5,11,17,23-tetrakis(1,1-dimethylethyl)-25,26-dihydroxycalix[4]arene-1,2-crown-4 | 189182-98-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,26-dihydroxycalix[4]arene-1,2-crown-4
• 英文别名: p-tert-butylcalix[4]arene-1,2-crown-4；p-tert-butylcalix[4]arene-monocrown-4；5,11,17,23-tetrakis(1,1-dimethylethyl)-25,26-dihydroxy-27,28-crown-4-calix[4]arene；3,9,15,21-Tetratert-butyl-25,28,31,34-tetraoxahexacyclo[21.12.1.17,11.113,17.05,35.019,24]octatriaconta-1,3,5(35),7,9,11(38),13(37),14,16,19(24),20,22-dodecaene-37,38-diol；3,9,15,21-tetratert-butyl-25,28,31,34-tetraoxahexacyclo[21.12.1.17,11.113,17.05,35.019,24]octatriaconta-1,3,5(35),7,9,11(38),13(37),14,16,19(24),20,22-dodecaene-37,38-diol
• CAS: 189182-98-7；824954-28-1
• 化学式: C₅₀H₆₆O₆
• 分子量: 763.07
• InChiKey: DTUSIAURTXQPQN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.1
• 重原子数：
  56
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5,11,17,23-tetrakis(1,1-dimethylethyl)-25,26-dihydroxycalix[4]arene-1,2-crown-4 在 草酰氯 、 四甲基氢氧化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 水 、 苯 为溶剂， 反应 108.0h， 生成 N-methylsulfonyl-2-[[3,9,15,21-tetratert-butyl-38-[2-(methanesulfonamido)-2-oxoethoxy]-25,28,31,34-tetraoxahexacyclo[21.12.1.17,11.113,17.05,35.019,24]octatriaconta-1(35),2,4,7(38),8,10,13,15,17(37),19,21,23-dodecaen-37-yl]oxy]acetamide
  参考文献：
  名称：

  二电离p -叔-butylcalix [4]芳烃-1,2-冠-4的配体：合成和高的二价金属离子提取选择性

  摘要：

  合成了具有圆锥构象的双电离对-叔丁基杯[4]芳烃-1,2-冠-4醚，并通过NMR光谱验证了它们的构象和区域选择性。新的配体是对Ba 2+具有高选择性的有效萃取剂，可竞争性地从水溶液中萃取碱土金属阳离子到氯仿中，对Ba 2+具有选择性。

  DOI：

  10.1016/j.tetlet.2006.03.060
• 作为产物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 、 三乙二醇二(对甲苯磺酸酯) 在 sodium hydride 、 水 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 49.0h， 以78%的产率得到5,11,17,23-tetrakis(1,1-dimethylethyl)-25,26-dihydroxycalix[4]arene-1,2-crown-4
  参考文献：
  名称：

  冠环尺寸和上基团对可电离Calixcrown 纳米篮提取s-嵌段金属的影响

  摘要：

  合成了8个锥形25,26-二(羧甲氧基)杯[4]芳烃冠-3,4,5,6的可电离纳米篮，并通过H和C NMR光谱、IR光谱和元素分析进行​​了验证。使用这种纳米篮研究了碱金属和碱土金属阳离子的竞争性溶剂萃取。本研究的新颖之处在于在一个独特的支架中包括三个结合单元，即杯芳烃碗、冠醚环和电子供体可电离部分，以评估对阳离子的结合趋势。这项工作的目的是研究此类配合物的萃取效率、选择性和 pH1/2。溶剂萃取实验结果表明，这些化合物是碱金属和碱土金属阳离子的有效萃取剂。它们的选择性很大程度上受溶液酸度和杯冠构象的影响。一种构象异构体在 pH ≥ 4 时对 Na 具有选择性，而另一种在 pH 6 及更高时对 Ba 具有高度选择性。

  DOI：

  10.5012/bkcs.2011.32.11.3979

文献信息

• Application of Nano-Baskets for Extraction of Lanthanides
  作者：Bahram Mokhtari、Kobra Pourabdollah

  DOI：10.3184/174751912x13527973569178

  日期：2012.12

  Eight proton di-ionisable diacid conformers of nano-baskets including 25,26-di(carboxymethoxy)calix[4]arene-crown-3, -crown-4, -crown-5 and -crown-6 in the cone conformation have been synthesised and shown to extract lanthanide cations effectively. Their selectivities were greatly influenced by the acidity of the solution and the conformations of the calix-crown. The extraction loading was improved by having the p-tert-butyl-moiety in the upper rim. The scaffold bearing the crown-4 ether moiety showed the least loading, while scaffolds with crown-3- and crown-5-ether moieties had the best selectivities.

  我们合成了八种质子可二离子化的二酸纳米篮构象，包括 25,26-二（羧基甲氧基）钙[4]烯-crown-3、-crown-4、-crown-5 和 -crown-6 锥构象，并证明它们能有效地萃取镧系阳离子。它们的选择性在很大程度上受溶液酸度和钙钛矿冠构象的影响。将对叔丁基分子置于上边缘可提高萃取负荷。带有冠-4-醚分子的支架的负载量最小，而带有冠-3-和冠-5-醚分子的支架的选择性最好。
• Facile synthesis and optical resolution of inherently chiral fluorescent calix[4]crowns: enantioselective recognition towards chiral leucinol
  作者：Jun Luo、Qi-Yu Zheng、Chuan-Feng Chen、Zhi-Tang Huang

  DOI：10.1016/j.tet.2005.06.015

  日期：2005.8

  series of tri-O-alkylated inherently chiral fluorescent calix[4]crowns in the cone conformations and a series of tetra-O-alkylated inherently chiral fluorescent calix[4]crowns in the partial cone conformations have been synthesized. By condensing with chiral auxiliary (S)-BINOL, the resulting diastereomers could be separated via preparative TLC. We found that the size of the crown moiety effected the separation

  合成了圆锥构象中的一系列三-O-烷基化的固有手性荧光杯[4]冠和一系列圆锥体构象中的一系列四-O-烷基化的固有手性荧光杯[4]冠。通过与手性助剂（S）-BINOL缩合，可以通过制备TLC分离得到的非对映异构体。我们发现冠部分的大小影响非对映异构体的分离。此外，通过水解除去BINOL单元提供了具有光学纯度的对映异构体对。此外，我们发现在部分锥构象6c中，四-O-烷基化的固有手性荧光杯[4] cro-6 对手性亮氨酸显示出相当高的对映选择性识别能力。
• Synthesis of 1,2-bridged calix[4]arene-biscrowns in the 1,2-alternate conformation
  作者：Arturo Arduini、Laura Domiano、Andrea Pochini、Andrea Secchi、Rocco Ungaro、Franco Ugozzoli、Oliver Struck、Willem Verboom、David N Reinhoudt

  DOI：10.1016/s0040-4020(97)00097-5

  日期：1997.3

  New methods to obtain 1,2-bridged calix[4]arene-biscrowns in the 1,2-alternate conformation are described. The stereochemistry of the proximal double functionalization reaction is mainly governed by the solvent, the length of the polyether units and the base used to deprotonate the calix[4]arene.

  描述了获得1,2-交替构象的1,2-桥联杯[4]芳烃-双冠的新方法。近端双官能化反应的立体化学主要由溶剂，聚醚单元的长度和用来使杯[4]芳烃去质子化的碱决定。
• Synthesis of New Calix[4]arene-Based Ionophores
  作者：Arturo Arduini、Marcella Bozzoli、Chiara Massera、Andrea Pochini、Andrea Secchi、Franco Ugozzoli

  DOI：10.1135/cccc20041309

  日期：——

  A synthesis of new calix[4]arene-based ionophores is reported. These ligands are characterized by the presence of two types of coordination sites on their lower rim: one crowning unit of different length, linking two proximal calix[4]arene phenolic oxygens, and two esters or amide groups acting as additional hard binding sites. The choice of the proper reaction conditions, such as the base counterion and the solvent polarity, during the functionalization of the macrocycle lower rim, allows to modulate the stereochemistry of the final ligands. In this way the ligands in cone and 1,2-alternate conformations were obtained in good yields. Complexation properties of these new compounds towards alkali and alkaline-earth cations were studied by means of liquid-liquid extraction experiments. The X-ray solid state structure of the p-tert-butylcalix[4]arene-N,N-diethylacetamide-crown-5 (6a) complex with strontium picrate shows the effective cooperativity among the two type of coordination site in the binding event.

  报道了一种新型的基于杯[4]芳烃的离子载体的合成方法。这些配体的特征在于它们的下缘具有两种配位位点：一种是不同长度的冠状单元，连接两个邻近的杯[4]芳烃酚氧原子；另一种是两个酯或酰胺基团，作为额外的硬配位位点。适当的反应条件选择，如碱基对离子和溶剂极性，在宏环下缘的官能化过程中，可以调节最终配体的立体化学。通过这种方式，锥形和1,2-交替构象的配体可以得到良好的产率。通过液液萃取实验研究了这些新化合物对碱金属和碱土金属离子的络合性质。用锶榴石酸盐对

  -叔丁基杯[4]芳烃-N,N-二乙酰胺-冠-5（6a）配合物进行了X射线固态结构分析，显示了两种配位位点在配位事件中的有效协同作用。

• Electrochemical Study of Structural Effects in Complexation of Nano-baskets: Calix[4]-1,2-crown-3, -crown-4, -crown-5, -crown-6
  作者：Bahram Mokhtari、Kobra Pourabdollah

  DOI：10.1080/15533174.2012.680131

  日期：2012.9.1

  Eight nano-baskets of calix[4]arene-1,2-crown-3, -crown-4, -crown-5, -crown-6 were synthesized and their binding abilities towards alkali and alkaline earth metals as well as some lanthanides were studied using differential pulse voltammetry. The novelty of this study was investigation of those macrocyclic complexes by voltammetric behaviors of two acidic moieties in each scaffold during complexation of crown ether ring. The results revealed that by increasing the binding ability of macrocycle and cation, the anodic oxidation peak of carboxylic acids was decreased. Moreover, the voltammetric traces of low energy complexes did not affected by encapsulated cations in the coordination space of crown ether.