Synthesis method of fluopyram intermediate

Abstract

The invention discloses a synthesis method of a fluopyram intermediate, and belongs to the field of organic synthesis of pesticides. The process comprises the following steps: by taking methanol amine as a starting raw material, carrying out esterification reaction on methanol amine and acetic anhydride in the presence of acetic acid to obtain methyl aminoacetate, and carrying out amidation reaction on methyl aminoacetate and o-trifluoromethyl benzoyl chloride to obtain N-acetoxymethyl-2-trifluoromethyl benzamide; and finally, carrying out a splicing reaction with diethyl 3-chloro-5-trifluoromethyl-2-pyridylmalonate, so as to obtain the 3-chloro-5-trifluoromethyl-2-pyridylethyl (diethyl ester)-2-trifluoromethyl benzamide. The method adopts a convergent synthesis route, has the characteristics of low raw material cost, high atom economy, high yield, simple process operation and the like, and is suitable for large-scale production.

Description

Technical field

[0001] The present invention relates to the technical field of preparation of pesticide intermediates, and more particularly to synthesis of 3-chloro-5-trifluoromethyl-2-pyridylethyl (diethyl ester) -2-trifluoromethylbenzamide. method. Background technique

[0002] Fluopyram, its chemical name is N- (2- (3-chloro-5- (trifluoromethyl) -2-pyridyl) ethyl) -2-trifluoromethylbenzamide, It is a novel benzamide bactericide developed by Bayer Crop Science, inhibits mitochondrial breathing by hindering electron transfer of succinate dehydrogenase in the breathing chain. Fluoropylamide can inhibit spore germination, germination tube growth, mycelial growth, and spores. In the plant, fluoropyroformam is conductive and metastatic in the wood portion, mainly for controlling gray mold, white powder, late disease, frosty mildew, rice blast, etc. caused by fungal pathogens. Exhibits high activity and has broad application prospects. Molecular formula: C16H11CLF6N2O, the structura...

Examples

Embodiment 1

[0029] 47.0 g (1.00 mol) methanolamine was added to 6.6 g (0.10 mol) acetic acid, 0.9 g (2%) tetrabutylalonyl chloride, 140.0 g of 1,2-dichloroethane to add mechanical stirring, condensed tube, thermometer In the 1000 ml of three flasks, 112.3 g (1.10 mol) acetic anhydride was dripped over 30 minutes, and the reaction endpoint was determined according to liquid chromatography analysis. After the reaction was completed, the reaction was used to regulate the system pH. = 7, the water layer, the water wash the reaction liquid once, and the organic phase often pressed back to flow water to obtain an amino acetate 1,2-dichloroethane solution to carry out the next reaction.

[0030] 157.8 g (0.83 mol) was added to 2000 ml of three-port flasks with mechanical stirring, condensed tubes, and thermometer, and 108.6 g (0.91 mol) in 30 minutes. The sulfoxide, 80 to 85 ° C for 2 to 3 hours, determined according to the liquid chromatographic analysis results, after the reaction is completed, th...

Embodiment 2

[0034]47.0 g (1.00 mol) methanolamine was added to 7.8 g (0.13 mol) acetic acid, 2.2 g (5%) tetrabutylammonium chloride, 185.0 g 1, 2-dichloroethane to add a mechanical stirring, condensation, and thermometer. In a 1000 ml of three flasks, 122.5 g (1.2 mol) acetic anhydride was dripped over 30 minutes, and the reaction endpoint was determined according to liquid chromatography analysis. After the reaction was completed, the reaction was used to adjust the hydrogencarbonate aqueous solution to regulate the system pH. = 7, the water layer, the water wash the reaction liquid once, and the organic phase often pressed back to flow water to obtain an amino acetate 1,2-dichloroethane solution to carry out the next reaction.

[0035] 157.8 g (0.83 mol) was added to the 2000 ml of the three-port flask with mechanical stirring, condensed tubes, and thermometer, and 108.6 g (0.91 mol) was added to 30 minutes in 30 minutes. The sulfoxide, 80 to 85 ° C for 2 to 3 hours, determined according to...

Embodiment 3

[0039] 47.0 g (1.00 mol) methanolamine was added to 9.6 g (0.16 mol) acetic acid, 3.6 g (8%) tetrabutylammonium chloride, 230.0 g of 1,2-dichloroethane with mechanical stirring, condensed tube, thermometer In the 1000 ml of three flasks, 132.7 g (1.30 mol) acetic anhydride was added over 30 minutes, and the reaction endpoint was determined according to liquid chromatography analysis. After the reaction was completed, the hydrogencarbonate aqueous solution was used to regulate the system pH. = 7, the water layer, the water wash the reaction liquid once, and the organic phase often pressed back to flow water to obtain an amino acetate 1,2-dichloroethane solution to carry out the next reaction.

[0040] 157.8 g (0.83 mol) was added to 2000 ml of three-port flask with mechanical stirring, condensed tubes, and thermometer, 30 minutes (0.91 mol) in 30 minutes, 780 g 1,2-dichloroethane. Chloride, 80 to 85 ° C for 2 to 3 hours, determined according to the liquid chromatographic analysis r...

Technical field

[0001] The present invention relates to the technical field of preparation of pesticide intermediates, and more particularly to synthesis of 3-chloro-5-trifluoromethyl-2-pyridylethyl (diethyl ester) -2-trifluoromethylbenzamide. method. Background technique

[0002] Fluopyram, its chemical name is N- (2- (3-chloro-5- (trifluoromethyl) -2-pyridyl) ethyl) -2-trifluoromethylbenzamide, It is a novel benzamide bactericide developed by Bayer Crop Science, inhibits mitochondrial breathing by hindering electron transfer of succinate dehydrogenase in the breathing chain. Fluoropylamide can inhibit spore germination, germination tube growth, mycelial growth, and spores. In the plant, fluoropyroformam is conductive and metastatic in the wood portion, mainly for controlling gray mold, white powder, late disease, frosty mildew, rice blast, etc. caused by fungal pathogens. Exhibits high activity and has broad application prospects. Molecular formula: C16H11CLF6N2O, the structura...

Examples

Embodiment 1

[0029] 47.0 g (1.00 mol) methanolamine was added to 6.6 g (0.10 mol) acetic acid, 0.9 g (2%) tetrabutylalonyl chloride, 140.0 g of 1,2-dichloroethane to add mechanical stirring, condensed tube, thermometer In the 1000 ml of three flasks, 112.3 g (1.10 mol) acetic anhydride was dripped over 30 minutes, and the reaction endpoint was determined according to liquid chromatography analysis. After the reaction was completed, the reaction was used to regulate the system pH. = 7, the water layer, the water wash the reaction liquid once, and the organic phase often pressed back to flow water to obtain an amino acetate 1,2-dichloroethane solution to carry out the next reaction.

[0030] 157.8 g (0.83 mol) was added to 2000 ml of three-port flasks with mechanical stirring, condensed tubes, and thermometer, and 108.6 g (0.91 mol) in 30 minutes. The sulfoxide, 80 to 85 ° C for 2 to 3 hours, determined according to the liquid chromatographic analysis results, after the reaction is completed, th...

Embodiment 2

[0034]47.0 g (1.00 mol) methanolamine was added to 7.8 g (0.13 mol) acetic acid, 2.2 g (5%) tetrabutylammonium chloride, 185.0 g 1, 2-dichloroethane to add a mechanical stirring, condensation, and thermometer. In a 1000 ml of three flasks, 122.5 g (1.2 mol) acetic anhydride was dripped over 30 minutes, and the reaction endpoint was determined according to liquid chromatography analysis. After the reaction was completed, the reaction was used to adjust the hydrogencarbonate aqueous solution to regulate the system pH. = 7, the water layer, the water wash the reaction liquid once, and the organic phase often pressed back to flow water to obtain an amino acetate 1,2-dichloroethane solution to carry out the next reaction.

[0035] 157.8 g (0.83 mol) was added to the 2000 ml of the three-port flask with mechanical stirring, condensed tubes, and thermometer, and 108.6 g (0.91 mol) was added to 30 minutes in 30 minutes. The sulfoxide, 80 to 85 ° C for 2 to 3 hours, determined according to...

Embodiment 3

[0039] 47.0 g (1.00 mol) methanolamine was added to 9.6 g (0.16 mol) acetic acid, 3.6 g (8%) tetrabutylammonium chloride, 230.0 g of 1,2-dichloroethane with mechanical stirring, condensed tube, thermometer In the 1000 ml of three flasks, 132.7 g (1.30 mol) acetic anhydride was added over 30 minutes, and the reaction endpoint was determined according to liquid chromatography analysis. After the reaction was completed, the hydrogencarbonate aqueous solution was used to regulate the system pH. = 7, the water layer, the water wash the reaction liquid once, and the organic phase often pressed back to flow water to obtain an amino acetate 1,2-dichloroethane solution to carry out the next reaction.

[0040] 157.8 g (0.83 mol) was added to 2000 ml of three-port flask with mechanical stirring, condensed tubes, and thermometer, 30 minutes (0.91 mol) in 30 minutes, 780 g 1,2-dichloroethane. Chloride, 80 to 85 ° C for 2 to 3 hours, determined according to the liquid chromatographic analysis r...

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