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Halogen substituted compound and preparation method and application thereof

A compound and halogen technology, applied in the field of industrial synthesis of halogen-substituted compounds, can solve the problems of unsuitability for industrial production, high price of ethyl propiolate, difficult separation of isomers, etc., to achieve easier recycling and high product quality , easy purification effect

Pending Publication Date: 2019-12-17
科莱博(江苏)科技股份有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although there are certain advantages in cost control, the reaction conditions are relatively harsh, in which dichloroacetyl chloride and vinyl ether compounds need to react at -40~-20°C; The temperature is 150°C, and the pressure in the kettle must be constantly changed during the process, which is inconvenient to operate, and the isomers are not easy to separate; 2) WO2009000442 reported that ethyl difluoroacetate was used as a raw material to react with hydrazine hydrate to form hydrazide, which was methylated and then 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid ethyl ester (DFMMP) is obtained by ring closure with ethyl propiolate, the yield of this method is not high, and ethyl propiolate Esters are more expensive and not suitable for industrial production

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0058] The preparation method of the pyrazole derivative of the present embodiment comprises the following steps:

[0059] In the reaction flask, add 28.2g (0.1mol) of N,N'-diacrylate ethyl piperazine (as shown in formula I, wherein R 1 for OC 2 h 5 ), 200g of chloroform, 22.2g (0.22mol) of triethylamine, temperature control within 10°C to 30°C, and 21.5g (0.22mol) of difluoroacetyl fluoride (DFAF), after the aeration, continue the insulation reaction After 5 hours, the solvent was concentrated under reduced pressure, and the residue was added with 100 g of water, stirred for 30 minutes, filtered, and dried to obtain 42.9 g of the corresponding halogen-substituted compound (as shown in formula II), with a yield of 98%.

[0060] Suspend 39g (0.0889mol) of halogen-substituted compound products in 200g of chloroform, stir and cool to -25°C, and slowly drop in 20.5g (0.178mol) of 40% methylhydrazine (MMH) to complete the dropwise addition Afterwards, continue the heat preservat...

Embodiment 2

[0063] The preparation method of the pyrazole derivative of the present embodiment comprises the following steps:

[0064] In the reaction flask, add 28.2g (0.1mol) of N,N'-diacrylate ethyl piperazine (as shown in formula I, wherein R 1 for OC 2 h 5 ), 200g of chloroform, 22.2g (0.22mol) of triethylamine, temperature control within 10°C to 30°C, and 21.5g (0.22mol) of difluoroacetyl fluoride (DFAF). After 5 hours, after the reaction was completed, 26.8g (0.2mol) of methylhydrazine benzaldehyde hydrazone (BzH) was added dropwise and the temperature was raised to 50°C, and the reaction was kept for 3 hours. The solvent was evaporated under reduced pressure, and the residue was added 200g of chloroform and 5g of sulfuric acid was reacted at room temperature for 8 hours, 50g of water was added, the organic layer was separated, the temperature was raised to 60°C, and 90g of sodium hydroxide solution with a concentration of 10% was added dropwise. Continue to react for 3 hours af...

Embodiment 3

[0066] The preparation method of the pyrazole derivative of the present embodiment comprises the following steps:

[0067] In the reaction flask, add 22.2g (0.1mol) of N,N'-divinylmethyl ketopiperazine (as shown in formula I, where R 1 for CH 3 ), 200g of chloroform, 22.2g (0.22mol) of triethylamine, temperature control within 10°C to 30°C, and 21.5g (0.22mol) of difluoroacetyl fluoride (DFAF), after the aeration, continue the insulation reaction After 5 hours, add 26.8g (0.2mol) of methylhydrazine benzaldehyde hydrazone (BzH) dropwise and raise the temperature to 50°C, keep the temperature for 3 hours, evaporate the solvent and the residue under reduced pressure, then add 200g of chloroform and 5g of sulfuric acid, React at room temperature for 8 hours, add 50g of water, separate the organic layer, concentrate the organic layer to dryness, add petroleum ether for recrystallization, filter and dry to obtain 3-trifluoromethyl-1-methyl-4-acetylpyrazole Derivatives (as shown in...

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Abstract

The invention relates to a preparation method of a halogen substituted compound. A piperazine derivative shown as a formula I reacts with a halogenated acetyl halide derivative shown as a formula VI to generate the halogen substituted compound shown as a formula II. The invention further relates to a preparation method of a pyrazole derivative from the halogen substituted compound, the halogen substituted compound shown in the formula II reacts with methylhydrazine, a pyrazole ring is closed, and a halogen substituted alkyl-1-methylpyrazole derivative shown in a formula IV is generated; or thehalogen substituted compound shown in the formula II reacts with methylhydrazine benzaldehyde hydrazone to generate a hydrazone compound as shown in a formula III, the pyrazole ring is closed, and the halogen substituted alkyl-1-methylpyrazole derivative shown in the formula IV is generated. The invention also relates to the structure of an intermediate compound. The preparation methods of the halogen substituted compound and the pyrazole derivative are suitable for industrial production.

Description

technical field [0001] The invention relates to an industrial synthesis method of a halogen-substituted compound, belonging to the technical field of chemical synthesis. Background technique [0002] Halogen-substituted pyrazole derivatives, especially fluorine-containing pyrazole derivatives are intermediates of many medicines or pesticides. Among these fluorine-containing pyrazole derivatives, 3-difluoromethyl-1-methylpyrazole-4-carboxylic acid is an important pesticide intermediate, and plays a very important role as an intermediate in many new pesticide varieties , such as the cereal fungicide Bixafen (Bixafen) launched by Bayer CropScience, the new fungicide Fluxapyroxad (Fluxapyroxad) launched by BASF, the pyrazapyrazam (Isopyrazam) launched by Syngenta, Fluxapyrox Sedaxane, etc. [0003] . [0004] International Patent WO 1992 / 12970 discloses 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid and its use as fungicides. This method converts 3-(difluorometh...

Claims

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Application Information

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IPC IPC(8): C07D295/104C07D295/145C07D231/14A01N43/56A01P3/00A01P1/00
CPCC07D295/104C07D295/145C07D231/14A01N43/56C07D295/14
Inventor 王明春李庆毅
Owner 科莱博(江苏)科技股份有限公司
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