5,10-bis(chloromethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene | 842171-98-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,10-bis(chloromethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene
• 英文别名: 5,11-bis(chloromethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene；5,11-bis(chloromethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3(28),4,6,9,11,13(27),15,17,19(26),21(25),22-dodecaene
• CAS: 842171-98-6
• 化学式: C₄₆H₅₈Cl₂O₈
• 分子量: 809.868
• InChiKey: MAXZGDYRCWMBCU-UHFFFAOYSA-N

物化性质

• 沸点：
  889.0±65.0 °C(Predicted)
• 密度：
  1.145±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.5
• 重原子数：
  56.0
• 可旋转键数：
  22.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.48
• 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：

  5,10-bis(chloromethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene 在 potassium carbonate 、 一水合肼 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 147.0h， 生成 5-(aminomethyl)-11-[N,N′-bis(tert-butoxycarbonyl)-1,4,7-triazacyclonon-1-yl-methyl]-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene
  参考文献：
  名称：

  Upper Rim Bifunctional cone-Calix[4]arenes Based on a Ligated Metal Ion and a Guanidinium Unit as DNAase and RNAase Mimics

  摘要：

  The catalytic activity of an artificial phosphodiesterase that combines a ligated metal ion (Cull, Znll) with a guanidinium unit connected by a 1,2-vicinal calix[4]arene spacer was investigated in the transesterification of RNA models HPNP and four diribonucleoside 3',S'-monophosphates. Comparison with previous data related to the 1,3-distal regioisomeric metal complexes confirms the superiority of the Cull complexes over the ZIP analogs and shows that in the reactions of HPNP, GpU, and UpU, the catalytic efficiency depends very little on whether the substitution pattern is 1,2vicinal or 1,3 -distal. On the other hand, CpA turned out to be a good substrate for the Cull complex of the 1,2-vicinal catalyst and a bad substrate for the corresponding 1,3 -distal regioisomer, whereas the opposite holds for GpA. Extension of the investigation to the cleavage of the DNA model BNPP showed that both Znll and Cull complexes exhibit good catalytic efficiency, with a superiority of the 1,2-vicinal catalyst in both cases. The data reported in this work show that rate accelerations over background for the best catalyst substrate combinations at 0.5 mM catalyst concentration are 3.6 x 10(5)-fold for HPNP, 1.1 x 10(6) -fold for BNPP, and range from 1.3 X 106- to 1.3 X 10(7) -fold for diribonucleoside monophosphates.

  DOI：

  10.1021/acs.joc.6b00644
• 作为产物：
  描述：

  5,11-bis(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 2.0h， 以100%的产率得到5,10-bis(chloromethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene
  参考文献：
  名称：

  杯[4]芳烃基配体的二核和三核Zn 2+配合物作为酰基和磷酰基转移反应的催化剂

  摘要：

  杯[4]芳烃支架，通过低级边缘羟基的适当烷基化而被封闭在视锥构象中，被用作设计双金属和三金属Zn 2+催化剂的便利分子平台。杯[4]芳烃的Zn 2+配合物在2,6-双[（二甲基氨基）的上边缘的1,2-，1,3-和1,2,3-位修饰的催化活性在酯6和RNA模型化合物HPNP的裂解中研究了甲基]吡啶单元。在许多催化剂-底物组合中观察到高达4个数量级的高速率增强。有趣的是，区域异构体双核配合物在酯6裂解中的催化效率顺序。是1,2-邻位≫ 1,3-远端，但在HPNP反应中相反。与双核配合物相比，三核效率更高，这表明了三个Zn 2+离子在催化机理中的协同作用。

  DOI：

  10.1021/jo0487350

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.