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Method for synthesizing 4-acyl pyrazole compound from non-cyclic ketone hydrazone

A technology for acylpyrazoles and acyclic ketone hydrazones, which is applied in the field of organic synthesis, can solve the problems of limited method of 4-acyl-substituted pyrazoles, poor regioselectivity, and difficulty in obtaining raw materials, avoiding purification treatment and easy operation. , a wide range of effects

Active Publication Date: 2017-08-25
HENAN NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In view of its importance, people have successively developed some effective methods for building pyrazoles, but the methods for synthesizing 4-acyl-substituted pyrazoles are still very limited, and the existing methods still have raw materials that are not easy to obtain, and the reaction Harsh conditions, poor regional selectivity and other problems, so that its application in actual production is limited to a certain extent

Method used

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  • Method for synthesizing 4-acyl pyrazole compound from non-cyclic ketone hydrazone
  • Method for synthesizing 4-acyl pyrazole compound from non-cyclic ketone hydrazone
  • Method for synthesizing 4-acyl pyrazole compound from non-cyclic ketone hydrazone

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Experimental program
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Effect test

Embodiment 1

[0011]

[0012] Add 1a (0.5mmol, 67mg), copper acetate (Cu(OAc) 2 , 0.05mmol, 9mg), 2,2'-bipyridine (bpy, 0.05mmol, 8mg), 2,2,6,6-tetramethylpiperidine nitrogen oxide (TEMPO, 0.5mmol, 78mg) and toluene ( toluene, 3mL), the reaction tube was sealed after evacuated and filled with nitrogen, and placed in an oil bath at 120°C to stir for 10 h. Then 2a (0.5 mmol, 112 mg) was added to the reaction system, and the stirring reaction was continued in an oil bath at 120° C. for 4 h in an air atmosphere. The reaction was quenched by adding 10 mL of water, extracted with ethyl acetate (10 mL×3), and then the organic phase was washed with water and saturated brine in sequence, and dried over anhydrous sodium sulfate. Filtration, spin-drying, and silica gel column separation (petroleum ether / ethyl acetate=20 / 1) gave the white solid product 1,3-diphenyl-4-benzoylpyrazole 3a (68 mg, 42%). The characterization data of this compound are as follows: 1 H NMR (400MHz, CDCl 3 )δ:7.32-7.42(m...

Embodiment 2

[0014] Add 1a (0.5mmol, 67mg), Cu(OAc) 2 (0.1mmol, 18mg), bpy (0.05mmol, 8mg), TEMPO (0.5mmol, 78mg) and toluene (3mL), vacuumize and fill the reaction tube with nitrogen, seal the reaction tube, and place it in an oil bath at 120°C for 10h with stirring. Then 2a (0.5 mmol, 112 mg) was added to the reaction system, and the stirring reaction was continued in an oil bath at 120° C. for 4 h in an air atmosphere. The reaction was quenched by adding 10 mL of water, extracted with ethyl acetate (10 mL×3), and then the organic phase was washed with water and saturated brine in sequence, and dried over anhydrous sodium sulfate. Filtration, spin-drying, and silica gel column separation (petroleum ether / ethyl acetate=20 / 1) gave white solid product 1,3-diphenyl-4-benzoylpyrazole 3a (97 mg, 60%).

Embodiment 3

[0016] Add 1a (0.6mmol, 80mg), Cu(OAc) 2 (0.1mmol, 18mg), bpy (0.05mmol, 8mg), TEMPO (0.5mmol, 78mg) and toluene (3mL), vacuumize and fill the reaction tube with nitrogen, seal the reaction tube, and place it in an oil bath at 120°C for 10h with stirring. Then 2a (0.5 mmol, 112 mg) was added to the reaction system, and the stirring reaction was continued in an oil bath at 120° C. for 4 h in an air atmosphere. The reaction was quenched by adding 10 mL of water, extracted with ethyl acetate (10 mL×3), and then the organic phase was washed with water and saturated brine in sequence, and dried over anhydrous sodium sulfate. Filtration, spin-drying, and silica gel column separation (petroleum ether / ethyl acetate=20 / 1) gave the white solid product 1,3-diphenyl-4-benzoylpyrazole 3a (105 mg, 65%).

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Abstract

The invention discloses a method for synthesizing a 4-acyl pyrazole compound from non-cyclic ketone hydrazine, and belongs to the technical field of organic synthesis. The technical scheme of the invention is characterized in that the method for synthesizing the 4-acyl pyrazole compound from the non-cyclic ketone hydrazine specifically comprises the following steps: dissolving an alpha,beta-saturated ketone compound in a solvent; adding a catalyst, a ligand and an oxidizing agent in sequence; stirring for reacting at the temperature of 100 to 140 DEG C in a nitrogen atmosphere; then, adding the non-cyclic ketone hydrazine into a reaction system; continually reacting at the temperature of 100 to 140 DEG C in an air atmosphere to obtain the 4-acyl pyrazole compound. By adopting the method, the alpha,beta-saturated ketone compound and the non-cyclic ketone hydrazine are subjected to a one-pot multi-step serial reaction under the catalysis of a copper salt to obtain the 4-acyl pyrazole compound; the method has the advantages of easiness and convenience in operation, mild conditions and wide substrate application range, and the suitable for industrial production.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for synthesizing 4-acylpyrazoles by reacting acyclic ketone hydrazone with α, β-saturated ketone. Background technique [0002] Pyrazole is a five-membered heterocyclic compound containing two adjacent nitrogen atoms. Due to its remarkable biological activity and unique optical properties, it has been widely used in the fields of medicine, pesticides and fluorescent materials. In view of its importance, people have successively developed some effective methods for building pyrazoles, but the methods for synthesizing 4-acyl-substituted pyrazoles are still very limited, and the existing methods still have raw materials that are not easy to obtain, and the reaction Harsh conditions, poor regional selectivity and other issues have limited its application in actual production. Therefore, researching and developing the synthesis of 4-acylpyrazoles using ...

Claims

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Application Information

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IPC IPC(8): C07D231/12C07D409/06C07D401/06C07D409/04
CPCC07D231/12C07D401/06C07D409/04C07D409/06
Inventor 范学森田苗苗张新迎师晓楠
Owner HENAN NORMAL UNIV
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