2-[2-(2-Methoxyethoxy)ethoxy]ethyl 3-amino-5-[2-[3-bromo-5-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]benzoate | 625847-37-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-[2-(2-Methoxyethoxy)ethoxy]ethyl 3-amino-5-[2-[3-bromo-5-[2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl]phenyl]ethynyl]benzoate
• CAS: 625847-37-2
• 化学式: C₃₀H₃₈BrNO₁₀
• 分子量: 652.536
• InChiKey: BELZBIIQBSFDJQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  42
• 可旋转键数：
  24
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  134
• 氢给体数：
  1
• 氢受体数：
  11

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 、 在 tris(dibenzylideneacetone)dipalladium (0) copper(l) iodide 、 三乙胺 、 三苯基膦 作用下， 以 乙腈 为溶剂， 以31%的产率得到2-[2-(2-Methoxyethoxy)ethoxy]ethyl 3-[2-[3-[2-[3-[2-[3-[2-[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-[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：

  2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-bromo-5-iodobenzoate 、 2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-amino-5-ethynylbenzoate 在 bis(dibenzylideneacetone)-palladium⁽⁰⁾ copper(l) iodide 、 三乙胺 、 三苯基膦 作用下， 以 乙腈 为溶剂， 以80%的产率得到2-[2-(2-Methoxyethoxy)ethoxy]ethyl 3-amino-5-[2-[3-bromo-5-[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

文献信息

• <i>m</i>-Phenylene Ethynylene Sequences Joined by Imine Linkages:  Dynamic Covalent Oligomers
  作者：Keunchan Oh、Kyu-Sung Jeong、Jeffrey S. Moore

  DOI：10.1021/jo035007o

  日期：2003.10.1

  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.