25-(benzyloxy)-26,27,28-tris((ethoxycarbonyl)methoxy)-5,11,17,23-tetra-tert-butylcalix<4>arene | 145395-61-5

• 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: 25-(benzyloxy)-26,27,28-tris((ethoxycarbonyl)methoxy)-5,11,17,23-tetra-tert-butylcalix<4>arene
• 英文别名: Ethyl 2-[[5,11,17,23-tetratert-butyl-26,27-bis(2-ethoxy-2-oxoethoxy)-28-phenylmethoxy-25-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9(27),10,12,15(26),16,18,21,23-dodecaenyl]oxy]acetate
• CAS: 145395-61-5；145511-80-4
• 化学式: C₆₃H₈₀O₁₀
• 分子量: 997.322
• InChiKey: YEPLFTFDNUBIDS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.6
• 重原子数：
  73
• 可旋转键数：
  22
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  116
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  25-(benzyloxy)-26,27,28-tris((ethoxycarbonyl)methoxy)-5,11,17,23-tetra-tert-butylcalix<4>arene 在 三甲基溴硅烷 、 caesium carbonate 作用下， 以 氯仿 、 丙酮 为溶剂， 反应 2.0h， 生成 4-叔丁基杯[4]芳烃-四乙酸乙酯
  参考文献：
  名称：

  Synthesis and ion selectivity of all conformational isomers of tetrakis[(ethoxycarbonyl)methoxy]calix[4]arene

  摘要：

  We have found that the conformer distribution in tetra-O-alkylation of 5,11,17,23-tetra-tert-butylcalix[4]-arene-25,26,27,28-tetrol by ethyl bromoacetate is remarkably affected by the metal cation present in the base. In general, the cone conformer predominantly results when the base contains template metal cations whereas the partial-cone and 1,3-alternate conformers result when the base contains nontemplate metal cations. In acetone solvent one can realize the change from the 100% cone selectivity to the 100% partial-cone selectivity. By combining the metal template effect with a protection-deprotection method with a benzyl group, we developed synthetic routes to all of the four conformers. Two-phase solvent extraction established that the cone conformer shows Na+ selectivity whereas the remaining three conformers show K+ selectivity. H-1 NMR studies established that the 1,3-alternate conformer can form both a 1:1 and a 2:1 metal/calixarene complex and the two metal-binding sites display negative allostericity. This paper thus demonstrates that the metal selectivity of ionophoric calix[n]aryl esters can be changed not only by the change in the ring size but also by the conformational change.

  DOI：

  10.1021/jo00052a016
• 作为产物：
  描述：

  25-benzyloxy-5,11,17,23-tetra-tert-butyl-26,27,28-trihydroxycalix[4]arene 、 溴乙酸乙酯 在 caesium carbonate 作用下， 以 丙酮 为溶剂， 反应 1.0h， 生成 25-(benzyloxy)-26,27,28-tris((ethoxycarbonyl)methoxy)-5,11,17,23-tetra-tert-butylcalix<4>arene
  参考文献：
  名称：

  Synthesis and ion selectivity of all conformational isomers of tetrakis[(ethoxycarbonyl)methoxy]calix[4]arene

  摘要：

  We have found that the conformer distribution in tetra-O-alkylation of 5,11,17,23-tetra-tert-butylcalix[4]-arene-25,26,27,28-tetrol by ethyl bromoacetate is remarkably affected by the metal cation present in the base. In general, the cone conformer predominantly results when the base contains template metal cations whereas the partial-cone and 1,3-alternate conformers result when the base contains nontemplate metal cations. In acetone solvent one can realize the change from the 100% cone selectivity to the 100% partial-cone selectivity. By combining the metal template effect with a protection-deprotection method with a benzyl group, we developed synthetic routes to all of the four conformers. Two-phase solvent extraction established that the cone conformer shows Na+ selectivity whereas the remaining three conformers show K+ selectivity. H-1 NMR studies established that the 1,3-alternate conformer can form both a 1:1 and a 2:1 metal/calixarene complex and the two metal-binding sites display negative allostericity. This paper thus demonstrates that the metal selectivity of ionophoric calix[n]aryl esters can be changed not only by the change in the ring size but also by the conformational change.

  DOI：

  10.1021/jo00052a016

文献信息

• Synthesis and ion selectivity of all conformational isomers of tetrakis[(ethoxycarbonyl)methoxy]calix[4]arene
  作者：Koji Iwamoto、Seiji Shinkai

  DOI：10.1021/jo00052a016

  日期：1992.12

  We have found that the conformer distribution in tetra-O-alkylation of 5,11,17,23-tetra-tert-butylcalix[4]-arene-25,26,27,28-tetrol by ethyl bromoacetate is remarkably affected by the metal cation present in the base. In general, the cone conformer predominantly results when the base contains template metal cations whereas the partial-cone and 1,3-alternate conformers result when the base contains nontemplate metal cations. In acetone solvent one can realize the change from the 100% cone selectivity to the 100% partial-cone selectivity. By combining the metal template effect with a protection-deprotection method with a benzyl group, we developed synthetic routes to all of the four conformers. Two-phase solvent extraction established that the cone conformer shows Na+ selectivity whereas the remaining three conformers show K+ selectivity. H-1 NMR studies established that the 1,3-alternate conformer can form both a 1:1 and a 2:1 metal/calixarene complex and the two metal-binding sites display negative allostericity. This paper thus demonstrates that the metal selectivity of ionophoric calix[n]aryl esters can be changed not only by the change in the ring size but also by the conformational change.