syn-Distal 5,11,17,23-Tetra-tert-butyl-25-<(2-pyridylmethyl)oxy>-27-<(2-quinolylmethyl)oxy>-26,28-dihydroxycalix<4>arene | 153170-93-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: syn-Distal 5,11,17,23-Tetra-tert-butyl-25-<(2-pyridylmethyl)oxy>-27-<(2-quinolylmethyl)oxy>-26,28-dihydroxycalix<4>arene
• 英文别名: 5,11,17,23-Tetratert-butyl-26-(pyridin-2-ylmethoxy)-28-(quinolin-2-ylmethoxy)pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene-25,27-diol
• CAS: 153170-93-5
• 化学式: C₆₀H₆₈N₂O₄
• 分子量: 881.211
• InChiKey: ZIIKOAKTRQCQQD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.9
• 重原子数：
  66
• 可旋转键数：
  10
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  84.7
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-氯甲基喹啉盐酸盐 、 syn-Distal 5,11,17,23-Tetra-tert-butyl-25-<(2-pyridylmethyl)oxy>-27-<(2-quinolylmethyl)oxy>-26,28-dihydroxycalix<4>arene 在 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 以28%的产率得到5,11,17,23-Tetra-tert-butyl-25,26,28-tris<(2-quinolylmethyl)oxy>-27-<(2-pyridylmethyl)oxy>calix<4>arene
  参考文献：
  名称：

  Synthetic strategies to inherently chiral calix[4]arenes with mixed ligating functionalities at the lower rim

  摘要：

  The syntheses of 19 atropisomeric inherently chiral calix[4]arenes derived from syn-proximal (1,2)-bis[(2-pyridylmethyl)oxy]calix[4]arene 2 and mixed syn-distal (1,3)-[(2-pyridylmethyl)oxy][(2-quinolylmethyl)oxy]calix[4] arene 6 are described. Treatment of 2 with 1 equiv of electrophile RX in DMF in the presence of Cs2CO3 afforded racemic tri-O-alkylated cone conformers 3a-k (A(alpha)A(alpha)B(alpha)C(alpha) type), while with an excess of alkylating agent under analogous conditions the chiral tetra-O-alkylated partial cone conformers 4a-d (A(alpha)A(alpha)B(alpha)B(beta) type) were formed. Similarly, exhaustive alkylation of 6 with either PicCl.HCl or QuinCl.HCl gave the chiral partial cone derivatives 7a,b (A(alpha)A(alpha)A(beta)B(alpha) type), respectively. Further alkylation of 3i (R=benzyl) with PicCl.HCl and Cs2CO3 provided partial cone derivative 7c (A(alpha)A(alpha)A(beta)B(alpha) type), while with PrBr and NaH cone tetraether 8 (A(alpha)A(alpha)B(alpha)C(alpha) type) was obtained. Proton and carbon NMR spectral features of these compounds are discussed. Atropisomerism in tri-O-alkylated calix[U arenes was demonstrated by dynamic NMR studies on the less encumbered allyl derivative 3a, which showed no hint for conformational inversion up to 375 K. 2D COSY spectra clearly show that in partial cone structures 4d and 7a-c the N-heteroaryl pendant group of the rotated aryl moiety lies in, and effectively fills, the calix cavity produced by the remaining three aryl rings, The structure of the trisubstituted racemic calix[4]arene 3i has been determined by X-ray crystallography. The molecule adopts a distorted cone conformation with the two pendant pyridinyl groups in the syn-proximal arrangement on one side of the pendant benzyl moiety. There is an intramolecular O-H...O hydrogen bond between the phenolic oxygen OD and the proximal ethereal oxygen OA (to which is bonded the benzyl residue) with O...O 2.85 Angstrom.

  DOI：

  10.1021/jo00080a010
• 作为产物：
  描述：

  2-氯甲基喹啉盐酸盐 、 Mono[(2-pyridylmethyl)oxy]calix[4]arene 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 10.0h， 以70%的产率得到syn-Distal 5,11,17,23-Tetra-tert-butyl-25-<(2-pyridylmethyl)oxy>-27-<(2-quinolylmethyl)oxy>-26,28-dihydroxycalix<4>arene
  参考文献：
  名称：

  Synthetic strategies to inherently chiral calix[4]arenes with mixed ligating functionalities at the lower rim

  摘要：

  The syntheses of 19 atropisomeric inherently chiral calix[4]arenes derived from syn-proximal (1,2)-bis[(2-pyridylmethyl)oxy]calix[4]arene 2 and mixed syn-distal (1,3)-[(2-pyridylmethyl)oxy][(2-quinolylmethyl)oxy]calix[4] arene 6 are described. Treatment of 2 with 1 equiv of electrophile RX in DMF in the presence of Cs2CO3 afforded racemic tri-O-alkylated cone conformers 3a-k (A(alpha)A(alpha)B(alpha)C(alpha) type), while with an excess of alkylating agent under analogous conditions the chiral tetra-O-alkylated partial cone conformers 4a-d (A(alpha)A(alpha)B(alpha)B(beta) type) were formed. Similarly, exhaustive alkylation of 6 with either PicCl.HCl or QuinCl.HCl gave the chiral partial cone derivatives 7a,b (A(alpha)A(alpha)A(beta)B(alpha) type), respectively. Further alkylation of 3i (R=benzyl) with PicCl.HCl and Cs2CO3 provided partial cone derivative 7c (A(alpha)A(alpha)A(beta)B(alpha) type), while with PrBr and NaH cone tetraether 8 (A(alpha)A(alpha)B(alpha)C(alpha) type) was obtained. Proton and carbon NMR spectral features of these compounds are discussed. Atropisomerism in tri-O-alkylated calix[U arenes was demonstrated by dynamic NMR studies on the less encumbered allyl derivative 3a, which showed no hint for conformational inversion up to 375 K. 2D COSY spectra clearly show that in partial cone structures 4d and 7a-c the N-heteroaryl pendant group of the rotated aryl moiety lies in, and effectively fills, the calix cavity produced by the remaining three aryl rings, The structure of the trisubstituted racemic calix[4]arene 3i has been determined by X-ray crystallography. The molecule adopts a distorted cone conformation with the two pendant pyridinyl groups in the syn-proximal arrangement on one side of the pendant benzyl moiety. There is an intramolecular O-H...O hydrogen bond between the phenolic oxygen OD and the proximal ethereal oxygen OA (to which is bonded the benzyl residue) with O...O 2.85 Angstrom.

  DOI：

  10.1021/jo00080a010

文献信息

• Ferguson George, Gallagher John F., Giunta Luigi, Neri Placido, Pappalard+, J. org. Chem, 59 (1994) N 1, S 42-53
  作者：Ferguson George, Gallagher John F., Giunta Luigi, Neri Placido, Pappalard+

  DOI：——

  日期：——
• Synthetic strategies to inherently chiral calix[4]arenes with mixed ligating functionalities at the lower rim
  作者：George Ferguson、John F. Gallagher、Luigi Giunta、Placido Neri、Sebastiano Pappalardo、Melchiorre Parisi

  DOI：10.1021/jo00080a010

  日期：1994.1

  The syntheses of 19 atropisomeric inherently chiral calix[4]arenes derived from syn-proximal (1,2)-bis[(2-pyridylmethyl)oxy]calix[4]arene 2 and mixed syn-distal (1,3)-[(2-pyridylmethyl)oxy][(2-quinolylmethyl)oxy]calix[4] arene 6 are described. Treatment of 2 with 1 equiv of electrophile RX in DMF in the presence of Cs2CO3 afforded racemic tri-O-alkylated cone conformers 3a-k (A(alpha)A(alpha)B(alpha)C(alpha) type), while with an excess of alkylating agent under analogous conditions the chiral tetra-O-alkylated partial cone conformers 4a-d (A(alpha)A(alpha)B(alpha)B(beta) type) were formed. Similarly, exhaustive alkylation of 6 with either PicCl.HCl or QuinCl.HCl gave the chiral partial cone derivatives 7a,b (A(alpha)A(alpha)A(beta)B(alpha) type), respectively. Further alkylation of 3i (R=benzyl) with PicCl.HCl and Cs2CO3 provided partial cone derivative 7c (A(alpha)A(alpha)A(beta)B(alpha) type), while with PrBr and NaH cone tetraether 8 (A(alpha)A(alpha)B(alpha)C(alpha) type) was obtained. Proton and carbon NMR spectral features of these compounds are discussed. Atropisomerism in tri-O-alkylated calix[U arenes was demonstrated by dynamic NMR studies on the less encumbered allyl derivative 3a, which showed no hint for conformational inversion up to 375 K. 2D COSY spectra clearly show that in partial cone structures 4d and 7a-c the N-heteroaryl pendant group of the rotated aryl moiety lies in, and effectively fills, the calix cavity produced by the remaining three aryl rings, The structure of the trisubstituted racemic calix[4]arene 3i has been determined by X-ray crystallography. The molecule adopts a distorted cone conformation with the two pendant pyridinyl groups in the syn-proximal arrangement on one side of the pendant benzyl moiety. There is an intramolecular O-H...O hydrogen bond between the phenolic oxygen OD and the proximal ethereal oxygen OA (to which is bonded the benzyl residue) with O...O 2.85 Angstrom.