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Synthesis method of clodinafop-propargyl

A synthesis process, clodinafop-propargyl technology, applied in the field of clodinafop-propargyl synthesis process, can solve the problems of low total yield, long process route, difficult product purification, etc., and achieve simple intermediate control process, high content and optical purity, good The effect of industrial application prospects

Inactive Publication Date: 2017-05-31
江苏长青生物科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

It can be synthesized by a variety of methods, such as the process route adopted by Rolf, using hydroquinone as raw material, first reacting with 5-chloro-2,3-difluoropyridine monoetherification, in order to improve the selectivity of monoetherification, Therefore, the ratio of hydroquinone is increased, and the separation of unreacted hydroquinone is quite troublesome, which affects product quality
The process route is long, product purification is difficult, there are many types of solvents used, the total yield is low, and the economy is unreasonable
Another method is to use clodinafop-propargyl acid as a raw material, generate clodinafop-propargyl chloride through thionyl chloride, and then generate clodinafop-propargyl with esterification with propynyl alcohol in the presence of triethylamine acid-binding agent. The requirements are relatively high, and a large amount of hydrogen chloride and sulfur dioxide are released, which is harmful to the environment and difficult to treat the three wastes

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

[0026] Step 1 Synthesis of 2-(4-hydroxyphenoxy) propionate-2-propynyl ester

[0027] Add 55g (0.5mol) of hydroquinone, 73g (0.5mol) of propynyl chloropropionate, 6g (0.05mol) of DMAP, 62.5g (0.6mol) ) 32% ionic membrane caustic soda, 200ml water and 200ml acetonitrile. Under nitrogen atmosphere, stir at 50°C for 2 hours, cool to room temperature, slowly add dilute hydrochloric acid dropwise until acidic (pH value is 2), at this time a large amount of solid precipitates, filter, and wash the filter cake with saturated brine to obtain 77.2g of the intermediate , yield 71%.

[0028] Synthesis of step clodinafop-propargyl

[0029] Add 55g (0.25mol) of intermediates, 14g (0.25mol) of potassium hydroxide, 200ml of toluene to a 1000ml three-neck flask equipped with a condenser, a thermometer, and a magnet, raise the temperature to 70°C under nitrogen protection, and add dropwise 36.9 g (0.25 mol) 5-chloro-2,3-difluoropyridine, the dropwise addition time is 0.5 h, after the dropwis...

example 2

[0031] Step 1 Synthesis of 2-(4-hydroxyphenoxy) propionate-2-propynyl ester

[0032] Add 55g (0.5mol) of hydroquinone, 88g (0.6mol) of propynyl chloropropionate, 6g (0.05mol) of DMAP, 62.5g (0.6mol) ) 32% ionic membrane caustic soda, 200ml water and 200ml acetonitrile. Under nitrogen atmosphere, stir at 50°C for 2 hours, cool to room temperature, slowly add dilute hydrochloric acid dropwise to acidity (pH value is 2), at this time, a large amount of solid precipitates, filter, and wash the filter cake with saturated brine to obtain 84g of the intermediate, Yield 76%.

[0033] Synthesis of step clodinafop-propargyl

[0034] Add 55g (0.25mol) of intermediates, 14g (0.25mol) of potassium hydroxide, 200ml of toluene to a 1000ml three-neck flask equipped with a condenser, a thermometer, and a magnet, raise the temperature to 70°C under nitrogen protection, and add dropwise 44.3g (0.3 mol) 5-chloro-2,3-difluoropyridine, the dropwise addition time is 0.5 h, after the dropwise addi...

example 3

[0036] Step 1 Synthesis of 2-(4-hydroxyphenoxy) propionate-2-propynyl ester

[0037] Add 55g (0.5mol) of hydroquinone, 88g (0.6mol) of propynyl chloropropionate, 6g (0.05mol) of DMAP, 62.5g (0.6mol) ) 32% ionic membrane caustic soda, 100ml water and 300ml acetonitrile. In a nitrogen atmosphere, stir at 50°C for 2 hours, cool to room temperature, slowly add dilute hydrochloric acid dropwise to acidity (pH value is 2), at this time a large amount of solids precipitate, filter, and wash the filter cake with saturated brine to obtain 94g of the intermediate, Yield 85%.

[0038] Synthesis of step clodinafop-propargyl

[0039] Add 55g (0.25mol) of intermediates, 14g (0.25mol) of potassium hydroxide, 200ml of toluene to a 1000ml three-neck flask equipped with a condenser, a thermometer, and a magnet, raise the temperature to 70°C under nitrogen protection, and add dropwise 44.3g (0.3 mol) 5-chloro-2,3-difluoropyridine, the dropwise addition time is 0.75 h, after the dropwise addit...

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Abstract

The invention relates to a synthesis method of clodinafop-propargyl and provides a mixture reaction system of water and an organic solvent in the presence of alkali. The method includes the steps of: performing etherification with benzenediol and propargyl chloropropionate as initial raw materials to generate 2-(4-hydroxyphenoxyl)-2-propargyl propionate, and performing condensation with 5-chloro-2,3-difluoropyridine in an organic solvent to prepare the clodinafop-propargyl. Compared with methods in the prior art, the method is simple in separation and purification and has convenient operations, and is high in content and optical purity of the product. The method utilizes a novel catalyst DMAP, so that the reaction is mild and intermediate control processes are simple. In conclusion, the preparation employs easy-to-obtain raw materials, has mild reactions, high yield and simple separation and purification, is low in cost, is environment-friendly, and has excellent industrial application prospect.

Description

technical field [0001] The invention relates to a synthesis process of clodinafop-propargyl, which belongs to the technical field of esterification and condensation reactions in organic synthesis. Background technique [0002] Clodinafop-propargyl is a phenoxypropionate herbicide developed and produced by Ciba-Geigy in 1981, which can effectively control sagegrass, oats, ryegrass, common bluegrass, foxtail, etc. It can be synthesized by a variety of methods, such as the process route adopted by Rolf, using hydroquinone as raw material, first reacting with 5-chloro-2,3-difluoropyridine monoetherification, in order to improve the selectivity of monoetherification, Therefore, the proportion of hydroquinone is increased, and the separation of unreacted hydroquinone is quite troublesome, which affects the product quality. The process route is long, product purification is difficult, many types of solvents are used, the total yield is low, and the economy is unreasonable. Anothe...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/643
CPCC07D213/643
Inventor 于国权孙霞林丁华平周鹏袁宇吕佳杭
Owner 江苏长青生物科技有限公司
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