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Ullmann C-N cross-coupling reaction catalyst and synthesis method based on catalyst

A technology of cross-coupling reaction and synthesis method, applied in the field of catalysis, can solve the problems of insufficient catalytic activity, harsh reaction conditions, long reaction time, etc., and achieve the effects of improving the conversion rate of raw materials, high selectivity and low cost

Inactive Publication Date: 2018-11-16
SHAANXI COAL & CHEM TECH INST
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the current Ullmann-type C-N cross-coupling reaction catalyzed by copper or copper salts still faces the problems of insufficient catalytic activity and harsh reaction conditions. about 90%

Method used

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  • Ullmann C-N cross-coupling reaction catalyst and synthesis method based on catalyst
  • Ullmann C-N cross-coupling reaction catalyst and synthesis method based on catalyst
  • Ullmann C-N cross-coupling reaction catalyst and synthesis method based on catalyst

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preparation example Construction

[0029] The synthetic method based on above-mentioned Ullmann C-N cross-coupling catalyst comprises the following steps,

[0030] Step 1, under the protection of argon, add aromatic amine, halogenated hydrocarbon, copper source, potassium carbonate, mixed organic ligands and DMF into the container, and heat to 150°C-180°C under the protection of argon for reflux reaction for 1-6h ;

[0031]Step 2, after the reaction is completed, filter while it is hot, and rinse the obtained solid with DMF; then, add water dropwise to the above-mentioned DMF filtrate under high-speed stirring, and a large amount of off-white solid precipitates; filter the solid, wash with water, and dry;

[0032] Step 3, the above off-white solid was separated by silica gel column chromatography, the eluent was petroleum ether, and the eluate was collected, concentrated and dried to obtain a light white solid.

[0033] Wherein, in step 1, the amount of copper source is 0.1-10% of the amount of halogenated hyd...

Embodiment 1

[0036] Under argon protection, 1.67g (10mmol) carbazole, 1.88g (12mmol) bromobenzene, 0.382g (2mol) cuprous iodide, 2.76g (20mmol) potassium carbonate, 0.113g ( 0.5mmol) of 18-crown-6, 0.078g (0.5mmol) of 2,2'-bipyridine and 25mL of DMF, heated to 156°C under argon protection for 2h under reflux. After the reaction was completed, a sample was taken for analysis. The conversion rate of the reaction was 99%. It was filtered while it was hot, and the solid was rinsed with 10 mL of DMF. Then, 30 mL of water was added dropwise to the above DMF filtrate under high-speed stirring, and a large amount of off-white solids were precipitated. The solid was filtered, washed with water and dried. The above off-white solid was separated by silica gel column chromatography, the eluent was petroleum ether, and the eluate was collected, concentrated and dried to obtain 2.19 g of off-white solid, with a yield of 90%. m.p.91-95°C; IR, ν, cm-1: 483, 563, 626, 749, 846, 1022, 1171, 1230, 1337, 13...

Embodiment 2

[0038] Under argon protection, 1.67g (10mmol) carbazole, 1.88g (12mmol) bromobenzene, 0.382g (2mol) cuprous iodide, 2.76g (20mmol) potassium carbonate, 0.226g ( 1mmol) of 18-crown-6 and 25mL of DMF were heated to 156°C under the protection of argon for 2h under reflux. After the reaction was completed, a sample was taken for analysis, and the conversion rate was measured to be 87%, filtered while hot, and the solid was rinsed with 10 mL of DMF. Then, 30 mL of water was added dropwise to the above DMF filtrate under high-speed stirring, and a large amount of off-white solids were precipitated. The solid was filtered, washed with water and dried. The above off-white solid was separated by silica gel column chromatography, the eluent was petroleum ether, and the eluate was collected, concentrated and dried to obtain 1.95 g of off-white solid, with a yield of 80%.

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Abstract

The invention provides an Ullmann C-N cross-coupling reaction catalyst and a synthesis method based on the catalyst. The catalyst comprises a copper source and mixed organic ligands. The mixed organicligands comprise a first ligand and a second ligand, wherein the first ligand is an O-O type ligand, and the second ligand is one or both of an N-N type ligand and an N-O type ligand. By using two ormore different kinds of the organic ligands and fully exerting the synergistic effect of the different types of ligands, the catalytic activity of the catalyst is raised, thereby improving feed stockconversion and product selectivity. With the organic combination of the ligands, adaptability of the substrate is greatly expanded, and the complicated synthesis process of complex ligands is avoided. The reaction cost can be effectively reduced, and the problem that the organic synthesis process brings environmental pollution and health injury also can be minimized. The catalyst has the advantages of high product conversion rate, high selectivity, low dosage, mild reaction conditions, low cost, etc.

Description

technical field [0001] The invention belongs to the field of catalysis, and in particular relates to a novel Ullmann C-N cross-coupling reaction catalyst and a synthesis method based thereon. Background technique [0002] The construction of C-N bonds is a very important reaction in the field of organic synthesis. It is widely used in the synthesis of natural products, medicines, pesticides, organic photoelectric materials, etc., and has become one of the hot spots in academic research and industrial development. Ullmann C-N cross-coupling reaction is a very important class of organic unit reactions that generate C-N bonds. As early as 1903, German chemist Ullmann first reported the coupling reaction of inactive aryl halides catalyzed by copper powder (F Ullmann, JBielecki.Ber.Dtsch.Chem.Ges.,1901,34:2174), then Goldberg et al. improved and expanded the Ullmann reaction (IGoldberg.Ber.Dtsch.Chem.Ges.,1906,39:1691), forming Copper-mediated classical Ullmann reaction. Howeve...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22B01J31/18C07D209/86
CPCB01J31/1815B01J31/2213B01J31/2217B01J2231/4283B01J2531/0213B01J2531/0241B01J2531/0258B01J2531/16C07D209/86
Inventor 张生军戚文博薛其才殷海龙
Owner SHAANXI COAL & CHEM TECH INST
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