2,6-bis[1-(2-fluorophenylimino)ethyl]pyridine | 462661-73-0

• 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-(2-fluorophenylimino)ethyl]pyridine
• 英文别名: 2,6-diacetylpyridinebis(2-fluororoanil)；2,6-diacetylpyridinebis(2-fluoroanil)；N-(2-fluorophenyl)-1-[6-[N-(2-fluorophenyl)-C-methylcarbonimidoyl]pyridin-2-yl]ethanimine
• CAS: 462661-73-0
• 化学式: C₂₁H₁₇F₂N₃
• 分子量: 349.383
• InChiKey: FMCYCZVKFVHUFK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  37.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  iron(II) chloride tetrahydrate 、 2,6-bis[1-(2-fluorophenylimino)ethyl]pyridine 以 四氢呋喃 为溶剂， 生成 [Fe(2,6-(2-FC6H4N=CCH3)2C5H3N)2](2+)[FeCl4](2-)*H2O
  参考文献：
  名称：

  Ethylene oligomerization catalyzed by a novel iron complex containing fluoro and methyl substituents

  摘要：

  A novel 2,6-bis(imino)pyridyl iron complex, [2,6-(2-F-4-CH3C6H3N=CCH3)(2)C5H3N]FeCl2.H2O (3) has been synthesized by the reaction of the corresponding bis(imino)pyridyl ligand with FeCl2.4H(2)O in tetrahydrofuran (THF). The activity of complex 3 reaches to 10(7) g/mol Fe h in ethylene oligomerization, and the products are mostly (>90%) 1-butene, 1-hexene and 1-octene. As reaction temperature increases, the activities decrease rapidly and the product distributions shift to the low-molecular-weight part. The product distributions are almost unchanged when the Al/Fe molar ratio increases from 420 to 2500, but the catalytic activities increase rapidly at first and then decrease. Other three complexes (2,6-(2-X-4-Y-6-ZC(6)H(3)N=CCH3)(2)C5H3N}FeCl2.nH(2)O (X = CH3, Y = CH3, Z = H, n = 0 (1), X = F, Y = H, Z = F, it = 1 (2)) and {Fe[2,6-(2-FC6H3N=CCH3)(2)C5H3N}(2)](2), [FeCl4](2)(-).H2O (4) have been also synthesized for comparison and used for ethylene oligomerization. The ortho and para substituents on aniline have performed effects on oligomerization activities and distributions of oligomers for 2,6-bis(imino)pyridyl iron complexes. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2004.05.014
• 作为产物：
  描述：

  2,6-二乙酰基吡啶 、 2-氟苯胺 在 MAO/SiO₂ 作用下， 以 甲苯 为溶剂， 反应 72.0h， 以61%的产率得到2,6-bis[1-(2-fluorophenylimino)ethyl]pyridine
  参考文献：
  名称：

  含降电子基双（亚氨基）吡啶配体的镍配合物上降冰片烯的乙烯基聚合

  摘要：

  制备了一系列新型的双（亚氨基）吡啶二氯化镍（II）配合物，其中双（亚氨基）吡啶配体含有吸电子基团（F，Cl，Br，CF 3），并通过元素分析和NMR进行了表征光谱学。所有配合物均表现出顺磁性位移的1 H NMR光谱，表明d 8镍（II）中心原子的高自旋（S = 1）状态。已发现这些络合物是经MAO活化的乙烯基型降冰片烯聚合的高活性催化剂，显示出高达1.16×10 7 g的PNB（摩尔摩尔数）-1 h –1的活性。（有史以来最高的降冰片烯在双（亚氨基）吡啶镍配合物上的聚合反应），并产生高分子量的聚降冰片烯（M w高达4.5×10 6）。报道了一些镍配合物的X射线结构。

  DOI：

  10.1021/om201213v

文献信息

• Catalytic ethylene oligomerization on cobalt(II) bis(imino)pyridine complexes bearing electron-withdrawing groups
  作者：Artem A. Antonov、Nina V. Semikolenova、Evgenii P. Talsi、Konstantin P. Bryliakov

  DOI：10.1016/j.jorganchem.2019.02.002

  日期：2019.3

  A series of novel bis(imino)pyridine cobalt(II) chlorides, LCoCl2, with the bis(imino)pyridine ligands bearing one or several electron-withdrawing substituents (F, Cl, Br, CF3) at the aniline moieties, have been prepared and characterized. In the presence of methylalumoxane (MAO), these complexes have demonstrated high ethylene oligo- and polymerization activity (up to 1.8·107 g products∙(mol Co)−1 h−1 bar−1)

  一系列新颖的双（亚氨基）吡啶钴（II）氯化物LCoCl 2具有在苯胺部分带有一个或多个吸电子取代基（F，Cl，Br，CF 3）的双（亚氨基）吡啶配体准备和表征。在甲基铝氧烷（MAO）的存在下，这些配合物表现出高的乙烯低聚和聚合活性（高达1.8·10 7  g产品∙（mol Co）-1  h -1  bar -1），提供的产品范围为1-丁烯和Z，E -2-丁烯至严格线性低分子量（M n 〜300…700）聚乙烯。讨论了反应结果对配体结构的依赖性。
• Bis(arylimino)pyridine iron(III) complexes as catalyst precursors for the oligomerization and polymerization of ethylene
  作者：Christian Görl、Tanja Englmann、Helmut G. Alt

  DOI：10.1016/j.apcata.2011.06.010

  日期：2011.6

  containing either electron withdrawing or electron donating substituents in their ligand frameworks was synthesized and characterized. After activation with methylaluminoxane (MAO), these catalysts oligomerize or polymerize ethylene to give both linear and branched products. In contrast to iron(II) complexes, the presence of at least one ortho-substituent at the iminophenyl rings is not obligative for catalytic

  合成并表征了一系列26种双（芳基）吡啶铁（III）配合物，这些配合物在其配体骨架中包含吸电子或供电子取代基。用甲基铝氧烷（MAO）活化后，这些催化剂使乙烯低聚或聚合，得到直链和支链产物。与铁（II）配合物相反，在亚氨基苯基环上存在至少一种邻位取代基对于铁（III）配合物的催化活性不是强制性的。含有间位和对位取代的双（芳基吡啶）吡啶化合物的这类铁（III）配合物很容易获得，并且它们的低聚行为表明与众所周知的铁（II）类似物存在有趣的差异，因为在烯烃中同时发现了内部和分支烯烃。预期的直链α-烯烃以外的产物混合物。
• Halogen-Substituted 2,6-Bis(imino)pyridyl Iron and Cobalt Complexes:  Highly Active Catalysts for Polymerization and Oligomerization of Ethylene
  作者：Yaofeng Chen、Ruifang Chen、Changtao Qian、Xicheng Dong、Jie Sun

  DOI：10.1021/om0302894

  日期：2003.10.1

  analyses indicate that 1, 8, 9, and 10 are five-coordinate complexes, while 11 is an ion-pair complex with one six-coordinate iron center and one four-coordinate iron center. These metal coordinative complexes, activated by modified methylaluminoxane (MMAO), lead to highly active ethylene polymerization and/or oligomerization catalysts. The catalyst productivity and product properties crucially depended

  一系列卤素取代的2,6-双（亚氨基）吡啶基配体及其铁和钴配合物[2,6-（2,6-X 1 X 2 C 6 H 3 N CCH 3）2 C 5 H 3 N} MCl 2 ]（X 1 = X 2 = Br，M = Fe（1），Co（2）; X 1 = X 2 = Cl，M = Fe（3），Co（4）; X 1 = Cl ，X 2 = H，M = Fe（5），Co（6）; X 1 = Br，X2 = H，M = Fe（7），Co（8）；X 1 = I，X 2 = H，M = Fe（9），Co（10））和[M 2,6-（2,6-X 1 X 2 C 6 H 3 N CCH 3）2 C 5 ħ 3 N} 2 ] 2+ [的MC1 4 ] 2 -（X 1 = F，X 2 = H，M = Fe（上11））已经被合成。配合物的分子结构1，8，9，10，和11是由X射线衍射测定。结晶分析表明，1，8，9，
• Vinyl Polymerization of Norbornene on Nickel Complexes with Bis(imino)pyridine Ligands Containing Electron-Withdrawing Groups
  作者：Artem A. Antonov、Nina V. Semikolenova、Vladimir A. Zakharov、Wenjuan Zhang、Youhong Wang、Wen-Hua Sun、Evgenii P. Talsi、Konstantin P. Bryliakov

  DOI：10.1021/om201213v

  日期：2012.2.13

  series of novel bis(imino)pyridine nickel(II) dichloride complexes, with the bis(imino)pyridine ligands containing electron-withdrawing groups (F, Cl, Br, CF3), have been prepared and characterized by elemental analysis and NMR spectroscopy. All complexes exhibit paramagnetically shifted 1H NMR spectra, indicative of the high-spin (S = 1) state of the d8 nickel(II) central atom. These complexes have been

  制备了一系列新型的双（亚氨基）吡啶二氯化镍（II）配合物，其中双（亚氨基）吡啶配体含有吸电子基团（F，Cl，Br，CF 3），并通过元素分析和NMR进行了表征光谱学。所有配合物均表现出顺磁性位移的1 H NMR光谱，表明d 8镍（II）中心原子的高自旋（S = 1）状态。已发现这些络合物是经MAO活化的乙烯基型降冰片烯聚合的高活性催化剂，显示出高达1.16×10 7 g的PNB（摩尔摩尔数）-1 h –1的活性。（有史以来最高的降冰片烯在双（亚氨基）吡啶镍配合物上的聚合反应），并产生高分子量的聚降冰片烯（M w高达4.5×10 6）。报道了一些镍配合物的X射线结构。
• Ethylene oligomerization catalyzed by a novel iron complex containing fluoro and methyl substituents
  作者：Zhicheng Zhang、Junfeng Zou、Nannan Cui、Yucai Ke、Youliang Hu

  DOI：10.1016/j.molcata.2004.05.014

  日期：2004.9

  A novel 2,6-bis(imino)pyridyl iron complex, [2,6-(2-F-4-CH3C6H3N=CCH3)(2)C5H3N]FeCl2.H2O (3) has been synthesized by the reaction of the corresponding bis(imino)pyridyl ligand with FeCl2.4H(2)O in tetrahydrofuran (THF). The activity of complex 3 reaches to 10(7) g/mol Fe h in ethylene oligomerization, and the products are mostly (>90%) 1-butene, 1-hexene and 1-octene. As reaction temperature increases, the activities decrease rapidly and the product distributions shift to the low-molecular-weight part. The product distributions are almost unchanged when the Al/Fe molar ratio increases from 420 to 2500, but the catalytic activities increase rapidly at first and then decrease. Other three complexes (2,6-(2-X-4-Y-6-ZC(6)H(3)N=CCH3)(2)C5H3N}FeCl2.nH(2)O (X = CH3, Y = CH3, Z = H, n = 0 (1), X = F, Y = H, Z = F, it = 1 (2)) and Fe[2,6-(2-FC6H3N=CCH3)(2)C5H3N}(2)](2), [FeCl4](2)(-).H2O (4) have been also synthesized for comparison and used for ethylene oligomerization. The ortho and para substituents on aniline have performed effects on oligomerization activities and distributions of oligomers for 2,6-bis(imino)pyridyl iron complexes. (C) 2004 Elsevier B.V. All rights reserved.