1,3-bis(α-picolyloxy)-p-tert-butylcalix[4]arene | 123207-97-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1,3-bis(α-picolyloxy)-p-tert-butylcalix[4]arene
• 英文别名: 25,27-dihydroxy-26,28-bis(2-pyridylmethoxy)-5,11,17,23-tetra-tert-butylcalix<4>arene；25,27-Dihydroxy-26,28-bis(2-pyridylmethyl)oxy-5,11,17,23-tetra-tert-butylcalix[4]arene；syn-distal-5,11,17,23-tetra-tert-butyl-25,27-bis<(2-pyridylmethyl)oxy>-26,28-dihydroxycalix<4>arene；5,11,17,23-Tetra-tert-butyl-25,27-dihydroxy-26,28-bis(2-pyridylmethoxy)calix<4>arene；5,11,17,23-tetra-tert-butyl-25,27-bis(2-methoxypyridine)calix[4]arene-26,28-diol；5,11,17,23-tetra-tert-butyl-25,27-bis(2-pyridylmethoxy)calix[4]arene；bispicolyl-p-tert-butylcalix[4]arene；5,11,17,23-Tetratert-butyl-26,28-bis(pyridin-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: 123207-97-6
• 化学式: C₅₆H₆₆N₂O₄
• 分子量: 831.151
• InChiKey: KGBQOKCTLZGRGX-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：

  1,3-bis(α-picolyloxy)-p-tert-butylcalix[4]arene 在 间氯过氧苯甲酸 作用下， 以 乙醚 为溶剂， 反应 24.0h， 以66%的产率得到syn-dist-5,11,17,23-Tetra-tert-butyl-25,27-bis<<(1-oxopyrid-2-yl)methyl>oxy>-26,28-dihydroxycalix<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：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 、 2-氯甲基吡啶盐酸盐 在 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以88.15%的产率得到1,3-bis(α-picolyloxy)-p-tert-butylcalix[4]arene
  参考文献：
  名称：

  一种含吡啶基杯[4]芳烃衍生物及其制备方法和作为锰离子萃取剂的应用

  摘要：

  本发明公开了一种含吡啶基杯[4]芳烃衍生物及其制备方法和作为锰离子萃取剂的应用。含吡啶基杯[4]芳烃衍生物由烷基杯[4]芳烃和2‑(卤代甲基)吡啶盐酸盐在碱催化下进行亲核取代反应得到；该含吡啶基杯[4]芳烃衍生物的物理化学稳定性高，油溶性较好，不溶于水，且具有较好金属离子识别络合能力，将其与P204组成协合萃取体系，对硫酸盐溶液体系中的锰离子存在很强的正协同萃取效果，而对镍、钴、镁、锂等金属离子存在明显的反协同萃取效果，非常适用于复杂金属离子体系中锰离子的选择性萃取分离，具有良好的工业应用前景。

  公开号：

  CN113072487B

文献信息

• Self-inclusion structure of 5,11,17,23-tetrakis(azidomethyl)-25,26,27,28-tetrahydroxycalix[4]arene, and 5,11,17,23-tetra-<i>tert</i>-butyl-25,27-bis(chloroacetoxy)-26,28-bis(2-pyridylmethoxy)calix[4]arene
  作者：Mei Zhao、Xin-Yan Zhang、Jian-Ping Ma、Ru-Qi Huang、Dian-Shun Guo

  DOI：10.1107/s0108270109010609

  日期：2009.4.15

  of the two title calix[4]arene derivatives, C32H28N12O4, (I), and C60H68Cl2N2O6, (II), compound (I) adopts an open‐cone conformation in which there are four intramolecular O—H...O hydrogen bonds, while compound (II) adopts a distorted chalice conformation where the two pendant pyridyl rings, one of which is disordered, are almost mutually perpendicular, with an interplanar angle of 79.2 (2) or 71.4 (2)°

  在两个标题杯[4]芳烃衍生物的结构中，C 32 H 28 N 12 O 4，（I）和C 60 H 68 Cl 2 N 2 O 6，（II），化合物（I）采用开环构型，其中有四个分子内OH-H ... O氢键，而化合物（II）采用扭曲的圣杯构型，其中两个侧基吡啶基环是一个杂乱无章的物体几乎相互垂直，平面角度为79.2（2）或71.4（2）°。四个桥接亚甲基C原子定义的虚拟平面与苯酚环之间的二面角（I）为120.27（7），124.03（6），120.14（8）和128.25（7）°，以及95.99（8） （II）分别为135.93（7），97.21（8）和126.10（8）°。在（I）的超分子结构中，成对的分子通过自包含而缔合，其中分子的一个叠氮基团插入与转化相关的分子的腔中，并且缔合通过弱分子间的CH稳定。 .N氢键和π（N3）–π（芳香）相互作用。分子对通过弱分子间的CH-H ... N
• Synthesis and ESI-MS Alkali Metal Ion Binding Selectivities of Cone, Partial Cone, and 1,3-Alternate 1,3-Bis(α-picolyloxy)-p-tert-butylcalix[4]arene Crown-6 and 1,1'-Binaphthalene-2,2'-diyl Crown-6 Conformers
  作者：George Ferguson、Alan J. Lough、Anna Notti、Sebastiano Pappalardo、Melchiorre F. Parisi、Giuseppe Resnati

  DOI：10.1135/cccc20041109

  日期：——

  The syntheses of 1,3-bis(α-picolyloxy)-p-tert-butylcalix[4]arene crown-6 and 1,1'-binaphthalene-2,2'-diyl crown-6 title conformers have been achieved by two complementary synthetic strategies, which differ in the order in which the polyether loop and the pendant picolyl groups are introduced. The structure and conformation of all new compounds have been firmly established by NMR spectroscopy, and further proven by X-ray analysis for the intermediate p-tert-butyl-25,27-(1,1'-binaphthalene-2,2'-diyl-crown-6)-26,28-dihydroxycalix[4]arene. Within each set of conformers, the nature of the polyether chain has little or no influence on the overall conformation of the calixarene platform. The alkali metal ion binding selectivities of the two series of calixarenes have been evaluated in competitive complexation experiments by electrospray ionization mass spectrometry. In the p-tert-butylcalix[4]arene crown-6 series, partial cone and 1,3-alternate conformers show a peak selectivity for the larger Cs⁺ ions, while the cone one preferentially binds the smaller Na⁺ ions. On the other hand, the cone and 1,3-alternate binaphthyl-containing analogues show a preference for Na⁺ ions, the partial cone being quite unselective.

  1,3-双(α-吡啶氧基)-p-叔丁基杯[4]芳烃冠-6和1,1'-联萘-2,2'-二基冠-6构象体的合成已通过两种互补的合成策略实现，这两种策略在引入聚醚环和挂链吡啶基的顺序上有所不同。所有新化合物的结构和构象均已通过NMR光谱确定，并通过中间体p-叔丁基-25,27-(1,1'-联萘-2,2'-二基冠-6)-26,28-二羟基杯[4]芳烃的X射线分析得到进一步证实。在每组构象体系中，聚醚链的性质对杯芳烃平台的总体构象几乎没有影响。通过电喷雾离子化质谱竞争络合实验评估了两系列杯芳烃的碱金属离子结合选择性。在p-叔丁基杯[4]芳烃冠-6系列中，部分圆锥和1,3-交替构象体对较大的Cs+离子具有峰值选择性，而圆锥构象体优先结合较小的Na+离子。另一方面，圆锥和1,3-交替联萘基类似物对Na+离子有偏好，而部分圆锥则相当不选择性。
• Monomeric, oligomeric, and polymeric copper(II) complexes of calix[4]arene-derived ligands
  作者：Adrián Castillo、José L. Martínez、Paulina R. Martínez-Alanis、Ivan Castillo

  DOI：10.1016/j.ica.2009.12.017

  日期：2010.4

  Abstract Deprotonation of the p - tert -butylcalix[4]arene disubstituted at alternate phenolic positions with picolyl groups 2 was achieved with alkali metal hydrides LiH, NaH, and KH. The dianionic calixarene derivatives were subjected to complete substitution at the phenolic rim with allyl bromide, providing the tetraalkylated derivatives in cone 3a and partial-cone conformations 3b ; both compounds

  摘要用碱金属氢化物LiH，NaH和KH实现了在2个具有甲基吡啶基的交替酚位置上双取代的对叔丁基杯[4]芳烃的质子化。对二价杯芳烃衍生物在苯酚边缘用烯丙基溴进行完全取代，得到圆锥3a和部分圆锥构象3b中的四烷基化衍生物。两种化合物都经过晶体学表征。测试化合物2以及3a和3b作为对CuCl 2的配体，在前两种情况下提供Cu 2+络合物。由2和CuCl 2在MeOH / CH 2 Cl 2溶液中获得聚合物[2·CuCl 2]，该聚合物由对位杯芳烃作为大环腔外Cu 2+离子的N供体的链组成。EtOH / CH 2 Cl 2混合物的使用产生了三铜配合物[（2）2 Cu 3 Cl 6（EtOH）2]。相反，配体3a与CuCl 2的反应提供了单体[3a·CuCl 2]，而当使用3b时不能获得Cu 2+络合物。2中分子内氢键的存在似乎可以控制低聚或聚合铜络合物的形成，而缺少这种氢键则可以使N供体正确对齐，从而在大环腔正上方配位Cu
• Unusual reactivity of copper(I) complexes of functionalised calix[4]arenes
  作者：Bernadette S. Creaven、Tammy L. Gernon、Timothy McCormac、John McGinley、Ann-Marie Moore、Hans Toftlund

  DOI：10.1016/j.ica.2005.03.003

  日期：2005.6

  Two functionalised calix[4]arenes, 5,11,17,23-tetra-tert-butyl-25,27-bis(2-pyridylmethoxy)calix[4]arene (L1) and 5,11,17,23-tetra-tert-butyl-25,27-bis(2-pyridylmethoxy)-26,28-dibutoxycalix[4]arene (L3), were prepared and characterised. The copper(I) complexes of both calix[4]arenes were synthesised and their reactivities were analysed and compared. The presence of the metal induced a radical in the

  两个功能化的杯[4]芳烃，5,11,17,23-四叔丁基-25,27-双（2-吡啶甲氧基）杯[4]芳烃（L1）和5,11,17,23-四制备并表征了25,27-二叔丁基-25,27-双（2-吡啶甲氧基）-26,28-二丁氧基杯[4]芳烃（L3）。合成了两个杯[4]芳烃的铜（I）配合物，并对其反应性进行了分析和比较。在L1的情况下，金属的存在诱导了自由基，而在配体L3的金属络合物中未观察到这样的自由基。
• 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