p-tert-Butylcalix[4]arene tris-ethoxycarbonylmethyl ether | 145395-62-6

• 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: p-tert-Butylcalix[4]arene tris-ethoxycarbonylmethyl ether
• 英文别名: 25-hydroxy-26,27,28-tris((ethoxycarbonyl)methoxy)-5,11,17,23-tetra-tert-butylcalix<4>arene；Ethyl 2-[[5,11,17,23-tetratert-butyl-26,27-bis(2-ethoxy-2-oxoethoxy)-28-hydroxy-25-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9(27),10,12,15(26),16,18,21,23-dodecaenyl]oxy]acetate
• CAS: 145395-62-6；145511-81-5；145514-32-5；199385-24-5
• 化学式: C₅₆H₇₄O₁₀
• 分子量: 907.198
• InChiKey: CPCSQEGMVANLIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.8
• 重原子数：
  66
• 可旋转键数：
  19
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  127
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  p-tert-Butylcalix[4]arene tris-ethoxycarbonylmethyl ether 在 吡啶 、 sodium hydroxide 、 氯化亚砜 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 5.0h， 生成 5,11,17,23-tetra-tert-butyl-25,26,27-tris(isoniazidylcarbonylmethoxy)-28-hydroxy-calix[4]arene
  参考文献：
  名称：

  带有吡啶鎓单元的新型“质子可转换”三和四取代的杯[4]芳烃衍生物的合成和萃取性能

  摘要：

  本文介绍了由5,11,17,23-四叔丁基-25,26,27-三（氯羰基甲氧基）-28-羟基杯[4]合成的新型杯芳烃类萃取剂的合成和络合特性。芳烃和5,11,17,23-四叔丁基-25,26,27,28-四（氯羰基甲氧基）杯[4]芳烃，分别在吡啶存在下用异烟肼（异烟酸酰肼）处理。p -叔-Butylcalix [4]芳烃teraamide通过用甲基碘在乙腈回流转化成它的甲基碘化物盐。在该合成中它被认为探索HCR的提取吡啶位点的角色2 ö 7 - / Cr的2 ö7 2−阴离子。朝向选择的碱金属/过渡金属阳离子和萃取剂的络合性能HCR 2 ö 7 - / Cr的2个ö 7 2-报告阴离子。已经观察到，两种受体均不提取碱金属阳离子，但是显示出对过渡金属的极好的选择性。该受体的质子化吡啶鎓形式是有效的HCR转印2 ö 7 - / Cr的2 ö 7 2-从含水阴离子成二氯甲烷层。

  DOI：

  10.1016/j.tet.2007.04.060
• 作为产物：
  描述：

  25-(benzyloxy)-26,27,28-tris((ethoxycarbonyl)methoxy)-5,11,17,23-tetra-tert-butylcalix<4>arene 在 三甲基溴硅烷 作用下， 以 氯仿 为溶剂， 反应 1.0h， 以98%的产率得到p-tert-Butylcalix[4]arene tris-ethoxycarbonylmethyl ether
  参考文献：
  名称：

  Synthesis and ion selectivity of all conformational isomers of tetrakis[(ethoxycarbonyl)methoxy]calix[4]arene

  摘要：

  We have found that the conformer distribution in tetra-O-alkylation of 5,11,17,23-tetra-tert-butylcalix[4]-arene-25,26,27,28-tetrol by ethyl bromoacetate is remarkably affected by the metal cation present in the base. In general, the cone conformer predominantly results when the base contains template metal cations whereas the partial-cone and 1,3-alternate conformers result when the base contains nontemplate metal cations. In acetone solvent one can realize the change from the 100% cone selectivity to the 100% partial-cone selectivity. By combining the metal template effect with a protection-deprotection method with a benzyl group, we developed synthetic routes to all of the four conformers. Two-phase solvent extraction established that the cone conformer shows Na+ selectivity whereas the remaining three conformers show K+ selectivity. H-1 NMR studies established that the 1,3-alternate conformer can form both a 1:1 and a 2:1 metal/calixarene complex and the two metal-binding sites display negative allostericity. This paper thus demonstrates that the metal selectivity of ionophoric calix[n]aryl esters can be changed not only by the change in the ring size but also by the conformational change.

  DOI：

  10.1021/jo00052a016

文献信息

• A new Na+ sensor based on intramolecular fluorescence energy transfer derived from calix[4]arene
  作者：Takashi Jin

  DOI：10.1039/a907457k

  日期：——

  A new calix[4]arene having pyrene (as a donor) and anthroyloxy (as an acceptor) moieties at the lower rim has been synthesized as a fluorescent Na+ sensor based on intramolecular energy transfer.

  新合成了一种在低位圈具有芘（作为供体）和苯甲酰氧基（作为受体）基团的杯[4]芳烃，作为基于分子内能量转移的荧光钠离子传感器。
• Directing the Cation Recognition Ability of Calix[4]arenes toward Asymmetric Phase-Transfer Catalysis
  作者：Nicola Alessandro De Simone、Rosaria Schettini、Carmen Talotta、Carmine Gaeta、Irene Izzo、Giorgio Della Sala、Placido Neri

  DOI：10.1002/ejoc.201700912

  日期：2017.10.10

  the first time in asymmetric phase-transfer catalysis. The binding affinities of a series of chiral α-methylbenzylamine-derived calix[4]arene-amides toward Na+ guest have been determined by 1H NMR spectroscopic titration experiments. The good apparent association constant values are consistent with the macrocycles' catalytic efficiency in the asymmetric alkylation reaction of N-(diphenylmethylene)glycine

  首次在不对称相转移催化中利用了手性杯芳烃主体对碱性阳离子客体的识别能力。一系列手性α-甲基苄胺衍生的杯[4]芳烃-酰胺对Na+客体的结合亲和力已通过1H NMR光谱滴定实验确定。良好的表观缔合常数值与大环在相转移条件下 N-（二苯基亚甲基）甘氨酸酯的不对称烷基化反应中的催化效率一致。
• The Use of Anhydrous Barium Hydroxide for Selective Alkylation of Dialkyloxy-tert-butyl-calix[4]arenes
  作者：Oleksandr A. Yesypenko、Oleksandr O. Trybrat、Vitaly I. Kalchenko

  DOI：10.3390/molecules28031089

  日期：——

  A practical method of selective alkylation of the third hydroxyl group of disubstituted tert-butyl-calix[4]arenes using anhydrous barium hydroxide as a base was developed in this study. The use of this method in the synthesis of inherently chiral derivatives is shown herein.

  本研究开发了一种以无水氢氧化钡为碱对双取代叔丁基杯[4]芳烃的第三个羟基进行选择性烷基化的实用方法。本文显示了此方法在合成固有手性衍生物中的用途。
• Lower rim substituted p-tert-butyl-calix[4]arene. Part 17. Synthesis, extractive and ionophoric properties of p-tert-butylcalix[4]arene appended with hydroxamic acid moieties
  作者：J. Kulesza、M. Guzinski、M. Bochenska、V. Hubscher-Bruder、F. Arnaud-Neu

  DOI：10.1016/j.poly.2014.04.009

  日期：2014.7

  The synthesis and characterization of four p-tert-butylcalix[4]arene-hydroxamic acids are reported. The dependence of the metal ion binding, assessed by liquid-liquid extraction of the metal nitrates from water into dichloromethane in individual and competitive experiments, on the ligand structure, is presented. The results showed that those ligands could be successfully used in separation process of transition and heavy metals often present together. Two of the ligands were used as active materials in Pb-ion-selective membrane electrodes. The characteristics of these electrodes, in particular their selectivity coefficients for Pb2+ over other metal ions, are discussed. (C) 2014 Elsevier Ltd. All rights reserved.
• Synthesis and ion selectivity of all conformational isomers of tetrakis[(ethoxycarbonyl)methoxy]calix[4]arene
  作者：Koji Iwamoto、Seiji Shinkai

  DOI：10.1021/jo00052a016

  日期：1992.12

  We have found that the conformer distribution in tetra-O-alkylation of 5,11,17,23-tetra-tert-butylcalix[4]-arene-25,26,27,28-tetrol by ethyl bromoacetate is remarkably affected by the metal cation present in the base. In general, the cone conformer predominantly results when the base contains template metal cations whereas the partial-cone and 1,3-alternate conformers result when the base contains nontemplate metal cations. In acetone solvent one can realize the change from the 100% cone selectivity to the 100% partial-cone selectivity. By combining the metal template effect with a protection-deprotection method with a benzyl group, we developed synthetic routes to all of the four conformers. Two-phase solvent extraction established that the cone conformer shows Na+ selectivity whereas the remaining three conformers show K+ selectivity. H-1 NMR studies established that the 1,3-alternate conformer can form both a 1:1 and a 2:1 metal/calixarene complex and the two metal-binding sites display negative allostericity. This paper thus demonstrates that the metal selectivity of ionophoric calix[n]aryl esters can be changed not only by the change in the ring size but also by the conformational change.