5-chloromethyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene | 656242-99-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5-chloromethyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene
• CAS: 656242-99-8
• 化学式: C₄₅H₅₇ClO₈
• 分子量: 761.396
• InChiKey: KVYQLKRNRQWKRH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.76
• 重原子数：
  54.0
• 可旋转键数：
  21.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  73.84
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  5-chloromethyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene 在 sodium azide 、 copper(II) sulfate 、 sodium ascorbate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 生成 5-methyl-1-((1-((12,32,52,72-tetrakis(2-ethoxyethoxy)-1,3,5,7(1,3)-tetrabenzenacyclooctaphane-15-yl)methyl)-1H-1,2,3-triazol-4-yl)methyl)pyrimidine-2,4(1H,3H)-dione
  参考文献：
  名称：

  Synthesis of nucleobase-calix[4]arenes via click chemistry and evaluation of their complexation with alkali metal ions and molecular assembly

  摘要：

  In this study, calix[4] arene derivatives (11 14) bearing a single nucleobase (adenine, thymine, cytosine or guanine) were synthesised via click chemistry. The complexation ability of the synthesised derivatives with alkali metal ions was measured using MALDI-TOF mass spectrometry, and their molecular assembly in CDCl3 was determined using H-1 NMR. Calix[4] arene derivatives (11-14) formed 1: 1 complexes with all alkali metal ions and the rank order for the complexation selectivity was Rb+ > Cs+ > K+ congruent to Na+ > Li+. The attachment of nucleobase at the upper rim of calix[4] arene had little effect on its complexation selectivity for alkali metal ions. Thymine-, adenine-and guanine-calix[4] arenes formed self-assembled structures in CDCl3 via base-base interactions. In addition, adenine-calix[4] arene (11) bound to thyminecalix[4]arene (12) to form a discrete species via Hoogsteen hydrogen bonding.

  DOI：

  10.1080/10610278.2011.632824
• 作为产物：
  描述：

  5-hydroxymethyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene 在 氯化亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以78%的产率得到5-chloromethyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene
  参考文献：
  名称：

  杯[4]亚芳基衍生物在上边缘具有环烯基-Zn（II）修饰的差异和底物选择性反应性。

  摘要：

  合成了新颖的“圆锥构象”杯[4]芳烃衍生物，其在上边缘带有一个或两个环（1,4,7,10-四氮杂环十二烷）部分。研究了这些杯芳烃的Zn（II）配合物的水解活性。用对-硝基苯基硬脂酸酯观察到令人惊讶的行为。而双环烯基-2Zn（II）配合物在背景下的水解活性可忽略不计，而单核配合物在pH 8.5时显示出明显的400倍速率增加。

  DOI：

  10.1021/ol0360694

文献信息

• Catalysis of Diribonucleoside Monophosphate Cleavage by Water Soluble Copper(II) Complexes of Calix[4]arene Based Nitrogen Ligands
  作者：Roberta Cacciapaglia、Alessandro Casnati、Luigi Mandolini、David N. Reinhoudt、Riccardo Salvio、Andrea Sartori、Rocco Ungaro

  DOI：10.1021/ja0632106

  日期：2006.9.1

  Calix[4]arenes functionalized at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with [12]ane-N-3 ligating units were synthesized, and their bi-and trimetallic zinc(II) and copper( II) complexes were investigated as catalysts in the cleavage of phosphodiesters as RNA models. The results of comparative kinetic studies using monometallic controls indicate that the subunits of all of the zinc(II) complexes and of the 1,3-distal bimetallic copper(II) complex 7-Cu-2 act as essentially independent monometallic catalysts. The lack of cooperation between metal ions in the above complexes is in marked contrast with the behavior of the 1,2-vicinal bimetallic copper(II) complex 6-Cu-2, which exhibits high catalytic efficiency and high levels of cooperation between metal ions in the cleavage of HPNP and of diribonucleoside monophosphates NpN'. A third ligated metal ion at the upper rim does not enhance the catalytic efficiency, which excludes the simultaneous cooperation in the catalysis of the three metal ions in 8-Cu-3. Rate accelerations relative to the background brought about by 6-Cu-2 and 8-Cu-3 (1.0 mM catalyst, water solution, pH 7.0, 50 degrees C) are on the order of 10(4)-fold, largely independent of the nucleobase structure, with the exception of the cleavage of diribonucleoside monophosphates in which the nucleobase N is uracil, namely UpU and UpG, for which rate enhancements rise to 10(5)-fold. The rationale for the observed selectivity is discussed in terms of deprotonation of the uracil moiety under the reaction conditions and complexation of the resulting anion with one of the copper(II) centers.