Halogen substituted intermediate compound and preparation method and application thereof

A technology for compounds and intermediates, applied in the field of industrialized synthesis of halogen-substituted compounds, can solve problems such as being unsuitable for industrial production, expensive ethyl propiolate, and difficult to separate isomers, and achieve easier recycling and product quality. High and easy purification effect

Pending Publication Date: 2019-12-17
SUQIAN KEYLAB BIOCHEMICAL CO LTD
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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

[0062] The preparation method of the pyrazole derivative of the present embodiment comprises the following steps:

[0063] In the reaction bottle, add 28.4g (0.1mol) of raw material compound (as shown in formula VII, wherein R 1 for OC 2 h 5 , R 3 for C 2 h 6 ), 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-fluoroalkyl-1-methylpyrazole-4-carboxylic acid ...

Embodiment 2

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

[0067] In the reaction bottle, add 28.4g (0.1mol) of raw material compound (as shown in formula VII, wherein R 1 for OC 2 h 5 , R 3 for C 2 h 6 ), 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, After reacting at room temperature for 8 hours, 50 g of water was added, the organic layer was separated, the temperature was raised to 60° C., and 90 g of sodium hydroxide solution with a concentration of 10% was added dropwise. Continue to re...

Embodiment 3

[0069] The preparation method of the pyrazole derivative of the present embodiment comprises the following steps:

[0070] In the reaction bottle, add 28.4g (0.1mol) of raw material compound (as shown in formula VII, wherein R 1 for CH 3 , R 3 for C 2 h 6 ), 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 Derivative...

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PUM

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Abstract

The invention relates to a preparation method of a halogen-substituted intermediate compound. The halogen-substituted intermediate compound shown as a formula VIII is generated by reacting a compoundshown as a formula VII with a halogenated acetyl halide derivative shown as a formula VI. The invention relates to a preparation method for preparing a pyrazole derivative from the halogen substitutedintermediate compound, and the preparation method comprises the following steps: reacting the halogen substituted intermediate compound as shown in the formula VIII with methylhydrazine, and closinga pyrazole ring to generate a halogen substituted alkyl-1-methylpyrazole derivative as shown in a formula IV; or reacting the halogen substituted intermediate compound as shown in the formula VIII with methylhydrazine benzaldehyde hydrazone to generate a hydrazone compound as shown in a formula III, and closing the pyrazole ring under the action of an acid to generate the halogen substituted alkyl-1-methylpyrazole derivative as shown in the formula IV. The invention also relates to the structure of the intermediate compound. The preparation methods of the halogen-substituted intermediate 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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Patent Type & Authority Applications(China)
IPC IPC(8): C07C243/16C07C241/02C07D231/14A01N43/56A01P3/00A01P1/00
CPCC07C243/16C07D231/14A01N43/56
Inventor 王明春李庆毅
Owner SUQIAN KEYLAB BIOCHEMICAL CO LTD
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