5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis<(2-pyridylmethyl)oxy>calix<4>arene | 123207-92-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis<(2-pyridylmethyl)oxy>calix<4>arene
• 英文别名: 2-[[5,11,17,23-Tetratert-butyl-26,27,28-tris(pyridin-2-ylmethoxy)-25-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-dodecaenyl]oxymethyl]pyridine
• CAS: 123207-92-1；139584-74-0；139683-30-0；139683-31-1；170553-89-6
• 化学式: C₆₈H₇₆N₄O₄
• 分子量: 1013.38
• InChiKey: FHXDMUBBDUJJMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.1
• 重原子数：
  76
• 可旋转键数：
  16
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  88.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis<(2-pyridylmethyl)oxy>calix<4>arene 在 间氯过氧苯甲酸 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis<<(1-oxopyrid-2-yl)methyl>oxy>calix<4>arene
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo00119a040
• 作为产物：
  描述：

  2-氯甲基吡啶盐酸盐 在 potassium carbonate 、 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 40.0h， 生成 5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis<(2-pyridylmethyl)oxy>calix<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

• Solvent Extraction and Stripping of Silver Ions in Room-Temperature Ionic Liquids Containing Calixarenes
  作者：Kojiro Shimojo、Masahiro Goto

  DOI：10.1021/ac049549x

  日期：2004.9.1

  calix[4]arene-bearing pyridine is soluble in a typical room-temperature ionic liquid (RTIL), 1-alkyl-3-methylimidazolium hexafluorophosphate. Pyridinocalix[4]arene showed a high extraction ability and selectivity for silver ions. The extraction performance of the calix[4]arene was greatly enhanced by dissolution in RTILs compared to in chloroform. In a competitive extraction test using five different metal ions (Ag+

  我们发现带有杯[4]芳烃的吡啶可溶于典型的室温离子液体（RTIL）1-烷基-3-甲基咪唑六氟磷酸盐。吡啶并杯[4]芳烃对银离子具有较高的萃取能力和选择性。相较于氯仿，通过溶解在RTIL中可以大大提高杯[4]芳烃的萃取性能。在使用五种不同金属离子（Ag +，Cu2 +，Zn2 +，Co2 +，Ni2 +）的竞争性萃取试验中，杯芳烃[4]芳烃通过阳离子交换机制仅将银离子从水进料相转移到RTIL中。通过斜率分析和乔布斯方法，发现吡啶吡啶杯[4]芳烃与银离子形成稳定的1：1络合物。由于通过控制水相pH值很容易从RTIL中去除银离子，
• Thermodynamics of cation (alkali-metal) complexation by 5,11,17,23-tetra-tert-butyl[25,26,27,28-tetrakis(2-pyridylmethyl)oxy]- calix(4)arene and the crystal structure–superstructure of its 1:1 complex with sodium and acetonitrile
  作者：Angela F. Danil de Namor、Eduardo E. Castellano、Lupe E. Pulcha Salazar、Oscar E. Piro、Olga Jafou

  DOI：10.1039/a806902f

  日期：——

  The interaction of 5,11,17,23-tetra-tert-butyl [25,26,27,28-tetrakis(2-pyridylmethyl)oxy]calix(4)arene 1a with alkali-metal cations in dipolar aprotic media (acetonitrile and benzonitrile) has been investigated. 1H NMR experiments were carried out by adding to the ligand an excess amount of the appropriate metal cation (Li+, Na+, K+) in CD3CN at 298 K. Measurements were taken at different time intervals ranging from 30 min to 10 days. It was found that the kinetics of the process in this solvent is fast. Conductance measurements demonstrated that 1:1 metal cation:ligand stoichiometries are found with these cations in these solvents. Thermodynamic parameters of complexation for this ligand and alkali-metal cations in acetonitrile and in benzonitrile at 298.15 K were derived from titration microcalorimetry. Stability constants were also determined by the competitive potentiometric method using silver electrodes. Excellent agreement is found between the data derived from calorimetry and those derived by potentiometry. The highest stability is found for lithium with this ligand. The results are compared with data previously reported for systems involving a calix(4)arene ester derivative and these cations in the same solvents. The implications of stability constant data on the selective behaviour of this ligand for metal cations in these solvents are discussed. It is shown that this ligand in these solvents is able to discriminate between the smaller cations (Li+ and Na+) and the larger ones (K+ and Rb+). The sodium perchlorate complex of 1a was synthesised and the molecular structure of this complex has been determined from X-ray diffraction data. The substance crystallises in the tetragonal group P4cc with a=21.791(2), c=26.958(3) Å and z=8. There are three different complexes in the lattice, two sited on fourfold axes and a third one on a twofold axis. All ligands exhibit a ‘cone’ conformation and the Na+ ion is encapsulated in their hydrophilic pockets with an acetonitrile molecule filling their hydrophobic cavities. Based on 1H NMR, conductimetric, microcalorimetric and X-ray diffraction studies final conclusions are given.

  研究了 5,11,17,23-四叔丁基 [25,26,27,28-四(2-吡啶基甲基)氧基]钙(4)炔 1a 与碱金属阳离子在双极性钝化介质（乙腈和苯甲腈）中的相互作用。在 298 K 的 CD3CN 中，通过向配体中加入过量的适当金属阳离子（Li+、Na+、K+）进行了 1H NMR 实验。结果发现，在这种溶剂中，反应过程的动力学速度很快。电导测量结果表明，在这些溶剂中，这些阳离子与配体的配位比为 1:1。通过滴定微量热法得出了该配体与碱金属阳离子在 298.15 K 的乙腈和苯甲腈中络合的热力学参数。此外，还通过使用银电极的竞争电位法测定了稳定性常数。量热法得出的数据与电位计法得出的数据非常一致。锂与这种配体的稳定性最高。研究结果与之前报告的涉及钙(4)炔酯衍生物和这些阳离子的体系在相同溶剂中的数据进行了比较。讨论了稳定性常数数据对这种配体在这些溶剂中对金属阳离子的选择性的影响。研究表明，这种配体在这些溶剂中能够区分较小的阳离子（Li+ 和 Na+）和较大的阳离子（K+ 和 Rb+）。我们合成了 1a 的高氯酸钠络合物，并通过 X 射线衍射数据确定了该络合物的分子结构。该物质结晶为 P4cc 四边形，a=21.791(2)，c=26.958(3) Ã，z=8。晶格中有三种不同的配合物，其中两种位于四倍轴上，第三种位于二倍轴上。所有配体都呈现 "锥 "构象，Na+离子被包裹在它们的亲水口袋中，而乙腈分子则填充了它们的疏水空腔。根据 1H NMR、电导率、微量热和 X 射线衍射研究得出了最终结论。
• 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
• 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.
• 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.