2-(N,N-bis((pyridin-2-yl)methyl)aminomethyl)-6-chloromethyl-4-methylphenol | 195621-22-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(N,N-bis((pyridin-2-yl)methyl)aminomethyl)-6-chloromethyl-4-methylphenol
• 英文别名: 2-{[bis(pyridin-2-ylmethyl)amino]methyl}-6-(chloromethyl)-4-methylphenol；2-(N,N-bis(2-methylpyridyl)aminomethyl)-6-(chloromethyl)-4-methylphenol
• CAS: 195621-22-8
• 化学式: C₂₁H₂₂ClN₃O
• 分子量: 367.878
• InChiKey: VRNDNPWFARWZDX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.43
• 重原子数：
  26.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  49.25
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-(N,N-bis((pyridin-2-yl)methyl)aminomethyl)-6-chloromethyl-4-methylphenol 在 potassium methanolate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  The Functional Model Complex [Fe₂(BPMP)(OPr)(NO)₂](BPh₄)₂ Provides Insight into the Mechanism of Flavodiiron NO Reductases

  摘要：

  Flavodiiron nitric oxide reductases (FNORs), found in many pathogenic bacteria, are able to detoxify NO by reducing it to N2O. In this way, FNORs equip these pathogens with immunity to NO, which is a central immune defense agent in humans. Hence, FNORs are thought to promote infection of the human body, leading to chronic diseases. Despite this importance of FNORs for bacterial pathogenesis, the mechanism of NO reduction by these enzymes is not well understood. Here we present the synthesis and spectroscopic characterization of the diiron dinitrosyl model complex [Fe-2(BPMP)(OPr)(NO)(2)](BPh4)(2). The crystal structure of this complex shows two end-on-coordinated {FeNO}(7) units that, based on spectroscopic and electrochemical results, are only weakly electronically coupled. Importantly, reduction of this complex by two electrons leads to the clean formation of N2O in quantitative yield. This complex therefore represents the first example of a functional model system for FNORs. The results provide key mechanistic insight into the mechanism of FNORs and, in particular, represent strong support for the proposed "super-reduced" mechanism for these enzymes.

  DOI：

  10.1021/ja309782m
• 作为产物：
  描述：

  8-(bromomethyl)-6-methyl-2-phenyl-2,4-dihydro-1,3-benzodioxine 在 tetrafluoroboric acid 、 氯化亚砜 、 sodium hydride 作用下， 以 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 52.0h， 生成 2-(N,N-bis((pyridin-2-yl)methyl)aminomethyl)-6-chloromethyl-4-methylphenol
  参考文献：
  名称：

  通用的关键合成子，可用于配体的合成，潜在地适用于制备具有两个非等价络合位点的μ-苯氧双金属络合物

  摘要：

  由2，6-双（羟甲基）-4-甲基苯酚分两步轻松制备（65％收率）的合成子S，可以合成具有两个化学不同配位环境的各种双核配体。由S制备二核配体意味着三个步骤。

  DOI：

  10.1016/0040-4039(94)88214-2

文献信息

• Catalytic Oxidation of Alkanes and Alkenes by H ₂ O ₂ with a μ‐Oxido Diiron(III) Complex as Catalyst/Catalyst Precursor
  作者：Biswanath Das、Afnan Al‐Hunaiti、Matti Haukka、Serhiy Demeshko、Steffen Meyer、Albert A. Shteinman、Franc Meyer、Timo Repo、Ebbe Nordlander

  DOI：10.1002/ejic.201500576

  日期：2015.7

  activity in cyclohexene oxidation (TOF = 72 h(-1)) were detected. Partial retention of configuration (RC = 53%) in cis- and trans-1,2-dimethylcyclohexane oxidation, moderate 3 degrees/2 degrees selectivity (4.1) in adamantane oxidation, and the observation of a relatively high kinetic isotope effect for cyclohexane oxidation (KIE = 3.27) suggest partial metal-based oxidation, probably in tandem with free-radical

  吡啶基不对称配体 3-[(3-[bis(pyridin-2-ylmethyl)amino]methyl}-2-hydroxy-5-methylbenzyl) 锂盐的新型 mu-oxo diiron(III) 络合物(pyridin2-ylmethyl)amino]propanoate (LiDPCPMPP), [Fe-2(mu-O)(LiDPCPMPP)(2)](ClO4)(2)，已被合成和表征。已经通过使用 CH3COOH/H2O2 (1:1) 作为氧化系统研究了配合物催化几种烷烃和烯烃氧化的能力。检测到环己烷氧化中的中等活性 (TOF = 33 h(-1)) 和环己烯氧化中的良好活性 (TOF = 72 h(-1))。顺式和反式 1,2-二甲基环己烷氧化中构型的部分保留 (RC = 53%)，金刚烷氧化中的中等 3 度/2 度选择性 (4.1)，以及观察到相对高的环己烷氧化动力学同位素效应(KIE
• Deprotonation in Mixed-Valent Diiron(II,III) Complexes with Aniline or Benzimidazole Ligands
  作者：Eric Gouré、Michaël Carboni、Angélique Troussier、Patrick Dubourdeaux、Martin Clémancey、Nathalie Gon、Ramachandran Balasubramanian、Colette Lebrun、Jacques Pécaut、Geneviève Blondin、Jean-Marc Latour

  DOI：10.1021/acs.inorgchem.5b00449

  日期：2015.7.6

  isomerization processes in phenoxido-bridged mixed-valent FeIIFeIII complexes that contain either one aniline or one anilide ligand. In this work, we compare the properties of similar complexes bearing one terminal protic ligand, either aniline or 1H-benzimidazole. Whatever the ligand, 1H NMR spectroscopy clearly evidences that the complexes are present in CH3CN as a mixture of cis- and trans-isomers in

  我们之前已经研究了苯氧基桥接的混合价Fe II Fe III配合物中的顺式/反式异构化过程，该配合物包含一种苯胺或一种苯胺配体。在这项工作中，我们比较了带有一个末端质子配体（苯胺或1 H-苯并咪唑）的类似络合物的性质。无论是哪种配体，1 H NMR光谱都清楚地表明，络合物以接近1：1的比例存在于CH 3 CN中，为顺式和反式异构体的混合物。我们在这里显示NEt 3的添加确实允许这些配体去质子化，所得的带有苯胺或苯并咪唑啉的配合物配位到三价铁上。后者是与苯并咪唑啉配体配位的高旋转三价铁离子的奇异实例。苯胺化合物的反式异构体占绝对优势，而苯并咪唑类化合物则是等比例的顺式和反式异构体的混合物。此外，循环伏安法研究表明，具有1 H-苯并咪唑的Fe III Fe III配合物比苯胺对应物更稳定，而去质子化的物质则相反。
• Effect of coordination dissymmetry on the catalytic activity of manganese catalase mimics
  作者：Ripul Mehrotra、Micaela Richezzi、Claudia Palopoli、Christelle Hureau、Sandra R. Signorella

  DOI：10.1016/j.jinorgbio.2020.111264

  日期：2020.12

  saturation kinetics on [H2O2]. Spectroscopic monitoring of the reaction mixtures revealed the two complexes disproportionate H2O2 employing a different redox cycle, with retention of dinuclearity. The higher catalytic efficiency of [Mn2L2(OAc)2] was rationalized in terms of the larger labilizing effect of the heptadentate ligand that favors the acetate-shift and the replacement of the non-coordinating

  两种混合价的Mn（II）Mn（III）络合物，[Mn 2 L 1（OAc）2（H 2 O）] BPh 4 ·2.5H 2 O和[Mn 2 L 2（OAc）2 ]·4H 2由不对称的N 4 O 2-六齿L 1（2-）（H 2 L 1  = 2-（N，N-双（2-（吡啶基甲基）氨基甲基）-6-（N-（2-羟基苄基））苄基氨基甲基）-4-甲基苯酚）和N 4 O 3七齿L 2（3-）（NaH 2 L制备并表征了2  ＝ 2-（N，N-双（2-（吡啶基甲基）氨基甲基）-6-（N'-（2-羟基苄基）（羧甲基）氨基甲基）-4-甲基苯酚钠盐）的配体。两种配合物在Mn（II）离子周围共享一个μ-酚盐-双（μ-乙酸盐）Mn（II）Mn（III）核和N 3 O 3-配位球，但在Mn（III）周围的供体基团上有所不同（NO 4（溶剂）和NO 5）。在非质子溶剂中，这两种络合物能够歧化至少3600当量。H 2 O
• Synthesis and Spectroscopic Characterisation of a Heterodinuclear Iron(III)‐Copper(II) Complex Based on an Asymmetric Dinucleating Ligand System
  作者：Florian Heims、Valeriu Mereacre、Antonella Ciancetta、Stefan Mebs、Annie K. Powell、Claudio Greco、Kallol Ray

  DOI：10.1002/ejic.201200156

  日期：2012.10

  The site-directed generation of a heterodinuclear FeIIICuII complex by using a new asymmetric dinucleating ligand FloH is reported. The iron(III) ion is introduced first on the preferential metal-binding site of the ligand that leads to the formation of the thermodynamically favored five-membered chelate rings upon metal-binding. Copper(II) is introduced in the next step. The stepwise metalation strategy

  报道了使用新的不对称双核配体 FloH 定点生成异双核 FeIIICuII 复合物。铁 (III) 离子首先引入配体的优先金属结合位点，导致在金属结合时形成热力学有利的五元螯合环。在下一步中引入铜 (II)。为了避免统计分布，这里报告的逐步金属化策略可以扩展到其他异金属配合物的制备。与它们的同金属类似物相比，这种配合物可以提供新的光谱特性、电子结构和反应性。
• Synthesis, Structure, and Phosphatase-Like Activity of a New Trinuclear Gd Complex with the Unsymmetrical Ligand H₃L As a Model for Nucleases
  作者：Maryene A. Camargo、Ademir Neves、Bruno Szpoganicz、Adailton J. Bortoluzzi、Franciele L. Fischer、Hernán Terenzi、Eduardo E. Castellano

  DOI：10.1021/ic100276z

  日期：2010.3.15

  The new trinuclear gadolinium complex [Gd3L2(NO3)2(H2O)4]NO3·8H2O (1) with the unsymmetrical ligand 2-[N-bis-(2-pyridylmethyl)aminomethyl]-4-methyl-6-[N-bis(2-hydroxy-2-oxoethyl)aminomethyl] phenol (H3L) was synthesized and characterized. The new ligand H3L was obtained in good yield. Complex 1 crystallizes in an orthorhombic cell, space group Pcab. Kinetic studies show that complex 1 is highly active

  新型三核g配合物[Gd 3 L 2（NO 3）2（H 2 O）4 ] NO 3 ·8H 2 O（1）与不对称配体2- [ N-双-（2-吡啶基甲基）氨基甲基]-合成并表征了4-甲基-6- [ N-双（2-羟基-2-氧代乙基）氨基甲基]苯酚（H 3 L）。以良好的产率获得了新的配体H 3L。配合物1在正交晶胞空间群Pcab中结晶。动力学研究表明，络合物1在底物2,4-双（二硝基苯基）磷酸酯的水解中具有高活性（K m = 4.09 mM，V max = 2.68×10 -2 mM s -1，k cat = V max / [ 1 ] = 0.67 s -1）。通过电位分析和确定1在乙腈/水溶液中的动力学行为，可以鉴定溶液中存在的物质，在温和条件下，三核一羟基物质似乎是最主要的催化剂。复合物1在DNA水解裂解中显示出高效率，并进行了完整的动力学研究（ķ米= 4.57×10 -4男，ķ '猫= 3