5,11,17,23-tetrakis(1,1-dimethylethyl)-25-benzyloxy-27-[2-(3-thienyl)ethoxy]-26,28-crown-5-calix[4]arene, 1,3-alternate conformer

• 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-benzyloxy-27-[2-(3-thienyl)ethoxy]-26,28-crown-5-calix[4]arene, 1,3-alternate conformer
• 英文别名: 5,11,17,23-tetrakis(1,1-dimethylethyl)-25-benzyloxy-27-[2-(3-thienyl)ethoxy]-26,28-crown-5-calix[4]arene, cone conformer；19,25,31,36-Tetratert-butyl-40-phenylmethoxy-41-(2-thiophen-3-ylethoxy)-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
• 化学式: C₆₅H₈₂O₇S
• 分子量: 1007.43
• InChiKey: AVILSYAGUADVEJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.7
• 重原子数：
  73
• 可旋转键数：
  11
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  92.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  3-噻吩乙醇酯 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-benzyloxy-27-[2-(3-thienyl)ethoxy]-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.