Synthesis method of difluoroalkyl substituted aromatic ketone compound under photocatalysis

The technology of a difluoroalkyl group and a synthesis method is applied in the field of synthesis of difluoroalkyl substituted aromatic ketone compounds, which can solve the problem of high temperature and achieve the effects of simple operation, wide substrate range and high regioselectivity.

Active Publication Date: 2020-04-17
天台宜生生化科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the temperature required for this reaction is too high

Method used

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  • Synthesis method of difluoroalkyl substituted aromatic ketone compound under photocatalysis
  • Synthesis method of difluoroalkyl substituted aromatic ketone compound under photocatalysis
  • Synthesis method of difluoroalkyl substituted aromatic ketone compound under photocatalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1 2-(4-Acetylphenyl)-2,2-difluoroethyl acetate (I-a)

[0026]

[0027] Add compound (II) acetophenone (48.1mg, 0.4mmol), Ir(ppy) into a 50mL round-bottomed flask equipped with a magnetic stir bar 3 (13mg, 0.02mmol), 1,10-phenanthroline (36mg, 0.2mmol), cesium carbonate (521mg, 1.6mmol) and ethyl bromodifluoroacetate (162.4mg, 0.8mmol), to the mixture was added normal Heptane (5mL), the mixture was irradiated with 3W blue light, and the reaction was stirred at 25°C for 24 hours. The reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layer was washed with anhydrous Mg 2 SO 4 Dry and concentrate under reduced pressure. The crude product was purified on a silica gel column using n-hexane / ethyl acetate to obtain 73.2 mg of product with a yield of 75.5% and an HPLC purity of 97.9%.

Embodiment 2

[0028] Example 2 2,2-Difluoro-2-(4-(4-methylbenzoyl)phenyl) ethyl acetate (I-b)

[0029]

[0030] In a 50 mL round bottom flask equipped with a magnetic stir bar, compound (II) phenyl(p-tolyl)methanone (78.5mg, 0.4mmol), rhodamine 6G (9.6mg, 0.02mmol), 2,2'- Bipyridine (31.2mg, 0.2mmol), sodium acetate (98.4mg, 1.2mmol) and ethyl bromodifluoroacetate (242.4mg, 1.2mmol), to the mixture was added n-hexane (5mL), the mixture in 3W Blue light was irradiated, the reaction was stirred at 30°C for 30 hours, and the reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layer was washed with anhydrous Mg 2 SO 4 Dry and concentrate under reduced pressure. The crude product was purified on a silica gel column using n-hexane / ethyl acetate to obtain 101.4 mg of the product with a yield of 79.6% and an HPLC purity of 98.2%.

Embodiment 3

[0031] Example 3 2-(4-Benzoylphenyl)-2,2-difluoroethyl acetate (I-c)

[0032]

[0033] Add compound (II) benzophenone (72.9mg, 0.4mmol), Ir(ppy) into a 50mL round-bottomed flask equipped with a magnetic stir bar 3 (19.6mg, 0.03mmol), 2,2'-bipyridine (31.2mg, 0.2mmol), potassium carbonate (110.4mg, 0.8mmol) and ethyl bromodifluoroacetate (323.2mg, 1.6mmol), add to the mixture DMSO (5mL) was added to the mixture, the mixture was irradiated with 3W blue light, and the reaction was stirred at 35°C for 18 hours. The reaction mixture was washed with saturated brine. The mixture was extracted with ethyl acetate, and the combined organic layer was washed with anhydrous Mg 2 SO 4 Dry and concentrate under reduced pressure. The crude product was purified on a silica gel column using n-hexane / ethyl acetate to obtain 94 mg of the product with a yield of 77.2% and an HPLC purity of 98.9%.

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Abstract

The invention discloses a synthesis method of a difluoroalkyl substituted aromatic ketone compound under photocatalysis. The preparation method comprises the following steps: dissolving an aromatic ketone compound, a CF2 reagent, a bidentate ligand, a photocatalyst and an alkali in an organic solvent, reacting for 10-48 h under an illumination condition, and carrying out post-treatment on the reacted solution after the reaction is finished in order to obtain the difluoroalkyl substituted aromatic ketone compound. The method provided by the invention realizes difluoroalkylation of aromatic ketone compounds under illumination, and has the advantages of easily available raw materials, mild reaction conditions, wide substrate applicability, good reaction selectivity, simplicity in operation and the like.

Description

Technical field [0001] The invention relates to a method for synthesizing difluoroalkyl substituted aromatic ketones under photocatalysis, in particular to a green synthesis of difluoroalkyl substituted aromatic ketones from aromatic ketones under photocatalytic catalysis resolve resolution. Background technique [0002] Organic fluorine compounds are widely used in pharmaceuticals, agrochemicals, materials, surfactants and catalysts. Because this group has special biological properties, such as improved membrane permeability, binding affinity and bioavailability, the difluoromethyl (CF 2 ) The selective introduction of organic molecules has attracted people's attention. CF 2 The functional group and hydroxyl (OH) are isotactic and isopolar, and have lipophilicity. At the same time, CF 2 The group is weakly acidic and can participate in weak hydrogen bond interactions. Because of these characteristics, CF 2 Groups are found in various biologically active compounds, such as enz...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/343C07C69/738C07C231/12C07C235/78
CPCC07C67/343C07C231/12C07C2602/10C07C2601/14C07C69/738C07C235/78
Inventor 李坚军周嘉第王芳林志豪
Owner 天台宜生生化科技有限公司
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