2-formyl-1,10-phenanthroline 2,6-diisopropylanil | 876126-87-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: 2-formyl-1,10-phenanthroline 2,6-diisopropylanil
• 英文别名: 1,10-C12H7N2CH=N(2,6-(i-Pr)2C6H3)；N-[2,6-di(propan-2-yl)phenyl]-1-(1,10-phenanthrolin-2-yl)methanimine
• CAS: 876126-87-3
• 化学式: C₂₅H₂₅N₃
• 分子量: 367.494
• InChiKey: WDQSEYRAMAGFOQ-UHFFFAOYSA-N

物化性质

• 熔点：
  192-194 °C
• 沸点：
  573.2±50.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  38.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-formyl-1,10-phenanthroline 2,6-diisopropylanil 、 cobalt(II) chloride 以 正丁醇 为溶剂， 以65%的产率得到[(1,10-C12H7N2CH=N(2,6-(i-Pr)2C6H3))CoCl2]
  参考文献：
  名称：

  Electronically variable imino-phenanthrolinyl-cobalt complexes; synthesis, structures and ethylene oligomerisation studies

  摘要：

  The 2-imino-1,10-phenanthroline ligands, 1,10-C12H7N2-2-CR=N(2,6-i-Pr-2-4-R-1-C6H2) [R = R-1 = H (L1); R = H, R-1 = Br (L2); R = H, R-1 = CN (L3); R = H, R-1 = i-Pr (L4); R = Me, R-1 = H (L5); R = Me, R-1 = i-Pr (L6)], have been prepared in high yield from the condensation reaction of 1,10-C12H7N2-2-CR=O (R = H, Me) with one equivalent of the corresponding 4-substituted 2,6-diisopro-pylaniline. The molecular structures of L2, L5 and L6 reveal the imino nitrogen atoms to adopt a transoid configuration with respect to the phenanthrolinyl nitrogen atoms. Treatment of Lx with one equivalent of CoCl2 in n-BuOH at 90 degrees C gives the high spin complexes, (Lx)CoCl2 [Lx = L1 (1a), L2 (1b), L3 (1c), L4 (1d), L5 (le), L6 (1f)], in which the metal centres exhibit distorted square pyramidal geometries. Activation of la-If with excess methylaluminoxane (MAO) gives catalysts that are modestly active for the oligomerisation of ethylene affording mainly linear alpha-olefins along with some degree of internal olefins. While the donor capability of the 4-position of the N-aryl group does not appear to affect the activity of the catalyst, it does have an influence on the ratio of a-olefins to internal olefins. Single crystal X-ray diffraction studies have been performed on L2, L5, L6, 1a, 1c and 1f (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.06.018
• 作为产物：
  描述：

  2-甲基-1,10-菲咯啉 在 selenium(IV) oxide 作用下， 以 1,4-二氧六环 、 乙醇 、 水 为溶剂， 反应 4.0h， 生成 2-formyl-1,10-phenanthroline 2,6-diisopropylanil
  参考文献：
  名称：

  一种用于 Ullmann 型 N-芳基化反应的新型高效 NHC/Cu(I) 催化剂体系

  摘要：

  设计并合成了一种基于1,10-菲咯啉的新型N-杂环卡宾（NHC）配体前体。通过核磁共振波谱和元素分析对该咪唑盐进行了表征。已评估了作为配体的性能。与 CuI 共存形成高效催化体系，用于（杂）芳基氯和唑类的乌尔曼型芳基化反应。该催化系统表现出广泛的官能团耐受性，并且可以在温和条件下以高至优异的产率（80-98%）提供所需的偶联产物。

  DOI：

  10.1016/j.mcat.2024.114284

文献信息

• Iron Complexes Bearing 2-Imino-1,10-phenanthrolinyl Ligands as Highly Active Catalysts for Ethylene Oligomerization
  作者：Wen-Hua Sun、Suyun Jie、Shu Zhang、Wen Zhang、Yingxia Song、Hongwei Ma、Jiutong Chen、Katrin Wedeking、Roland Fröhlich

  DOI：10.1021/om050891p

  日期：2006.1.1

  diffraction analysis. Activated with methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), these iron(II) complexes show high catalytic activities up to 8.95 × 107 g mol-1(Fe) h-1 for ethylene oligomerization. The distribution of oligomers produced follows Schluz−Flory rules with high selectivity for α-olefins. Both the steric and electronic effects of coordinative ligands affect the catalytic

  合成了一系列由2-亚氨基-1,10-菲咯啉基配体LFeCl 2（L = 2-（ArN CR）-1,10-phen）连接的铁配合物，并通过元素和光谱分析以及X进行了充分表征射线衍射分析。这些铁（II）配合物被甲基铝氧烷（MAO）或改性甲基铝氧烷（MMAO）活化，显示出高达8.95×10 7 g mol - 1（Fe）h - 1的高催化活性。用于乙烯低聚。产生的低聚物的分布遵循对α-烯烃具有高选择性的Schluz-Flory规则。配位体的空间和电子效应都影响催化活性和催化产物的性质。还研究了反应条件的参数以探索这些配合物的催化潜力。
• Ethylene oligomerization processes
  申请人：Chevron Phillips Chemical Company LP

  公开号：US10407360B2

  公开（公告）日：2019-09-10

  Disclosed herein is a process for forming an oligomer product comprising (a) introducing into a reaction zone (i) ethylene; (ii) a heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt; (iii) a second metal salt wherein an equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex is at least 0.5:1 and where the second metal salt is an iron salt, a cobalt salt, or any combination thereof; (iv) an organoaluminum compound; and (b) forming an oligomer product. Also disclosed herein is a process comprising (a) introducing into a reaction zone (i) ethylene; (ii) a heteroatomic ligand; (iii) a metal salt where an equivalent molar ratio of the metal salt to the heteroatomic ligand is at least 1.5:1; (iv) an organoaluminum compound; and (b) forming an oligomer product.

  本文公开了一种形成低聚物产品的工艺，包括(a)向反应区引入(i)乙烯；(ii)杂原子配体金属盐络合物，包括与第一金属盐络合的杂原子配体；(iii)第二金属盐，其中第二金属盐与杂原子配体金属盐络合物的杂原子配体的等效摩尔比至少为0.5:1，其中第二金属盐为铁盐、钴盐或其任意组合；(iv)有机铝化合物；以及(b)形成低聚物产物。本文还公开了一种工艺，包括(a)向反应区引入(i)乙烯；(ii)杂原子配体；(iii)金属盐，其中金属盐与杂原子配体的当量摩尔比至少为 1.5:1；(iv)有机铝化合物；以及(b)形成低聚物产物。
• Ethylene oligomerization process
  申请人：Chevron Phillips Chemical Company LP

  公开号：US10544070B2

  公开（公告）日：2020-01-28

  Disclosed herein is a process for forming an oligomer product comprising (a) introducing into a reaction zone (i) ethylene; (ii) a heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt; (iii) a second metal salt wherein an equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex is at least 0.5:1 and where the second metal salt is an iron salt, a cobalt salt, or any combination thereof; (iv) an organoaluminum compound; and (b) forming an oligomer product. Also disclosed herein is a process comprising (a) introducing into a reaction zone (i) ethylene; (ii) a heteroatomic ligand; (iii) a metal salt where an equivalent molar ratio of the metal salt to the heteroatomic ligand is at least 1.5:1; (iv) an organoaluminum compound; and (b) forming an oligomer product.

  本文公开了一种形成低聚物产品的工艺，包括(a)向反应区引入(i)乙烯；(ii)杂原子配体金属盐络合物，包括与第一金属盐络合的杂原子配体；(iii)第二金属盐，其中第二金属盐与杂原子配体金属盐络合物的杂原子配体的等效摩尔比至少为0.5:1，其中第二金属盐为铁盐、钴盐或其任意组合；(iv)有机铝化合物；以及(b)形成低聚物产物。本文还公开了一种工艺，包括(a)向反应区引入(i)乙烯；(ii)杂原子配体；(iii)金属盐，其中金属盐与杂原子配体的当量摩尔比至少为 1.5:1；(iv)有机铝化合物；以及(b)形成低聚物产物。
• Chromium(III) complexes bearing 2-imino-1,10-phenanthrolines: Synthesis, molecular structures and ethylene oligomerization and polymerization
  作者：Shu Zhang、Suyun Jie、Qisong Shi、Wen-Hua Sun

  DOI：10.1016/j.molcata.2007.07.012

  日期：2007.10

  A series of chromium(III) complexes ligated by tridentate ligands of 2-imino-1,10-phenanthrolines, LCrCl3 (L=2-(2,6-(R')(2)C6H3N=CR)-1,10-phen) was synthesized and characterized by elemental and spectroscopic analyses as well as single-crystal X-ray crystallography. X-ray crystallographic analysis of 2 (R=Ph, R-1=Et), 4 (R=Me,R-1=Me) and 12 (R=H, R-1=i-Pr)reveals that the geometry around the chromium atom is octahedral. Upon activation with MAO, these complexes exhibited high activities for ethylene oligornerization (up to 1.15 x 10(7) gmol(-1) (Cr)h(-1)) and moderate activities for ethylene polymerization. The oligomers and polymers obtained were alpha-olefins, and the distribution of oligomers resembled the Schultz-Flory rule. Various reaction parameters were investigated in detail, and the results revealed that both the steric and electric effects of ligands affected the catalytic activities of their chromium complexes as well as the distribution of the products. (c) 2007 Elsevier B.V. All rights reserved.
• Synthesis, characterization and ethylene oligomerization studies of nickel complexes bearing 2-imino-1,10-phenanthrolines
  作者：Wen-Hua Sun、Shu Zhang、Suyun Jie、Wen Zhang、Yan Li、Hongwei Ma、Jiutong Chen、Katrin Wedeking、Roland Fröhlich

  DOI：10.1016/j.jorganchem.2006.06.028

  日期：2006.10

  A series of nickel (11) complexes ligated by 2-imino-1,10-phenanthrolines were synthesized and characterized by elemental and spectroscopic analysis as well as by single-crystal X-ray crystallography. X-ray crystallographic analysis reveals complexes 3, 5, 7 and 11 as the five-coordinated distorted trigonal-bipyramidal geometry. Upon activation with Et(2)AlCl, these complexes exhibited considerably high activity for ethylene oligomerization (up to 3.76 x 10(7) g mol(-1) (Ni) h(-1) for 12 with 10 equiv. of PPh(3)). The ligand environment and reaction conditions significantly affect the catalytic activity of their nickel complexes. (c) 2006 Elsevier B.V. All rights reserved.