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Air stabilized type catalyst as well as preparation and application thereof in catalyzing generation of N1-substituted pyrazole derivatives

A catalyst and stable technology, applied in catalytic reactions, physical/chemical process catalysts, organic compounds/hydrides/coordination complex catalysts, etc., can solve the requirements of harsh reactants, diversification of unfavorable reactions, high production costs, etc. problems, to achieve the effect of mild reaction conditions, environmentally friendly solvents, and low cost

Active Publication Date: 2020-01-17
SHENYANG SINOCHEM AGROCHEMICALS R&D CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The N1-substituted pyrazole derivatives reported in the literature can be synthesized from β-keto esters and analogs and hydrazine derivatives. Although this method is convenient and easy to implement, the process is too cumbersome, which is not conducive to the diversification of reactions.
In 2017, Adrian Huang, KellieWO et al. proposed a catalyst-free method for generating N1-substituted pyrazole derivatives. Although this method is efficient, it has strict requirements on the reactants and is only suitable for substitution by 3-position strong electron-withdrawing groups The synthesis of pyrazole compounds and fluorine-substituted or individual bromine-substituted aromatic rings or heterocyclic rings has high production costs and narrow scope of application

Method used

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  • Air stabilized type catalyst as well as preparation and application thereof in catalyzing generation of N1-substituted pyrazole derivatives
  • Air stabilized type catalyst as well as preparation and application thereof in catalyzing generation of N1-substituted pyrazole derivatives
  • Air stabilized type catalyst as well as preparation and application thereof in catalyzing generation of N1-substituted pyrazole derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Reaction formula:

[0026]

[0027] Put 10 mmol of nickel bromide into a dry three-neck round bottom flask, add 60 mL of absolute ethanol, and then add 10 mmol of 4,5-bisdiphenylphosphine-9,9-dimethylxanthene. After heating to reflux under nitrogen for 30 minutes, it was cooled to 0 °C under ice bath. Suction filtration, rinse with cold absolute ethanol and diethyl ether three times respectively. Finally, it was rinsed with dichloromethane, the rinse solution was collected, and spin-dried to obtain a dark green solid—the compound represented by structural formula (I)—with a yield of 89.6%.

[0028]

[0029] Under nitrogen, add 8 mmol of the compound represented by formula (I) and 40 mL of dry-treated tetrahydrofuran into a dry round-bottomed flask, and drop 8 mmol of 2,4,6-trimethylphenyl bromide at 0°C magnesium. After the dropwise addition, it was raised to room temperature and reacted for 30 minutes. Spin to dry the solvent, add 30mL cold absolute ethanol, ...

Embodiment 2

[0031] Reaction formula:

[0032] Add 6.58g of pyrazole, 3.4g of benzyl chloride, 0.84g of catalyst represented by structural formula (II), 5.52g of potassium tert-butoxide, and 70mL of tetrahydrofuran into a round bottom flask, and heat to reflux under nitrogen for 7 hours. After filtration, the filtrate was spin-dried and passed through the column (ethyl acetate:petroleum ether (v / v)=1:4) to obtain 6.60 g of colorless liquid with a yield of 83.4%.

Embodiment 3

[0034] Reaction formula:

[0035] Add 0.57g of 3-nitropyrazole, 0.89g of benzyl chloride, 0.21g of catalyst represented by structural formula (II), 0.56g of potassium tert-butoxide, and 50mL of tetrahydrofuran into a round bottom flask, and heat to reflux under nitrogen for 7 hours. After filtration, the filtrate was spin-dried and passed through the column (ethyl acetate:petroleum ether (v / v)=1:2) to obtain 0.73g of yellow liquid with a yield of 71.9%.

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Abstract

The invention relates to the field of pesticides and medicines and in particular relates to an air stabilized type catalyst as well as a preparation and application thereof in catalyzing generation ofN1-substituted pyrazole derivatives. The catalyst is a compound of a structural formula (II) shown in the description; and the catalyst is used for catalyzing synthesis of N1-substituted pyrazole derivatives. The catalyst provided by the invention is simple, cheap and stable to prepare, when being used for catalyzing pyrazole compounds and halogen-containing aromatic rings or heterocyclic rings,the catalyst is wide in application range, simple to prepare, high in yield and mild in reaction condition, and a used solvent is green and environment-friendly and non-toxic or low-toxic.

Description

technical field [0001] The invention relates to the fields of pesticides and medicines, in particular to the preparation of a catalyst stable in air and the application of the preparation and catalysis to generate N1-substituted pyrazole derivatives. Background technique [0002] As an important member of the nitrogen-containing heterocyclic ring system, pyrazole compounds not only have unique structural forms, but also have broad-spectrum biological activities, and play an important role in insecticide, herbicide, bactericide and anticancer. Pyrazole derivatives substituted by N1- are widely used in pesticide and pharmaceutical fields, such as the insecticide pyrolan (pyrolan) listed by Ciba-Geigy in Switzerland in 1947; the pyrazole listed by BASF in 1979 The herbicide metazachlor (metazachlor); in 1999 the U.S. Searle pharmaceutical factory developed and listed celecoxib (celecoxib) for the treatment of rheumatism, rheumatoid and osteoarthritis; in 2001, Selwood et al. re...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07D231/12C07D231/16
CPCB01J31/2452B01J2231/4277B01J2531/847C07D231/12C07D231/16
Inventor 姜鹏朱琳娜王嫱于海波
Owner SHENYANG SINOCHEM AGROCHEMICALS R&D CO LTD