N-(4-甲氧基苯基)-1-(6-甲基吡啶-2-基)甲亚胺 | 26825-36-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: N-(4-甲氧基苯基)-1-(6-甲基吡啶-2-基)甲亚胺
• 英文名称: 2-(C(H)=N-p-anisyl)-6-(Me)C5H3N
• 英文别名: 6-MeC5H4N-2-CH=N-C6H4OMe-p；4-methoxy-N-(6-methyl-pyridin-2-ylmethylene)-aniline；(6-Me)C5H3N-2-CH=NC6H4OMe-4；(E)-N-(4-Methoxyphenyl)-1-(6-methylpyridin-2-yl)methanimine；N-(4-methoxyphenyl)-1-(6-methylpyridin-2-yl)methanimine
• CAS: 26825-36-5
• 化学式: C₁₄H₁₄N₂O
• 分子量: 226.278
• InChiKey: AIKFIELGUAAMPE-UHFFFAOYSA-N

物化性质

• 沸点：
  387.9±37.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  N-(4-甲氧基苯基)-1-(6-甲基吡啶-2-基)甲亚胺 、 [Pd₂(μ-Cl)₂Me₂(SMe₂)₂] 以 乙醚 为溶剂， 以80-90的产率得到PdClMe(6-MeC5H3N-2-CH=NC6H4OMe-p)
  参考文献：
  名称：

  钯（II）五配位烯烃配合物的合成与表征。（2,9-二甲基-1,10-菲咯啉）（马来酸酐）甲基氯钯的丙酮溶剂化物的分子结构

  摘要：

  DOI：

  10.1021/om00118a058
• 作为产物：
  描述：

  6-甲基-2-吡啶甲醛 、 甲氧苯胺 反应 6.0h， 以100%的产率得到N-(4-甲氧基苯基)-1-(6-甲基吡啶-2-基)甲亚胺
  参考文献：
  名称：

  结构动态库和网络从动力学分布到热力学分布的瞬态切换

  摘要：

  组成动态库 (CDL) 的成分分布可能会随时间发生变化，作为从其成分生成 CDL 的过程动力学的函数。因此，代表成分之间联系的构成动态网络 (CDN) 作为时间的函数从动力学分布变为热力学分布。我们研究了四种成分的动态共价库 (DCL) 的行为，这些成分由四种成分（2 种醛和 2 种氨基化合物）在金属阳离子不存在和存在下可逆形成 C=N 键产生。相关的 [2 × 2] 网络经历了从初始动力学分布到最终热力学分布的时间相关变化，涉及从正方形 [2 × 2] 网络的一条对角线到另一条对角线的正交切换，导致分布发生非常大的变化。基于组分的反应性和组分的热力学稳定性，DCL 组分可以从动力学产物（亚胺）转换为热力学产物（肟或酰基腙），而无需添加任何外部效应剂，仅基于其固有性质独立的系统。对于纯有机 DCL/CDN 以及包含两种金属阳离子的无机 DCL/CDN 都实现了这样的过程，后者从亚胺的银 (I)

  DOI：

  10.1021/jacs.9b09395

文献信息

• Metal Cation‐Driven Dynamic Covalent Formation of Imine and Hydrazone Ligands Displaying Synergistic Co‐catalysis and Auxiliary Amine Effects
  作者：Meixia He、Jean‐Marie Lehn

  DOI：10.1002/chem.202100662

  日期：2021.5.12

  Optimizing C=N bond formation and C/N component exchange has major significance in Dynamic Covalent Chemistry (DCC). Imine and hydrazone generation from their aldehyde, amine and hydrazine components showed large accelerations in presence of AgOTf or Zn(OTf)2, up to 104 for the Zn(II)‐(p‐anisidine)imine complex. Zn(OTf)2 and auxiliary p‐anisidine together accelerated 630 times the formation of the Zn(II)‐hydrazone

  在动态共价化学（DCC）中，优化C = N键形成和C / N组分交换具有重要意义。在存在AgOTf或Zn（OTf）2的情况下，由它们的醛，胺和肼成分生成的亚胺和显示出较大的加速作用，对于Zn（II）-（对茴香胺）亚胺络合物，其加速高达10 4。Zn（OTf）2和辅助p茴香胺共同促进了Zn（II）-hydr配合物形成的630倍，显示出强大的协同效应，可追溯到非常快的反应性Zn（II）-亚胺配合物的初始形成，呈现出C = N键被金属活化与肼组分反应。由于复杂性较高的混合物之间的动态竞争，涉及更多实体的反应显示出动力学上更快，热力学上更简单的输出。金属盐和辅助胺的催化量给出了相似的明显的速率加速和周转率，表明是真正的催化作用。通过将金属催化和有机催化结合起来所产生的协同效应表明，通过相互连接的化学转化，DCC中强大的共形成键的共催化策略。
• Cucciolito, Maria Elena; De Felice, Vincenzo; Panunzi, Achille, Organometallics, 1989, vol. 8, # 5, p. 1180 - 1187
  作者：Cucciolito, Maria Elena、De Felice, Vincenzo、Panunzi, Achille、Vitagliano, Aldo

  DOI：——

  日期：——
• Kinetics and mechanism of regioselective amination of the 1-phenylallyl group in cationic palladium(II) complexes bearing bidentate ligands
  作者：Bruno Crociani、Simonetta Antonaroli、Luciano Canovese、Fabiano Visentin、Paolo Uguagliati

  DOI：10.1016/s0020-1693(01)00333-4

  日期：2001.4

  The complexes [Pd(eta (3)-1-PhC3H4)(L-L')(=) [L-L' = 2-(PPh2)C6H4-1-CH=N (R = Me (1a), i-Pr (1b), t-Bu (1c), (R)-bornyl (1d), C6H4OMe-4 (1e), C6H3Me2-2,6 (1f), C6H3(i-Pr)(2)-2,6 (1g)), 6-MeC5H3N-2-CH=NC6H4OMe-4 (2a), C5H4N-2-CH=N-t-Bu (2b) and C5H4N-2-CH2S-t-Bu (3a)] are generally present in solution as two geometrical isomers, the relative abundance of which depends essentially on the steric requirements of the L-L' ligand. In the presence of fumaronitrile the cationic complexes undergo a regioselective amination by secondary amines HY at the CH, allyl terminus, yielding [Pd(eta (2)-fn)(L-L')] and the allylamines (E)-PhCH=CHCH2Y. Under pseudo-first-order conditions the amination rates (k(obs)) are found to depend on the k(2)[HY] term for 2a and 3a, and on the sum k(2)[HY] + k(3)[HY](2) for the other complexes. The second-order term k(2) is related to direct nucleophilic attack on the CH, allyl terminus of the substrate whereas the third-order term k(3) is ascribed to parallel attack by a further HY molecule on the intermediate [Pd(1-PhC3H4)(L-L')(HY)](+). The k(2) values depend on the steric and electronic properties of both the amine HY and the ligand L-L'. For complexes 1a-1g, the relatively higher k(2) values and their increase with increasing steric crowding at the nitrogen-bonded carbon of substituent R are interpreted in terms of a greater reactivity of the isomer with the CH2 allyl terminus trans to phosphorus and cis to the NR group. The high amination rate of 2a, as compared with that of 2b, is related to substantial steric interaction of the CH2 allyl terminus with the 6-Me pyridine group in close proximity in the predominant isomer. (C) 2001 Elsevier Science B.V. All rights reserved.
• Di Bianca, Francesca; Bandoli, Giuliano; Dolmella, Alessandro, Journal of the Chemical Society. Dalton Transactions (2001), 2002, # 2, p. 212 - 217
  作者：Di Bianca, Francesca、Bandoli, Giuliano、Dolmella, Alessandro、Antonaroli, Simonetta、Crooiani, Bruno

  DOI：——

  日期：——
• Reactions of [RhCl(diene)]₂ with Bi- and Terdentate Nitrogen Ligands. X-ray Structures of Five-Coordinate Complexes
  作者：Hendrikus F. Haarman、Frank R. Bregman、Jan-Meine Ernsting、Nora Veldman、Anthony L. Spek、Kees Vrieze

  DOI：10.1021/om960760b

  日期：1997.1.1

  Reaction of [RhCl(diene)](2) (diene = 1,5-cyclooctadiene (COD) or bicyclo[2.2.1] hepta-2,5-diene (NBD)) with the N-N-N nitrogen ligands 2,6-(C(R(1))=N-R(2))(2)C5H3N in CD(2)CL(2) or CH2Cl2 yielded the five-coordinate complexes [RhCl(2,6-(C(H)=N-R(2))(2)C5H3N)(diene)] (diene = NBD; R(2) = i-Pr, t-Bu, and p-anisyl), which has been isolated for NBD but not for COD. A single-crystal X-ray determination showed that [RhCl(2,6-(C(H)=N-p-anisyl)(2)C5H3N)(NBD)] has a distorted trigonal bipyramidal configuration with the pyridyl N-atom, one imine N-atom, and one alkene double bond in the equatorial plane, while the second alkene bond and the chloride atom occupy the axial positions. This conformation containing one noncoordinated imine moiety is clearly retained at 183 K in CD2Cl2, as is also the case for the other complexes. For the COD complexes, the reaction is more complicated, as the intermediates that are observed depend on the substituents R(1) and R(2) of the N-N-N nitrogen ligand. The five-coordinate complexes [RhCl(2,6-(C(R(1))=N-R(2))(2)C5H3N)(COD)] could be observed at low temperatures for R(1) = H and R(2) = i-Pr, t-Bu, and p-anisyl, while for R(1) = Me and R(2) = p-anisyl, this intermediate could not be observed; instead, [Rh(2,6-(C(Me)=N-p-anisyl)(2)C5H3N)(2)]Cl-+(-) was found, which shows the presence of one N-N-N Ligand bonded as a bidentate ligand and one N-N-N Ligand bonded as a terdentate ligand at low temperatures. Further reaction of [Rh(2,6-(C(Me)=N-p-anisyl)(2)C5H3N)(2)]Cl-+(-) with [RhCl(COD)](2) afforded [RhCl(2,6-(C(Me)=N-p-anisyl)(2)C5H3N)] and subsequently, via oxidative addition of CD2Cl2, the complex [RhCl2(CD2Cl)(2,6-(C(Me)=N-p-anisyl)(2)C5H3N)]. The dynamic properties of the five-coordinate diene complexes [RhCl(2-(C(H)=N-R(2))-6-(Me)C5H3N)(NBD)] (R(2) = i-Pr, t-Bu, and p-anisyl), which contain N-N nitrogen Ligands, and of the new complexes [Rh(2-(C(H)=N-R(2))-6-(Me)C5H3N)(NBD)]OTf (R(2) i-Pr, t-Bu, and p-anisyl) and of [Rh(2,2'-bipyrimidine)(NBD)]OTf have been investigated. A single-crystal X-ray determination of [RhCl(2-(C(H)=N-i-Pr)-6-(Me)C5H3N)(NBD)] showed structural features which are analogous to those of RhCl(2,6-(C(H)=N-p-anisyl)(2)C5H3N)(NBD)].