2,3,7,8,12,13,17,18-octakis(3,6-dioxaheptylthio)-5,10,15,20-tetraazaporphyrin

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2,3,7,8,12,13,17,18-octakis(3,6-dioxaheptylthio)-5,10,15,20-tetraazaporphyrin
• 英文别名: 4,5,9,10,14,15,19,20-Octakis[2-(2-methoxyethoxy)ethylsulfanyl]-2,7,12,17,21,22,23,24-octazapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1,3,5,7,9,11,13(22),14,16,18(21),19-undecaene；4,5,9,10,14,15,19,20-octakis[2-(2-methoxyethoxy)ethylsulfanyl]-2,7,12,17,21,22,23,24-octazapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1,3,5,7,9,11,13(22),14,16,18(21),19-undecaene
• 化学式: C₅₆H₉₀N₈O₁₆S₈
• 分子量: 1387.9
• InChiKey: GGKSAJVMXGQHSI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  88
• 可旋转键数：
  56
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  459
• 氢给体数：
  2
• 氢受体数：
  30

反应信息

• 作为产物：
  描述：

  1-溴-2-(2-甲氧基乙氧基)乙烷 在 magnesium n-propoxide 、 sodium iodide 作用下， 以 异丙醇 为溶剂， 反应 60.0h， 生成 2,3,7,8,12,13,17,18-octakis(3,6-dioxaheptylthio)-5,10,15,20-tetraazaporphyrin
  参考文献：
  名称：

  Metal ion mediated mesomorphism and thin film behaviour of amphitropic tetraazaporphyrin complexes

  摘要：

  合成了具有 3,6-二氧杂庚基硫代和 3,6,9-三氧杂癸基硫代两亲链的八代四氮杂卟啉及其金属配合物（Co(II)、Ni(II)、Cu(II)、Zn(II)）的合成，以便将它们的热致性和溶致性介形以及薄膜特性与之前报道过的相关四氮卟啉、酞菁和三苯基膦进行比较。钴、镍和铜络合物熔化成六角柱状介相，而锌（II）络合物和游离基卟啉没有显示出介相性。事实上，锌络合物在冷却时不会结晶，而是在室温下生成高粘度的各向同性油，在低于 -50 °C 时凝固成玻璃。这种不寻常的行为可能是锌离子与聚醚基团的氧之间的轴向相互作用造成的。所有 3,6,9-三氧代十六烷硫基取代衍生物的凝固温度都远远低于 0 °C，因此 Co(II)、Ni(II) 和 Cu(II) 复合物在室温下会产生柱状六方介相。长链衍生物的柱状六方介相夹在两种基质之间时会自发地顺向排列，这与短链类似物形成鲜明对比。X 射线衍射显示，长链和短链 Co(II) 复合物都显示出相当无序的六角柱状堆积。短链衍生物与非极性或极性有机溶剂的二元混合物没有显示出额外的裂解介相。不过，六方柱状介相的转变温度和热焓以及质地都受到了影响，假设溶剂在趋热介相中具有溶解性，如 Cu(II) 衍生物所示。所有长链衍生物也都可溶于水，但在水中和有机溶剂中均未观察到各向同性介相。通过旋涂和朗缪尔-布洛杰特（LB）技术研究了一些衍生物的成膜特性。通过旋涂法获得了介形短链铜络合物的均匀薄膜。X 射线反射率测量和偏振紫外/可见分光光谱显示，这些薄膜在环境温度下呈边缘取向的层状结构，尽管它们是晶体形态。枸橼酸法只能转移短链和长链衍生物的单层薄膜。同样，通过 X 射线测定的单层厚度与四氮杂卟啉的边缘取向一致。与此相反，推断出的水面分子面积表明，大环的取向是平向，低聚（氧乙烯）链溶解在次相中。

  DOI：

  10.1039/b100112o

文献信息

• Microwave assisted solid-phase synthesis of substituted tetraazaporphyrins and a phthalocyanine-peptide conjugate
  作者：Mercy Mudyiwa、Margaret W. Ndinguri、Steven A. Soper、Robert P. Hammer

  DOI：10.1142/s1088424610002744

  日期：2010.10

  Various asymmetrically substituted phthalocyanines (Pcs) and porphyrazines (Pzs) have been synthesized in good yields using a solid-phase synthesis method with a poly(ethylene glycol) (PEG) resin attached to an indole linker as the solid support. These compounds are formed by cross condensation of maleonitrile or phthalonitrile with another phthalonitrile covalently bonded to the solid support with an amino linking group. The polymer bound Pc or Pz is separated by filtration, and washing the symmetrical Pc or Pz by-product. The amine Pc -appended to polyethylene glycol resin is further reacted to yield azide whilst still on the solid support. Cleavage of the Pc or Pz off the solid support results in 3:1 asymmetric Pz or Pz with high degree of purity, requiring minimal further purification. The use of hydrophilic PEG-based resin allows the symmetrical compound to be removed completely by washing whereas the acid labile indole linker makes it easier to cleave the product under mild conditions. The conjugation abilities of these compounds have been demonstrated by the successful conjugation of one of the azide Pcs with a peptide elaborated with an alkyne function. Use of microwave for the synthesis of these compounds results in shorter reaction times, higher yields and higher degree of purity.

  采用固相合成法，以连接到吲哚连接体上的聚乙二醇（PEG）树脂为固体支持物，合成了各种不对称取代的酞菁（Pcs）和卟嗪（Pzs），并获得了良好的产率。这些化合物是由马来腈或邻苯二腈与另一种邻苯二腈通过氨基连接基团共价键合到固体支持物上进行交叉缩合而形成的。聚合物结合的 Pc 或 Pz 通过过滤分离，并洗涤对称的 Pc 或 Pz 副产品。附着在聚乙二醇树脂上的胺 Pc 会进一步反应，生成叠氮化物，同时仍附着在固体支持物上。将 Pc 或 Pz 从固体支持物上剥离，可得到 3:1 的不对称 Pz 或 Pz，纯度很高，只需极少的进一步纯化。亲水性 PEG 树脂的使用使得对称化合物可以通过水洗完全去除，而易受酸腐蚀的吲哚连接体则使产品更容易在温和的条件下裂解。这些化合物的共轭能力通过其中一种叠氮片段与炔功能肽的成功共轭得到了证明。使用微波合成这些化合物可以缩短反应时间，提高产率和纯度。
• Metal ion mediated mesomorphism and thin film behaviour of amphitropic tetraazaporphyrin complexes
  作者：S. Holger Eichhorn、Duncan W. Bruce、Daniel Guillon、Jean­Louis Gallani、Thomas Fischer、Joachim Stumpe、Thomas Geue

  DOI：10.1039/b100112o

  日期：——

  Octa-substituted tetraazaporphyrins with amphiphilic 3,6-dioxaheptylthio and 3,6,9-trioxadecylthio chains and their metal complexes (Co(II), Ni(II), Cu(II), Zn(II)) were synthesised in order to compare their thermotropic and lyotropic mesomorphism as well as their thin film properties with related tetraazaporphyrins, phthalocyanines and triphenylenes, which have been reported previously. The Co, Ni, and Cu complexes melted into hexagonal columnar mesophases, whereas the Zn(II) complexes and the free-base porphyrins did not display mesomorphism. In fact, the zinc complexes did not crystallise on cooling, rather giving highly viscous isotropic oils at room temperature that solidified below −50 °C to glasses. This unusual behaviour may be caused by axial interactions between the zinc ion and the oxygen of the polyether groups. All 3,6,9-trioxadecylthio substituted derivatives solidified far below 0 °C giving rise to columnar hexagonal mesophases at room temperature for the Co(II), Ni(II), and Cu(II) complexes. The columnar hexagonal mesophases of the long chain derivatives spontaneously align homeotropically when sandwiched between two substrates, in contrast to the short chain analogues. Both the long chain and the short chain Co(II) complexes displayed a rather disordered hexagonal columnar packing as revealed by X-ray diffraction. Binary mixtures of the short chain derivatives with non-polar or polar organic solvents did not display additional lyotropic mesophases. However, the transition temperatures and enthalpies, as well as the texture of the hexagonal columnar mesophase were affected, assuming a solubility of the solvent in the thermotropic mesophase as shown for the Cu(II) derivative. All long chain derivatives were also soluble in water but, again, lyotropic mesomorphism was observed neither with water nor with organic solvents. The film forming properties of some derivatives were investigated by spin-coating and the Langmuir–Blodgett (LB) technique. Homogeneous films of the mesomorphic short chain copper complex were obtained by the spin-coating method. The films displayed a layer structure with edge-on orientation at ambient temperature, although they were of crystalline morphology, as shown by X-ray reflectivity measurements and polarised UV/VIS spectroscopy. Only monolayer films of short and long chain derivatives could be transferred by the LB method. Again, determination of the thickness of the monolayer by X-ray agreed with an edge-on orientation of the tetraazaporphyrins. In contrast, the extrapolated molecular areas on the water surface suggested a flat-on orientation of the macrocycle with the oligo(oxyethylene) chains being dissolved in the sub-phase.

  合成了具有 3,6-二氧杂庚基硫代和 3,6,9-三氧杂癸基硫代两亲链的八代四氮杂卟啉及其金属配合物（Co(II)、Ni(II)、Cu(II)、Zn(II)）的合成，以便将它们的热致性和溶致性介形以及薄膜特性与之前报道过的相关四氮卟啉、酞菁和三苯基膦进行比较。钴、镍和铜络合物熔化成六角柱状介相，而锌（II）络合物和游离基卟啉没有显示出介相性。事实上，锌络合物在冷却时不会结晶，而是在室温下生成高粘度的各向同性油，在低于 -50 °C 时凝固成玻璃。这种不寻常的行为可能是锌离子与聚醚基团的氧之间的轴向相互作用造成的。所有 3,6,9-三氧代十六烷硫基取代衍生物的凝固温度都远远低于 0 °C，因此 Co(II)、Ni(II) 和 Cu(II) 复合物在室温下会产生柱状六方介相。长链衍生物的柱状六方介相夹在两种基质之间时会自发地顺向排列，这与短链类似物形成鲜明对比。X 射线衍射显示，长链和短链 Co(II) 复合物都显示出相当无序的六角柱状堆积。短链衍生物与非极性或极性有机溶剂的二元混合物没有显示出额外的裂解介相。不过，六方柱状介相的转变温度和热焓以及质地都受到了影响，假设溶剂在趋热介相中具有溶解性，如 Cu(II) 衍生物所示。所有长链衍生物也都可溶于水，但在水中和有机溶剂中均未观察到各向同性介相。通过旋涂和朗缪尔-布洛杰特（LB）技术研究了一些衍生物的成膜特性。通过旋涂法获得了介形短链铜络合物的均匀薄膜。X 射线反射率测量和偏振紫外/可见分光光谱显示，这些薄膜在环境温度下呈边缘取向的层状结构，尽管它们是晶体形态。枸橼酸法只能转移短链和长链衍生物的单层薄膜。同样，通过 X 射线测定的单层厚度与四氮杂卟啉的边缘取向一致。与此相反，推断出的水面分子面积表明，大环的取向是平向，低聚（氧乙烯）链溶解在次相中。