((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine | 86894-20-4

• 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
• 英文名称: ((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine
• 英文别名: (6-Methyl-2-pyridylmethyl)bis(2-pyridylmethyl)amine；N-[(6-methylpyridin-2-yl)methyl]-1-pyridin-2-yl-N-(pyridin-2-ylmethyl)methanamine
• CAS: 86894-20-4
• 化学式: C₁₉H₂₀N₄
• 分子量: 304.395
• InChiKey: MHERDSVHKRZMJL-UHFFFAOYSA-N

物化性质

• 沸点：
  416.4±40.0 °C(Predicted)
• 密度：
  1.155±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  41.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine 以 乙醚 、 乙腈 为溶剂， 生成 Fe(C₁₈H₁₇N₄CH₃)(OOC₄H₉)(H₂O)⁽²⁺⁾*2ClO₄^(1-)=[Fe(C₁₈H₁₇N₄CH₃)(H₂O)(OOC₄H₉)](ClO₄)2
  参考文献：
  名称：

  Models for Nonheme Iron Intermediates:  Structural Basis for Tuning the Spin States of Fe(TPA) Complexes

  摘要：

  Our efforts to model the oxygen activation chemistry of nonheme iron enzymes have yielded transient intermediates with novel properties. These properties can be dramatically affected by the introduction of a 6-methyl substituent on the pendant pyridines of the tetradentate ligand TPA (TPA = tris(2-pyridylmethyl)amine). A series of Fe(TPA) complexes has thus been synthesized and characterized to provide the structural basis for these dramatic effects. The following complexes have been obtained: [Fe(L)(CH3CN)(2)](ClO4)(2) (1, L = TPA; 2, L = 6-MeTPA; 3, L = 6-Me(2)TPA; 4, L = 6-Me(3)TPA) and [Fe(L)(acac)](ClO4)(2) (5, L = TPA; 6, L = 5-Me(3)TPA; 7, L = 6-MeTPA). As indicated by H-1 NMR and/or EPR, 1, 5, and 6 wish no 6-methyl substituent are low spin, while complexes 2, 3, 4, and 7 with at least one 6-methyl substituent are all high spin, with higher redox potentials than their low-spin counterparts. The ligands with 6-methyl substituents thus favor a metal center with a larger ionic radius, i.e., Fe-II over Fe-III and high spin over low spin. Careful scrutiny of the crystal structures of 1, 4, 6, and 7 reveals that one hydrogen of the 6-methyl group is only 2.7 Angstrom away from the metal center in the high-spin complexes. Its presence thus prevents the pyridine nitrogen from forming an Fe-N bond shorter than 2.1 Angstrom as required for an iron center to adopt a low-spin configuration. This steric effect of the 6-methyl substituent serves as a simple but very useful ligand design tool to tune the electronic properties of the metastable alkylperoxoiron(III) species derived from the reactions of 1-4 with tert-butyl hydroperoxide. These intermediates serve as models for low-spin and high-spin peroxoiron(III) species in the reaction cycles of the antitumor drug bleomycin and lipoxygenase, respectively. Similar principles apply in the design of nonheme diiron(II) complexes that reversibly bind dioxygen and of high-valent bis(mu-oxo)diiron complexes that model the high-valent intermediates in the redox cycles of nonheme diiron enzymes such as methane monooxygenase and ribonucleotide reductase.

  DOI：

  10.1021/ja9638521
• 作为产物：
  描述：

  6-甲基-2-吡啶基甲醇 在 磺酰氯 作用下， 以 四氯化碳 为溶剂， 生成 ((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine
  参考文献：
  名称：

  基于三脚架吡啶胺衍生物的 铜（ii）配合物作为有效的抗癌药†

  摘要：

  的配合物[铜（TPA）CL] CLO 4 ·½H 2 O（1-CLO 4），[Cu（上6- MeTPA）CL] CLO 4 / PF 6（ 2-CLO 4 / 2-PF 6），[铜（6-Me 2 TPA）Cl] PF 6（3-PF 6），[Cu（BPQA）Cl] ClO 4 / PF 6（4-ClO 4 / 4-PF 6），[Cu（BPQA）Cl] ClO 4 / PF 6（4-ClO 4 / 4-PF 6），[Cu（BQPA）Cl] ClO 4 / PF 6（5-ClO 4 / PF 6），[Cu（L 1）Cl] ClO 4 / PF 6（6-ClO 4 / 6-PF 6），[Cu（L 2）Cl] ClO 4（7-ClO 4）合成了[Cu（L 3）Cl] ClO 4（8-ClO 4），并通过光谱技术和单X射线晶体学对其结构进行了表征。在体外的细胞毒性所制备的铜（II）针对A2780（卵巢

  DOI：

  10.1039/c9nj00061e

文献信息

• Efficient hydrolytic cleavage of plasmid DNA by chloro-cobalt(ii) complexes based on sterically hindered pyridyl tripod tetraamine ligands: synthesis, crystal structure and DNA cleavage
  作者：Salah S. Massoud、Richard S. Perkins、Febee R. Louka、Wu Xu、Anne Le Roux、Quentin Dutercq、Roland C. Fischer、Franz A. Mautner、Makoto Handa、Yuya Hiraoka、Gabriel L. Kreft、Tiago Bortolotto、Hernán Terenzi

  DOI：10.1039/c4dt00615a

  日期：——

  Four new cobalt(II) complexes [Co(6-MeTPA)Cl]ClO4/PF6 (2/2a), [Co(6-Me2TPA)Cl]ClO4/PF6 (3/3a), [Co(BPQA)Cl]ClO4/PF6 (4/4a) and [Co(BQPA)Cl]ClO4/PF6 (5/5a) as well as [Co(TPA)Cl]ClO4 (1) where TPA = tris(2-pyridylmethyl)amine, 6-MeTPA = ((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine, 6-Me2TPA = bis(6-methyl-2-pyridyl)methyl)-(2-pyridylmethyl)amine, BPQA = bis(2-pyridylmethyl)-(2-quinolylmethyl)-amine

  四种新的钴（II）配合物[Co（6-MeTPA）Cl] ClO 4 / PF 6（2 / 2a），[Co（6-Me 2 TPA）Cl] ClO 4 / PF 6（3 / 3a），[ Co（BPQA）Cl] ClO 4 / PF 6（4 / 4a）和[Co（BQPA）Cl] ClO 4 / PF 6（5 / 5a）以及[Co（TPA）Cl] ClO 4（1）其中TPA =三（2-吡啶基甲基）胺，6-MeTPA =（（6-甲基-2-吡啶基）甲基）双（2-吡啶基甲基）胺，6-Me 2TPA =双（6-甲基-2-吡啶基）甲基）-（2-吡啶基甲基）胺，BPQA =双（2-吡啶基甲基）-（2-喹啉基甲基）-胺，BQPA =双（2-喹啉基甲基）-（2合成了-吡啶基甲基）胺并对其结构进行了表征。单晶X射线晶体学证实了配合物2a-5a的扭曲的三角双锥体几何形状。CH 3 CN–H 2 O混合物中配合物的分光
• Reactivity of Copper(I) Complexes Containing Various Tetradentate Tripodal Ligands with Molecular Oxygen
  作者：Kounosuke Uozumi、Yoshihito Hayashi、Masatatsu Suzuki、Akira Uehara

  DOI：10.1246/cl.1993.963

  日期：1993.6

  Reactivity of copper(I) complexes [Cu(L)]+ containing a series of tetradentate tripodal ligands, (6-methyl-2-pyridylmethyl)m(2-pyridylmethyl)(3−m)amine (m = 1, 2, or 3) with molecular oxygen was in...

  铜 (I) 配合物 [Cu(L)]+ 的反应性包含一系列四齿三足配体，(6-甲基-2-吡啶基甲基)m(2-吡啶基甲基)(3-m)胺 (m = 1, 2,或 3) 分子氧在...
• Comparative Structural, Spectroscopic and Redox Studies of Isostructural Complexes of Ruthenium(III), Osmium(III), and Rhenium(III):<i>cis</i>-Dichloro Complexes Containing Tris(2-pyridylmethyl)amine and Its 6-Methylpyridyl Derivative
  作者：Hideki Sugimoto、Chikako Matsunami、Chikako Koshi、Mikio Yamasaki、Keisuke Umakoshi、Yoichi Sasaki

  DOI：10.1246/bcsj.74.2091

  日期：2001.11

  A series of the complexes, [MCl2(L)]+ (M = Ru, L = tpa (1), Metpa (1a); M = Os, L = tpa (2); M = Re, L = tpa (3), Metpa (3a); tpa = tris(2-pyridylmethyl)amine, Metpa = ((6-methyl-2-pyridylmethyl)bis(2-pyridylmethyl)amine), have been prepared. X-ray structural analyses of the series of isostructural complexes [1a]BF4, [2]PF6·C2H5OC2H5, [3]BF4, and [3a]BF4 together with that of the previously reported

  甲基的引入对 Re(III) 复合物的结构产生显着影响：Re-N（甲基化吡啶基）和 Re-N（吡啶基）与其反式的键长增加。与甲基相关的金属离子周围的键角...
• The systematic influence of tripodal ligands on the catechol cleaving activity of iron(III) containing model compounds for catechol 1,2-dioxygenases †
  作者：Matthias Pascaly、Mark Duda、Florian Schweppe、Kristin Zurlinden、Felizitas K. Müller、Bernt Krebs

  DOI：10.1039/b008511l

  日期：——

  A series of mononuclear iron(III) complexes as functional and structural model compounds for intradiol cleaving catechol dioxygenases were synthesized. For all model compounds the iron(III) cores are in a distorted octahedral environment derived from tripodal tetradentate N4-donor ligands and a catechol. Model complexes for enzyme–substrate adducts were characterized by spectroscopic and electrochemical

  合成了一系列单核铁（III）配合物，作为用于内二醇切割儿茶酚双加氧酶的功能和结构模型化合物。对于所有模型化合物，铁（III）核均处于扭曲的八面体环境中，该环境由三脚架四齿N 4-供体配体和邻苯二酚衍生而来。酶-底物加合物的模型配合物通过光谱和电化学方法表征，在四种情况下通过单晶X射线晶体学表征。在结构表征的配合物中一个配体臂的系统变化产生了铁的不同空间屏蔽（III）中心，显着影响邻苯二酚底物的键合以及随后与双氧的反应。 探索了具有上述配体的原位生成的配合物的光谱特征和邻苯二酚裂解活性。在空气存在下，所有复合物对各种邻苯二酚的二醇内裂解均具有高反应性。邻苯二酚1,2-二加氧酶反应取决于铁（III）配合物和邻苯二酚衍生物的氧化还原电势以及三脚架配体的空间需求。某些配合物显示出高催化活性，相对于儿茶酚的空中裂解，产率高达84％。
• A polypyridyl Co(<scp>ii</scp>) complex-based water reduction catalyst with double H₂ evolution sites
  作者：Junfei Wang、Chao Li、Qianxiong Zhou、Weibo Wang、Yuanjun Hou、Baowen Zhang、Xuesong Wang

  DOI：10.1039/c6cy01897a

  日期：——

  A series of Co(II) complexes, Co(X-TMPA)Cl2 (X-TMPA = 1-(6-substituted-pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methane amine, X = Cl (1), Br (2), H (3), and CH3 (4)), were synthesized and fully characterized. The crystal structures of 2 and 4 show that TMPA and CH3-TMPA coordinate to the Co(II) center as tetradentate ligands, while Br-TMPA coordinates as a tridentate ligand, leaving the Br-substituted

  一系列Co（II）配合物Co（X-TMPA）Cl 2（X-TMPA = 1-（6-取代-吡啶-2-基）-N，N-双（吡啶-2-基甲基）甲烷胺，X = Cl（1），Br（2），H（3）和CH 3（4）），被合成并充分表征。2和4的晶体结构表明TMPA和CH 3 -TMPA作为四齿配体与Co（II）中心配位，而Br-TMPA作为三齿配体进行配位，而在第二配位球中留下Br-取代的吡啶基。所有的配合物都是有效的光催化氢2种在CH进化催化剂3 CN / H 2 o使用[的Ir（ppy）（9/1） 2（dtbpy）]氯（PPY = 2-苯基吡啶，dtbpy = 4,4'-二-叔丁基2， 2'-联吡啶）作为光敏剂（PS），三乙胺（TEA）作为牺牲电子供体。在6小时的照射过程中， 1和2的周转率（TONs）达到20,000，明显高于3和4。这些高的光催化活性可以归因于悬垂的Cl / Br-取代的吡啶基，其