5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trimethoxy-38-[2-[[(5-nitro-2-hydroxy)benzyl]amino]ethoxy]-40,42-bis[(1-methyl-2-imidazolyl)methoxy]calix[6]arene | 649555-68-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trimethoxy-38-[2-[[(5-nitro-2-hydroxy)benzyl]amino]ethoxy]-40,42-bis[(1-methyl-2-imidazolyl)methoxy]calix[6]arene
• 英文别名: 2-[[2-[[5,11,17,23,29,35-Hexatert-butyl-38,40,42-trimethoxy-39,41-bis[(1-methylimidazol-2-yl)methoxy]-37-heptacyclo[31.3.1.13,7.19,13.115,19.121,25.127,31]dotetraconta-1(36),3(42),4,6,9(41),10,12,15,17,19(40),21,23,25(39),27,29,31(38),33(37),34-octadecaenyl]oxy]ethylamino]methyl]-4-nitrophenol
• CAS: 649555-68-0；603106-71-4
• 化学式: C₈₈H₁₁₂N₆O₉
• 分子量: 1397.89
• InChiKey: ZZQPIKPVLSVWPG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  21.7
• 重原子数：
  103
• 可旋转键数：
  21
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  169
• 氢给体数：
  2
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  copper(II) perchlorate hexahydrate 、 5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trimethoxy-38-[2-[[(5-nitro-2-hydroxy)benzyl]amino]ethoxy]-40,42-bis[(1-methyl-2-imidazolyl)methoxy]calix[6]arene 在 Et₃N 作用下， 以 乙醇 为溶剂， 生成
  参考文献：
  名称：

  Supramolecular control of an organic radical coupled to a metal ion embedded at the entrance of a hydrophobic cavity

  摘要：

  本文介绍了一种新型的 N3ArO-萼[6]炔基体系。它可以形成一个与金属离子（CuII 或 ZnII）结合的芳氧基自由基，该金属离子在凹腔中呈现一个自由配位位点。它的氧化活性似乎受到超分子体系的高度控制，因此为半乳糖氧化酶等自由基酶提供了一个很好的模型。

  DOI：

  10.1039/b308255e
• 作为产物：
  描述：

  在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 1.0h， 以384 mg的产率得到5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trimethoxy-38-[2-[[(5-nitro-2-hydroxy)benzyl]amino]ethoxy]-40,42-bis[(1-methyl-2-imidazolyl)methoxy]calix[6]arene
  参考文献：
  名称：

  杯[6]芳烃小边缘的选择性官能化。新型非对称N 3，N 4和N 3 Ar O仿生配体的合成

  摘要：

  合成了八种新颖的基于杯[6]芳烃的仿生配体，用于过渡金属离子。它们显示出非对称的N 3，N 4或N 3 Ar O结合核心，该核心模仿存在组氨酸和酪氨酸残基的酶活性位点。它们合成的关键步骤是在t Bu-calix [6] arene的C 3v对称三甲基醚衍生物的小边缘上与N -Boc-2-氯乙胺进行单烷基化，以生成新的calix [6] arene合成子。其与氯甲基芳族胺和N的O-烷基化结合用水杨醛衍生物进行脱保护或烷基化或还原性烷基化反应，得到具有混合N / O供体的基于杯[6]芳烃的配体。

  DOI：

  10.1016/s0040-4020(03)00780-4

文献信息

• Biomimetic Zinc Funnel Complexes Based on Calix[6]<i>N</i>₃Ar<i>O</i> Ligands:  An Acid−Base Switch for Guest Binding
  作者：Olivier Sénèque、Marie-Noëlle Rager、Michel Giorgi、Thierry Prangé、Alain Tomas、Olivia Reinaud

  DOI：10.1021/ja053620e

  日期：2005.10.1

  The coordination chemistry of Zn in an N3ArOH environment has been explored. The ligands are based on calix[6]arenes that present two imidazole arms and an amino phenol moiety at the narrow rim. Three different types of complexes have been characterized. One is dicationic with Zn2+ coordinated to the three nitrogen atoms and to the oxygen of the phenol group of the calix[6]ligand. This complex is very sensitive to exogenous coordinating molecules and exists as a 5-coordinate species due to the endocomplexation of a guest. The second species is a monocationic complex for which the phenol group has been deprotonated. The resulting N3ArOZn complex can also bind a guest ligand albeit with a lower affinity than the dicationic complex. The third species is neutral. It can be obtained upon reaction with a base to yield a hydroxo complex or with an anion such as a chloride that coordinates the metal center from the outside of the calixarene cavity. The simultaneous binding of two anionic donors decreases the Zn Lewis acidity, allowing an impressive conformational reorganization of the system. One imidazole arm is released by the metal center. The other one undergoes self-inclusion into the pi-basic calixarene cavity because the low affinity of the metal center for neutral ligand does not allow the endo-coordination of an exogenous guest. Hence, the calix[6]N3Ar OH-based Zn complexes act as an acid-base switch for guest binding. Several aspects of this system appear reminiscent of Zn-peptidases of the astacin and serralisin families.