syn-Proximal 5,11,17,23-tetra-tert-butyl-25,26-bis<(2-pyridylmethyl)oxy>-27,28-dihydroxycalix<4>arene | 139342-85-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: syn-Proximal 5,11,17,23-tetra-tert-butyl-25,26-bis<(2-pyridylmethyl)oxy>-27,28-dihydroxycalix<4>arene
• 英文别名: 5,11,17,23-Tetratert-butyl-27,28-bis(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-diol
• CAS: 139342-85-1
• 化学式: C₅₆H₆₆N₂O₄
• 分子量: 831.151
• InChiKey: CEYBNVAADIPPNK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.5
• 重原子数：
  62
• 可旋转键数：
  10
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.39
• 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：

  syn-Proximal 5,11,17,23-tetra-tert-butyl-25,26-bis<(2-pyridylmethyl)oxy>-27,28-dihydroxycalix<4>arene 在 sodium hydride 、 caesium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 生成 5,11,17,23-Tetra-tert-butyl-25,26-bis-<(2-pirydylmethyl)oxy>-27-(benzyloxy)-28-propoxycalix<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：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 、 2-氯甲基吡啶盐酸盐 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以85%的产率得到syn-Proximal 5,11,17,23-tetra-tert-butyl-25,26-bis<(2-pyridylmethyl)oxy>-27,28-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

• Novel 1,2-bridged calix[4]crowns in the 1,2-alternate conformation
  作者：Sebastiano Pappalardo、Ada Petringa、Melchiorre F. Parisi、George Ferguson

  DOI：10.1016/0040-4039(96)00686-7

  日期：1996.5

  Treatment of 1,2-di[(2-pyridylmethyl)oxy]calix[4]arenes 1 (R = t-Bu, H) with tri- to pentaethylene glycol ditosylates in anhydrous toluene in the presence of t-BuOK affords a mixture of 1,2-alternate and cone (1,2)-calix[4]crown conformers 2 and 3 in a 55–70% overall yield. The conformational features of 2 have been deduced by NMR, and further confirmed by single-crystal X-ray analysis on crown-5 derivative

  在t -BuOK存在下，在无水甲苯中用三至五乙二醇二甲苯磺酸酯处理1,2-二[（2-吡啶基甲基）氧基]杯[4]芳烃1（R = t -Bu，H）1,2-交替和圆锥（1,2）-杯[4]冠状构象异构体2和3的总产率为55-70％。的构象特征2已经通过NMR推导出，并且进一步通过单晶X射线分析对冠-5衍生物证实2E。
• Stereoselective synthesis and optical resolution of chiral calix[4]arenes with mixed ligating functionalities
  作者：Sebastiano Pappalardo、Salvatore Caccamese、Luigi Giunta

  DOI：10.1016/0040-4039(91)80581-p

  日期：1991.12

  Exhaustive alkylation of syn-proximal bis[(2-pyridylmethyl)oxy]calix[4]arene 1 with t-butyl bromoacetate or 2-(chloromethyl)quinoline hydrochloride in the presence of Cs2CO3 affords selectively a new type of inherently chiral calix[4]arenes 2a,b in the partial cone conformation. (±) 2b has been resolved into its optical antipodes by an HPLC method.

  在Cs 2 CO 3存在下用溴乙酸叔丁酯或2-（氯甲基）喹啉盐酸盐将近邻双[（2-吡啶基甲基）氧基]杯[4]芳烃1进行彻底的烷基化，选择性地提供了一种新型的固有手性杯[4]芳烃2a，b处于部分圆锥构象。（±）2b已通过HPLC方法拆分为其旋光对映体。
• Synthesis and Complexation Studies of Regioisomers and Conformational Isomers of p-tert-Butylcalix[4]arene Bearing Pyridine or Pyridine N-Oxide Pendant Groups at the Lower Rim
  作者：Sebastiano Pappalardo、George Ferguson、Placido Neri、Concetta Rocco

  DOI：10.1021/jo00119a040

  日期：1995.7

  Selected title compounds have been prepared in order to provide calix[4]arene ligands having different shapes of the calix[4]arene skeleton (cone, partial cone, 1,2-alternate, or 1,3-alternate) and spacial arrangements (syn-proximal, syn-distal, or anti-distal) of pendant pyridine or pyridine N-oxide binding groups. The structure of 1,2-alternate tetrakis[(2-pyridylmethyl)oxy]calix[4]arene 9, obtained in low yield by direct alkylation of the parent p-tert-butylcalix[4]arene 1 with PicCl . HCl and Cs2CO3, has been elucidated by single crystal X-ray analysis. N-Oxide derivatives have been obtained in good yield by m-CPBA oxidation of the appropriate pyridinocalix[4]arene precursors in dry Et(2)O or THF. The H-1 and C-13 NMR spectral changes upon N-oxide formation are discussed. Extraction studies with alkali metal picrates from an aqueous solution into CH2Cl2 have shown that the ionophoric efficiency is low. The highest phase-transfer values are observed for cone tetrapyridinocalix[4]arene 7 (selectivity follows the order Na+ > K+ > Rb+ > Cs+ > Li+), whereas the corresponding N-oxide 7a has no activity. However, NMR complexation studies with Na+ and K+, while confirming a low complexation rate, indicate that in aprotic solvents tetra-N-oxide derivative 7a is a good complexer having a faster kinetic than its pyridino precursor 7.
• 1,2-Bridged Calix[4]arene Monocrowns and Biscrowns in the 1,2-Alternate Conformation
  作者：George Ferguson、Alan J. Lough、Anna Notti、Sebastiano Pappalardo、Melchiorre F. Parisi、Ada Petringa

  DOI：10.1021/jo9810516

  日期：1998.12.1

  The condensation of 1, 2-di[(2-pyridylmethyl)oxy]calix[4]arenes 1 (R = Bu-t, H) with glycol ditosylates 2a-e in anhydrous toluene in the presence of (BuOK)-Bu-t has led to a mixture of 1,2-alternate and cone 1,2-calix[4]arene crown conformers 3 and 4, respectively. Similarly, the reaction of 1,2-bridged calix[4]arene crown-4 5 with tri- to pentaethylene glycol ditosylates 2a-c has produced 1,2-alternate and cone calix[4]arene biscrown conformers 6 and 7, respectively. The distribution of conformers depends on the para-substituent at the upper rim and the length and bulkiness of the ditosylates. The best yields of the 1,2-alternate conformer (up to 51%) are observed in the absence of tBu groups and with the longer polyether chain. The conformational features of 3 and 6 have been deduced by NMR spectroscopy and by X-ray crystallography. X-ray analysis of 25,26-27,28-biscrown-4-calix[4]arene (6a) shows that there are two independent molecules in the asymmetric unit, both in the 1,2-alternate conformation.
• Calix[4]arenes with pyridine pendant groups. Regioselective proximal alkylation at the "lower rim"
  作者：Francesco Bottino、Luigi Giunta、Sebastiano Pappalardo

  DOI：10.1021/jo00284a001

  日期：1989.11