三(2-吡啶基)甲基醇 | 73569-80-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 中文名称: 三(2-吡啶基)甲基醇
• 英文名称: tris(2-pyridyl)methyl alcohol
• 英文别名: tris(2-pyridyl)methanol；Tri(2-pyridinyl)methanol；tripyridin-2-ylmethanol
• CAS: 73569-80-9
• 化学式: C₁₆H₁₃N₃O
• 分子量: 263.299
• InChiKey: DFJPILHAIIXZCR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  58.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  三(2-吡啶基)甲基醇 在 氯化亚砜 、 三正丁基氢锡 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 tris(2-pyridyl)methane
  参考文献：
  名称：

  Strong Lewis acids derived from molybdenum and tungsten nitrosyls containing the tri-2-pyridylmethane ligand. Dynamic NMR studies of their adducts with aldehydes, ketones, and esters

  摘要：

  The doubly charged Lewis acid precursors [HC(py)3M(NO)2(CO)](SbF6)2 (M = Mo, W; HC(py)3 = tri-2-pyridylmethane) are conveniently synthesized by reaction of HC(py)3M(CO)3 and 2 equiv of NOSbF6. Facile loss of CO from the precursors generates the [HC(py)3M(NO)2](SbF6)2 Lewis acids. The Lewis acidity of the tungsten complex is greater than that of the molybdenum complex. With the H-1 NMR chemical shifts of bound crotonaldehyde as a qualitative assessment of relative acidity, the acidity of the tungsten species is comparable to that of BF3 and AlCl3, while that of the molybdenum species is similar to that of TiCl4. Analysis of the NMR spectra of the Lewis acid-organic carbonyl base adducts, which include the adducts of aldehydes, ketones, and esters, showed that eta-1-M(O = C) interactions dominate the chemistry. The barriers of rotation about the aldehyde C1-C2 bonds in the p-anisaldehyde adducts of the molybdenum and tungsten species were measured to be 12.8 and 13.7 kcal/mol, respectively, which are significantly higher than that for the free p-anisaldehyde. The exchange behavior between the E and Z isomers of the acetate adducts could be observed on the NMR time scale. The E to Z interconversion barriers of 12.2 +/- 0.1 and 12.3 +/- 0.1 kcal/mol for the methyl acetate and ethyl acetate complexes, respectively, were calculated from the results of variable-temperature proton NMR experiments. The free energy differences between the E and Z conformers of the methyl acetate and ethyl acetate adducts are 1.27 +/- 0.01 and 0.96 +/- 0.01 kcal/mol at 229 K, respectively.

  DOI：

  10.1021/ja00005a021
• 作为产物：
  描述：

  2-吡啶基锂 在 乙醚 作用下， 生成 三(2-吡啶基)甲基醇
  参考文献：
  名称：

  Wibaut et al., Recueil des Travaux Chimiques des Pays-Bas, 1951, vol. 70, p. 1054,1061

  摘要：

  DOI：

文献信息

• Preparation of substituted tris(2-pyridyl)methanol derivatives as mimics of the metal binding site of carbonic anhydrase
  作者：Michael J. Hannon、Paul C. Mayers、Paul C. Taylor

  DOI：10.1016/s0040-4039(98)01850-4

  日期：1998.11

  A series of novel mono-substituted and summetrically tri-substituted tris(2-pyridyl)methanols have been prepared in a one-step reaction from the corresponding 2-bromopyridines. Metal complexes of these compounds and their further functionalised derivatives are of interest as carbonic anhydrase (CA) mimics.

  在一步反应中，由相应的2-溴吡啶制备了一系列新颖的单取代和三取代的三（2-吡啶基）甲醇。这些化合物及其进一步官能化的衍生物的金属络合物作为碳酸酐酶（CA）的模拟物是令人感兴趣的。
• Bioinspired models for an unusual 3-histidine motif of diketone dioxygenase enzyme
  作者：Ramamoorthy Ramasubramanian、Karunanithi Anandababu、Nadia C. Mösch-Zanetti、Ferdinand Belaj、Ramasamy Mayilmurugan

  DOI：10.1039/c9dt02518a

  日期：——

  the resting state of the enzyme, as obtained by EXAFS studies. The diketonate substrate-adduct complexes [Fe(L)(acacR)](SO3CF3) (R = Me, Ph) of 1-3 have been obtained using Na(acacR) in acetonitrile. The Fe2+/3+ redox potentials of the complexes (1.05 to 1.2 V vs. Fc/Fc+) and their substrate adducts (1.02 to 1.19 V vs. Fc/Fc+) appeared at almost the same redox barrier. All diketonate adducts exhibit two

  报告了生物启发的模型，用于对比中性的三组氨酸与阴离子的2-组氨酸-1-羧酸盐面部基序的电子性质及其对催化的后续影响。据此，合成了基于三（2-吡啶基）基配体（L）的铁（ii）配合物[Fe（L）（CH3CN）3]（SO3CF3）21-3，并将其表征为中性3-的准确结构模型二酮双加氧酶（DKDO）的组氨酸三联体。一种配合物的分子结构表现出八面体配位几何结构和Fe-N11py键长[1.952（4）至1.959（4）Å]接近于3-His三元组中Fe-NHis键的距离（1.98Å）。通过EXAFS研究获得的酶的静止状态。使用乙腈中的Na（acacR）获得了1-3的二酮酸酯底物加合物[Fe（L）（acacR）]（SO3CF3）（R = Me，Ph）。复合物的Fe2 + / 3 +氧化还原电势（相对于Fc / Fc +为1.05至1.2 V）和其底物加合物（相对于Fc / Fc +为1.02至1.19 V
• A Structural and Functional Model for the Tris‐Histidine Motif in Cysteine Dioxygenase
  作者：Karunanithi Anandababu、Ramamoorthy Ramasubramanian、Hubert Wadepohl、Peter Comba、Neethinathan Johnee Britto、Madhavan Jaccob、Ramasamy Mayilmurugan

  DOI：10.1002/chem.201901005

  日期：2019.7.17

  The iron(II) complexes [Fe(L)(MeCN)3](SO3CF3)2 (L are two derivatives of tris(2‐pyridyl)‐based ligands) have been synthesized as models for cysteine dioxygenase (CDO). The molecular structure of one of the complexes exhibits octahedral coordination geometry and the Fe−Npy bond lengths [1.953(4)–1.972(4) Å] are similar to those in the Cys‐bound FeII‐CDO; Fe−NHis: 1.893–2.199 Å. The iron(II) centers

  已经合成了铁（II）配合物[Fe（L）（MeCN）3 ]（SO 3 CF 3）2（L是基于三（2-吡啶基）配体的两个衍生物）作为半胱氨酸双加氧酶（CDO）的模型。其中一种配合物的分子结构表现出八面体配位几何结构，Fe-N py键长[1.953（4）–1.972（4）Å]与与Cys键合的Fe II - CDO相似。Fe-N His：1.893–2.199Å。模型配合物的铁（II）中心显示出较高的Fe III / II氧化还原电势（相对于二茂铁/二茂铁电极Fc / Fc +，E 1/2 = 0.988–1.380 V ）2活化和典型的为相应的非血红素铁酶。原位生成的[Fe（L）（MeCN）（SPh）] +与过量的O 2在乙腈（MeCN）中的反应选择性地产生了双加氧的苯亚磺酸产物。利用同位素标记研究18 ö 2确认的O两个氧原子的掺入2到产品中。动力学和初步DFT研究揭示一种Fe的参与III p
• Synthesis and Characterization of a Binuclear Porphyrin Complex as a Model for Heme a₃-Cu_BSite of Cytochrome<i>c</i>Oxidase
  作者：Hiroshi Fujii、Tetsuhiko Yoshimura、Hitoshi Kamada

  DOI：10.1246/cl.1996.581

  日期：1996.8

  A binuclear complex, 1, involving copper and heme complexes is synthesized and characterized by paramagnetic 1H-NMR, FAB mass, and ESR spectroscopies. These measurements indicate a fairly weak magnetic interaction between iron and copper ions when a bridege ligand is absent.

  合成并表征了一种涉及铜和血红素配合物的双核配合物1，采用了顺磁性1H-NMR、FAB质谱和ESR光谱。测量结果表明，当桥联配体缺失时，铁和铜离子之间的磁相互作用相对较弱。
• Co-ordination chemistry of dimethylgold(III). Synthesis, spectroscopic, and structural studies of complexes with neutral aromatic nitrogen-donor ligands
  作者：Allan J. Canty、Nigel J. Minchin、Peter C. Healy、Allan H. White

  DOI：10.1039/dt9820001795

  日期：——

  cis-square-planar co-ordination for gold(III), AuC2N2, with Au–C 2.023(7)–2.041(12)Å and Au–N 2.127(8)–2.142(8)Å. In complexes of the potential tridentate ligands one pyridyl group is not co-ordinated in the tpm complex, and one pyrazolyl group is involved in a weak axial Au ⋯ N interaction [3.139(7)Å] in the tpzm complex. Comparison of the 1H n.m.r. spectra of complexes of the potentially tridentate ligands (tpzm

  硝酸二甲基金（III）与中性配体反应形成配合物[AuMe 2（tpm）] NO 3 ·2H 2 O（tpm =三-2-吡啶甲烷）和[AuMe 2 L] NO 3 [L = tri-2-吡啶甲醇（tpmo），二-2-吡啶基甲烷（dpm），αα-二-2-吡啶基甲苯（dpt），二-1-吡唑基甲烷（dpzm）和三-1-吡唑基甲烷（tpzm）]。已经通过在295 K下进行单晶X射线衍射确定了tpzm，tpm和dpt的配合物的晶体结构，并通过最小二乘法将3,043,1,616和3的R分别设为R = 0.033、0.029和0.042。分别有2 529个独立的“观察”反射。在这些结构中，[AuMe 2 L]+阳离子对于金（ III），AuC 2 N 2，Au–C 2.023（7）–2.041（12）Å和Au–N 2.127（8）–2.142（8）本质上具有顺式-方形平面配位作用一种。在潜在的三齿配体的配