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Synthesis method of 3,3-difluoro-4-pyrroline-2-one compound

A technology of ketone compound and synthesis method, which is applied in the field of chemical organic synthesis and achieves the effects of high yield, wide substrate range and simple reaction operation

Active Publication Date: 2017-06-20
ANYANG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] So far, there are few reports on the synthesis of 3,3-difluoro-4-pyrrolin-2-one compounds

Method used

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  • Synthesis method of 3,3-difluoro-4-pyrroline-2-one compound
  • Synthesis method of 3,3-difluoro-4-pyrroline-2-one compound
  • Synthesis method of 3,3-difluoro-4-pyrroline-2-one compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] First, put a stirring bar in a 35 mL sealed tube, and add 79.2 mg (0.3 mmol) bromodifluoroacetyl-p-toluidine, 3.0 ml acetonitrile, and 49 μL phenylacetylene (0.45 mmol) in sequence and mix well. Second, 5.4 mg Phen (0.03 mmol), 5.7 mg CuI (0.03 mmol) and 82.9 mg K 2 CO 3 (0.6 mmol), sealed the mouth of the tube with a cock, heated to 110°C and stirred for 2 hours. After the reaction, the system was cooled to room temperature, 3 ml of distilled water was added to the reaction mixture, extracted with ethyl acetate (5 ml×3), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was passed through a silica gel column. Chromatography (V 石油醚 :V 乙酸乙酯 =50:1) 78.7 mg of white solid product 3a was isolated with a yield of 92%. The reaction is shown in the following formula:

[0021]

[0022] Spectral analysis data

[0023] 1 H NMR (400 MHz, CDCl 3 ): δ = 2.32 (s, 3H), 5.63 (t, J ...

Embodiment 2

[0025]First, put a stirring bar in a 35 mL sealed tube, and add 79.2 mg (0.3 mmol) bromodifluoroacetyl-p-toluidine, 3.0 ml acetonitrile, and 52 μL p-fluorophenylacetylene (0.45 mmol) in sequence and mix well. Second, 5.4 mg Phen (0.03 mmol), 5.7 mg CuI (0.03 mmol) and 82.9 mg K 2 CO 3 (0.6 mmol), seal the nozzle tightly with a cock, heat to 110°C and stir for 2 hours. After the reaction, the system was cooled to room temperature, 3 ml of distilled water was added to the reaction mixture, extracted with ethyl acetate (5 ml×3), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was passed through a silica gel column. Chromatography (V 石油醚 :V 乙酸乙酯 =50:1) to isolate 82.9 mg of white solid product 3b with a yield of 91%. The reaction is shown in the following formula:

[0026]

[0027] Spectral analysis data

[0028] 1 H NMR (400 MHz, CDCl 3 ): δ = 2.33 (s, 3H), 5.61 (d, J = 1....

Embodiment 3

[0030] First, put a stirring bar in a 35 mL sealed tube, and add 79.2 mg (0.3 mmol) bromodifluoroacetyl-p-toluidine, 3.0 ml acetonitrile, and 81.5 mg p-bromophenylacetylene (0.45 mmol) in sequence and mix well. Second, 5.4 mg Phen (0.03 mmol), 5.7 mg CuI (0.03 mmol) and 82.9 mg K 2 CO 3 (0.6 mmol), seal the nozzle tightly with a cock, heat to 110°C and stir for 2 hours. After the reaction, the system was cooled to room temperature, 3 ml of distilled water was added to the reaction mixture, extracted with ethyl acetate (5 ml×3), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was passed through a silica gel column. Chromatography (V 石油醚 :V 乙酸乙酯 =50:1) 89.6 mg of white solid product 3c was isolated with a yield of 82%. The reaction is shown in the following formula:

[0031]

[0032] Spectral analysis data

[0033] 1 H NMR (400 MHz, CDCl 3 ): δ = 2.33 (s, 3H), 5.64 (s, 1H),...

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Abstract

The invention belongs to the technical field of organic synthesis and in particular relates to a synthesis method of a 3,3-difluoro-4-pyrroline-2-one compound. The synthesis method comprises the following steps: dissolving a bromo-difluoroacetamide compound with a solvent; adding alkyne and uniformly mixing; then adding a ligand ortho-phenanthroline, a catalyst CuI and an alkali K2CO3; raising temperature to 110 DEG C+ / -10 DEG C under a sealed condition and stirring and reacting for 1h to 3h; after reacting, carrying out post-treatment to obtain the product. By adopting the synthesis method, a 3,3-difluoro-4-pyrroline-2-one derivative is synthesized for the first time; the synthesis method has the characteristics of high atomic economy, simple reaction steps, cheap and easy-to-obtain raw materials, wide substrate application range and the like, is applicable to synthesis of various 3,3-difluoro-4-pyrroline-2-one compounds and is suitable for industrialized production.

Description

Technical field: [0001] The invention belongs to the technical field of chemical organic synthesis, and specifically relates to a method for catalytically synthesizing 3,3-difluoro-4-pyrroline-2-one compounds using alkynes and brominated difluoroacetamide compounds as raw materials. Background technique: [0002] Fluorine-containing heterocyclic compounds are widely used in the fields of medicine, agrochemicals, and materials. The introduction of fluorine atoms in heterocycles can enhance their biological activity and improve the stability of biomolecules ((a) Uneyama, K.; Sasaki, K.Pharmaceuticals containing fluorinated heterocyclic compounds. In Fluorinated Heterocyclic Compounds: Synthesis, Chemistry and Application; Petrov, V. A., Ed.; John Wiley & Sons: Hoboken. 2009, 419. (b) Kwiatkowski, P.; Beeson, T.D.; Conrad, J. C.; , D. W. C. J. Am. Chem. Soc. 2011, 133, 1738. (c) Silvester, M. J. Aldrichimica Acta. 1991, 24, 31.). At present, some fluorine-containing heterocycl...

Claims

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Application Information

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IPC IPC(8): C07D207/38C07D409/04
CPCC07D207/38C07D409/04
Inventor 吕允贺蒲卫亚孙凯李刚张前
Owner ANYANG NORMAL UNIV
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