4,7-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-2,9-dimethyl-1,10-phenanthroline

• 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: 4,7-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-2,9-dimethyl-1,10-phenanthroline
• 英文别名: 4,7-Bis[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-2,9-dimethyl-1,10-phenanthroline；4,7-bis[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-2,9-dimethyl-1,10-phenanthroline
• 化学式: C₂₈H₄₀N₂O₈
• 分子量: 532.634
• InChiKey: BNNKVFMSRXAEPQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  38
• 可旋转键数：
  20
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  99.6
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  氯化镍二甲氧基乙烷 、 4,7-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-2,9-dimethyl-1,10-phenanthroline 以 乙腈 为溶剂， 反应 24.0h， 以25.3 g的产率得到4,7-Bis[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-2,9-dimethyl-1,10-phenanthroline;dichloronickel
  参考文献：
  名称：

  [EN] CHROMIUM-MEDIATED COUPLING AND APPLICATION TO THE SYNTHESIS OF HALICHONDRINS
  [FR] COUPLAGE INDUIT PAR CHROME ET APPLICATION À LA SYNTHÈSE D'HALICHONDRINES

  摘要：

  公开号：

  WO2016176560A8
• 作为产物：
  描述：

  三甘醇单甲醚 、 4,7-dichloro-2,9-dimethyl-1,10-phenanthroline 在 15-冠醚-5 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 、 四氢呋喃 为溶剂， 反应 3.5h， 以98%的产率得到4,7-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-2,9-dimethyl-1,10-phenanthroline
  参考文献：
  名称：

  Selective Activation/Coupling of Polyhalogenated Nucleophiles in Ni/Cr-Mediated Reactions: Synthesis of C1–C19 Building Block of Halichondrin Bs

  摘要：

  The C1-C19 building block 46 of halichondrin Bs was synthesized via a selective activation/coupling of beta-bromoenone 34 with aldehyde 35 in a Ni/Cr-mediated reaction. The first phase of study was a method development to effect a coupling of a naked vinylogous anion with an aldehyde. The study with the coupling of 9 + 10 -> 11 revealed: (1) beta-bromoenone 9b is a better nucleophile than the corresponding beta-iodo- and beta-chloroenones 9a,c; (2) (Me)(2)Phen(OMe)(2)center dot NiCl2 13b is a better Ni-catalyst than (Me)(2)Phen(H)(2)center dot NiCl2 13a; and (3) a low Ni-catalyst loading, for example, 0.05-0.1 mol % Ni-catalyst against 10 mol % Cr-catalyst, is crucial for an effective coupling. The second phase of study was a method development to realize a selective activation/coupling of polyhalogenated nucleophiles such as 34. The competition experiment of 10 + 9b over 10 + 31a-c revealed: (1) (Me)(2)Phen(OMe)(2)center dot NiCl2 13b is more effective than (Me)(2)Phen(H)(2)center dot NiCl2 13a for the required selective activation/coupling; (2) a low Ni-catalyst loading, for example, 0.05-0.1 mol % Ni-catalyst against 10 mol % Cr-catalyst, is crucial for discriminating beta-bromoenone 9b from the three types of vinyl iodides 31a-c. The third phase of study was an application of the developed method to execute the proposed coupling of 34 + 35 -> 36. For this application, a polyether-type Ni-catalyst 37c, readily soluble in the reaction medium, was introduced to achieve the selective activation/coupling with higher efficiency. With use of ion-exchange resin-based device, the coupling product 36 was transformed to the C1-C19 building block 46 of halichondrin Bs without purification/separation of the intermediates.

  DOI：

  10.1021/jacs.5b03498

文献信息

• COPPER (I) COMPLEXES FOR OPTOELECTRONIC DEVICES
  申请人：Yersin Hartmut

  公开号：US20130150581A1

  公开（公告）日：2013-06-13

  The invention relates to neutral mononuclear copper (I) complexes for emitting light and with a structure according to formula (A) in which: M represents: Cu(I); L∩L represents: a single, negatively charged, bidentate ligand; N∩N represents: a diimine ligand (substituted with R and FG), in particular a substituted 2,2′-bipyridine derivative (bpy) or a substituted 1,10-phenanthroline derivative (phen); R represents: at least one sterically demanding substituent for preventing the planarisation of the complex in the excited state; FG=functional group, and represents: at least one second substituent for increasing solubility in organic solvents. The substituent can also be used for electron transport or alternatively for hole transport, said functional group being bound to the diimine ligands either directly or by means of suitable bridges; and the copper (I) complex: having a ΔE(S 1 −T 1 ) value of less than 2500 cm −1 between the lowest excited singlet state (S 1 ) and the triplet state (T 1 ) which lies below; having an emission lifespan of at most 20 μs; having an emission quantum yield of greater than 40%, and a solubility of at least 1 g/L in organic solvents, in particular polar organic hydrocarbons such as acetone, methyl ethyl ketone, benzene, toluene, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, dichloroethane, tetrachloroethylene, alcohols, acetonitrile or water.

  本发明涉及一种中性的单核铜(I)配合物，用于发光，其结构符合公式(A)，其中：M表示：Cu(I)；L∩L表示：一种单负离子的双齿配体；N∩N表示：一种二亚胺配体（用R和FG取代），特别是取代的2,2′-联吡啶衍生物（bpy）或取代的1,10-邻菲啰啉衍生物（phen）；R表示：至少一个空间位阻取代基，以防止激发态下配合物的平面化；FG表示：功能基团，代表至少一个第二取代基，以增加在有机溶剂中的溶解度。该取代基还可用于电子输运或孔传输，该功能基团直接或通过适当的桥连接到二亚胺配体上；铜(I)配合物：具有最低激发单重态（S1）和三重态（T1）之间的ΔE(S1−T1)值小于2500 cm−1；具有最多20 μs的发射寿命；具有大于40％的发射量子产率，并且在有机溶剂中的溶解度至少为1 g/L，特别是在极性有机烃中，如丙酮、甲基乙酮、苯、甲苯、氯苯、二氯苯、二氯甲烷、氯仿、二氯乙烷、四氯乙烯、醇、乙腈或水中。
• REDOX MELTS FORMED BY COPPER (I)/(II) COMPLEXES AS CHARGE TRANSFER AND CHARGE STORAGE MATERIALS
  申请人：Ecole Polytechnique Fédérale de Lausanne (EPFL)

  公开号：EP3407361A1

  公开（公告）日：2018-11-28

  The present invention relates to a redox copper complex melt comprising a metalorganic complex of formula (I) [Cu (La)n] (I), wherein n is an integer 2; and La is a bidentate ligand selected from a ligand according to any one of formulae (1) and (2):

  本发明涉及一种氧化还原铜络合物熔体，包括式（I）的金属有机络合物 [Cu (La)n] (I)、 其中 n 为整数 2；以及 La 是双齿配体，选自式（1）和式（2）中任意一种配体：
• Chromium-mediated coupling and application to the synthesis of halichondrins
  申请人：President and Fellows of Harvard College

  公开号：US10344038B2

  公开（公告）日：2019-07-09

  The present invention provides unified synthesis of the CI-CI 9 building blocks of halichondrins and analogs thereof using selective coupling of poly-halogenated nucleophiles in chromium-mediated coupling reactions. The present invention also provides a practical and efficient synthesis of C20-C38 building blocks of halichondrins and analogs thereof. Also provided herein are general methods of selective activation and coupling of poly-halogenated analogs with an aldehyde. The provided coupling reactions are selective for halo-enone and halo-acetylenic ketal over vinyl halide and halide attached to a sp hydridized carbon. The provided efficient selective coupling reactions can allow easy access to the CI-CI 9 building blocks and C20-C38 building blocks of halichondrins and analogs thereof with limited or no purification or separation of the intermediates.

  本发明提供了在铬介导的偶联反应中利用多卤代亲核物的选择性偶联来统一合成卤代姜黄素及其类似物的 CI-CI 9 结构单元。本发明还提供了一种实用高效的卤代龙毒素及其类似物的 C20-C38 结构单元的合成方法。本发明还提供了选择性活化多卤代类似物并将其与醛偶联的一般方法。所提供的偶联反应对卤代烯酮和卤代乙炔缩酮具有选择性，而对乙烯基卤化物和连接到 sp 水化物碳上的卤化物则没有选择性。所提供的高效选择性偶联反应可以方便地获得卤代烯酮及其类似物的 CI-CI 9 结构单元和 C20-C38 结构单元，中间产物的纯化或分离程度有限或根本不需要。
• SYNTHESIS OF HALICHONDRINS
  申请人：President and Fellows of Harvard College

  公开号：EP3649135B1

  公开（公告）日：2022-12-28
• CHROMIUM-MEDIATED COUPLING AND APPLICATION TO THE SYNTHESIS OF HALICHONDRINS
  申请人：President and Fellows of Harvard College

  公开号：US20200031843A1

  公开（公告）日：2020-01-30

  The present invention provides unified synthesis of the C1-C19 building blocks of halichondrins and analogs thereof using selective coupling of poly-halogenated nucleophiles in chromium-mediated coupling reactions. The present invention also provides a practical and efficient synthesis of C20-C38 building blocks of halichondrins and analogs thereof. Also provided herein are general methods of selective activation and coupling of poly-halogenated analogs with an aldehyde. The provided coupling reactions are selective for halo-enone and halo-acetylenic ketal over vinyl halide and halide attached to a sp hybridized carbon. The provided efficient selective coupling reactions can allow easy access to the C1-C19 building blocks and C20-C38 building blocks of halichondrins and analogs thereof with limited or no purification or separation of the intermediates.