25,27-bis(1-octyloxy)calix<4>warene-crown-6 | 162301-47-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 25,27-bis(1-octyloxy)calix<4>warene-crown-6
• 英文别名: 43,44-dioctoxy-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: 162301-47-5
• 化学式: C₅₄H₇₄O₈
• 分子量: 851.177
• InChiKey: FNRLFHMTAOXYRH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.6
• 重原子数：
  62
• 可旋转键数：
  16
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.56
• 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-bis(1-octyloxy)calix<4>warene-crown-6 在 硝酸 、 乙酸酐 作用下， 以 二氯甲烷 为溶剂， 反应 0.08h， 以81%的产率得到22,28,34,39-Tetranitro-43,44-dioctoxy-3,6,9,12,15,18-hexaoxahexacyclo[18.15.7.126,30.137,41.02,32.019,24]tetratetraconta-1,19,21,23,26(44),27,29,32,34,37,39,41(43)-dodecaene
  参考文献：
  名称：

  Study of the nitration of di-n-octylcrown-6 calix[4]arene using LC–MS, NMR, and molecular modelling

  摘要：

  使用不同条件进行有选择性的硝化反应，利用LC-MS和NMR (¹H和¹³C)光谱技术研究了二正辛基冠-6杯[4]芳烃的硝化反应，鉴定了大部分预期的硝基衍生物同分异构体化合物。利用分子模拟探讨了这些同分异构体在酸性和辐射条件下的形成。关键词：杯冠化合物，杯芳烃的硝化反应，同分异构体硝基杯芳烃的NMR，LC-ESI-MS。

  DOI：

  10.1139/v05-126
• 作为产物：
  描述：

  1-碘辛烷 在 potassium carbonate 、 caesium carbonate 作用下， 以 乙腈 为溶剂， 生成 25,27-bis(1-octyloxy)calix<4>warene-crown-6
  参考文献：
  名称：

  Dideoxygenated calix[4]arene crown-6 ethers enhanced selectivity for caesium over potassium and rubidium

  摘要：

  源自双脱氧杯[4]芳烃的杯[4]芳烃冠6醚对铯的萃取选择性高于对钾的萃取选择性；未络合的杯[4]芳烃单苯并冠6醚的晶体结构在固态时以1,3-alt构象存在。

  DOI：

  10.1039/a905682c

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.
• Dideoxygenated calix[4]arene crown-6 ethers enhanced selectivity for caesium over potassium and rubidium
  作者：Richard A. Sachleben、Agathe Urvoas、Jeffrey C. Bryan、Tamara J. Haverlock、Bruce A. Moyer、Benjamin P. Hay

  DOI：10.1039/a905682c

  日期：——

  Calix[4]arene crown-6 ethers derived from dideoxygenated calix[4]arene exhibit enhanced extraction selectivity for caesium over potassium; the crystal stucture of the uncomplexed calix[4]arene monobenzocrown-6 ether exists in the 1,3-alt conformation in the solid state.

  源自双脱氧杯[4]芳烃的杯[4]芳烃冠6醚对铯的萃取选择性高于对钾的萃取选择性；未络合的杯[4]芳烃单苯并冠6醚的晶体结构在固态时以1,3-alt构象存在。
• Study of the nitration of di-<i>n</i>-octylcrown-6 calix[4]arene using LC–MS, NMR, and molecular modelling
  作者：C K Jankowski、M- R Van Calsteren、N Aychet、J F Dozol、C Moulin、C Lamouroux

  DOI：10.1139/v05-126

  日期：2005.8.1

  The selective HNO₃ nitration of di-n-octylcrown-6 calix[4]arene using different conditions, studied with LC–MS and NMR (¹H and ¹³C) spectroscopic techniques, lead to the identification of most of the expected nitro derivative isomeric compounds. The formation of these isomers under acidic and radiolytic conditions is discussed with the help of molecular modelling.Key words: calix crown compounds, nitration of calixarenes, NMR of isomeric nitrocalixarenes, LC-ESI-MS.

  使用不同条件进行有选择性的硝化反应，利用LC-MS和NMR (¹H和¹³C)光谱技术研究了二正辛基冠-6杯[4]芳烃的硝化反应，鉴定了大部分预期的硝基衍生物同分异构体化合物。利用分子模拟探讨了这些同分异构体在酸性和辐射条件下的形成。关键词：杯冠化合物，杯芳烃的硝化反应，同分异构体硝基杯芳烃的NMR，LC-ESI-MS。