25-<(2-pyridylmethyl)oxy>-26,27,28-trihydroxycalix<4>arene | 139584-71-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 25-<(2-pyridylmethyl)oxy>-26,27,28-trihydroxycalix<4>arene
• 英文别名: 28-(Pyridin-2-ylmethoxy)pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3(28),4,6,9,11,13(27),15,17,19(26),21(25),22-dodecaene-25,26,27-triol
• CAS: 139584-71-7
• 化学式: C₃₄H₂₉NO₄
• 分子量: 515.609
• InChiKey: WTKSPUINGIRMCZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  39
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  82.8
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  杯[4]芳烃 、 2-氯甲基吡啶盐酸盐 在 potassium tert-butylate 作用下， 以 甲苯 为溶剂， 反应 20.0h， 以11%的产率得到syn-distal-25,27-bis<(2-pyridylmethyl)oxy>-26,28-dihydroxycalix<4>arene
  参考文献：
  名称：

  Functionalization of calix[4]arenes by alkylation with 2-(chloromethyl)pyridine hydrochloride

  摘要：

  The syntheses, structures, and conformations of nine of the 13 possible [(2-pyridylmethyl)oxy]calix[4]arene conformers obtainable by direct substitution on calix[4]arenes 1a,b are described. The conformer distribution in the exhaustive O-alkylation of 1a,b with 2-(chloromethyl)pyridine hydrochloride (PicCl.HCl) in N, N,N-dimethylformamide (DMF) is strongly affected by the base applied: NaH induces only cone conformers, while K2CO3 or Cs2CO3 lead preferentially to partial cone and/or 1,3-alternate conformers, depending on the para substituent of the starting calix[4]arene. Single-crystal X-ray analyses on tetra-O-alkylated cone 1k,1 and partial cone 2c have been conducted. Molecule 1k has a distorted cone conformation with pendant OCH2Py groups; a methanol of solvation is hydrogen bonded to one pyridine N atom and is exo to the calix cavity. The crystal structure of 11 contains two independent distorted cone shaped molecules per asymmetric unit which differ principally in the relative orientations of the OCH2Py groups. In the partial cone conformer 2c the conformation adopted is such that the pendant OCH2Py group of the rotated aryl ring lies in, and effectively fills, the calix cavity produced by the remaining three aryl rings; as in 1k a methanol of solvation is hydrogen bonded to a pyridine N atom exo to the calix cavity. Regioselective syn-proximal (1,2-) or syn-distal (1,3-) difunctionalization at the lower rim of calix[4]arenes has been also achieved. Syn-1,2-disubstituted derivatives have proved to be useful intermediates for the stereoselective synthesis of tri-O-alkylated cone conformers, calix[4]arenes with mixed ligating groups in the sequence AABB at the lower rim, for inherently chiral calix[4]arenes, and for the transfer of proximal regioselectivity from the lower to the upper rim. On the basis of stepwise O-alkylation of calix[4]arenes, and with the aid of MM2 calculations on the involved intermediates and their anions, a possible genesis of the various conformers is proposed.

  DOI：

  10.1021/jo00035a016

文献信息

• Functionalization of calix[4]arenes by alkylation with 2-(chloromethyl)pyridine hydrochloride
  作者：Sebastiano Pappalardo、Luigi Giunta、Mario Foti、George Ferguson、John F. Gallagher、Branko Kaitner

  DOI：10.1021/jo00035a016

  日期：1992.4

  The syntheses, structures, and conformations of nine of the 13 possible [(2-pyridylmethyl)oxy]calix[4]arene conformers obtainable by direct substitution on calix[4]arenes 1a,b are described. The conformer distribution in the exhaustive O-alkylation of 1a,b with 2-(chloromethyl)pyridine hydrochloride (PicCl.HCl) in N, N,N-dimethylformamide (DMF) is strongly affected by the base applied: NaH induces only cone conformers, while K2CO3 or Cs2CO3 lead preferentially to partial cone and/or 1,3-alternate conformers, depending on the para substituent of the starting calix[4]arene. Single-crystal X-ray analyses on tetra-O-alkylated cone 1k,1 and partial cone 2c have been conducted. Molecule 1k has a distorted cone conformation with pendant OCH2Py groups; a methanol of solvation is hydrogen bonded to one pyridine N atom and is exo to the calix cavity. The crystal structure of 11 contains two independent distorted cone shaped molecules per asymmetric unit which differ principally in the relative orientations of the OCH2Py groups. In the partial cone conformer 2c the conformation adopted is such that the pendant OCH2Py group of the rotated aryl ring lies in, and effectively fills, the calix cavity produced by the remaining three aryl rings; as in 1k a methanol of solvation is hydrogen bonded to a pyridine N atom exo to the calix cavity. Regioselective syn-proximal (1,2-) or syn-distal (1,3-) difunctionalization at the lower rim of calix[4]arenes has been also achieved. Syn-1,2-disubstituted derivatives have proved to be useful intermediates for the stereoselective synthesis of tri-O-alkylated cone conformers, calix[4]arenes with mixed ligating groups in the sequence AABB at the lower rim, for inherently chiral calix[4]arenes, and for the transfer of proximal regioselectivity from the lower to the upper rim. On the basis of stepwise O-alkylation of calix[4]arenes, and with the aid of MM2 calculations on the involved intermediates and their anions, a possible genesis of the various conformers is proposed.