in ionic liquids (ILs). The recovery of the catalyst is facilitated by the hydrophobic nature of the [bmim]PF6 ionic liquid. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)01565-x

文献信息

• Convergent Synthesis of Rigid Macrocycles Containing One or Two Tetrathiafulvalene Units
  作者：Klaus B. Simonsen、Niels Thorup、Jan Becher

  DOI：10.1055/s-1997-1363

  日期：1997.12

  The synthesis of rigid tetrathiafulvalenenophanes containing one or two tetrathiafulvalene units is presented, together with a stepwise convergent synthesis of macrocyclic bis-tetrathiafulvalenes via several open dimeric tetrathiafulvalenes. These systems were investigated by cyclic voltammetry, which revealed that intramolecular interaction between the electroactive units only took place if the units were fixed in a rigid conformation. The X-ray structure of 10a confirmed the cis configuration of a concave molecule, which is packed in antiparallel stacks.

  介绍了包含一个或两个四硫富瓦烯单元的刚性四硫富瓦烯衍生物的合成，并逐步通过几种开链二聚四硫富瓦烯合成了大环双四硫富瓦烯。通过循环伏安法研究了这些系统，结果表明，只有在电活性单元固定在刚性构象中时，才会发生单元间的分子内相互作用。10a的X射线结构证实了其凹面分子的顺式构型，该分子以反平行堆叠方式排列。
• Synthesis of a Series of Symmetrically Disubstituted Diacetylenes with Polychlorophenyl Rings as Side Groups and Linear Polyether Chains as Spacers
  作者：Esteve Hernàndez、Angels Galan、Concepció Rovira、Jaume Veciana

  DOI：10.1055/s-1992-26327

  日期：——

  Aryl disubstituted diacetylenes with spacers of different lengths (CH2O, CH2OCH2CH2O, and CH2OCH2CH2CH2O) have been synthesized.Smaller homologues of the series were readily obtained by nucleophilic substitutions on 2,4-hexadiynylene bis(p-toluenesul-fonate). However higher homologues could not be prepared by this method from the corresponding extended bistosylates due to their low reactivities. The observed decrease of reactivity with phenoxides of such extended bistosylates is ascribed to folded conformations adopted by these derivatives. Consequently, the synthesis of higher members of the series was carried out by a multistep procedure involving appropriately functionalized monoacetylenes.

  具有不同长度间隔基（CH2O、CH2OCH2CH2O 和 CH2OCH2CH2CH2O）的芳基二取代二乙炔已被合成。通过亲核取代2,4-己二炔二基双(对甲苯磺酸酯)，较小的同系物系列容易获得。然而，由于其低反应性，无法通过这种方法从相应的延长双磺酸酯中制备更高同系物。观察到的这种延长双磺酸酯的酚盐反应性下降被归因于这些衍生物采用的折叠构象。因此，该系列的更高成员的合成是通过涉及适当功能化的单乙炔的多步骤程序进行的。
• Hexakis(isopropylthio)-1,5-hexadien-3-yne and its fluorescent Ag(i) coordination polymers: assembly of helicates with thioether sites
  作者：Yuan-Te Fu、Vincent M. Lynch、Richard J. Lagow

  DOI：10.1039/b314292b

  日期：——

  A new thioether-rich ligand with a conjugated dienyne backbone and its fluorescent Ag(I) coordination networks have been synthesized and characterized by single crystal X-ray diffraction studies, which reveal that the supramolecular architectures of the networks contain assembled helicates with thioether sites.

  合成了一种富含硫醚的新配体，其具有共轭二炔主链，并通过单晶X射线衍射研究对其荧光银(I)配位网络进行了表征，结果揭示了该网络的超分子结构包含了具有硫醚位点的组装螺旋体。
• Photoluminescent supramolecular networks from metal-mediated assembly of polythia conjugated dieneyne
  作者：Yuan-Te Fu、Vincent M. Lynch、Richard J. Lagow

  DOI：10.1039/b212789j

  日期：2003.4.16

  Polythia conjugated dieneyne 1,1,2,5,6,6-hexakis(phenyl-thio)-1,5-diene-3-yne and its one- and two-dimensional silver(I) coordination polymers, which exhibited fluorescence and redox properties, were prepared and investigated.

  合成了聚TIA共轭二烯炔1,1,2,5,6,6-六苯硫-1,5-二烯-3-炔及其一维和二维银(I)配位聚合物，并对其荧光和氧化还原性质进行了研究。
• Joint Experimental and Computational Investigation of the Flexibility of a Diacetylene-Based Mixed-Linker MOF: Revealing the Existence of Two Low-Temperature Phase Transitions and the Presence of Colossal Positive and Giant Negative Thermal Expansions
  作者：Alysson Duarte Rodrigues、Karim Fahsi、Xavier Dumail、Nathalie Masquelez、Arie van der Lee、Sonia Mallet-Ladeira、Romain Sibille、Jean-Sébastien Filhol、Sylvain G. Dutremez

  DOI：10.1002/chem.201703711

  日期：2018.2.1

  158–188 K. Furthermore, the three structurally similar phases of UMON‐44 show giant negative and/or colossal positive thermal expansions. These unusual phenomena exist without any change in the contents of the unit cell. DFT calculations using the PBE+D3 dispersion scheme were able to distinguish between these polymorphs by accurately reproducing their salient structural features, although corrections

  在溶剂热反应Ñ，Ñ 1,6-双（1-咪唑基）-2,4-己二炔一水合物（二甲基甲酰胺之间（DMF）L1⋅ ħ 2 O），间苯二甲酸（ħ 2 L2），和Zn（NO 3）2 ⋅ 6 H 2 O的表达式基于乙炔的混合配位体的配位聚合物[锌（L1）（L2）]（DMF）2 } ñ（UMON-44），收率为38％。DSC与可变温度单晶X射线衍射的结合显示了发生在129–144 K和158–188 K范围内的两个相变。此外，UMON-44的三个结构相似的相显示出巨大的负和/或巨大的正热膨胀。这些异常现象的存在没有改变晶胞的含量。使用PBE + D3分散方案进行的DFT计算能够通过精确地再现其显着的结构特征来区分这些多晶型物，尽管事实证明，为了使高温相具有较大的热度，必须校正晶胞的尺寸扩张。此外，还计算了这些理论模型的红外光谱（振动频率和峰强度），从而可以明确鉴定相应的多晶型物。最后，通过计算相变温度及其相关的焓来测试我们的计算方法的局限性，