3-((bis(pyridin-2-ylmethyl)amino)methyl)-2-hydroxy-5-methylbenzaldehyde | 192819-69-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-((bis(pyridin-2-ylmethyl)amino)methyl)-2-hydroxy-5-methylbenzaldehyde
• 英文别名: 2-[N-bis(2-pyridylmethyl)aminomethyl]-4-methyl-6-formylphenol；2-[Bis(pyridylmethyl)amino-methyl]-4-methyl-6-formylphenol；3-[[bis(pyridin-2-ylmethyl)amino]methyl]-2-hydroxy-5-methylbenzaldehyde
• CAS: 192819-69-5
• 化学式: C₂₁H₂₁N₃O₂
• 分子量: 347.417
• InChiKey: MNHHORNPYLWWTP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  66.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-((bis(pyridin-2-ylmethyl)amino)methyl)-2-hydroxy-5-methylbenzaldehyde 在 sodium tetrahydroborate 、 氯化亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 27.75h， 生成 2-(N,N-bis(2-methylpyridyl)aminomethyl)-6-(N-(2-hydroxybenzyl)-N-(2-pyridylmethyl)aminomethyl)-4-methylphenol
  参考文献：
  名称：

  Synthesis, Structural, Magnetic, and Redox Properties of Asymmetric Diiron Complexes with a Single Terminally Bound Phenolate Ligand. Relevance to the Purple Acid Phosphatase Enzymes

  摘要：

  New asymmetrical ligands (H2L) have been synthesized to provide both a bridging and a terminal phenolate to a pair of iron ions in order to mimic the binding of a single terminal tyrosinate at the diiron center of the purple acid phosphatases. H(2)L1 is 2-[(bis(2-pyridylmethyl)amino)methyl]-6-[((2-pyridylmethyl)(2-phenol)amino of methyl]-4-methylphenol and H2L'1 and H(2)L2 are obtained by replacing the a-phenol group by the 5-nitro-2-phenol and the 6-methyl-2-phenol residues, respectively, A series of mixed valence diiron complexes [(FeFeL)-Fe-II-L-III(X)(2)](Y) have been obtained where (X)(2) is the dianion of m-phenylenedipropionate or (H2PO4)(2) and Y = BPh4 or PF6 (L = L1, Ba (X)(2) mpdp, Y = BPh4, db: (X)(2) = (OAC)(2), Y = BPh4, Ic: (X)(2) = (OBZ)(2), Y = BPh4, Id: (X)(2) = (H2PO4)(2), Y = PF6; L = L'1: 1'a (X)(2) = mpdp, Y = BPh4; L = L2: 2c: (X)(2) = (OBz)(2), Y = BPh4, 2d: (X)(2) = (H2PO4)(2), Y = PF6. Diferric complexes have been obtained also either by direct synthesis or by iodine oxidation of the mixed valence precursor (L = L1, 3a (X)(2) = mpdp, Y = BPh4, 3d: (X)(2) = (H2PO4)(2), Y = PF6; L = L2, 4d: (X)(2) = (H2PO4)(2). Y PF6. Complex la [(FeFeL)-Fe-II-L-III(mpdp)](BPh4) has been characterized by X-ray diffraction techniques, la crystallizes in the monoclinic space group P21/a with the following unit cell parameters: a 22.038 (9) Angstrom, b = 16.195 (8) Angstrom, c = 16.536 (7) Angstrom, beta = 97.26 (1)degrees, Z = 4, The significant differences in the Fe-O bond lengths indicate that the metal centers are ordered. The complexes have been studied by electronic spectral, resonance Raman, magnetic susceptibility, Mossbauer, NMR, and electrochemical techniques, Mossbauer and NMR spectroscopies concur to probe that the valences of the mixed valence compounds are trapped in solution as well as in the solid state at room temperature. The electronic spectrum of the mixed-valence compounds are dominated by a charge transfer transition in the 400-600 nm domain which moves to the 550-660 nm range upon oxidation to the diferric state. In addition they exhibit a weak and broad intervalence transition close to 1100 nm. Electrochemical studies show that the systems exist in the three redox states Fe-II/Fe-II/(FeFeIII)-Fe-II/(FeFeIII)-Fe-III. Moreover they show that the introduction of the terminal phenol group results in a thermodynamic destabilization of the diferrous state higher than the stabilization of the diferric state. An expanded stability domain of the mixed valence state is therefore observed which is probably due mostly to the asymmetry of the compounds, in addition a chemical destabilization of the reduced state of la, Ic, and 1'a is observed, Comparison of the carboxylate and phosphate derivatives leads to attribute it to the partial dissociation in solution of the carboxylate oxygen trans to the phenolate. The latter feature bears an intrinsic resemblance with the dissociation of iron which is observed when purple acid phosphatases are reduced by dithionite. These studies clearly show the importance of tyrosine binding on the redox properties of the PAP enzymes.This questions the relationship of such a redox specificity with a hydrolytic function and raises the possibility that the latter may be redox regulated or that another (redox based) function is actually involved, possibly in line with the ability of the enzymes to react with peroxides.

  DOI：

  10.1021/ja970345q
• 作为产物：
  描述：

  2-羟基-5-甲基间苯二甲醇 在 manganese(IV) oxide 、 氯化亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成 3-((bis(pyridin-2-ylmethyl)amino)methyl)-2-hydroxy-5-methylbenzaldehyde
  参考文献：
  名称：

  具有苯胺或苯并咪唑配体的混合价二价铁（II，III）配合物的去质子化

  摘要：

  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。

  DOI：

  10.1021/acs.inorgchem.5b00449

文献信息

• Hydrolytic Protein Cleavage Mediated by Unusual Mononuclear Copper(II) Complexes:  X-ray Structures and Solution Studies
  作者：Mauricio C. B. de Oliveira、Marciela Scarpellini、Ademir Neves、Hernán Terenzi、Adailton J. Bortoluzzi、Bruno Szpoganics、Alessandra Greatti、Antônio S. Mangrich、Emanuel M. de Souza、Pablo M. Fernandez、Marcia R. Soares

  DOI：10.1021/ic0485864

  日期：2005.2.1

  bovine serum albumin (BSA) and the thermostable enzyme Taq DNA polymerase at micromolar concentration, under mild pH and temperature conditions. The cleavage activity seems to be specific with defined proteolytic fragments appearing after protein treatment. The location of the specific cleavage sites was tentatively assigned to solvent-accessible portions of the protein. These are two of the most active

  两种新的单核铜（II）配合物[Cu（HL1）Cl2]（1）和[Cu（L1）Cl]（2）的晶体结构，氧化还原和UV-vis / EPR光谱性质是通过据报道，在不同的碱性条件下，氯化铜（II）和配体2-[（（（吡啶基甲基）氨基）甲基] -4-甲基-6-甲酰基苯酚（HL1）以及溶液研究也有所报道。此外，我们证明了这些CuII复合物能够在温和的pH和温度条件下以微摩尔浓度从牛血清白蛋白（BSA）和热稳定酶Taq DNA聚合酶裂解未活化的肽键。裂解活性似乎是特异性的，在蛋白质处理后出现了确定的蛋白水解片段。特定切割位点的位置被暂时分配给蛋白质的溶剂可及部分。
• Multivariate analysis applied to oxidation of cyclohexane and benzyl alcohol promoted by mononuclear iron and copper complexes
  作者：Andrei F. Vailati、Ricardo D. Huelsmann、Edmar Martendal、Adailton J. Bortoluzzi、Fernando R. Xavier、Rosely A. Peralta

  DOI：10.1039/c9nj05534g

  日期：——

  examine the catalytic activity of an iron(III) (1) and a copper(II) (2) complex under mild conditions in the oxidation of cyclohexane (Cy) and benzyl alcohol (BnOH) with hydrogen peroxide, following a Box–Behnken multivariate experimental design. To the best of our knowledge, this is the first report of the application of this tool to the homogeneous oxidation of these organic substrates. The multivariate

  尽管单变量方法有助于结果的解释，但它们可能不符合催化过程的理想条件。在此，我们研究了铁（Ⅲ）（1）和铜（Ⅱ）（2）配合物在温和条件下用过氧化氢氧化环己烷（Cy）和苯甲醇（BnOH）后的催化活性。–Behnken多元实验设计。据我们所知，这是该工具在这些有机基质的均匀氧化中应用的第一份报告。多元方法允许为研究的变量确定一系列最佳条件。综合大楼1与2相比，它能够将更多数量的被研究底物转化为产品。然而，2呈现朝向（CyOH）比代环己醇和苯甲醛（BA）具有更高的选择性1，虽然转化率较低。
• Novel Cu^II–M^II–Cu^II(M = Cu or Ni) trinuclear and [NaI2CuII6] hexanuclear complexes assembled by bi-compartmental ligands: syntheses, structures, magnetic and catalytic studies
  作者：Surajit Biswas、Arpan Dutta、Malay Dolai、Indrani Bhowmick、Mathieu Rouzières、Rodolphe Clérac、Anangamohan Panja、Mahammad Ali

  DOI：10.1039/c4dt03728f

  日期：——

  Complexes5–7synthesized from twoin situgenerated ligands, HL¹and HL²exhibited excellent TON for epoxidation of olefins.

  从两个in situ生成的配体HL¹和HL²合成的复合物5–7对烯烃环氧化表现出优异的TON。
• Synthesis, characterization and structure of a new dinickel(II) complex as model for urease
  作者：Alessandra Greatti、Marcos Aires de Brito、Adailton João Bortoluzzi、Augusto Susin Ceccato

  DOI：10.1016/j.molstruc.2003.10.008

  日期：2004.1

  Abstract A new dinuclear nickel(II) complex [Ni 2 (L)(OAc) 2 (H 2 O)]·ClO 4 ·H 2 O 1 with the unsymmetrical N 5 O donor ligand 2-[bis(2-pyridylmethyl)amino]methyl}-4-methyl-6-[2-pyridylmethyl)amino]methyl}phenol (HL) has been synthesized and characterized by conductivity, UV–Vis–NIR and IR spectroscopy, electrochemical methods and X-ray crystallography. Complex 1 crystallizes as blue crystals in

  摘要 一种新的双核镍 (II) 配合物 [Ni 2 (L)(OAc) 2 (H 2 O)]·ClO 4 ·H 2 O 1 与不对称 N 5 O 供体配体 2-[bis(2-pyridylmethyl )amino]methyl}-4-methyl-6-[2-pyridylmethyl)amino]methyl}phenol (HL) 已被合成并通过电导率、UV-Vis-NIR 和 IR 光谱、电化学方法和 X 射线晶体学表征. 配合物1在单斜晶系中结晶为蓝色晶体，空间群I 2/ a a =21.171(4) A, b =12.147(2) A, c =29.771(6) A, β =99.67(3)°, V =7547(2) A 3 和 Z =8。在该复合物中，两种镍离子都具有扭曲的八面体几何形状。镍中心由去质子化配体的酚氧原子内源性桥接，也由作为外源性桥接的两个乙酸酯基团桥接。作为末端配体的水分子与
• Metal-templated ligand architectures for trinuclear chemistry: tricopper complexes and their O₂reactivity
  作者：Davide Lionetti、Michael W. Day、Theodor Agapie

  DOI：10.1039/c2sc21758a

  日期：——

  substrates. The dioxo-tricopper species deprotonates weak acids, undergoes oxygen atom transfer with one equivalent of triphenylphosphine to yield triphenylphosphine oxide, and abstracts two hydrogen atom equivalents from tetramethylpiperidine-N-hydroxide (TEMPO-H). Thiophenols reduce the oxygenated species to a CuI 3 complex and liberate two equivalents of disulfide, consistent with a four-electron four-proton

  通过围绕钇和镧系元素的七齿配体的模板化，形成了三核构架。生成的复合物使三组两个或三个N供体相互结合，以结合其他金属中心。添加三当量的铜（I）会导致形成三铜（I）物种。在低温下与双氧反应生成其光谱特征与mu3，mu3-dioxo-tricopper配合物一致的物质。对各种底物进行了反应性研究。二氧三环物种将弱酸去质子，与一当量的三苯基膦进行氧原子转移，生成三苯膦氧化物，并从四甲基哌啶-N-氢氧化物（TEMPO-H）中提取出两个氢原子当量。