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Intermediate for preparing trifloxystrobin and synthesis method of intermediate

A synthetic method, the technology of trifloxystrobin, applied in the field of organic synthesis, can solve the problems of expensive raw materials, serious three wastes, and large amount of three wastes, etc.

Active Publication Date: 2020-10-23
阜新孚隆宝医药科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] Prior art has reported the preparation technology of multiple intermediate I and II, but all there is different problem: either raw material is expensive, or uses hypertoxic cyanide, or reaction condition is harsh (as using metal reagent) or three wastes are serious ( diazotization or heavy metal oxidation), etc.
[0010] CN108863845A discloses the following reaction process, which requires four steps, and the total yield of Example 4 is 75%; this patent divides the methyl esterification into two times, and there is a process of repeatedly adjusting the base and then adjusting the acid, and the four steps consume a total of 5.4 equivalents of base , and 4.4 equivalents of acid, the amount of three wastes is large; each step needs to use an organic solvent to extract the product from the reaction system, and the cost is relatively high
[0012] Based on existing bibliographical reports, so far there is no one that meets the requirements of simple operation, safety and reliability, less three wastes, low cost, high yield, and high purity to prepare trifloxystrobin key intermediate I (i.e. (E)-2-( Methoxyimine)-o-methylphenylacetic acid methyl ester) process route

Method used

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  • Intermediate for preparing trifloxystrobin and synthesis method of intermediate
  • Intermediate for preparing trifloxystrobin and synthesis method of intermediate
  • Intermediate for preparing trifloxystrobin and synthesis method of intermediate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0066] Embodiment 1 (free acid is used for dimethylation reaction)

[0067] Preparation of 2-oxime-o-tolueneacetonitrile: it is a prior art, such as Example 1 of CN108863845A.

[0068]

[0069] The preparation of (E)-2-oxime-o-methylphenylacetic acid:

[0070] In the reaction flask, add 2-oxime-o-tolueneacetonitrile (64.1 g, 0.4 mol), 36.6 g of sodium hydroxide (0.916 mol), 120 ml of methanol and 100 ml of water, heat to reflux, and intermittently evaporate under reduced pressure Methanol. The internal temperature of the system continued to rise and finally reached about 106°C, which took about 6 hours in total. Cool to room temperature, add 230 ml (0.92 mol) of 4N hydrochloric acid to adjust to pH=1~2, extract 3 times with ethyl acetate, wash with water after combining, dry, and concentrate to obtain 68.3 g of (E)-2-oxime-o-methylbenzene Acetic acid, the liquid phase shows that the trans configuration content is greater than 99%, and the yield is 95%.

[0071] 1 H NMR...

Embodiment 2

[0074] Embodiment 2 (single sodium salt is used for dimethylation reaction)

[0075] Preparation of 2-oxime-o-tolueneacetonitrile: it is a prior art, such as Example 1 of CN108863845A.

[0076]

[0077] The preparation of (E)-2-oxime-o-methylphenylacetic acid monosodium salt:

[0078]

[0079] In the reaction flask, add 2-oxime-o-methylphenylacetonitrile (64.1 g, 0.4 mol), 36.6 g of sodium hydroxide (0.916 mol, 120 ml of methanol and 100 ml of water, heat to reflux, and intermittently distill off methanol The internal temperature of the system continues to rise, and finally reaches about 106 ° C, and takes about 6 hours. Cool to 0 ° C, add 43 ml of concentrated hydrochloric acid (0.51 mol) dropwise under stirring, the reaction solution is directly concentrated, distilled to remove water, and dried to obtain (E)-2-oxime-o-methylphenylacetic acid monosodium salt was directly used in the next methylation reaction without purification, and the purity by HPLC was 99%.

[00...

Embodiment 3

[0084] Embodiment 3 (replace NaOH with KOH, monopotassium salt / chloromethane is used for methylation reaction)

[0085] Preparation of 2-oxime-o-tolueneacetonitrile: it is a prior art, such as Example 1 of CN108863845A.

[0086] (E)-2-oxime-o-methylphenylacetic acid monopotassium salt preparation:

[0087]

[0088] In the reaction flask, add 2-oxime-o-tolueneacetonitrile (64.1 g, 0.4 mol), 51.3 g of potassium hydroxide (0.916 mol), 120 ml of methanol and 300 ml of water, heat to reflux, and intermittently evaporate under reduced pressure Methanol, shared for about 6 hours, the internal temperature of the system continued to rise, and finally reached about 106°C, shared for about 6 hours. Cool to 0°C, add 43ml of concentrated hydrochloric acid (0.51mol) dropwise under stirring, concentrate the reaction solution directly, distill off water, and dry to obtain (E)-2-oxime-o-methylphenylacetic acid monopotassium salt without purification , directly used in the next step of met...

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Abstract

The invention relates to an intermediate for preparing trifloxystrobin and a synthesis method of the intermediate, wherein the synthesis method comprises the steps: by taking 2-oxime-o-methyl phenylacetonitrile as a raw material, heating and hydrolyzing in an alkaline aqueous solution to obtain 2-oxime-o-methyl phenylacetic acid or mono-sodium salt / mono-potassium salt or disodium salt / di-potassiumsalt of 2-oxime-o-methyl phenylacetic acid; and under an alkaline condition, carrying out a reaction with a methylation reagent to obtain (E)-2-(methoxyimine)-methyl o-methyl phenyl acetate. The method has the characteristics of easily available raw materials, single trans-configuration of the product, and simple operation, and is suitable for industrial production.

Description

Technical field [0001] The present invention relates to the technical field of organic synthesis, to the preparation of pesticide intermediates, and in particular to an intermediate for preparing trifloxystrobin and its synthesis method. Background technique [0002] Trifloxystrbin (trade name Flint) chemical name: (2Z)-2-methoxyimino-2-[2-[[1-[3-(trifluoromethyl)phenyl]ethylideneamino) ]oxymethyl]phenyl]methyl acetate: [0003] [0004] Trifloxystrobin is a fungicide created by Syngenta and developed by Bayer in Germany. It has the characteristics of high efficiency, broad spectrum, protection, treatment, eradication, penetration, systemic activity, resistance to rain erosion, and long duration of effect. . It has good activity against almost all fungal diseases. It is safe for crops because it can be quickly degraded in soil and water, so it is safe for the environment. [0005] The prior art discloses a variety of synthetic process routes for trifloxystrobin, and t...

Claims

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Application Information

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IPC IPC(8): C07C249/12C07C251/48C07C251/70
CPCC07C249/12C07C251/48C07C251/70
Inventor 蔡凡平李新明张彦斌杨显文符雨
Owner 阜新孚隆宝医药科技有限公司
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