Quinoxaline double N-oxide derivative ligand and application thereof in promotion on copper-catalyzed C-O coupling reaction

A technology of quinoxaline bis-coupling reaction, applied in the field of new ligands, can solve the problems of long reaction time and high price

Inactive Publication Date: 2013-01-09
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these ligands have the disadvantages of high price and long reaction time

Method used

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  • Quinoxaline double N-oxide derivative ligand and application thereof in promotion on copper-catalyzed C-O coupling reaction
  • Quinoxaline double N-oxide derivative ligand and application thereof in promotion on copper-catalyzed C-O coupling reaction
  • Quinoxaline double N-oxide derivative ligand and application thereof in promotion on copper-catalyzed C-O coupling reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] The structural formula of diphenyl ether is as follows:

[0041] Used in this example:

[0042] The aprotic polar solvent solvent is DMF;

[0043] Quinoxaline bis N -Oxide derivative ligand is 2-methoxycarbonyl-3-hydroxyquinoxaline bis N - oxides;

[0044] Catalyst copper salt is CuI;

[0045] The inorganic base reagent is Cs 2 CO 3 ;

[0046] The aryl halide is iodobenzene;

[0047] Phenols are phenols;

[0048] Add CuI (19.1 mg, 0.1 mmol, 10 mol%), 2-methoxycarbonyl-3-hydroxyquinoxaline bis N -Oxide (47.2 mg, 0.2 mmol, 20 mol%), Cs 2 CO 3 (812.5 mg, 2.5 mmol). The reaction flask was evacuated and flushed with argon. Add iodobenzene (0.112 mL, 1.0 mmol), phenol (0.134 mL, 1.5 mmol) and DMF (1.5 mL) under the protection of argon. The reactant was stirred at 100° C. for 12 h until the starting material was completely reacted (reaction monitored by TLC). After stopping the reaction, the obtained brown oily substance was diluted with ethyl acetate, filtered ...

Embodiment 2

[0052] The structural formula of 2-phenoxynaphthalene is as follows:

[0053]

[0054] Used in this example:

[0055] The aprotic polar solvent solvent is DMF;

[0056] Quinoxaline bis N -Oxide derivative ligand is 2-methoxycarbonyl-3-hydroxyquinoxaline bis N - oxides;

[0057] Catalyst copper salt is CuI;

[0058] The inorganic base reagent is Cs 2 CO 3 ;

[0059] The aryl halide is iodobenzene;

[0060] Phenols are naphthalene-2-ols;

[0061] Add CuI (19.1 mg, 0.1 mmol, 10 mol%), 2-methoxycarbonyl-3-hydroxyquinoxaline bis N -Oxide (47.2 mg, 0.2 mmol, 20 mol%), Cs 2 CO 3 (812.5 mg, 2.5 mmol). The reaction flask was evacuated and flushed with argon. Add iodobenzene (0.112 mL, 1.0 mmol), naphthalene-2-ol (216.3 mg, 1.5 mmol) and DMF (1.5 mL) under the protection of argon. The reactant was stirred at 100° C. for 12 h until the starting material was completely reacted (reaction monitored by TLC). After stopping the reaction, the obtained brown oily substance was...

Embodiment 3

[0065] N The structural formula of -(4-phenoxyphenyl)acetamide is as follows:

[0066]

[0067] Used in this example:

[0068] The aprotic polar solvent solvent is DMF;

[0069] Quinoxaline bis N -Oxide derivative ligand is 2-methoxycarbonyl-3-hydroxyquinoxaline bis N - oxides;

[0070] Catalyst copper salt is CuI;

[0071] The inorganic base reagent is Cs 2 CO 3 ;

[0072] The aryl halide is iodobenzene;

[0073] Phenols are N -(4-hydroxyphenylphenyl)acetamide;

[0074] Add CuI (19.1 mg, 0.1 mmol, 10 mol%), 2-methoxycarbonyl-3-hydroxyquinoxaline bis N -Oxide (47.2 mg, 0.2 mmol, 20 mol%), Cs 2 CO 3 (812.5 mg, 2.5 mmol). The reaction flask was evacuated and flushed with argon. Add iodobenzene (0.112 mL, 1.0 mmol) under the protection of argon, N -(4-Hydroxyphenylphenyl)acetamide (226.7 mg, 1.5 mmol) and DMF (1.5 mL). The reactant was stirred at 100° C. for 15 h until the starting material was completely reacted (reaction monitored by TLC). After stopping th...

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PUM

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Abstract

The invention discloses a quinoxaline double N-oxide derivative ligand for promoting a copper-catalyzed C-O coupling reaction and application thereof. The novel quinoxaline double N-oxide derivative ligand is characterized by comprising hetero atoms (O or N and the like), wherein the hetero atoms can be coordinated with copper ions to form a transitional hexatomic ring. The ligand can promote thecoupling reaction between aryl iodide, aryl bromide or aryl chloride and a phenolic compound. A cheap catalyst system provided by the invention has excellent reaction selectivity and a higher reaction yield coefficient.

Description

technical field [0001] The present invention relates to a novel ligand, specifically a quinoxaline bis N -Oxide-derived ligands and their use in promoting copper-catalyzed C–O coupling reactions at room temperature. Background technique [0002] Diaryl ethers are ubiquitous in various natural products, macromolecules and pharmaceutically active compounds [1,2] . Since the traditional Ullmann etherification reaction requires high reaction temperature (125-220°C), stoichiometric amount of copper catalyst and long reaction time, and the yield is low, many direct and efficient synthesis methods have been explored in recent years. Research on Diaryl Ethers is Gradually Rising [3] . The use of transition metals such as palladium, copper and iron as catalysts has achieved ideal results in the C-O coupling reaction. [4-6] . Due to the high price of palladium catalyst and high requirements on air and humidity, palladium catalysis is only applied in small-scale production. ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D241/52C07C43/275C07C41/01C07C233/24C07C205/38C07C201/12C07C69/78C07C67/31C07C49/84C07C45/64C07C43/263C07C43/257C07D215/26
Inventor 姚志艺蒋晟
Owner SHANGHAI INST OF TECH
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