hexakis(pyrazol-1-yl)benzene | 148807-09-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: hexakis(pyrazol-1-yl)benzene
• 英文别名: hexa(pyrazol-1-yl)benzene；Hexa(1H-pyrazole-1-yl)benzene；1-[2,3,4,5,6-penta(pyrazol-1-yl)phenyl]pyrazole
• CAS: 148807-09-4
• 化学式: C₂₄H₁₈N₁₂
• 分子量: 474.487
• InChiKey: ZLSPXFMOKCUGIY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  36
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  107
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (COD)Pd^II(C₆H₅)₂ 、 hexakis(pyrazol-1-yl)benzene 以 四氢呋喃 为溶剂， 以0%的产率得到[(κ(6)-N1N2,N3N4,N5N6-hexakis(pyrazol-1-yl)benzene)[Pd(C6F5)2]3]
  参考文献：
  名称：

  Variety in the Coordination Modes of the Ligand Hexakis(pyrazol-1-yl)benzene (Hpzb) to PdII, PtII and CuI Centres

  摘要：

  The structure and conformational analysis of eight complexes derived from hexakis(pyrazol-1-yl)benzene (hpzb) have been carried out by means of X-ray crystallography and NMR spectroscopy. The metallic fragments [Pd(C6F5)(2), [Pd(eta(3)-2-Me-C3H4)](+), PtCl2 and Cu(PMe3)(+)] coordinate with two adjacent pyrazole residues yielding complexes with one, two or three metallic centres. The crystal and molecular structures of [(Pd(C6F5)2)2(hpzb)], [(Pd(eta(3)-C4H7)}(2-)(hpzb)](TfO)(2), [(Cu(PMe3))(2)(hpzb)](BF4)(2) and [fPd(eta(3)-C4H7)}(3)(hpzb)](TfO)(3) have been determined. The structure of each of the complexes depends on the fact that the metal atoms, when two or three are present, prefer to be situated on opposite faces of the benzene ring. Evidence for restricted rotation of the uncoordinated pyrazolyl groups has been found for the free ligand and monometallic derivatives, while free rotation of these groups at room temperature has been observed for the dimetallic complexes. Furthermore, the derivative [[Cu(PMe3)]2(hpzb))(BF4)(2) and probably [(Pd(eta(3)-C4H2))(2)(hpzb)](TfO)(2) exhibit metallotropy on the NMR time scale. (C) Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.

  DOI：

  10.1002/1099-0682(200212)2002:12<3178::aid-ejic3178>3.0.co;2-r
• 作为产物：
  描述：

  吡唑 、 六氟苯 在 sodium hydride 作用下， 生成 hexakis(pyrazol-1-yl)benzene
  参考文献：
  名称：

  Henrie, Robert N.; Yeager, Walter H., Heterocycles, 1993, vol. 35, # 1, p. 415 - 426

  摘要：

  DOI：

文献信息

• Polykis(pyrazol-1-yl)benzenes: preparation, structure, and complexation with copper and palladium
  作者：Olga Ivashchuk、Vladimir I. Sorokin

  DOI：10.1016/j.tet.2009.04.035

  日期：2009.6

  and palladium(II) was analyzed by ESI mass spectrometry. X-ray structures were determined for palladium(II) complex with 1,2-bis(pyrazol-1-yl)benzene and copper(II) complex with 1,4-difluoro-2,3-bis(pyrazol-1-yl)benzene, revealing an unusual seven-membered chelate cycle formation.

  通过在1,2-二氟，1,2,3,4-四氟，1,2 ，4，5-四氟和六氟苯。观察到的取代模式表明了早期TS的形成，从而使得氟被邻位亲核攻击位点激活。通过ESI质谱分析合成的配体与铜（II）和钯（II）的络合。确定了具有1,2-双（吡唑-1-基）苯的钯（II）配合物和具有1,4-二氟-2,3-双（吡唑-1-基）的铜（II）配合物的X射线结构）苯，揭示了一个不寻常的七元螯合物循环形成。
• Multinuclear NMR solution studies on complexes of hexakis(pyrazol-1-yl)benzene (hpzb) with Ag(I)
  作者：Agustı́n Caballero、Ana Guerrero、Félix A Jalón、Blanca R Manzano、Rosa M Claramunt、M.Dolores Santa Marı́a、Consuelo Escolástico、José Elguero

  DOI：10.1016/s0020-1693(02)01451-2

  日期：2003.4

  the derivative [Ag(hpzb)]SbF6 (2) is also obtained, while in the case of ClO4− the insoluble salt AgClO4 is formed. The same reactions performed with hpzb–15N12 confirmed the presence of the N-donor ligand in 1–3. At room temperature a Ag–P dissociation process is observed for all the derivatives containing Ag–PPh3 fragments. Complexes 1–3 show in solution an intramolecular argentotropic shift that

  摘要多齿N-供体配体六（吡唑-1-基）苯（hpzb）与AgSbF6 / PPh3或Ag PPh3以1：1的比例反应生成[Ag（PPh3）（hpzb）] SbF6（1 ）或[Ag（PPh3）（hpzb）] ClO4（3）。当使用两或三当量的银衍生物时，除1或3外还形成了[Ag（PPh3）2] X物种。在SbF6-的情况下，其余的Ag +与AgPPh3 +竞争与hpzb和衍生物[b]配位。还获得了Ag（hpzb）] SbF6（2），而在 -的情况下，形成了不溶性盐Ag 。用hpzb-15N12进行的相同反应证实了1-3中存在N-供体配体。在室温下，观察到所有含Ag-PPh3片段的衍生物的Ag-P解离过程。配合物1-3在溶液中显示出分子内的亲核移位，使得hpzb配体的六个吡唑基环在1H NMR时标上相等。当溶液中存在的抗衡阴离子的量足够高时，在低温31P NMR谱图中，除三配位
• Aromatic propellenes. Part 2. Study of conformational isomerism of hexa(pyrazol-1-yl)benzene: X-ray crystallography and semiempirical calculations
  作者：Concepci�n Foces-Foces、Antonio L. Llamas-Saiz、Consuelo Escol�stico、Rosa Mar�a Claramunt、Jos� Elguero

  DOI：10.1002/(sici)1099-1395(199603)9:3<137::aid-poc767>3.0.co;2-y

  日期：1996.3

  The molecular and crystal structures of two crystalline forms of hexa(pyrazol-1-yl)benzene were determined by x-ray analysis. They correspond to two conformational polymorphs: form I is obtained in acetic acid and form II in ethanol or dichloromethane. The crystal packing of both conformers is different; however, that of form I is analogous to that of hexa(3,5-dimethylpyrazol-1-yl)benzene, having similar cell dimensions and space groups R-3. No significant interactions except the van der Waals interactions were observed. Semiempirical calculations at the AM1 and SAM1 levels, exploring all possible conformations of the pyrazole rings, reveal that the most stable conformation presents the pyrazole rings with the N(2) alternating between both sides of the phenyl plane as it occurs in the solid state, crystalline form I (conformation 8h). The computed minimum energy for conformer 7a, which is related to crystal form II, presents a different sequence of pyrazole arrangements [N(2) up or down] and is only 1.6-2.0 kcal mol(-1) less stable than the previous one in both parametrizations. The SAM1 method yields pyrazole moieties more perpendicular to the benzene ring than the AM1 one.
• Synthesis, spectral characterization and cytotoxicity of Ru–bipyridyl complexes containing hexakis(pyrazol-1-yl)benzene (hpzb) as a co-ligand
  作者：Blanca R. Manzano、Félix A. Jalón、Gustavo Espino、Ana Guerrero、Rosa M. Claramunt、Consuelo Escolástico、José Elguero、M. Aránzazu Heras

  DOI：10.1016/j.poly.2007.05.043

  日期：2007.9

  A novel ruthenium bisbipyridine complex, [Ru(bpy)(2)(hpzb)](PF6)(2) (1) (hpzb = hexakis(pyrazol-l-yl)benzene) was obtained in the reaction between [Ru(bpy)(2)Cl-2], the tritopic ligand hpzb and NH4PF6. A high selectivity has been found in the reaction and when the hpzb ligand was made to react with more than one ruthenium fragment, it coordinated selectively only to the first metallic fragment, and it was not possible to introduce two or three ruthenium centres. A similar complex with a deuterated bipyridine has also been obtained. The reaction with the methylated ligand hexakis(3,5-dimethylpyrazol-1-yl)benzene does not take place. A complete assignment of all the proton and carbon NMR signals of I was carried out. The orientation of the free pyrazolyl groups is also discussed. The redox properties and the anticancer activity of complex I have been studied. (c) 2007 Elsevier Ltd. All rights reserved.