5,11,17,23-tetrakis(1,1-dimethylethyl)-25-propoxy-27-benzyloxy-26,28-crown-5-calix[4]arene, 1,3-alternate conformer | 247247-65-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,11,17,23-tetrakis(1,1-dimethylethyl)-25-propoxy-27-benzyloxy-26,28-crown-5-calix[4]arene, 1,3-alternate conformer
• 英文别名: 5,11,17,23-tetrakis(1,1-dimethylethyl)-25-propoxy-27-benzyloxy-26,28-crown-5-calix[4]arene, cone conformer；19,25,31,36-Tetratert-butyl-40-phenylmethoxy-41-propoxy-3,6,9,12,15-pentaoxahexacyclo[15.15.7.123,27.134,38.02,29.016,21]hentetraconta-1(32),2(29),16(21),17,19,23(41),24,26,30,34,36,38(40)-dodecaene
• CAS: 247247-65-0；247248-27-7
• 化学式: C₆₂H₈₂O₇
• 分子量: 939.329
• InChiKey: FNLFETIBERKJFS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16
• 重原子数：
  69
• 可旋转键数：
  10
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  64.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  5,11,17,23-tetrakis(1,1-dimethylethyl)-25-propoxy-27-benzyloxy-26,28-crown-5-calix[4]arene, 1,3-alternate conformer 在 10percent Pd/C 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 4.0h， 以93%的产率得到5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-(crown-5)^α-26-hydroxy^α-28-propoxy^α-calix[4]arene
  参考文献：
  名称：

  杯芳烃-聚二噻吩基化学修饰电极。

  摘要：

  逐步合成锥和部分锥1,3-桥联的正丙氧基杯[4]冠醚（“单体” 2和3），在下部具有可电聚合的2,2'-二噻吩-3-基-己烯官能团边缘，描述。通过NaSCN和KSCN的1H NMR滴定实验研究了2和3作为碱金属离子传感剂的潜力。获得的结果证实，杂环亚基的存在不会影响用杯[4]冠观察到的众所周知的尺寸选择性。单体2和3进行电聚合（Pt作为工作电极，CH2Cl2 / CH3CN，Bu4NPF6）以生产标题化学修饰的电极（CME）。用含有脂族阳离子交换剂的PVC膜涂覆后，测试了基于calix [4] -crown-5 2b（圆锥）和3b（部分圆锥）的CME，用于电位滴定法识别水溶液中的碱金属离子。与NMR滴定研究一致，仅使用CME 2b（pK（K / Na）1.51）获得了满意的K + / Na +选择性电位响应。通过循环伏安法（CV）在CH3CN溶液中研究了未涂覆PVC的CME的安培响应。基于部分圆锥杯[4]

  DOI：

  10.1002/1521-3765(20010803)7:15<3354::aid-chem3354>3.0.co;2-u
• 作为产物：
  描述：

  25-benzyloxy-5,11,17,23-tetra-tert-butyl-26,27,28-trihydroxycalix[4]arene 在 potassium carbonate 、 caesium carbonate 作用下， 以 乙腈 为溶剂， 生成 5,11,17,23-tetrakis(1,1-dimethylethyl)-25-propoxy-27-benzyloxy-26,28-crown-5-calix[4]arene, 1,3-alternate conformer
  参考文献：
  名称：

  1,3-Calix[4]arene Crown Ether Conformers with a 3-Thienyl Pendant Functionality at the Lower Rim

  摘要：

  Synthetic protocols to novel thienyl-calix[4]crown building blocks are reported. The selective distal introduction of a 2-(3-thienyl)ethoxy functionality into mono-O-alkylated calix[4]arenes 1 (R = Me, Bn), followed by cyclization of the mixed di-O-alkylated intermediates 2 with tetra- and pentaethylene glycol ditosylate and base, produced mixtures of 1,3-alternate and cone 1,3-calix[4]arene crown ether conformers 3 and 4, respectively. On the other hand, the selective debenzylation (Me3SiCl) of 1-benzyloxy-3-propoxycalix[4]arene crown-5 (cone conformer 4c) led to cone monohydroxy-derivative 5, which upon alkylation with 2-(3-thienyl)ethanol tosylate and Cs2CO3 afforded the rigid partial cone calix[4]arene crown-5 6, having the heterocyclic pendant functionality anti to the polyether ring. The H-1 NMR resonances of Bu-t substituents at the upper rim of conformationally rigid mixed 1,3-dialkoxycalix[4]arene crown ethers provide a diagnostic tool for establishing the mutual inclinations of the opposing pairs of aromatic rings. The structures of 5,11,17,23-tetrakis-(1,1-dimethylethyl)-25-methoxy-27-{[2-(3-thienyl)ethoxy]}(beta)-26,28-(crown-6)(alpha)-calix[4]arene (anti-3aa) and 5,11,17,23-tetrakis(1,1-dimethylethyl)-25-methoxy-27-{[2-(3-thienyl)ethoxy]}(alpha)-26,28-(crown-6)(alpha)-calix[4]arene calix[4]arene (syn-4aa) conformers were determined by single-crystal X-ray analyses. Methoxy-containing calix[4]arene crown ethers possess fluxional properties, and the conformational equilibria in solution are strongly affected by alkali-metal complexation.

  DOI：

  10.1021/jo990336v

文献信息

• 1,3-Calix[4]arene Crown Ether Conformers with a 3-Thienyl Pendant Functionality at the Lower Rim
  作者：George Ferguson、John F. Gallagher、Alan J. Lough、Anna Notti、Sebastiano Pappalardo、Melchiorre F. Parisi

  DOI：10.1021/jo990336v

  日期：1999.8.1

  Synthetic protocols to novel thienyl-calix[4]crown building blocks are reported. The selective distal introduction of a 2-(3-thienyl)ethoxy functionality into mono-O-alkylated calix[4]arenes 1 (R = Me, Bn), followed by cyclization of the mixed di-O-alkylated intermediates 2 with tetra- and pentaethylene glycol ditosylate and base, produced mixtures of 1,3-alternate and cone 1,3-calix[4]arene crown ether conformers 3 and 4, respectively. On the other hand, the selective debenzylation (Me3SiCl) of 1-benzyloxy-3-propoxycalix[4]arene crown-5 (cone conformer 4c) led to cone monohydroxy-derivative 5, which upon alkylation with 2-(3-thienyl)ethanol tosylate and Cs2CO3 afforded the rigid partial cone calix[4]arene crown-5 6, having the heterocyclic pendant functionality anti to the polyether ring. The H-1 NMR resonances of Bu-t substituents at the upper rim of conformationally rigid mixed 1,3-dialkoxycalix[4]arene crown ethers provide a diagnostic tool for establishing the mutual inclinations of the opposing pairs of aromatic rings. The structures of 5,11,17,23-tetrakis-(1,1-dimethylethyl)-25-methoxy-27-[2-(3-thienyl)ethoxy]}(beta)-26,28-(crown-6)(alpha)-calix[4]arene (anti-3aa) and 5,11,17,23-tetrakis(1,1-dimethylethyl)-25-methoxy-27-[2-(3-thienyl)ethoxy]}(alpha)-26,28-(crown-6)(alpha)-calix[4]arene calix[4]arene (syn-4aa) conformers were determined by single-crystal X-ray analyses. Methoxy-containing calix[4]arene crown ethers possess fluxional properties, and the conformational equilibria in solution are strongly affected by alkali-metal complexation.
• Calixarene-Poly(dithiophene)-Based Chemically Modified Electrodes
  作者：Marco Giannetto、Giovanni Mori、Anna Notti、Sebastiano Pappalardo、Melchiorre F. Parisi

  DOI：10.1002/1521-3765(20010803)7:15<3354::aid-chem3354>3.0.co;2-u

  日期：2001.8.3

  The stepwise synthesis of cone and partial cone 1,3-bridged n-propoxy-calix[4]crown ethers ("monomers" 2 and 3) with an electropolymerizable 2,2'-dithiophene-3-yl-hexylene functionality at the lower rim, is described. The potential of 2 and 3 as sensing agents for alkali metal ions was investigated by 1H NMR titration experiments with NaSCN and KSCN. The results obtained have confirmed that the presence

  逐步合成锥和部分锥1,3-桥联的正丙氧基杯[4]冠醚（“单体” 2和3），在下部具有可电聚合的2,2'-二噻吩-3-基-己烯官能团边缘，描述。通过NaSCN和KSCN的1H NMR滴定实验研究了2和3作为碱金属离子传感剂的潜力。获得的结果证实，杂环亚基的存在不会影响用杯[4]冠观察到的众所周知的尺寸选择性。单体2和3进行电聚合（Pt作为工作电极，CH2Cl2 / CH3CN，Bu4NPF6）以生产标题化学修饰的电极（CME）。用含有脂族阳离子交换剂的PVC膜涂覆后，测试了基于calix [4] -crown-5 2b（圆锥）和3b（部分圆锥）的CME，用于电位滴定法识别水溶液中的碱金属离子。与NMR滴定研究一致，仅使用CME 2b（pK（K / Na）1.51）获得了满意的K + / Na +选择性电位响应。通过循环伏安法（CV）在CH3CN溶液中研究了未涂覆PVC的CME的安培响应。基于部分圆锥杯[4]