2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-ethynyl-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]phenyl]ethynyl]phenyl]ethynyl]benzoate | 625847-38-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-ethynyl-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]phenyl]ethynyl]phenyl]ethynyl]benzoate
• CAS: 625847-38-3
• 化学式: C₆₄H₇₄O₂₀
• 分子量: 1163.28
• InChiKey: GXSDVOFJKUVKSB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  84
• 可旋转键数：
  51
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  216
• 氢给体数：
  0
• 氢受体数：
  20

反应信息

• 作为反应物：
  描述：

  2-[2-(2-Methoxyethoxy)ethoxy]ethyl 3-amino-5-[2-[3-bromo-5-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]benzoate 、 2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-ethynyl-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]phenyl]ethynyl]phenyl]ethynyl]benzoate 在 tris(dibenzylideneacetone)dipalladium (0) copper(l) iodide 、 三乙胺 、 三苯基膦 作用下， 以 乙腈 为溶剂， 生成 2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-[2-[3-[2-[3-[2-[3-[2-[3-amino-5-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]-5-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]-5-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]-5-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]benzoate
  参考文献：
  名称：

  m-Phenylene Ethynylene Sequences Joined by Imine Linkages:  Dynamic Covalent Oligomers

  摘要：

  Imine metathesis between m-phenylene ethynylene oligomers of various lengths was performed in acetonitrile, a solvent in which oligomers containing eight or more repeat units adopt a compact helical conformation. The equilibrium constants and corresponding free energy change for the imine metathesis reactions were estimated. The results showed that the magnitude of equilibrium shifting measured by the free energy change for the formation of imine-containing oligomers increases linearly below a critical product chain length and grows asymptotically above it. The linear region is ascribed to the constant increase in contact area between monomer units of adjacent helical turns as the product chain grows to the 12-mer. Once the ligation product is 12 units in length, full contact is made between adjacent helical turns. On the other hand, for imine metathesis between oligomers leading to products having more than 12 units, the driving force is the difference between the folding energy of products and that of reactants. The additional stabilizing energy is roughly constant, regardless of the chain length, since the contact area between adjacent helical turns is unchanged. Consistent with the notion that the imine bond only minimally destabilizes the helical conformation, the position of the imine bond in the ligation product has been observed to have no significant effect on the folding stability. The magnitudes of equilibrium shifting are similar for ligation products of the same length but having the imine at various positions along the sequence. This suggests that the imine bond is compatible with the m-phenylene ethynylene backbone, regardless of the position in the sequence. Imine metathesis of m-phenylene ethynylene oligomers could allow a quick access to an unbiased, dynamic library of oligomer sequences joined by imine linkages.

  DOI：

  10.1021/jo035007o
• 作为产物：
  描述：

  在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以93%的产率得到2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-ethynyl-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]-5-[2-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]phenyl]ethynyl]phenyl]ethynyl]benzoate
  参考文献：
  名称：

  The Size-Selective Synthesis of Folded Oligomers by Dynamic Templation

  摘要：

  A dynamic pool of m-phenylene ethynylene oligomers generated by sequence ligation using the imine metathesis reaction was equilibrated under a variety of conditions, and the mixture of products was analyzed by HPLC. The equilibration was performed in the presence and absence of rodlike ligand 2b, which exhibits an affinity for the helical oligomers that is very length specific. Among the eight oligomers generated during metathesis equilibrium, the formation of 22-mer 6b was enhanced in acetonitrile in the presence of 2b. This particular oligomer has the highest binding affinity for 2b. Quantitative analysis by HPLC of the products indicated that 6b was produced in 66% yield in the presence of 2 equiv 2b while a 37% yield was produced in the absence of 2b. Judging from the binding affinities of oligomers 6 with 2b, the equilibrium shifting was driven by the selective binding of 6b with 2b.

  DOI：

  10.1021/ja025698q