Difluoromethyl aldehyde hydrazone compound and preparation method thereof

A technology of difluoromethylated aldehyde hydrazone and difluoromethyl, which is applied in the field of difluoromethylated aldehyde hydrazone compounds and their preparation, can solve the problems of high cost and complex process, and achieve environmental friendliness and step-by-step operation Simple, high-yield results

Active Publication Date: 2017-11-24
LIAONING UNIVERSITY OF PETROLEUM AND CHEMICAL TECHNOLOGY
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Problems solved by technology

[0004] In order to solve the existing problems of complicated process and high cost in the preparation method of difluoromethyl-substituted aldehyde hydrazone derivatives, the present invention provides a visible light redox reaction starting from aldehyde compounds and using 4CzIPN as a photosensitizer, one-step synthesis of two Fluoromethyl-substituted difluoromethylated aldehyde hydrazone compounds and preparation method thereof

Method used

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  • Difluoromethyl aldehyde hydrazone compound and preparation method thereof
  • Difluoromethyl aldehyde hydrazone compound and preparation method thereof
  • Difluoromethyl aldehyde hydrazone compound and preparation method thereof

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Effect test

Embodiment 1

[0062]

[0063] The reactor was evacuated and replaced with argon three times, and 0.2mmol (21.2mg) benzaldehyde (1a), 0.24mmol (24.5mg) N-aminomorphine (2a), 0.40mmol (80.8mg) difluorobromide were added successively Ethyl acetate (3a), 0.006 mmol (4.73 mg) 4CzIPN, 75 mg anhydrous MgSO 4 , 1mL DMF, 8W blue LED, stirred at room temperature for 12 hours. After the reaction was finished, the solvent was removed with a rotary evaporator, and the crude product was subjected to column chromatography, and the eluent was sherwood oil: ethyl acetate=10:1 mixed solvent to obtain 44.32 mg of difluoromethyl-substituted phenylaldehyde hydrazone Compound 4a. The isolated yield was 71%.

[0064] The characterization data of compound 4a are as follows:

[0065] E:Z=19:1. 1 H NMR (500MHz, CDCl 3 ):δ7.48-7.46(m,2H),7.42-7.40(m,2H),4.38(q,J=7.0Hz,2H),3.59(t,J=4.5Hz,4H),2.92(t, J=5.0Hz, 4H), 1.38(t, J=7.0Hz, 3H). 13 C NMR (125MHz, CDCl 3 ): δ163.7(t, 31.5Hz), 140.7(t, 31.5Hz), 131.3, 1...

Embodiment 2

[0067]

[0068] The reactor was evacuated and replaced with argon three times, and 0.2mmol (21.2mg) p-chlorobenzaldehyde (1b), 0.24mmol (24.5mg) N-aminomorphine (2a), 0.40mmol (80.8mg) di Ethyl fluorobromoacetate (3a), 0.006mmol (4.73mg) 4CzIPN, 75mg anhydrous MgSO 4 , 1mL DMF, 8W blue LED, stirred at room temperature for 12 hours. After the reaction was finished, the solvent was removed with a rotary evaporator, and the crude product was subjected to column chromatography, and the eluent was sherwood oil: ethyl acetate=10:1 mixed solvent to obtain 64.37 mg of difluoromethyl-substituted p-chlorophenylaldehyde Hydrazone compound 4b. The isolated yield was 93%.

[0069] The characterization data of compound 4b are as follows

[0070] E:Z=19:1. 1 H NMR (500MHz, CDCl 3 ):δ7.45-7.40(m,4H),4.38(q,J=7.0Hz,2H),3.61(t,J=4.5Hz,4H),2.94(t,J=5.0Hz,4H),1.38 (t,J=7.0Hz,3H); 13 C NMR (125MHz, CDCl 3 ): δ=163.4(t, J=31.3Hz), 139.5(t, J=31.8Hz), 135.9, 130.1, 129.6, 129.1, 114.2(t, ...

Embodiment 3

[0072]

[0073] The reactor was evacuated and replaced with argon three times, and 0.2mmol (21.2mg) p-tolualdehyde (1c), 0.24mmol (24.5mg) N-aminomorphine (2a), 0.40mmol (80.8mg) were added successively Ethyl difluorobromoacetate (3a), 0.006 mmol (4.73 mg) 4CzIPN, 75 mg anhydrous MgSO 4 , 1mL DMF, 8W blue LED, stirred at room temperature for 12 hours. After the reaction was finished, the solvent was removed with a rotary evaporator, and the crude product was subjected to column chromatography, and the eluent was sherwood oil: ethyl acetate=10:1 mixed solvent to obtain 54.80 mg of difluoromethyl-substituted p-methylphenyl Aldehydrazone compound 4c. The isolated yield was 84%.

[0074] The characterization data of compound 4c are as follows

[0075] E:Z=18:1. 1 H NMR (500MHz, CDCl 3 ): δ7.39(d, J=8.0Hz, 2H), 7.23(d, J=8.0Hz, 2H), 4.40(q, J=7.0Hz, 2H), 3.62(t, J=4.5Hz, 4H ), 2.95(t, J=4.5Hz, 4H), 2.40(s, 3H), 1.40(t, J=7.0Hz, 3H); 13 C NMR (125MHz, CDCl 3 ): δ163.8(t, ...

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Abstract

The invention relates to a difluoromethyl aldehyde hydrazone compound and a preparation method thereof. The method comprises the following steps: vacuumizing a reactor and then introducing argon for replacing, successively adding photosensitizer, alkali, additive, aldehyde derivative, hydrazine derivative, difluromethylation reagent and solvent, irradiating under visible light and reacting for 12-24h under normal temperature; after ending the reaction, removing the solvent through rotary evaporation, thereby acquiring a crude product; dissolving the crude product in dichloromethane and performing column chromatography on silica gel, thereby acquiring a difluoromethyl substituted difluoromethyl aldehyde hydrazone compound. According to the method provided by the invention, the clean sustainable visible light is taken as an energy source, the high-cost toxic ruthenium and iridium pyridine complex need not be used and the difluoromethylation of the aldehyde hydrazone compound can be conveniently realized through a simple operation step.

Description

technical field [0001] The invention belongs to the field of organic synthetic chemistry, and in particular relates to a difluoromethylated difluoromethylated aldehyde hydrazone compound and a preparation method thereof. Background technique [0002] In recent years, studies have found that the introduction of fluorine atoms into physiologically active molecules can increase their biological activity by affecting fat solubility, stability, permeability, etc. has important research significance. Although a large number of fluorination methods and reactions have been reported one after another, most of the research reports revolve around the introduction of fluorine atoms and trifluoromethyl groups, which usually have the disadvantages of expensive fluorination reagents and relatively harsh reaction conditions. Recently, difluoromethyl (CF 2 ) has gradually attracted people's attention in the research and development of medicine and pesticides because of its special properti...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D295/30C09K11/06C07D209/86
CPCC07D209/86C07D295/30C09K11/06C09K2211/1029
Inventor 李蕾李金雪王贺周明东
Owner LIAONING UNIVERSITY OF PETROLEUM AND CHEMICAL TECHNOLOGY
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