5,11,17,23-tetrakis(1-adamantyl)-calix[4]arene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5,11,17,23-tetrakis(1-adamantyl)-calix[4]arene
• 英文别名: p-(1-adamantyl)calix-[4]arene；p-(1-adamantyl)calix[4]arene；5,11,17,23-Tetrakis(1-adamantyl)pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene-25,26,27,28-tetrol
• 化学式: C₆₈H₈₀O₄
• 分子量: 961.381
• InChiKey: IYTHYUPXYIPIAT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  19.9
• 重原子数：
  72
• 可旋转键数：
  4
• 环数：
  21.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  80.9
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-(3-溴丙基)苯二胺 、 5,11,17,23-tetrakis(1-adamantyl)-calix[4]arene 在 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 48.5h， 以72%的产率得到
  参考文献：
  名称：

  窄边CMPO /金刚烷杯[4]芳烃，用于萃取镧系元素和act系元素

  摘要：

  六个p - （1-金刚烷基）杯[4]芳烃7，8具有四个不同的附连二苯基- carbamoylmethylphosphine氧化物（CMPO）函数在窄边沿合成。该系列被具有两个CMPO和两个酯，酸或（二乙基膦酰基）乙酰氨基基团的金刚烷基杯[4]芳烃扩展。通过NMR，质谱和单晶X射线分析对中间体二邻苯二甲酰亚胺10 3证实了新化合物的结构。对选定的镧系元素和th的萃取研究表明，配体7超过了相应的对-H，对-叔丁基和对-叔丁基-辛基类似物3 - 5中的镧系元素提取而钍用相同的或较小的程度上萃取。对于镧系元素提取d LN（7 4）> d LN（7 3）≈ d LN（7 2），它遵循先前针对配体确定的顺序进行3 - 5。间型的四CMPO衍生物8，配体8 3 / 4是针对最佳的萃取剂的d LN和d的Th值可与7 4相媲美。

  DOI：

  10.1016/j.tet.2011.08.059
• 作为产物：
  描述：

  1-金刚烷醇 、 25,27-bis(benzyloxy)-26,28-dihydroxycalix[4]arene 在 三氟乙酸 作用下， 以 氯仿 为溶剂， 反应 9.0h， 以99%的产率得到5,11,17,23-tetrakis(1-adamantyl)-calix[4]arene
  参考文献：
  名称：

  杯[4]芳烃的选择性上缘金刚烷基化

  摘要：

  Lower-rim mono- and diacylated calix[4]arenes [acyl = C6H5CO, 3,5-(NO2)(2)C6H3CO] undergo selective adamantylation with 3-Y-1-adamantanols (Y = H, i-Pr, 4-MeC6H4) in trifluoroacetic acid at the free phenolic fragments of the macroring. The reaction provides a convenient preparative route to di-, tri-, and tetraadamantylated calix[4]arenes.

  DOI：

  10.1023/a:1012423128245

文献信息

• Conducting Polymers Incorporating Tungsten-Capped Calixarenes
  作者：Arkadi Vigalok、Zhengguo Zhu、Timothy M. Swager

  DOI：10.1021/ja0160142

  日期：2001.8.1

  sensors. 1,5,6As part of our continued interest in conjugated polymer-based sensors 7 we endeavored to make conducting polymeric materials containing conformationally rigid metallocalixarene repeat units. In pursuing this system we considered that the communication between the polymer and the calixarene moiety could be mediated via a transition metal center. Calixarenes1a-c were prepared by literature methods

  杯芳烃是用于设计 3-D 空腔 1 的高度通用的支架，并且在主客体化学和分子识别中具有广泛的用途。2 杯芳烃在其下缘选择性结合各种阳离子的能力已广泛用于小分子 3 和聚合物感官材料的设计。4 然而，尽管有许多杯芳烃与疏水口袋中的有机分子形成包合配合物的例子，但这种结合模式在很大程度上尚未在传感器方面得到探索。1,5,6 作为我们对基于共轭聚合物的传感器 7 的持续兴趣的一部分，我们努力制造包含构象刚性金属局部环芳烃重复单元的导电聚合物材料。在研究该系统时，我们认为聚合物和杯芳烃部分之间的通讯可以通过过渡金属中心进行介导。杯芳烃1a-c 通过文献方法制备。8,9
• Substituent control of potassium and rubidium uptake by asymmetric calix[4]-thiacalix[4]tubes
  作者：Elena Khomich、Marat Kashapov、Ivan Vatsouro、Elvira Shokova、Vladimir Kovalev

  DOI：10.1039/b601709f

  日期：——

  Herein we report on the synthesis and ionophore properties of the first asymmetric p-tert-butylcalix[4]-p-R-thiacalix[4]tubes 7a–c (R = t-Bu, H, 1-adamantyl). The target compounds were obtained by the condensation of tosyloxyethoxy-p-tert-butylcalix[4]arene with the corresponding p-R-thiacalix[4]arenes in the presence of K2CO3 in acetonitrile. The complexation with sodium, potassium and rubidium iodides was studied in CDCl3–CD3OD (4 : 1) medium by means of 1H NMR measurements. It was found that the ionophore properties of calixtubes 7a–c are controlled by the character of the substituents at the upper rim of the thiacalix[4]arene fragment and it was shown that only the molecular tube 7c with an adamantane-containing thiacalixarene unit is capable of quantitatively binding potassium (swiftly) and rubidium (slowly) cations.

  在此，我们报告了第一个不对称对叔丁基calix[4]-p-R-thiacalix[4]管7a–c（R = t-Bu，H，1-金刚烷基）的合成和离子载体特性。通过甲苯磺氧基乙氧基-对叔丁基杯[4]芳烃与相应的对-R-硫代杯[4]芳烃在K2CO3存在下在乙腈中缩合得到目标化合物。通过 1 H NMR 测量，在 CDCl3-CD3OD (4:1) 介质中研究了与钠、钾和铷碘化物的络合。结果发现，杯管7a-c的离子载体性质受硫代杯芳烃片段上边缘取代基的特征控制，并且表明只有具有含金刚烷的硫代杯芳烃单元的分子管7c是能够定量结合钾（快速）和铷（缓慢）阳离子。
• Calix[4]arene-Based Receptors with Hydrogen-Bonding Groups Immersed into a Large Cavity
  作者：Evgueni Pinkhassik、Vladimir Sidorov、Ivan Stibor

  DOI：10.1021/jo9804543

  日期：1998.12.1

  A one-pot procedure, which combines the Ritter and Friedel-Crafts reactions, produced the first members of a new type of calix[4]arene-based receptors. The cavity in these receptors is formed by a calix[4]arene framework fixed in the cone conformation and bulky adamantyl or (and) phenylacetylene moieties. Amido and amino groups were used as potential hygrogen bond donors. Preliminary studies revealed interesting complexation properties, in particular, the tetrahedral recognition of water molecules performed by one of the receptors.
• Asymmetric calix[4]-thiacalix[4]arene tubes: Synthesis and ionophore properties
  作者：E. V. Khomich、M. N. Kashapov、I. M. Vatsuro、E. A. Shokova、B. B. Kovalev

  DOI：10.1134/s1070428007020078

  日期：2007.2

  Asymmetric p-tert-butylcalix[4]-p-R-thiacalix[4]arene tubes (R = tert-Bu, H, 1-adamantyl) were prepared for the first time by reaction of tosyloxyethoxy derivative of p-tert-butylcalix-[4]arene and the corresponding p-R-thiacalix[4]arenas in acetonitrile in the presence of K2CO3. Complex formation of compounds obtained with sodium, potassium, and rubidium iodides in CDCl3-CD3OD, 4:1, was studied by means of H-1 NMR. The ionophore properties of the molecule were governed by the character of substituents on the upper rim of the thiacalixarene fragment, and only the molecular tube containing a fragment of the p-(1-adamantyl)-thiacalix[4]arene quantitatively bound potassium ions (quickly) and rubidium ions (slowly).
• Narrow rim CMPO/adamantylcalix[4]arenes for the extraction of lanthanides and actinides
  作者：Ivan Vatsouro、Alina Serebryannikova、Leyong Wang、Véronique Hubscher-Bruder、Elvira Shokova、Michael Bolte、Françoise Arnaud-Neu、Volker Böhmer、Vladimir Kovalev

  DOI：10.1016/j.tet.2011.08.059

  日期：2011.10

  Six p-(1-adamantyl)calix[4]arenes 7, 8 with four differently attached diphenyl-carbamoylmethylphosphine oxide (CMPO) functions at the narrow rim were synthesized. This series was extended by adamantylcalix[4]arenes with two CMPO and two ester, acid or (diethylphosphono)acetylamino groups. Structures of new compounds were proved by NMR, mass-spectrometry and a single-crystal X-ray analysis for the intermediate

  六个p - （1-金刚烷基）杯[4]芳烃7，8具有四个不同的附连二苯基- carbamoylmethylphosphine氧化物（CMPO）函数在窄边沿合成。该系列被具有两个CMPO和两个酯，酸或（二乙基膦酰基）乙酰氨基基团的金刚烷基杯[4]芳烃扩展。通过NMR，质谱和单晶X射线分析对中间体二邻苯二甲酰亚胺10 3证实了新化合物的结构。对选定的镧系元素和th的萃取研究表明，配体7超过了相应的对-H，对-叔丁基和对-叔丁基-辛基类似物3 - 5中的镧系元素提取而钍用相同的或较小的程度上萃取。对于镧系元素提取d LN（7 4）> d LN（7 3）≈ d LN（7 2），它遵循先前针对配体确定的顺序进行3 - 5。间型的四CMPO衍生物8，配体8 3 / 4是针对最佳的萃取剂的d LN和d的Th值可与7 4相媲美。