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NNN tridentate ligand with far-end hydroxyl group, preparation method and application thereof, and ruthenium complex

A technology of ruthenium complexes and hydroxyl groups is applied to ruthenium complexes, NNN tridentate ligands and their preparation methods and application fields, which can solve the problems of modulation limitation and the like, and achieve the effect of excellent catalytic activity

Active Publication Date: 2019-01-11
NORTHWEST UNIV(CN) +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, due to the limitation of the inherent properties of the coordination site atoms, the modulation of the properties of the tridentate complexes based on this strategy is greatly limited.

Method used

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  • NNN tridentate ligand with far-end hydroxyl group, preparation method and application thereof, and ruthenium complex
  • NNN tridentate ligand with far-end hydroxyl group, preparation method and application thereof, and ruthenium complex
  • NNN tridentate ligand with far-end hydroxyl group, preparation method and application thereof, and ruthenium complex

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preparation example Construction

[0038] The present invention also provides a preparation method of the NNN tridentate ligand having a remote hydroxyl group described in the above technical solution. When the NNN tridentate ligand having a distal hydroxyl group has a structure shown in formula A or B, the preparation method includes the following steps:

[0039] Under the protection of nitrogen, after mixing 3,5-dimethyl-1H-pyrazole and DMF, NaH was added in batches in an ice-water bath, and then 2,6-difluoropyridine was added dropwise for monoamination reaction to obtain 2-(3,5-Dimethyl-1H-pyrazol-1-yl)-6-fluoropyridine;

[0040] Under nitrogen protection, after mixing the compound with the structure shown in formula I and DMF, in an ice-water bath, add NaH in batches, and then combine with the 2-(3,5-dimethyl-1H-pyrazole- 1-yl)-6-fluoropyridine is mixed for amination reaction to obtain a compound having the structure shown in formula II, and the compound having the structure shown in formula I is ethyl 1H-...

Embodiment 1

[0099] Preparation of Ligand A

[0100] Step 1: under nitrogen protection, 3,5-dimethyl-1H-pyrazole (16.7g, 1.74mol) was dissolved in dry DMF (60mL), and 60% NaH was added in four equal batches at 0°C ( 9.0 g, 2.26 mol). After stirring for 30 min, 2,6-difluoropyridine was added dropwise, warmed to room temperature and stirred for 4 h. Add an appropriate amount of water to quench the reaction, extract three times with dichloromethane, combine the organic phases, and wash with MgSO 4 dry. Filter out MgSO 4 , the solvent was removed, and the crude product was subjected to column chromatography to obtain a white solid (24 g, yield 73%).

[0101] Step 2: Under nitrogen protection, 1H-pyrazole-4-carboxylic acid ethyl ester (5.6g, 40.3mmol) was dissolved in dry DMF (30mL), and 60% NaH (1.6g , 40.3 mmol). After stirring for 15 min, 2-(3,5-dimethyl-1H-pyrazol-1-yl)-6-fluoropyridine (6.0 g, 31 mmol) was added in batches, and the temperature was raised to 110° C. and stirred overni...

Embodiment 2

[0105] Preparation of Ligand B

[0106] Step 1: under nitrogen protection, 3,5-dimethyl-1H-pyrazole (16.7g, 1.74mol) was dissolved in dry DMF (60mL), and 60% NaH (9.0 g, 2.26mol). After stirring for 30 min, 2,6-difluoropyridine was added dropwise, warmed up to room temperature and stirred for 4 h. Add an appropriate amount of water to quench the reaction, extract three times with dichloromethane, combine the organic phases, MgSO 4 Dry for 2h. Filter out MgSO 4 , the solvent was evaporated by rotary evaporation, and the crude product was subjected to column chromatography to obtain a white solid (24 g, yield 73%).

[0107] Step 2: Under nitrogen protection, 1H-pyrazole-3-carboxylic acid ethyl ester (3.7g, 26.2mmol) was dissolved in dry DMF (25mL), and 60% NaH (1.0g , 26.2 mmol). After stirring for 15 min, 2-(3,5-dimethyl-1H-pyrazol-1-yl)-6-fluoropyridine (4.0 g, 20.9 mmol) was slowly added, and the temperature was raised to 110° C. and stirred overnight. Add an appropria...

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Abstract

The invention provides an NNN tridentate ligand with a far-end hydroxyl group, and belongs to the technical field of metal organic chemistry. An auxiliary cantilever hydroxyl group is introduced to the far end of a coordination point nitrogen atom of the NNN tridentate ligand with the far-end hydroxyl group, and the hydroxyl group does not coordinate with a central metal due to spatial position limitation, and can interact with an exogenous molecule through a hydrogen bond or an electrostatic effect, so the regulation of the properties of the complex is achieved by the synergistic effect of the far-end groups. The synergistic mechanism is used to achieve efficient catalysis of a specific conversion process, so the ligand has an excellent catalytic activity in a hydrogen transfer reaction,and has a broad prospect in the development of high-efficiency catalysts.

Description

technical field [0001] The invention belongs to the technical field of metal organic chemistry, and in particular relates to a NNN tridentate ligand with a remote hydroxyl group, a preparation method and application thereof, and a ruthenium complex. Background technique [0002] Tridentate ligands play a pivotal role in the field of coordination chemistry. At present, it has been widely used in synthetic chemistry, catalytic chemistry, materials chemistry, chemical biology and other fields. NNN tridentate ligands have become one of the most important branches of tridentate pincer ligands due to the good stability of nitrogen-containing ligands, a wide range of raw material sources, and the ability to form coordination with many metals. [0003] Traditionally, the control of the central metal is achieved by adjusting the electrochemical properties and geometric configuration of the coordination site atoms, that is, the "inner layer effect". However, due to the limitation of...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D401/14C07F15/00B01J31/24
CPCB01J31/2404B01J2531/821C07D401/14C07F15/0053
Inventor 曾凡龙曹正强乔红和媛
Owner NORTHWEST UNIV(CN)
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