calix<4>crown-6 | 162209-37-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: calix<4>crown-6
• 英文别名: calix[4]arene-crown-6；crown-6-calix[4]arene；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-43,44-diol
• CAS: 162209-37-2
• 化学式: C₃₈H₄₂O₈
• 分子量: 626.747
• InChiKey: KAEAKDIAKRARKG-UHFFFAOYSA-N

物化性质

• 熔点：
  182-184 °C
• 沸点：
  772.4±60.0 °C(Predicted)
• 密度：
  1.171±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  46
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  95.8
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  calix<4>crown-6 在 potassium hydrogensulfate 、 四氯化锡 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 10.0h， 生成 5,7-di[bis(indolyl)phenyl]calix[4]arene-crown-6
  参考文献：
  名称：

  Dual colorimetric sensoring bis(indolyl)calix[4]crown-6

  摘要：

  Calix-chromophore, bis(indolyl)calix[4]crown-6 (1) in an oxidized form showing selective colorimetric changes for both alkaline earth cations and F- in CH3CN, has been newly synthesized. It is observed that the binding ability of 1 for the Ca2+ binding enhances in the presence of F-. Compound 1 can operate three independent combinational NOR logic gates toward metal cations and anions. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.02.026
• 作为产物：
  描述：

  二对甲苯磺酸戊乙二醇 在 碘代三甲硅烷 、 caesium carbonate 作用下， 以 氯仿 、 乙腈 为溶剂， 反应 2.0h， 生成 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

文献信息

• Synthesis of Cone, Partial-Cone, and 1,3-Alternate 25,27-Bis[1-(2-ethyl)hexyl]- and 25,27-Bis[1-(2-<i>tert</i>-butoxy)ethyl]calix[4]arene-crown-6 Conformers as Potential Selective Cesium Extractants
  作者：Jean Guillon、Jean-Michel Léger、Pascal Sonnet、Christian Jarry、Max Robba

  DOI：10.1021/jo001023z

  日期：2000.12.1

  27-bis[1-(2-tert-butoxy)ethyl]calix[4]arene-crown-6 combining one polyether crown-6 and one alkylchain O-attached on each side of a calix[4]arene in the cone, partial-cone, and 1,3-alternate conformations are reported. The control over 25, 27-bisalkylcalix[4]arene-crown-6 conformation via varying specific reaction conditions was studied. The series of calix[4]arenes have been prepared by two routes

  结合一个聚醚冠的25,27-双[1-（2-（乙基）己基]-]和25,27-双[1-（2-叔丁氧基）乙基]杯[4]芳烃-冠-6的制备-6和一个烷基链O分别连接在圆锥形，部分圆锥形和1,3-交替构象的杯[4]亚芳基的每一侧。研究了通过改变特定的反应条件控制25，27-双烷基杯[4]芳烃-冠-6构象。杯[4]芳烃系列是通过两种途径制备的，它们的引入烷基或聚醚基团的顺序不同。此外，已经开发了通过在烷基化反应中使用适当的碱来选择性地制备圆锥和部分圆锥构象体的方法。这些新的衍生物的构象已通过（1）1 H NMR分析和X射线晶体学探测。25的（1）H和（13）C NMR光谱，
• Effect of para-substituents on alkaline earth metal ion extraction by proton di-ionizable calix[4]arene-crown-6 ligands in cone, partial-cone and 1,3-alternate conformations
  作者：Hui Zhou、Dazhan Liu、Jerzy Gega、Kazimierz Surowiec、David W. Purkiss、Richard A. Bartsch

  DOI：10.1039/b611570e

  日期：——

  structures verified by NMR spectroscopy. Competitive solvent extractions of alkaline earth metal cations from aqueous solutions into chloroform were performed and the results compared with those reported previously for di-ionizable p-tert-butylcalix[4]arene-crown-6 analogues to probe the influence of the para-substituent on the calix[4]arene scaffold on extraction selectivity and efficiency.

  将两个羧酸或N-（X）磺酰基羧酰胺基团掺入杯[4]芳烃-冠-6化合物中，以提供可二离子化的配体，用于二价金属离子分离。通过改变X的吸电子特性来调节N-（X）磺酰基羧酰胺基团的酸度。通过不同的合成策略获得了圆锥，部分圆锥和1,3-交替构象，并通过NMR光谱证实了它们的结构。进行了竞争性溶剂从水溶液中萃取碱土金属阳离子到氯仿中的分析，并将结果与​​先前报道的可电离的对叔丁基杯[4]芳烃-冠-6类似物进行了比较，以探讨对位取代基的影响在杯[4]芳烃支架上对提取的选择性和效率的影响。
• Bis-triethylene Glycolic Crown-5-calix[4]arene: A Promoter of Nucleophilic Fluorination Using Potassium Fluoride
  作者：Seok Min Kang、Chul Hee Kim、Kyo Chul Lee、Dong Wook Kim

  DOI：10.1021/acs.orglett.9b00649

  日期：2019.5.3

  a bis-triethylene glycolic crown-5-calix[4]arene (BTC5A) as a multifunctional promoter for nucleophilic fluorination using KF. The synergetic effect of the calix-crown moiety and ethylene glycols of BTC5A enabled KF to be easily dissolved in organic solvents and activated the fluoride in even nonpolar aprotic media. To validate its practicality, the SN2 fluorinations including 18F-fluorination of various

  我们设计和合成了双三甘醇的Crown-5calix [4] arene（BTC5A）作为使用KF进行亲核氟化的多功能促进剂。BTC5A的杯冠部分和乙二醇的协同作用使KF易于溶解在有机溶剂中，甚至在非极性非质子介质中活化了氟化物。为了验证其实用性，在BTC5A存在下，使用KF（或[ 18 F] F –）成功地进行了S N 2氟化，包括各种底物的18 F氟化。
• Synthesis, crystal structures and competitive complexation property of a family of calix-crown hybrid molecules and their application in extraction of potassium from bittern
  作者：Vallu Ramakrishna、E. Suresh、Vinod P. Boricha、Anjani K. Bhatt、Parimal Paul

  DOI：10.1080/10610278.2015.1080367

  日期：2015.10.3

  ions. Complexation with K+ has been investigated by 1H NMR, association constants and thermodynamic parameters have been determined by isothermal calorimetric study. The molecular structures of one of the receptors and two of the K+ complexes have been established by single crystal X-ray study. One of the receptors formed bimetallic complex and it exhibited interesting polymeric network structure with

  合成、表征了下缘或上下缘含有杯[4]芳烃和冠5/6的杯冠杂化分子家族，并表征了它们对碱金属和碱土金属离子的竞争性络合性能在水性介质中进行了研究。在水性介质中使用 Li+、Na+、K+、Mg2+、Ca2+ 和 Sr2+ 的等摩尔混合物进行的竞争性金属离子萃取研究表明，与其他金属离子相比，K+ 的萃取量非常高。通过 1H NMR 研究了与 K+ 的络合，通过等温量热研究确定了缔合常数和热力学参数。一种受体和两种 K+ 复合物的分子结构已通过单晶 X 射线研究确定。其中一个受体形成双金属络合物，并表现出有趣的聚合物网络结构，桥接苦味酸阴离子。这些受体已被用于从卤水中提取金属离​​子。
• Bis-<i>tert</i> -Alcohol-Functionalized Crown-6-Calix[4]arene: An Organic Promoter for Nucleophilic Fluorination
  作者：Vinod H. Jadhav、Wonsil Choi、Sung-Sik Lee、Sungyul Lee、Dong Wook Kim

  DOI：10.1002/chem.201504602

  日期：2016.3.18

  The role of BACCA was revealed to be separation of the metal fluoride to a large distance (>8 Å), thereby producing an essentially “free” F−. The synergistic actions of the crown‐6‐calix[4]arene subunit (whose O atoms coordinate the counter‐cation Cs+) and the terminal tert‐alcohol OH groups (forming controlled hydrogen bonds with F−) of BACCA led to tremendous efficiency in SN2 fluorination of base‐sensitive

  甲二-叔-醇官能冠-6-杯[4]芳烃（浆果）被设计并作为与亲核的CsF氟化反应的多官能有机启动子制备。通过形成CsF / BACCA复合物，BACCA可以释放出具有显着活性和选择性的氟化物源，用于S N 2氟化反应。通过量子化学方法研究了BACCA促进作用的起源。浆果的作用显露是金属氟化物分离到一个大的距离（> 8），从而产生基本上“自由” F - 。冠-6-杯的协同作用[4]芳烃亚基（其O原子坐标抗衡阳离子铯+）与终端叔-醇OH基团（形成有F控制氢键- ）的浆果导致S中巨大效率Ñ 2氟化碱敏感的底物。