2,6-bis[1-(4-methoxyphenyliminoethyl)]pyridine | 55157-92-1

• 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: 2,6-bis[1-(4-methoxyphenyliminoethyl)]pyridine
• 英文别名: N-(4-methoxyphenyl)-1-[6-[N-(4-methoxyphenyl)-C-methylcarbonimidoyl]pyridin-2-yl]ethanimine
• CAS: 55157-92-1
• 化学式: C₂₃H₂₃N₃O₂
• 分子量: 373.455
• InChiKey: PFJMGNCCLIVUFI-UHFFFAOYSA-N

物化性质

• 沸点：
  522.5±50.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  56.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,6-bis[1-(4-methoxyphenyliminoethyl)]pyridine 以 二氯甲烷-D2 为溶剂， 生成 [RhCl2(CD2Cl)(2,6-(C(Me)=N-p-anisyl)2C5H3N)]
  参考文献：
  名称：

  Reactions of [RhCl(diene)]₂ with Bi- and Terdentate Nitrogen Ligands. X-ray Structures of Five-Coordinate Complexes

  摘要：

  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)].

  DOI：

  10.1021/om960760b
• 作为产物：
  描述：

  2,6-二乙酰基吡啶 、 甲氧苯胺 在 magnesium sulfate 、 对甲苯磺酸 作用下， 以 neat (no solvent) 为溶剂， 反应 4.0h， 以94%的产率得到2,6-bis[1-(4-methoxyphenyliminoethyl)]pyridine
  参考文献：
  名称：

  合成乙酰基和双（亚氨基）吡啶配体和有机金属的机械化学途径†

  摘要：

  有机金属预催化剂在有机合成中起关键作用。然而，它们的制备通常依赖于多个时间，能量和溶剂密集的步骤，包括合成支持有机配体结构，并最终安装在所需的金属中心上。我们报告了可持续的机械化学合成的乙酰基和双-（亚氨基）吡啶钳配合物，有机金属预催化剂普遍存在的配体类。该方法扩展到乙酰（亚氨基）吡啶-CoCl 2的一锅法合成，其中配体在原位形成。

  DOI：

  10.1039/c8dt03608j

文献信息

• An Octahedral Template Based on a New Molecular Turn:  Synthesis and Structure of a Model Complex and a Reactive, Diphenolic Ligand and Its Metal Complexes
  作者：Andrew L. Vance、Nathaniel W. Alcock、Joseph A. Heppert、Daryle H. Busch

  DOI：10.1021/ic9714201

  日期：1998.12.1

  The design and synthesis of a new family of tridentate Schiff base ligands for use in octahedral molecular templates has been successfully demonstrated. As anticipated, two molecules of the ligand, 2,6-pyridinedicarboxaldhydebis(p-hydroxyphenylimine), coordinate equatorially to six-coordinate octahedral metal ions to give orthogonally oriented molecular turns around the anchoring metal ion. This new

  已经成功证明了用于八面体分子模板的新的三齿席夫碱配体家族的设计和合成。如预期的那样，配体的两个分子2,6-吡啶二芳基醛二（对羟基苯基亚胺）赤道配位至六配位八面体金属离子，从而围绕锚定金属离子产生正交取向的分子转向。这种新的模板具有以下优点：（1）配体及其配合物的合成简单明了，可通过简单的一锅法反应获得高收率，并且（2）易于实现结构变化。X射线结构分析表明，只有当配体的空间组织受金属离子的配位控制时，配体才会起转向作用。螯合后，酚基直接穿过金属离子中心，并且 与缺少反应性部分的这种一般类型的较早配体不同，取代反应可以在八面体络合物的游离酚基上进行。这些反应仍有待优化，以实现长期目标，证明其作为互锁分子的合成子具有价值。
• Oxidative Addition of Carbon−Chloride Bonds to Rhodium(I) Complexes Containing Terdentate Nitrogen Ligands. X-ray Analyses of Rhodium(I) Chloride and Rhodium(III) Chloromethyl Complexes
  作者：Hendrikus F. Haarman、Jan M. Ernsting、Mirko Kranenburg、Huub Kooijman、Nora Veldman、Anthony L. Spek、Piet W. N. M. van Leeuwen、Kees Vrieze

  DOI：10.1021/om9607614

  日期：1997.3.1

  which all contain two interconverting isomers; one five-coordinate Rh(III) isomer has a ligand which coordinates in a bidentate manner, while the other six-coordinate isomer has a ligand which coordinates in a terdentate fashion, as evidenced by low-temperature NMR measurements. Molecular modeling has shown that the formation of the five-coordinate Rh(III) species is caused by the axial ligands, which

  潜在的半不稳定的2,6-双（R 2-碳二亚氨基）吡啶和2,6-双（R 2-乙二亚氨基亚氨基）吡啶配体（2,6-（C（R 1）NR 2）2 C 5 H 3 N; R 1＝ H，R 2＝i- Pr（1），t- Bu（2），环己基（3），p-茴香基（4）； R 1＝ Me，R 2＝p-茴香基（5），i -Pr（6））已用于高产率制备新型且高度亲核的络合物[RhCl（2,6-（C（R 1）NR 2）2 C 5 H 3 N）]（R 1 = H，R 2 = i -Pr（7），t -Bu（8），环己基（9），对-茴香基（10）; R 1 = Me，R 2 =对-茴香基（11），i -Pr（12））[RhCl （烯烃）2 ] 2（烯烃＝乙烯，环辛烯）作为起始原料。的透视分析7，8，和12示出了R的严重的空间相互作用2组和所述赤道氯原子，导致外的平面弯曲的氯化物原子。所述N之间的角度Ñ Ñ平面和铑氯轴是5.34（16）°，7，11
• New Complexes of Chromium(III) Containing Organic π-Radical Ligands: An Experimental and Density Functional Theory Study
  作者：Mei Wang、Jason England、Thomas Weyhermüller、Swarna-Latha Kokatam、Christopher J. Pollock、Serena DeBeer、Jingmei Shen、Glenn P.A. Yap、Klaus H. Theopold、Karl Wieghardt

  DOI：10.1021/ic302743s

  日期：2013.4.15

  (iPrNH2) [CrIII(bpy•)(iPrNH2)2(CH3CO2)2]0 (S = 1) (2) was obtained. Both 1 and 2 contain a CrIII ion and a single (bpy•)1– ligand, so are not low-spin CrII species. One-electron oxidation of 1 and 2 yielded [CrIII(bpy0)2(CH3CO2)2]PF6 (S = 3/2) (3) in both cases. In addition, the new neutral species [CrIII(DAD•)3]0 (S = 0) (4) and [CrIII(CF3AP•)3]0 (S = 0) (5) have been synthesized. Both complexes contain three

  一系列铬配合物的电子结构1 - 7已经用X射线晶体学，磁和电化学的组合被实验研究，以及Cr K-边缘X射线吸收和UV-VIS光谱。二聚体的反应[CR II 2（μ-CH 3 CO 2）4 ] 0与2,2'-联吡啶（BPY 0）中产生的复合物[CR III（BPY 0）（BPY •）（CH 3 CO 2）2 ] 0（S = 1）（1），但在异丙胺（i PrNH 2）存在下[Cr III（bpy •）（i PrNH 2）2（CH 3 CO 2）2 ] 0（S = 1）（2）。既1和2含有铬III离子和单（BPY •）1-配体，所以是不低自旋铬II物种。1和2的单电子氧化产生[Cr III在两种情况下均为（bpy 0）2（CH 3 CO 2）2 ] PF 6（S = 3/2）（3）。此外，新的中性物种[Cr III（DAD •）3 ] 0（S = 0）（4）和[Cr III（CF 3 AP •）3
• Organometallic mediated radical polymerization of vinyl acetate using bis(imino)pyridine vanadium trichloride complexes
  作者：Mitchell R. Perry、Laura E. N. Allan、Andreas Decken、Michael P. Shaver

  DOI：10.1039/c3dt32625j

  日期：——

  trichloride complexes is described. The controlled radical polymerization activity towards vinyl acetate of these, and eight other bis(imino)pyridine vanadium trichloride complexes previously reported, is investigated. Those complexes possessing variation at the N-aryl para-position with no steric protection offered by ortho-substituents (4 examples) result in poor control over poly(vinyl acetate) polymerization

  描述了一种新型配体和六种新型三氯化钒（III）配合物的合成和表征。受控的自由基聚合活性醋酸乙烯酯在这些化合物中，还研究了先前报道的其他八种双（亚氨基）吡啶三氯化钒钒配合物。那些在N-芳基对位具有变化而没有由邻位取代基提供的空间保护的络合物（4个实施例）导致对聚（乙酸乙烯酯）聚合的控制较差。控制与在增加的空间体积改善邻的位上的Ñ-芳基取代基（4个例子），尽管试图增加空间体积超过异丙基是不成功的。当使用脂族取代基时，合成具有取代的亚胺主链的双（亚氨基）吡啶三氯化钒钒配合物可恢复聚合控制（4个实例），但不再对催化剂寿命产生任何大的改善。为了改善催化剂寿命，还研究了聚合条件的改变。单体范围扩大到包括其他乙烯基酯，特别是衍生自可再生资源的乙烯基酯，显示出令人鼓舞的结果。
• Ruthenium(II) complexes with 2,6-pyridyl-diimine ligands: synthesis, characterization and catalytic activity in epoxidation reactions
  作者：Bekir Çetinkaya、Engin Çetinkaya、Maurice Brookhart、Peter S. White

  DOI：10.1016/s1381-1169(98)00285-4

  日期：1999.6

  with the tridentate N-N′-N ligands, 2,6-pyridyl-diimines, led to substitution of p-cymene. The resulting complexes, believed to be coordinatively unsaturated, exhibit efficient activity for the epoxidation of cyclohexene in the presence of iodosobenzene (PhIO): the complexes formed initially take up donor molecules such as acetonitrile to achieve hexacoordination. The molecular structure for one of

  将[RuCl的反应2（p -cymene）] 2与三齿Ñ - ñ ' - ñ配体，2,6-二吡啶基二亚胺，导致了替代p -cymene。所得配合物据信是配位不饱和的，在碘代苯（PhIO）的存在下对环己烯的环氧化表现出有效的活性：最初形成的配合物吸收供体分子（如乙腈）以实现六配位。这些（乙腈）2，6-双[1-（4-甲氧基苯基亚氨基）乙基]吡啶}二氯钌（II）2的分子结构已经通过X射线衍射测定。即时协调范围是扭曲的八面体，具有反式氯原子和一个短的Ru–N（py）（1.906Å）键。