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Method for preparing fluorinated aromatic hydrocarbons by photo/nickle concerted catalysis

A technology of synergistic catalysis and biaromatic hydrocarbons, which is applied in the preparation of carbon-based compounds, chemical instruments and methods, and the preparation of organic compounds. It can solve the problems of difficult coupling reactions and achieve the effect of low dosage

Active Publication Date: 2018-08-07
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In addition, due to the strong electronegativity of the fluorine atom, the coupling reaction is difficult, and the first three methods often require high temperature to be effective.

Method used

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  • Method for preparing fluorinated aromatic hydrocarbons by photo/nickle concerted catalysis
  • Method for preparing fluorinated aromatic hydrocarbons by photo/nickle concerted catalysis
  • Method for preparing fluorinated aromatic hydrocarbons by photo/nickle concerted catalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Synthesis of 2-methyl-5-(2′,3′,5′,6′-tetrafluorophenyl)thiophene with the following structural formula

[0023]

[0024] Under anhydrous and oxygen-free conditions, add 1.0 mL tetrahydrofuran, 2.0 mL N,N-dimethylformamide, 7.7 mg (0.025 mmol) nickel bromide (ethylene glycol dimethyl ether) complex to the reaction tube in sequence , 88mg (0.5mmol) 2-methyl-5-bromothiophene, 100μL 10mmol / L (0.001mmol) THF solution of photosensitizer i, 1.0mL 1.0mol / L (1mmol) 2,3,5,6-tetrafluoro The tetrahydrofuran solution of phenyl zinc reagent, put the reaction tube under the light of white light (5W, 1cm away from the reaction test tube), stir and react at 50°C for 12 hours, after the reaction, add 0.5mL methanol and stir for 10 minutes, until the reaction is quenched Completely, the reaction solution was diluted with saturated brine and extracted three times with ethyl acetate, the ethyl acetate extract was dried over anhydrous sodium sulfate, evaporated to dryness under reduced pr...

Embodiment 2

[0026] Synthesis of 4-(2′,3′,5′,6′-tetrafluorophenyl)acetophenone with the following structural formula

[0027]

[0028] In this example, the 2-methyl-5-bromothiophene in Example 1 was replaced with equimolar p-bromoacetophenone, and the other steps were the same as in Example 1 to obtain 4-(2′,3′,5′ , 6′-tetrafluorophenyl) acetophenone, its productive rate is 98%, and the structural characterization data is: 1 H NMR (400MHz, CDCl 3 ): δ8.08 (d, J = 8.4Hz, 2H), 7.58 (d, J = 8.0Hz, 2H), 7.15-7.10 (m, 1H), 2.66 (s, 3H).

Embodiment 3

[0030] Synthesis of 2,3,5,6-tetrafluoro-1,1'-biphenyl with the following structural formula

[0031]

[0032] In this example, the 2-methyl-5-bromothiophene in Example 1 was replaced with an equimolar bromobenzene, and the other steps were the same as in Example 1 to obtain 2,3,5,6-tetrafluoro-1,1 '-biphenyl, its yield is 98%, and the structural characterization data is: 1 H NMR (400MHz, CDCl 3 ): δ7.54-7.44 (m, 5H), 7.13-7.01 (m, 1H).

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PUM

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Abstract

The invention discloses a method for preparing fluorinated aromatic hydrocarbons by photo / nickle concerted catalysis. According to the method, cheap metal nickel salt is used as a catalyst, adding ofa ligand is not needed, and the catalyst cooperates with trace photosensitizer in visible light radiation to catalyze a fluoro aryl zinc reagent and an aryl halide to generate Negishi cross-coupling,so as to prepare a fluorinated aromatic hydrocarbons compound. The coupling reaction functional group is good in tolerance, a substrate is wide in applicability, and multiple fluorinated aromatic hydrocarbons compounds (80-96%) can be obtained at high yield in a near room temperature. Compared with a palladium catalysis system reported in the literature, the photo-nickle concerted catalysis systemadopted by the method disclosed by the invention has the advantages that the use amount of the photosensitizer is low, a nickel catalyst is low in price, expensive ligand does not need to be added, and environment-friendly, economical and practical effects are achieved; by combining with a flowing synthesis technology, the method can easily realize automatic synthesis of important fluorinated aromatic hydrocarbons compounds.

Description

technical field [0001] The invention belongs to the technical field of fluorinated biaryls synthesis, and in particular relates to a method for preparing fluorinated bisaryls through light / nickel synergistic catalysis. Background technique [0002] Fluorinated biaryl hydrocarbons are one of the important skeletons of drug molecules and functional material molecules, and cross-coupling reactions are an important means of preparing such fluorinated biaryl hydrocarbon compounds. At present, the methods for the synthesis of fluorinated biaromatics reported in literature or patents mainly include: palladium-catalyzed Suzuki coupling reaction (Takashi Sakai.Org.Lett.2005, 7, 4915), palladium-catalyzed direct arylation of polyfluoroaromatics (for a review, see : ChemCatChem 2014, 6, 1824; representative papers in: J.Am.Chem.Soc.2006, 128, 8574; Org.Lett.2009, 11, 3346; Org.Lett.2010, 12, 2116; J.Am. .Chem.Soc.2010,132,16377; Org.Lett.2011,13,276; J.FluorineChem.2013,151,50; Appl.O...

Claims

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Application Information

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IPC IPC(8): C07D333/12C07C45/68C07C49/813C07C17/263C07C25/18C07C25/22C07C41/30C07C43/225C07C67/343C07C69/76C07D333/38C07D213/803C07D307/79C07D333/54C07D213/79C07D215/12C07D209/08B01J31/30B01J31/22B01J31/02B01J31/04
CPCC07C17/263C07C41/30C07C45/68C07C67/343C07D209/08C07D213/79C07D213/803C07D215/12C07D307/79C07D333/12C07D333/38C07D333/54B01J31/0244B01J31/04B01J31/1815B01J31/2208B01J31/2291B01J31/30B01J35/39C07C49/813C07C25/18C07C25/22C07C43/225C07C69/76
Inventor 黄治炎解昆孟鸽马俊杰王俊亚薛东杨俊
Owner SHAANXI NORMAL UNIV
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