25,27-dimethoxycalix<4>arene-crown-6 | 190672-65-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 25,27-dimethoxycalix<4>arene-crown-6
• 英文别名: 43,44-dimethoxy-3,6,9,12,15,18-hexaoxahexacyclo[18.15.7.126,30.137,41.02,32.019,24]tetratetraconta-1(35),2(32),19(24),20,22,26,28,30(44),33,37(43),38,40-dodecaene
• CAS: 190672-65-2
• 化学式: C₄₀H₄₆O₈
• 分子量: 654.8
• InChiKey: CRABXXODSQKJPN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  48
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  73.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  25,27-dimethoxycalix<4>arene-crown-6 在 碘代三甲硅烷 作用下， 以 氯仿 为溶剂， 反应 2.0h， 以84%的产率得到calix<4>crown-6
  参考文献：
  名称：

  Synthesis, Complexation, and Membrane Transport Studies of 1,3-Alternate Calix[4]arene-crown-6 Conformers: A New Class of Cesium Selective Ionophores

  摘要：

  1,3-Dialkoxycalix[3]arene-crown-6 ionophores (4a-d) are obtained in the fixed 1,3-alternate conformation in 63-85% yield by the reaction of the corresponding 1,3-dialkoxycalix[4]arenes 3a-d with pentaethylene glycol ditosylate in CH3CN in the presence of Cs2CO3. The corresponding cone conformer of the diisopropyl derivative (6) was synthesized via selective demethylation of the 1,3-dimethoxycalix-crown (2a) and subsequent dialkylation. Extraction experiments with alkali picrates reveal a strong preference of ligands 4 for Cs+. Thermodynamic parameters obtained for the complexation of 4a show that the high stability constant in MeOH (log beta = 6.4 +/- 0.4) is reflected mainly in the large -Delta H-c value of 50.2 +/- 0.2 kJ . mol(-1). The entropy of complexation (T Delta S-c = -15 kJ . mol(-1)), less negative than for other crown ethers, is explained in terms of preorganization of 4a. The X-ray structure of the cesium picrate . 4a complex shows clearly that the cation is positioned between the two aromatic rings with short Cs-C distances of 3.49 and 3.69 Angstrom, respectively. H-1 MMR spectroscopy confirms this type of structure in solution. Ligands 4 incorporated in supported liquid membranes transport Cs+ cations with a high preference over Na+. By the application of an anion gradient, traces of Cs+ can be removed (greater than or equal to 99.8%) from acidic solutions (pH = 0) that contain 4 M of NaNO3.

  DOI：

  10.1021/ja00115a012
• 作为产物：
  描述：

  二对甲苯磺酸戊乙二醇 、 26,28-dimethoxycalix[4]arene-25,27-diol 在 四丁基溴化铵 、 caesium carbonate 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以57%的产率得到25,27-dimethoxycalix<4>arene-crown-6
  参考文献：
  名称：

  Stilbene-bridged 1,3-alternate calix[4]arene crown ether for selective alkali ion extraction

  摘要：

  A series of stilbene-bridged calix[4]arenes was synthesized through an intramolecular reductive McMurry coupling of hisbenzaldehyde calix[4]arene in high yields. Tetra- and pentaethylene glycol chains were tethered to the phenolic groups of calix[4]arene to form stilbene-bridged calix[4]arene crown-5 and crown-6, respectively. The presence of stilbene bridge over the calix[4]arene rim effectively prevented the connection of the polyether chains in the cone conformation resulting in the exclusive formation of 1,3-alternate stilbene-bridged calix[4]arene crown product. Compared to the cone analogues, the 1,3-alternate calix[4]arene crown ethers showed a greater extraction ability and selectivity toward Cs+. (c) 2007 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetlet.2007.01.026

文献信息

• Synthesis, Complexation, and Membrane Transport Studies of 1,3-Alternate Calix[4]arene-crown-6 Conformers: A New Class of Cesium Selective Ionophores
  作者：Alessandro Casnati、Andrea Pochini、Rocco Ungaro、Franco Ugozzoli、Francoise Arnaud、Stefano Fanni、Marie-Jose Schwing、Richard J. M. Egberink、Feike de Jong、David N. Reinhoudt

  DOI：10.1021/ja00115a012

  日期：1995.3

  1,3-Dialkoxycalix[3]arene-crown-6 ionophores (4a-d) are obtained in the fixed 1,3-alternate conformation in 63-85% yield by the reaction of the corresponding 1,3-dialkoxycalix[4]arenes 3a-d with pentaethylene glycol ditosylate in CH3CN in the presence of Cs2CO3. The corresponding cone conformer of the diisopropyl derivative (6) was synthesized via selective demethylation of the 1,3-dimethoxycalix-crown (2a) and subsequent dialkylation. Extraction experiments with alkali picrates reveal a strong preference of ligands 4 for Cs+. Thermodynamic parameters obtained for the complexation of 4a show that the high stability constant in MeOH (log beta = 6.4 +/- 0.4) is reflected mainly in the large -Delta H-c value of 50.2 +/- 0.2 kJ . mol(-1). The entropy of complexation (T Delta S-c = -15 kJ . mol(-1)), less negative than for other crown ethers, is explained in terms of preorganization of 4a. The X-ray structure of the cesium picrate . 4a complex shows clearly that the cation is positioned between the two aromatic rings with short Cs-C distances of 3.49 and 3.69 Angstrom, respectively. H-1 MMR spectroscopy confirms this type of structure in solution. Ligands 4 incorporated in supported liquid membranes transport Cs+ cations with a high preference over Na+. By the application of an anion gradient, traces of Cs+ can be removed (greater than or equal to 99.8%) from acidic solutions (pH = 0) that contain 4 M of NaNO3.
• Stilbene-bridged 1,3-alternate calix[4]arene crown ether for selective alkali ion extraction
  作者：Arisa Jaiyu、Rojrit Rojanathanes、Mongkol Sukwattanasinitt

  DOI：10.1016/j.tetlet.2007.01.026

  日期：2007.3

  A series of stilbene-bridged calix[4]arenes was synthesized through an intramolecular reductive McMurry coupling of hisbenzaldehyde calix[4]arene in high yields. Tetra- and pentaethylene glycol chains were tethered to the phenolic groups of calix[4]arene to form stilbene-bridged calix[4]arene crown-5 and crown-6, respectively. The presence of stilbene bridge over the calix[4]arene rim effectively prevented the connection of the polyether chains in the cone conformation resulting in the exclusive formation of 1,3-alternate stilbene-bridged calix[4]arene crown product. Compared to the cone analogues, the 1,3-alternate calix[4]arene crown ethers showed a greater extraction ability and selectivity toward Cs+. (c) 2007 Published by Elsevier Ltd.