2-methoxy-N-((pyridin-2-yl)methylene)ethanamine | 150975-29-4

• 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: 2-methoxy-N-((pyridin-2-yl)methylene)ethanamine
• 英文别名: N-(2-methoxyethyl)-1-pyridin-2-ylmethanimine
• CAS: 150975-29-4
• 化学式: C₉H₁₂N₂O
• 分子量: 164.207
• InChiKey: WFVNIXUILDXHTB-UHFFFAOYSA-N

物化性质

• 沸点：
  261.4±20.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  34.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-methoxy-N-((pyridin-2-yl)methylene)ethanamine 在 sodium tetrahydroborate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 48.0h， 生成 ethyl 4-hydroxy-3,5-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)benzoate
  参考文献：
  名称：

  Cadmium(II) Complexes: Mimics of Organophosphate Pesticide Degrading Enzymes and Metallo-β-lactamases

  摘要：

  Cadmium(II) complexes of ethyl 4-hydroxy-3,5-bis(((2-hydroxyethyl)(pyridin-2-ylmethyl)amino)methyl)-benzoate (CO(2)EtH(3)L1) and ethyl 4-hydroxy-3,5-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)benzoate (CO(2)EtHL2) are described. The two ligands possess an ethyl ester (CO2Et-) at the position para to the phenolic -OH; CO(2)EtHL2, with methyl ether donors in contrast to potentially nucleophilic alkoxide donors in CO(2)EtH(3)L1, offers a direct comparison of potential ligand-centered nucleophiles. The complex with CO(2)EtH(3)L1 was characterized using H-1 and C-13 NMR spectroscopy, mass spectrometry and microanalysis; X-ray crystallography defined a tetranuclear structure [Cd-4(CO(2)EtH(2)L1)(2)(CH3COO)(3.75)Cl-0.25(H2O)(2)](PF6)(2). Functional studies of the cadmium(II) complexes were undertaken with the substrates bis(2,4-dinitrophenyl)phosphate (BDNPP), and nitrocelin to assess their phosphatase and beta-lactamase activities, respectively. The complexes with CO(2)EtH(3)L1 and CO(2)EtHL2 are competent phosphoesterase mimics with K-M = 9.4 +/- 2.1 mM and 10.1 +/- 3.4 mM, k(cat) = 9.4 +/- 0.2 x 10(-3) s(-1) and 9.7 +/- 2.7 x 10(-3) s(-1), respectively. Use of a solvent mixture containing (H2O)-O-18/(H2O)-O-16 in the reaction with BDNPP showed that for the complex with CO(2)EtH(3)L1 the O-18 label was incorporated in the reaction product suggesting that the nucleophile involved is a Cd-OH moiety and not a metal bound alkoxide; for CO(2)EtHL2 the presence of the methyl-ether dictates that the active nucleophile must also be a hydroxide. The cadmium(II) complex with CO(2)EtH(3)L1 was furthermore found to be a competent beta-lactamase mimic with k(cat) = 1.39 x 10(-2) +/- 3 x 10(-3) s(-1), K-M = 0.11 +/- 0.03 mM, and pK(a) = 7.9 +/- 0.1. Mass spectral evidence suggested that the active nucleophile in this reaction is the alkoxide; lack of beta-lactamase activity of the complex with CO(2)EtHL2 supports this assignment. Similar to enzyme-catalyzed reactions, a blue reaction intermediate in the beta-lactamase reaction of the CO(2)EtH(3)L1 complex was also identified. It is proposed that the Cd(II) complexes of CO(2)EtH(3)L1 and CO(2)EtHL2 react identically as phosphatases, with a terminal hydroxide as the nucleophile; the former exhibits beta-lactamase activity with the alkoxide as a nucleophile, while the latter, without a potentially nucleophilic alkoxide, is inactive.

  DOI：

  10.1021/ic300687y
• 作为产物：
  描述：

  吡啶-2-甲醛 、 2-甲氧基乙胺 在 magnesium sulfate 作用下， 以 乙醚 为溶剂， 生成 2-methoxy-N-((pyridin-2-yl)methylene)ethanamine
  参考文献：
  名称：

  带有吡啶基亚胺配体的阳离子钯 (II)-乙酰丙酮络合物作为苯乙炔加氢胺化和降冰片烯聚合的催化剂

  摘要：

  通过2-C 5 型双齿配体L 在 [Pd(acac)(MeCN) 2 ]BF 4中进行腈置换，合成了带有吡啶基亚胺配体 [Pd(acac)(L) ]BF 4的乙酰丙酮钯 ( II)配合物H 4 N–CH=N–(CH 2 ) n OMe 或 2-C 5 H 4 N–CH=N–Ar。通过X射线衍射、核磁共振和密度泛函理论分析了配合物的结构。该络合物催化苯乙炔与苯胺的加氢胺化反应生成马尔可夫尼科夫亚胺产物以及降冰片烯的聚合反应。

  DOI：

  10.1016/j.mencom.2023.02.011

文献信息

• Re(I) carbonyl complexes containing pyridyl-imine and amine ligands: Synthesis, characterization and their catalytic olefin epoxidation activities
  作者：Xiaolu Song、Min Hwee Lim、Dara Khairunnisa Binte Mohamed、See Mun Wong、Jin Zhao、T.S. Andy Hor

  DOI：10.1016/j.jorganchem.2016.04.010

  日期：2016.7

  Re(I) carbonyl complexes containing pyridyl-imine or amine ligands have been synthesized and crystallographically characterized. Their catalytic activity for the cis-cyclooctene epoxidation with tert-butyl hydroperoxide (TBHP) as oxidant and the oxidation of these Re(I) complexes by TBHP have been investigated.

  含有吡啶基-亚胺或胺配体的Re（I）羰基配合物已经合成并通过晶体学表征。研究了它们对叔丁基过氧化氢（TBHP）作为氧化剂对顺式环辛烯环氧化的催化活性以及TBHP对这些Re（I）配合物的氧化作用。
• Syntheses and Structures of Closely Related Copper(I) Complexes of Tridentate (2-Pyridylmethyl)imine and (2-Pyridylmethyl)amine Ligands and Their Use in Mediating Atom Transfer Radical Polymerizations
  作者：Sara A. Turner、Zachary D. Remillard、Desire T. Gijima、Emily Gao、Robert D. Pike、Christopher Goh

  DOI：10.1021/ic3011585

  日期：2012.10.15

  A series of five copper(I) bromide complexes of tridentate (N,N,L) pyridine–imine and pyridine–amine ligands with a third amine, ether, or thioether neutral donor was synthesized and utilized in the atom transfer radical polymerization of styrene. The ligand design illustrated a systematic approach to the development of copper complexes for use in ATRP. Variations in the nature of the ligand impacted

  合成了三齿（N，N，L）吡啶-亚胺和吡啶-胺配体与第三种胺，醚或硫醚中性供体的一系列五个溴化铜（I）配合物，并将其用于苯乙烯的原子转移自由基聚合中。配体设计说明了开发用于ATRP的铜络合物的系统方法。配体性质的变化影响了复合物的固态结构。对于L =吡啶-胺-胺，观察到单核[CuBr（L）]络合物，而L =吡啶-亚胺-胺和-硫醚的络合物形成双核[CuBr（L）] 2具有中央10元环的结构。L =吡啶-亚胺-醚的[CuBr（L）]配合物和[CuBr（L）]的聚合物种类揭示了双溴桥联的二聚体，其中L =吡啶-亚胺-胺和亚胺胺间隔基从两个碳原子延伸到三个碳原子。在将这些配合物应用于苯乙烯的ATRP中，发现该配合物的氧化还原电势是ATRP效率的指标之一。在所提出的系列中，特别是两种配合物提供了快速的聚合速率，并且对分子量的控制非常好。在这两种络合物中，配体均包含所有基于氮的供体部分。
• The role of Zn–OR and Zn–OH nucleophiles and the influence of para-substituents in the reactions of binuclear phosphatase mimetics
  作者：Lena J. Daumann、Kristian E. Dalle、Gerhard Schenk、Ross P. McGeary、Paul V. Bernhardt、David L. Ollis、Lawrence R. Gahan

  DOI：10.1039/c1dt11187f

  日期：——

  Analogues of the ligand 2,2′-(2-hydroxy-5-methyl-1,3-phenylene)bis(methylene)bis((pyridin-2-ylmethyl)azanediyl)diethanol (CH3H3L1) are described. Complexation of these analogues, 2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)-4-methylphenol (CH3HL2), 4-bromo-2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)phenol (BrHL2), 2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)-4-nitrophenol (NO2HL2) and 4-methyl-2,6-bis(((2-phenoxyethyl)(pyridin-2-ylmethyl)amino)methyl)phenol (CH3HL3) with zinc(II) acetate afforded [Zn2(CH3L2)(CH3COO)2](PF6), [Zn2(NO2L2)(CH3COO)2](PF6), [Zn2(BrL2)(CH3COO)2](PF6) and [Zn2(CH3L3)(CH3COO)2](PF6), in addition to [Zn4(CH3L2)2(NO2C6H5OPO3)2(H2O)2](PF6)2 and [Zn4(BrL2)2(PO3F)2(H2O)2](PF6)2. The complexes were characterized using 1H and 13C NMR spectroscopy, mass spectrometry, microanalysis, and X-ray crystallography. The complexes contain either a coordinated methyl- (L2 ligands) or phenyl- (L3 ligand) ether, replacing the potentially nucleophilic coordinated alcohol in the previously reported complex [Zn2(CH3HL1)(CH3COO)(H2O)](PF6). Functional studies of the zinc complexes with the substrate bis(2,4-dinitrophenyl) phosphate (BDNPP) showed them to be competent catalysts with, for example, [Zn2(CH3L2)]+, kcat = 5.70 ± 0.04 × 10−3 s−1 (Km = 20.8 ± 5.0 mM) and [Zn2(CH3L3)]+, kcat = 3.60 ± 0.04 × 10−3 s−1 (Km = 18.9 ± 3.5 mM). Catalytically relevant pKas of 6.7 and 7.7 were observed for the zinc(II) complexes of CH3L2− and CH3L3−, respectively. Electron donating para-substituents enhance the rate of hydrolysis of BDNPP such that kcatp-CH3 > p-Br > p-NO2. Use of a solvent mixture containing H2O18/H2O16 in the reaction with BDNPP showed that for [Zn2(CH3L2)(CH3COO)2](PF6) and [Zn2(NO2L2)(CH3COO)2](PF6), as well as [Zn2(CH3HL1)(CH3COO)(H2O)](PF6), the 18O label was incorporated in the product of the hydrolysis suggesting that the nucleophile involved in the hydrolysis reaction was a Zn–OH moiety. The results are discussed with respect to the potential nucleophilic species (coordinated deprotonated alcohol versus coordinated hydroxide).

  描述了配体2,2-(2-羟基-5-甲基-1,3-亚苯基)双(亚甲基)双((吡啶-2-基甲基)氮烷二基)二乙醇( H3L1)的类似物。这些类似物的络合，2,6-双(((2-甲氧基乙基)(吡啶-2-基甲基)氨基)甲基)-4-甲基苯酚( HL2)，4-溴-2,6-双(((2-甲氧基乙基)(吡啶-2-基甲基)氨基)甲基)苯酚(BrHL2)、2,6-双(((2-甲氧基乙基)(吡啶-2-基甲基)氨基)甲基)-4-硝基苯酚( HL2)和4 -甲基-2,6-双(((2-苯氧基乙基)(吡啶-2-基甲基)氨基)甲基)苯酚( HL3)与乙酸锌(II)得到[Zn2(CH3L2)( COO)2](PF6) 、[Zn2(NO2L2)( COO)2](PF6)、[Zn2(BrL2)( COO)2](PF6) 和 [Zn2( L3)( COO)2](PF6)，以及 [Zn4( L2) )2( C6H5OPO3)2(H2O)2](PF6)2 和 [Zn4(BrL2)2(PO3F)2( )2](PF6)2。使用 1H 和 13C NMR 光谱、质谱、微量分析和 X 射线晶体学对配合物进行了表征。该配合物含有配位的甲基-（L2配体）或苯基-（L3配体）醚，取代了先前报道的配合物[Zn2( HL1)( COO)( )](PF6)中潜在的亲核配位醇。锌配合物与底物双(2,4-二硝基苯基)磷酸酯 (BDNPP) 的功能研究表明它们是有效的催化剂，例如 [Zn2( L2)]+, kcat = 5.70 ± 0.04 × 10â 3 s–1 (Km = 20.8 ± 5.0 mM) 和 [Zn2( L3)]+, kcat = 3.60 ± 0.04 × 10–3 s–1 (Km = 18.9 ± 3.5 mM)。 L2- 和 L3- 的锌 (II) 配合物的催化相关 pKa 分别为 6.7 和 7.7。给电子对位取代基提高了 BDNPP 的水解速率，使得 kcatp- > p-Br > p- 。在与 BDNPP 的反应中使用含有 18/ 16 的溶剂混合物表明，对于 [Zn2( L2)( COO)2](PF6) 和 [Zn2( L2)( COO)2](PF6)，以及 [Zn2 ( HL1)( COO)( )](PF6)，18O标记被掺入水解产物中，表明参与水解反应的亲核试剂是Zn-OH部分。就潜在的亲核物质（配位去质子醇与配位氢氧化物）讨论了结果。
• Palladium(II) complexes of (pyridyl)imine ligands as catalysts for the methoxycarbonylation of olefins
  作者：Zethu Zulu、George S. Nyamato、Thandeka A. Tshabalala、Stephen O. Ojwach

  DOI：10.1016/j.ica.2019.119270

  日期：2020.2

  Reactions of 2-methoxy-N-((pyridin-2-yl)methylene)ethanamine (L1), 2-((pyridin-2-yl)methyleneamino)ethanol (L2) and 3-methoxy-N-((pyridin-2-yl)methylene)propan-1-amine (L3) ligands with either [PdCl2(COD)] or [PdCl(Me)(COD)] produced the corresponding monometallic complexes [PdCl2(L1)] (1), [PdClMe(L1)] (2), [PdCl2(L2)] (3) and [PdCl2(L3)] (4). The solid state structure of complex 1 confirmed the bidentate coordination mode of L1, giving a distorted square planar geometry. All the complexes (1-4) formed active catalysts for the methoxycarbonylation of higher olefins to give linear and branched esters. The catalytic behavior of complexes 1-4 were influenced by both the complex structure and olefin chain length.
• Synthesis, characterization and polymerisation studies of cadmium(II) complexes containing N,N′,X-tridentate X-substituted (X = N, O) 2-iminomethylpyridines
  作者：Jaegyeong Lee、Hyosun Lee、Saira Nayab、Keun Byoung Yoon

  DOI：10.1016/j.poly.2018.11.033

  日期：2019.1

  The reaction of [CdBr(2)4H(2)O] with N-1,N-1-dimethyl-N-2-(pyridin-2-ylmethylene)ethane-1,2-diamine) (L-A), 2-methoxy-N-(pyridin-2-ylmethylene)ethanamine (L-B), 2-(piperidin-1-yl)-N-(pyridin-2-ylmethylene)ethanamine (L-C), 2-morpholino-N-(pyridin-2-ylmethylene)ethanamine (L-D), N-1,N-1-dimethyl-N-3-(pyridin-2-ylmethylene)propane-1,3-diamine (L-E) and 3-methoxy-N-(pyridin-2-ylmethylene)propan-1-amine (L-F) in methanol produced the tridentate [(NN'X)CdBr2] complexes, namely [LACdBr2], [LBCdBr2], [LCCdBr2], [LDCdBr2], [LECdBr2] and [LFCdBr2], respectively. The molecular structures of the Cd(II) complexes revealed that the cadmium atom in [LnCdBr2] (L-n=L-A, L-C-L-E) has a distorted square pyramidal geometry involving two nitrogen atoms and one nitrogen or oxygen atom of the N,N',X-tridentate ligands and two bromo ligands. The dimethyl derivatives, generated in situ, [LnCdMe2] (L-A-L-F) initiated the polymerisation of rac-Lactide (rac-LA) and yielded heterotactic PLA. Notably, the substituent attached to ligand architecture affects the activities towards the rac-LA polymerisation, whereas the stereoselectivities remained unchanged. Moderate activities towards the polymerisation of methylmethacrylate (MMA) polymerisation in the presence of modified methylaluminoxane (MMAO) at 60C were observed for [LnCdBr2] (L-A-L-F). The preliminary results showed that these complexes yielded syndio-rich poly(methylmethacrylate) (PMMA) ([rr]=0.66). (C) 2018 Elsevier Ltd. All rights reserved.