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Preparation method of electron-deficient group-containing multi-substituted pyrazole derivative

An electron-deficient and multi-substituted technology is applied in the field of preparation of multi-substituted pyrazole derivatives, which can solve problems such as insufficient group compatibility, and achieve the effects of simple operation and easy availability of raw materials.

Active Publication Date: 2012-11-07
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Aiming at the defect of insufficient group compatibility existing in the existing preparation method, the present invention provides a new method for easily synthesizing pyrazole derivative compounds compatible with various carbonyl, cyano, amido and other groups

Method used

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  • Preparation method of electron-deficient group-containing multi-substituted pyrazole derivative
  • Preparation method of electron-deficient group-containing multi-substituted pyrazole derivative
  • Preparation method of electron-deficient group-containing multi-substituted pyrazole derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Weigh 3-benzylidene-5-phenyl-4-pentyn-2-one (0.20mmol, 49.2mg), tert-butylnitrile hydrochloride (0.24mmol, 29.9mg), potassium carbonate (0.28mmol , 38.6mg), all of them were added to a small reaction tube, and 2.0ml N,N-dimethylacetamide was added at room temperature. After stirring at room temperature (23°C) for 1.2 hours, the completion of the reaction was monitored by thin-layer chromatography silica gel (TLC), and 4 mL of water and 10 mL of ether were added for extraction, and the aqueous phase was extracted twice with 10 mL of ether. After washing with salt water for 2-3 times, add anhydrous sodium sulfate to dry, filter, the filtrate is rotary evaporated at 20°C to remove the solvent, and then separated by column chromatography (eluent: petroleum ether: ethyl acetate = 1:8) to obtain White solid pyrazole derivative pure product IA-1. Yield 97% (64.4 mg). m.p.: 127~128℃.

[0054]

[0055] 1 H NMR (400MHz, CDCl 3 ):δ=7.55(d,J=7.2Hz,2H),7.45~7.37(m,3H),7.26(t...

Embodiment 2

[0057] Weigh 3-(4-methoxybenzylidene)-5-phenyl-4-pentyn-2-one (0.20mmol, 55.2mg), tert-butylnitrile hydrochloride (0.24mmol, 29.9mg ), potassium carbonate (0.28mmol, 38.6mg), all of them were added into a small reaction tube, and 2.0ml of N,N-dimethylacetamide was added at room temperature. After continuing to stir at room temperature for 4 hours, monitor the completion of the reaction by thin-layer chromatography silica gel (TLC), add 4 mL of water and 10 mL of diethyl ether for extraction, and then extract the aqueous phase with 10 mL of diethyl ether twice, combine the organic phases, and wash with saturated saline After 2-3 times, add anhydrous sodium sulfate to dry, filter, the filtrate is rotary evaporated at 20°C to remove the solvent, and then separated by column chromatography (eluent: petroleum ether: ethyl acetate = 1:8) to obtain a yellow solid pyridine Azole Derivatives Pure Product IA-2. Yield 85% (62.0 mg). m.p.: 105~106℃.

[0058]

[0059] 1 H NMR (400MH...

Embodiment 3

[0061] Weigh 3-(4-cyanobenzylidene)-5-phenyl-4-pentyn-2-one (0.20mmol, 54.2mg), tert-butylnitrile hydrochloride (0.24mmol, 29.9mg) , potassium carbonate (0.28mmol, 38.6mg), all of them were added into a small reaction tube, and 2.0ml of N,N-dimethylacetamide was added at room temperature. After continuing to stir at room temperature for 1 hour, the completion of the reaction was monitored by thin chromatography silica gel plate (TLC), and 4 mL of water and 10 mL of diethyl ether were added for extraction, and the aqueous phase was extracted twice with 10 mL of diethyl ether. After -3 times, add anhydrous sodium sulfate to dry, filter, and the filtrate is rotary evaporated at 20°C to remove the solvent, and then separated by column chromatography (eluent: petroleum ether: ethyl acetate = 1:8) to obtain pyrazole as a white solid Derivatives Pure Product IA-3. Yield 90% (64.3 mg). m.p.: 161~162℃.

[0062]

[0063] 1 H NMR (400MHz, CDCl 3 ):δ=7.73(d,J=8.4Hz,2H),7.69(d,J=8....

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Abstract

The invention relates to a preparation method of an electron-deficient group-containing multi-substituted pyrazole derivative. The preparation method comprises the following steps of: dissolving electron-deficient conjugated enyne, hydrazine and alkali in an organic solvent, and enabling the mixture to react in a range of room temperature to 40 DEG C, removing the solvent and obtaining a crude product; and obtaining the electron-deficient group-containing multi-substituted pyrazole derivative shown in a formula (I) or formula (II) by column chromatography. The preparation method has the advantages of simple and easy obtaining of raw materials, simplicity and safety in operation, high atom economy, high yield and high selectivity. The aldehyde ketone and other functional groups containing multi-substituted pyrazole derivative with a single isomer can be conveniently and effectively obtained by one step, various compound skeletons are provided, and the method has important significance on synthesis of the substituted pyrazole compound.

Description

technical field [0001] The invention relates to a preparation method of pyrazole derivatives containing electron-deficient groups such as aldehydes and ketones, in particular to a preparation method of multi-substituted pyrazole derivatives containing electron-deficient groups, and belongs to the field of new synthesis methods. Background technique [0002] After years of research, a series of synthetic methods of pyrazole derivatives have been supplemented and improved (Heterocycles1991, 32, 1745., Chem. Rev., 2011, 111, 6984., R.Kinjo, B.Donnadieu, G. Bertrand, Angew. Chem., Int. Ed. 2011, 50, 5560). Usually, the more common synthesis methods of multi-substituted pyrazole derivatives are mostly through the condensation of 1,3-diketone or its equivalent with hydrazines, or from 1,3-dipolar diazo compounds or iminonitriles with different Saturated alkenes or alkynes are obtained. However, the disadvantages of these methods in terms of regioselectivity, activity or danger o...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D231/12C07D231/14C07D413/06C07D231/54C07D491/048C07D487/04C07D231/56
Inventor 张俊良于秀招李文博
Owner EAST CHINA NORMAL UNIV
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