2-(2 ', 2'-difluoro-ethoxy)-6-trifluoromethyl-phenylpropyl sulfur ether synthesis process

Abstract

The present invention discloses a 2-(2 ', 2'-difluoro-ethoxy)-6-trifluoromethyl-phenylpropyl sulfur ether synthesis process. The process is as follows: 2-propyl mercapto-3-trifluoromehtyl phenol, 2,2-difluoroethanol and methanesulfonyl chloride are used as raw materials for two-step reaction to obtain the desired product. The synthesis process uses inexpensive industrial chemicals as the raw materials and reactants for avoiding the use of expensive or highly toxic raw materials, is high in the reaction conversion rate, easy in separation and purification and simple to in process operation, and reduces production costs.

Description

technical field

[0001] The invention belongs to the field of fine chemicals, and specifically relates to a synthesis process of 2-(2',2'-difluoroethoxy)-6-trifluoromethylphenylpropyl sulfide. Background technique

[0002] Penoxsulam, chemical name 2-(2,2-difluoroethoxy)-N-[5,8-dimethoxy(1,2,4)triazolo-(1,5-C )pyrimidin-2-yl]-6-trifluorotolyl-benzenesulfonamide is a post-emergence herbicide developed by DowAgroSciences in the United States. It is a triazolopyrimidinesulfonamide herbicide. It works by inhibiting acetolactate synthase (ALS). Penoxsulam is a broad-spectrum herbicide for paddy fields, which can effectively control barnyardgrass (including barnyardgrass resistant to propanil, quinclorac and acetyl-CoA carboxylase), annual Cyperaceae weeds , and is effective against many broad-leaved weeds, such as Heterostachys marsh, Carp sausage, Osmanthus japonica, Phyllostachys japonica, Commodityria chinensis, etc. The effective period is as long as 30 to 60 days, and one ...

Examples

Embodiment 1

[0021] Synthesis of 2,2-difluoroethyl methanesulfonate:

[0022] Add 41.44g (0.5mol, 99%, 1.0eq) of 2,2-difluoroethanol, 150mL of toluene, and 75.21g of methanesulfonyl chloride (0.65mol, 99%, 1.3eq) into a 500mL four-neck bottle for nitrogen replacement. , the system was a colorless transparent solution. The system was cooled to 0-5°C, and 66.31g (0.65mol, 99%, 1.3eq) of triethylamine was started to be added dropwise to the system, and the temperature was raised to 20-25°C for 1 hour of insulated reaction. Add 200mL of water to the system for extraction and separation, the oil layer was washed with 150mL of water for separation, and the solvent was removed by rotary evaporation under reduced pressure to obtain 79.27g of an orange liquid product with a content of 95.61% and a yield of 94.8%.

[0023] Synthesis of 2-(2',2'-difluoroethoxy)-6-trifluoromethylphenylpropylsulfide

[0024] 24.4g (0.1mol, 96.82%, 1.0eq) of 2-propylmercapto-3-trifluoromethylphenol, 21.7g of 2,2-diflu...

Embodiment 2

[0026] Synthesis of 2,2-difluoroethyl methanesulfonate:

[0027] Add 41.44g (0.5mol, 99%, 1.0eq) of 2,2-difluoroethanol, 150mL of ethyl acetate, and 75.21g of methanesulfonyl chloride (0.65mol, 99%, 1.3 eq), the system was a colorless transparent solution. The system was cooled to 0-5°C, and 66.31g (0.65mol, 99%, 1.3eq) of triethylamine was started to be added dropwise to the system, and the temperature was raised to 20-25°C for 1 hour of insulated reaction. Add 200 mL of water to the system for extraction and separation, wash the oil layer with 150 mL of water for separation, and remove the solvent by rotary evaporation under reduced pressure to obtain 77.9 g of an orange liquid product with a content of 95.6% and a yield of 93.2%.

[0028]Synthesis of 2-(2',2'-difluoroethoxy)-6-trifluoromethylphenylpropyl sulfide:

[0029] 24.4g (0.1mol, 96.82%, 1.0eq) of 2-propylmercapto-3-trifluoromethylphenol, 21.7g of 2,2-difluoroethyl methanesulfonate (0.13mol, 95.6%, 1.3eq), anhydro...

technical field

[0001] The invention belongs to the field of fine chemicals, and specifically relates to a synthesis process of 2-(2',2'-difluoroethoxy)-6-trifluoromethylphenylpropyl sulfide. Background technique

[0002] Penoxsulam, chemical name 2-(2,2-difluoroethoxy)-N-[5,8-dimethoxy(1,2,4)triazolo-(1,5-C )pyrimidin-2-yl]-6-trifluorotolyl-benzenesulfonamide is a post-emergence herbicide developed by DowAgroSciences in the United States. It is a triazolopyrimidinesulfonamide herbicide. It works by inhibiting acetolactate synthase (ALS). Penoxsulam is a broad-spectrum herbicide for paddy fields, which can effectively control barnyardgrass (including barnyardgrass resistant to propanil, quinclorac and acetyl-CoA carboxylase), annual Cyperaceae weeds , and is effective against many broad-leaved weeds, such as Heterostachys marsh, Carp sausage, Osmanthus japonica, Phyllostachys japonica, Commodityria chinensis, etc. The effective period is as long as 30 to 60 days, and one ...

Examples

Embodiment 1

[0021] Synthesis of 2,2-difluoroethyl methanesulfonate:

[0022] Add 41.44g (0.5mol, 99%, 1.0eq) of 2,2-difluoroethanol, 150mL of toluene, and 75.21g of methanesulfonyl chloride (0.65mol, 99%, 1.3eq) into a 500mL four-neck bottle for nitrogen replacement. , the system was a colorless transparent solution. The system was cooled to 0-5°C, and 66.31g (0.65mol, 99%, 1.3eq) of triethylamine was started to be added dropwise to the system, and the temperature was raised to 20-25°C for 1 hour of insulated reaction. Add 200mL of water to the system for extraction and separation, the oil layer was washed with 150mL of water for separation, and the solvent was removed by rotary evaporation under reduced pressure to obtain 79.27g of an orange liquid product with a content of 95.61% and a yield of 94.8%.

[0023] Synthesis of 2-(2',2'-difluoroethoxy)-6-trifluoromethylphenylpropylsulfide

[0024] 24.4g (0.1mol, 96.82%, 1.0eq) of 2-propylmercapto-3-trifluoromethylphenol, 21.7g of 2,2-diflu...

Embodiment 2

[0026] Synthesis of 2,2-difluoroethyl methanesulfonate:

[0027] Add 41.44g (0.5mol, 99%, 1.0eq) of 2,2-difluoroethanol, 150mL of ethyl acetate, and 75.21g of methanesulfonyl chloride (0.65mol, 99%, 1.3 eq), the system was a colorless transparent solution. The system was cooled to 0-5°C, and 66.31g (0.65mol, 99%, 1.3eq) of triethylamine was started to be added dropwise to the system, and the temperature was raised to 20-25°C for 1 hour of insulated reaction. Add 200 mL of water to the system for extraction and separation, wash the oil layer with 150 mL of water for separation, and remove the solvent by rotary evaporation under reduced pressure to obtain 77.9 g of an orange liquid product with a content of 95.6% and a yield of 93.2%.

[0028]Synthesis of 2-(2',2'-difluoroethoxy)-6-trifluoromethylphenylpropyl sulfide:

[0029] 24.4g (0.1mol, 96.82%, 1.0eq) of 2-propylmercapto-3-trifluoromethylphenol, 21.7g of 2,2-difluoroethyl methanesulfonate (0.13mol, 95.6%, 1.3eq), anhydro...

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