Synthesis method of tetrahydropyrazolone derivative

A technology of tetrahydropyrazolone and synthesis method, which is applied in the field of synthesis of tetrahydropyrazolone derivatives, can solve the problems of high price, difficult to store, environmental pollution, etc., achieves high yield and product purity, is convenient for storage and Transportation, the effect of reducing environmental pollution

Inactive Publication Date: 2013-11-13
李佰林 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Among the synthesis methods reported, only Rao V.K. used ytterbium trifluoroacetate as a catalyst to synthesize tetrahydropyrazolone derivatives at 100°C in imidazolium ionic liquid (Bioorg.Med.Chem.Lett.2012, 22:410-414), The characteristic of the reaction is that rare metals are used as catalysts, heated in ionic liquids, and the reaction time is long. The catalysts are not only expensive, but also difficult to recycle, which will bring a certain degree of pollution to the environment.
At the same time, the raw material of aromatic hydrazine is not only highly toxic, expensive, but also difficult to preserve

Method used

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  • Synthesis method of tetrahydropyrazolone derivative
  • Synthesis method of tetrahydropyrazolone derivative
  • Synthesis method of tetrahydropyrazolone derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022]

[0023] Add benzaldehyde (25mmol), 5,5-dimethylcyclohexanedione (25mmol), phenylhydrazine hydrochloride (25mmol), ionic liquid (0.125mmol), and absolute ethanol 10mL into the reaction vessel in sequence , put the reaction vessel in a microwave reactor, microwave reaction at 80°C for 20 minutes (ultrasonic input power 400W), after the reaction, distill off ethanol, wash the remaining solid with 20mL water, filter, and recrystallize the filter cake with ethanol to obtain the product , yield 85%.

[0024] Characterization data: 1 H NMR (400MHz, DMSO-d 6 ):δ=7.50(s,1H),7.38–7.31(m,6H),7.18–7.25(m,2H),6.94(d,J=8.0Hz,1H),2.82(s,2H),2.43( s,2H),1.17(s,6H); 13 C NMR (100MHz, CDCl 3 ): δ28.47, 34.85, 53.73, 105.01, 116.21, 124.19, 127.67, 129.85, 130.21, 130.27, 132.09, 133.13, 138.38, 143.46, 156.96, 193.38.

Embodiment 2

[0026]

[0027] Add p-tolualdehyde (25mmol), 5,5-dimethylcyclohexanedione (25mmol), phenylhydrazine hydrochloride (25mmol), ionic liquid (0.125mmol), and absolute ethanol 10mL to the In the reaction vessel, place the reaction vessel in a microwave reactor and react with microwaves at 80°C for 20 minutes (ultrasonic input power 400W). After the reaction, ethanol is distilled off, and the remaining solid is washed with 20mL of water, filtered, and the filter cake is weighed with ethanol. The product was crystallized with a yield of 87%.

[0028] Characterization data: 1 H NMR (400MHz, DMSO-d 6 ):δ=7.44–7.35(m,3H),7.35-7.28(m,2H),7.17(d,J=8.0Hz,2H),6.90(d,J=4.0Hz,2H),2.85(s, 2H),2.41(s,2H),2.23(s,3H),1.20(s,6H); 13 CNMR (100MHz, CDCl 3 ): δ19.75, 28.44, 34.87, 37.13, 53.70, 123.49, 126.01, 126.25, 128.71, 130.97, 131.68, 134.69, 135.70, 136.48, 137.68, 156.73, 193.55.

Embodiment 3

[0030]

[0031] Add p-chlorobenzaldehyde (25mmol), 5,5-dimethylcyclohexanedione (25mmol), phenylhydrazine hydrochloride (25mmol), ionic liquid (0.125mmol), and absolute ethanol 10mL to the reaction in sequence In the container, put the reaction container in a microwave reactor, microwave reaction at 80°C for 20 minutes (ultrasonic input power 400W), after the reaction, distill off ethanol, wash the remaining solid with 20mL water, filter, and recrystallize the filter cake with ethanol The product was obtained with a yield of 88%.

[0032] Characterization data: 1 H NMR (400MHz, DMSO-d 6 ):δ=7.50-7.43(m,2H),7.38–7.31(m,4H),7.18–7.25(m,2H),6.93(d,J=8.0Hz,1H),2.81(s,2H), 2.43(s,2H),1.18(s,6H); 13 C NMR (100MHz, CDCl 3 ): δ28.46, 34.86, 53.63, 105.05, 116.22, 125.19, 127.67, 129.87, 130.21, 130.27, 132.09, 133.13, 138.38, 144.46, 156.97, 193.38.

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Abstract

The invention discloses a synthesis method of a tetrahydropyrazolone derivative. The structural formula of the tetrahydropyrazolone derivative is shown by a formula (4a) in a reaction equation 1. The synthesis method comprises the following steps of: by taking aromatic aldehyde shown by a structural formula (1a) in the reaction equation 1, 5,5-dimethylcyclohexanedione shown by a formula (2a) and phenylhydrazine hydrochloride shown by a formula (3a) as substrates and taking an ionic liquid shown by a formula (b) as a catalyst and ethanol as a reaction solvent, performing microwave reaction at 70-80 DEG C for 15-25 minutes; after the reaction, evaporating the solvent, washing solids with water and filtering; and drying filter cakes, and then re-crystallizing by use of ethanol to obtain the tetrahydropyrazolone derivative. The method disclosed by the invention has the characteristics of mild reaction conditions, simple and convenient operation, short reaction time, recyclable ionic liquid, environment-friendly synthesis process, high yield and purity and the like. The reaction equation is shown in the specification.

Description

(1) Technical field [0001] The invention relates to a synthesis method of tetrahydropyrazolone derivatives. (2) Background technology [0002] Tetrahydropyrazolone is a compound with a wide range of physiological and pharmacological activities. Compounds containing pyrazole and pyrazolone structures have herbicide, anti-infection, anti-cancer and anti-tuberculosis effects. The structure of tetrahydropyrazolone has the similar structure of heat shock protein inhibitor (HSP-90) and anti-proliferation activity of breast cancer cells, such as structural formula 1. At the same time, tetrahydropyrazole also has a similar structural unit (MTB) of Mycobacterium tuberculosis inhibitors such as structural formula 2. Therefore, the synthesis of tetrahydropyrazolone derivatives has become a research hotspot. Among the synthesis methods reported, only Rao V.K. used ytterbium trifluoroacetate as a catalyst to synthesize tetrahydropyrazolone derivatives at 100°C in imidazolium ionic liq...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D231/56
CPCY02P20/584
Inventor 李佰林
Owner 李佰林
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