3-methoxy-N-((pyridin-2-yl)methylene)propan-1-amine | 1603164-14-2

• 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: 3-methoxy-N-((pyridin-2-yl)methylene)propan-1-amine
• 英文别名: N-(3-methoxypropyl)-1-pyridin-2-ylmethanimine
• CAS: 1603164-14-2
• 化学式: C₁₀H₁₄N₂O
• 分子量: 178.234
• InChiKey: BTRXCYUSIHJWTC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  双(乙腈)氯化钯(II) 、 3-methoxy-N-((pyridin-2-yl)methylene)propan-1-amine 以 乙醇 为溶剂， 以84%的产率得到[PdCl2(L3)]
  参考文献：
  名称：

  N,N',X-双齿与 N,N',X-三齿 N-取代的 2-亚氨基甲基吡啶-和 2-亚氨基甲基喹啉-配位钯 (II) 配合物

  摘要：

  [Pd(CH3CN)2Cl2]与N-官能团取代的2-亚氨基甲基吡啶和2-亚氨基甲基喹啉反应生成N,N',X-二齿Pd(II)配合物和N,N',X-三齿Pd( II) 复合物取决于亚胺部分氮上的官能团取代。例如，N,N-二甲基-3-((吡啶-2-基亚甲基)氨基)丙-1-胺(L1)、N,N-二甲基-3-((喹啉-2-基亚甲基)氨基)丙- 1-胺（L2）和N-（3-（甲硫基）丙基）-1-（吡啶-2-基）甲胺（L3）在存在下以N，N'，X-三齿模式与钯配位NaClO4 分别以高产率生成两个稠环金属环 [(NN'X)PdCl]ClO4 配合物，即 [LnPdCl]ClO4 (Ln = L1, L2, L3)。然而，N-甲基-N-(3-((吡啶-2-基亚甲基)氨基)丙基)苯胺(L4)和N-(3-甲氧基丙基)-1-(吡啶-2-基)甲胺(L5)产率(以不存在 NaClO4) N,N',X-双齿金属环 [(NN')PdCl2]

  DOI：

  10.1080/00958972.2014.947971
• 作为产物：
  描述：

  吡啶-2-甲醛 、 3-甲氧基丙胺 在 sodium sulfate 作用下， 以 四氢呋喃 为溶剂， 反应 72.0h， 以99%的产率得到3-methoxy-N-((pyridin-2-yl)methylene)propan-1-amine
  参考文献：
  名称：

  用于末端炔烃的环境温度反马尔可夫尼科夫还原水合的高活性和空气稳定的钌配合物

  摘要：

  通过直接添加基于杂原子的亲核试剂将末端炔烃转化为功能化产物是催化的一个重要目标。我们报告了半夹心钌配合物 12 的设计、合成和机理研究，它是炔烃的反马尔科夫尼科夫还原水合的高活性催化剂。12 的关键设计元素涉及一个三齿氮基配体，其中包含一个半稳定的 3-（二甲氨基）丙基取代基。在中性条件下，二甲氨基取代基与钌中心协调，生成空气稳定的 18 电子 κ(3) 复合物。机理研究表明，二甲氨基取代基在反应介质中从钌中心部分解离（通过质子化），从而产生用于催化的空配位点。这些研究还表明，该取代基通过促进还原剂的活化来提高氢化活性。至少三个催化循环，包括甲酸的脱羧、炔烃的水合和中间体醛的氢化，在由 12 介导的反应中同时运行。 使用少至 2在环境温度下 mol % 为 12，并且配合物 12 在空气中稳定至少两周。本文概述的研究将 12 确立为迄今为止发现的用于反马尔科夫尼科夫还原水合的最活跃和最实用的催化剂，定义了

  DOI：

  10.1021/ja501738a

文献信息

• Cationic palladium(II)–acetylacetonate complexes bearing pyridinyl imine ligands as catalysts for the hydroamination of phenylacetylene and polymerization of norbornene
  作者：Dmitrii S. Suslov、Anastasia V. Suchkova、Mikhail V. Bykov、Zorikto D. Abramov、Marina V. Pakhomova、Timur S. Orlov、Igor A. Ushakov、Tatyana N. Borodina、Vladimir I. Smirnov

  DOI：10.1016/j.mencom.2023.02.011

  日期：2023.3

  Acetylacetonate palladium(II) complexes bearing pyridinyl imine ligands [Pd(acac)(L)]BF4 were synthesized via nitrile displacement in [Pd(acac)(MeCN)2]BF4 by the bidentate ligands L of type 2-C5H4N–CH=N–(CH2)nOMe or 2-C5H4N–CH=N–Ar. The structures of complexes were analyzed by X-ray diffractometry, NMR, and DFT. The complexes catalyze hydroamination of phenylacetylene with aniline to give the Markovnikov

  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。
• 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.
• Potential Hemilabile (Imino)pyridine Palladium(II) Complexes as Selective Ethylene Dimerization Catalysts: An Experimental and Theoretical Approach
  作者：George S. Nyamato、Stephen O. Ojwach、Matthew P. Akerman

  DOI：10.1021/acs.organomet.5b00860

  日期：2015.12.14

  The (imino)pyridine ligands bearing pendant arms 2-methoxy-N-(1-(pyridin-2-yl) ethylidene) ethanamine (L1), 2-methoxy-N-((pyridin-2-yl)methylene)ethanamine (L2), 3-methoxy-N-((pyridin-2-yl)methylene)propan-1-amine (L3), N,N-diethyl-N-((pyridin-2-yl)methylene)ethane-1,2-diamine (L4), and N-((6-bromopyridin-2-yl)methylene)-2-methoxyethanamine (L5) were synthesized by condensation of the appropriate aldehyde and the corresponding amines. Reactions of L1-L5 with [PdCl(Me)(cod)] afforded the corresponding palladium complexes [PdCl(Me)(L1)] (1), [PdCl(Me) (L2)] (2), [PdCl(Me) (L3)] (3), [PdCl(Me) (L4)] (4), and [PdCl(Me)(L5)] (5) in good yields. Treatment of the neutral complexes 1-5 with one molar equivalent of Na[BAr4] (Ar = 3,5-(CF3)(2)C6H3) led to in situ formation of the corresponding cationic compounds [Pd(Me) (L1)](+) (1a), [Pd(Me) (L2)](+) (2a), [Pd(Me) (L3)](+) (3a), [Pd(Me) (L4)](+) (4a), and [Pd(Me)(L5)](+) (5a). In the presence of ethylene, the catalyst systems 1-5/MAO and 1a-5a exhibited high catalytic activities in selective ethylene dimerization producing mainly butenes. H-1 NMR spectroscopy and DFT studies provided valuable insight into the role of ligand architecture on ethylene-binding energies, catalytic activities, and stabilities of the resultant catalysts.