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Copper catalyst for synthesizing quinoline compounds and preparation method thereof

A technology of copper catalyst and compound, which is applied in the field of copper catalyst for the synthesis of quinoline compounds and its preparation, and can solve the problems of unsafe, highly corrosive, and expensive preparation of quinoline derivatives

Active Publication Date: 2021-05-11
JIANGNAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] In 2015, Yu et al. reported that Cu(OTf) 2 Catalyzes quinoline synthesis reaction, but in this reaction, TsOH·H 2 O participates in the reaction as an auxiliary agent, however, p-toluenesulfonic acid (TsOH·H 2 O) is an organic strong acid, which is one million times more acidic than benzoic acid. For experimenters, it is relatively unsafe to prepare quinoline derivatives
In 2017, Yao group reported that CsOH·H 2 An example of O-catalyzed synthesis of quinolines, but CsOH·H 2 O (cesium hydroxide) is the strongest alkali known, known as the king of alkalis, it is highly corrosive and strongly irritating to the skin, etc.
In the same year, Paul's group reported a NNN-Cu catalyst, which was not recyclable due to its homogeneous catalyst.
Also in 2019, the Ke research group reported a manganese catalyst to catalyze the synthesis of quinoline. However, before preparing this manganese catalyst, a precursor of manganese pentacarbonyl manganese bromide metal is required, and the price of commercially available manganese pentacarbonyl bromide 500-1000RMB / g, the price is quite expensive

Method used

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  • Copper catalyst for synthesizing quinoline compounds and preparation method thereof
  • Copper catalyst for synthesizing quinoline compounds and preparation method thereof
  • Copper catalyst for synthesizing quinoline compounds and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0054] Embodiment 1: the preparation of ligand

[0055] Under nitrogen atmosphere, to a 25 mL Schlenk tube, first add (6-(1H-benzotriazol-1-yl)pyridin-2-amine) (211 mg, 1.0 mmol) in dry tetrahydrofuran (2.0 mL), Slowly stir evenly, add dry triethylamine to the reaction tube, then cool down the reaction mixture to 0°C, and finally add Ph to the system drop by drop under the protection of nitrogen 2 PCl (220 mg, 1.0 mmol). After the dropwise addition, move the reaction device to room temperature first, then gradually raise the temperature to 70°C for 6 hours, cool to room temperature and filter, remove the ammonium salt, and distill off the solvent under reduced pressure to obtain a crude product. Flash chromatography using petroleum ether / ethyl acetate (10 / 1) as eluent afforded ligand 1a, 6-(1H-benzo[d][1,2,3]triazole- 1-yl)-N-(diphenylphosphino)pyridin-2-amine.

[0056] Structural characterization of ligand 1a: 1 H NMR (400MHz, CDCl 3 )δ8.55(d, J=8.1Hz, 1H), 8.08(d, J=8.2...

Embodiment 2

[0057] Embodiment 2: the preparation of homogeneous copper catalyst

[0058] Under nitrogen atmosphere, into a 25mL Schlenk tube, first add CuCl 2 (191mg, 0.2mmol) in dry tetrahydrofuran (1.0mL), after stirring evenly, the ligand 1a prepared in Example 1 was slowly added, and the mixture was reacted at room temperature for 24 hours. Diethyl ether was added to the system, after the solid was precipitated, the crude product was obtained by filtration and washing, and purified by column chromatography, using dichloromethane / methanol (9 / 1) as the eluent to obtain a homogeneous copper catalyst triazole-pyridine-diphenyl Phosphine copper, referred to as NNP-Cu.

Embodiment 3

[0059] Embodiment 3: the preparation of heterogeneous copper catalyst

[0060] Urea was dried at 70° for 12 hours before use.

[0061] The triazole-pyridine-diphenylphosphine copper complex NNP-Cu (200mg) and urea (2.0g) obtained in Example 2 were ground uniformly, moved into a tube furnace, and added 2.0g hydrotalcite, nitrogen protection calcination at 500°C for 2 hours to obtain Cu@HT@g-C 3 N 4 , and then washed three times with water and ethanol respectively, and after ultrasonic washing and drying, the heterogeneous Cu@HT@g-C 3 N 4 catalyst.

[0062] Cu@HT@g-C 3 N 4 Product characterization of the catalyst: figure 1 is the prepared heterogeneous Cu@HT@g-C 3 N 4 The scanning electron microscope image of the catalyst, it can be seen that Cu@HT@g-C 3 N 4 The form is thin layer, piled up in clusters.

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Abstract

The invention discloses a copper catalyst for synthesizing quinoline compounds and a preparation method of the copper catalyst, and belongs to the technical field of catalysts. The invention provides a novel method for combining nitrogen-containing and phosphine-containing ligands with metal copper to prepare the homogeneous copper catalyst, and the metal complex, hydrotalcite and C3N4 can be continuously subjected to high-temperature calcination to obtain the heterogeneous copper catalyst. The homogeneous copper catalyst and the corresponding heterogeneous catalyst can be applied to reaction of 2-aminobenzyl alcohol and acetophenone to generate quinoline derivatives, and have excellent catalytic activity.

Description

technical field [0001] The invention belongs to the technical field of catalysts, and in particular relates to a copper catalyst for synthesizing quinoline compounds and a preparation method thereof. Background technique [0002] The synthesis of the nitrogen-containing heterocyclic compound quinoline has attracted considerable attention in recent years due to its special biological and pharmacological activities, such as anticancer, antimalarial, anti-inflammatory, antibacterial, antituberculosis, and antihypertensive properties. So far, many synthetic methods have shown that the synthesis of quinolines under the conditions of noble metal homogeneous catalysts or strong acids (bases) is the main strategy. [0003] In 2015, Yu et al. reported that Cu(OTf) 2 Catalyzes quinoline synthesis reaction, but in this reaction, TsOH·H 2 O participates in the reaction as an auxiliary agent, however, p-toluenesulfonic acid (TsOH·H 2 O) is an organic strong acid, and its acidity is on...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22B01J27/24B01J37/08C07D215/06C07D215/12C07F9/6558
CPCC07D215/06C07D215/12B01J31/188B01J37/086B01J37/082B01J27/24C07F9/65586B01J2531/16
Inventor 王大伟曹飞夏晓峰吴强
Owner JIANGNAN UNIV