CN115340479A - Synthetic method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride - Google Patents
Synthetic method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride Download PDFInfo
- Publication number
- CN115340479A CN115340479A CN202211115153.1A CN202211115153A CN115340479A CN 115340479 A CN115340479 A CN 115340479A CN 202211115153 A CN202211115153 A CN 202211115153A CN 115340479 A CN115340479 A CN 115340479A
- Authority
- CN
- China
- Prior art keywords
- water
- difluoroethoxy
- hours
- compound
- dichloromethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/16—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by oxidation of thiols, sulfides, hydropolysulfides, or polysulfides with formation of sulfo or halosulfonyl groups
Abstract
The invention relates to the technical field of herbicide production, and particularly relates to a synthetic method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride. The invention adopts a brand-new synthesis method with shorter steps, and isomers do not exist in the reaction process. 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride is synthesized by using 2-methylthio-3-amino benzotrifluoride as a raw material through diazotization, fluorination, etherification and chlorination. The process has the advantages of low cost, mild conditions, simple operation and high yield, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of herbicide production, and particularly relates to a synthetic method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride.
Background
2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride is an important raw material for herbicide penoxsulam. Penoxsulam has the characteristics of high efficiency, low toxicity, safety and low volatility, and is particularly suitable for being applied to rice. The herbicide is safe to use for rice crops and high in weeding efficiency, is developed into an important herbicide product at present, and has a wide market prospect.
The current synthesis methods of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride include the following two.
The method comprises the following steps:
2,3-dichlorobenzotrifluoride is used as a raw material, and a finished product is obtained by high-temperature fluorination, ethylthio substitution, difluoroethanol etherification and chlorine introduction in an acetic acid solution. The fluorination requires special equipment and the second thioethyl substitution step results in isomers that are difficult to separate. The generation process has certain limitations.
The second method comprises the following steps:
meta-trifluoromethylphenol is taken as a raw material, is protected by chloromethyl methyl ether, then the ethyl sulfenyl on the hydrogen is extracted by n-butyl lithium at the temperature of minus 50 ℃, then the deprotection is carried out by hydrochloric acid, and then the ethyl sulfenyl and difluoroethanol mesylate are made into ether, and then chlorine is added to obtain the finished product. The price of the m-trifluoromethylphenol obtained by the method is higher, the operation is dangerous when n-butyllithium is used below-70 ℃, and the cost is higher.
Disclosure of Invention
Aiming at the problems in the background art, a synthetic method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride is provided. The invention adopts a brand-new synthesis method with shorter steps, and isomers do not exist in the reaction process. 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride is synthesized by using 2-methylthio-3-amino benzotrifluoride as a raw material through diazotization, fluorination, etherification and chlorination. The process has the advantages of low cost, mild conditions, simple operation and high yield, and is suitable for industrial production.
The invention provides a synthesis method of 2- (2,2-difluoroethoxy) -6-trifluoromethyl benzene sulfonyl chloride, which takes 2-methylthio-3-amino benzotrifluoride as a raw material to synthesize the 2- (2,2-difluoroethoxy) -6-trifluoromethyl benzene sulfonyl chloride through diazotization conversion, etherification and chlorination,
the synthesis method of the 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride comprises the following specific steps:
s1, 110-130 g of 2-methylthio-3-aminotrifluorotoluene are added in portions to 1400-1600 g of 40% fluoroboric acid and cooled to 0 ℃; dropwise adding a mixed solution of 42-44 g of sodium nitrite and 90-110 g of water, stirring for 2 hours at 0 ℃ after the dropwise adding is finished, and filtering; sequentially washing with water, ethanol and diethyl ether; adding the obtained solid into 900-100 ml of dimethylbenzene at 130 ℃ in batches, then preserving the heat at 130 ℃ for 2 hours, cooling to 25 ℃, adding 250-350 g of water, stirring for 15 minutes, separating liquid, and pressurizing and desolventizing a dimethylbenzene layer to obtain a compound 1;
s2, adding 450-550 g of DMF, 28-30 g of 60% sodium hydrogen and 43-45 g of difluoroethanol into the compound 1 in the S1, reacting for 3 hours at 25 ℃, adding 1400-1600 ml of water and 650-750 g of dichloromethane, and separating; extracting the water layer with 450-550 g of dichloromethane for 1 time, combining dichloromethane, washing with water for 1 time, and removing the solvent by reduced pressure evaporation to obtain a compound 2;
and S3, adding 550-650 g of acetic acid and 55-65 g of water into the compound 2 in the S2, dissolving, introducing liquid chlorine at 45 ℃ for 2 hours, completely reacting, pouring into 1.5-2.5 kg of ice water, filtering, washing with water for 3 times, and drying in vacuum at 40 ℃ to obtain the 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride.
Preferably, the synthetic method comprises the following steps:
s1, 120 g of 2-methylthio-3-amino benzotrifluoride is added into 1500 g of 40 percent fluoroboric acid in batches, the mixture is cooled to 0 ℃, 43 g of mixed solution of sodium nitrite and 100 g of water is dripped, after the dripping is finished, the mixture is stirred for 2 hours at 0 ℃, and then is filtered, and is washed by water, ethanol and ether; adding the obtained solid into 1000 ml of dimethylbenzene at 130 ℃ in batches, then preserving the heat at 130 ℃ for 2 hours, cooling to 25 ℃, adding 300 g of water, stirring for 15 minutes, separating liquid, and pressurizing and desolventizing a dimethylbenzene layer to obtain a compound 1;
s2, adding 500 g of DMF, 29 g of 60% sodium hydride and 44 g of difluoroethanol into the compound 1 in the S1, reacting for 3 hours at 25 ℃, adding 1500 ml of water and 700 g of dichloromethane, separating, extracting a water layer for 1 time by using 500 g of dichloromethane, combining the dichloromethane, washing for 1 time, and evaporating under reduced pressure to remove the solvent to obtain a compound 2;
and S3, adding 600 g of acetic acid and 60 g of water into the compound 2 in the S2, dissolving, introducing chlorine into the solution at 45 ℃ for 2 hours to react completely, pouring the solution into 2 kg of ice water, filtering and washing the solution for 3 times, and performing vacuum drying at 40 ℃ to obtain the 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride.
Compared with the prior art, the invention has the following beneficial technical effects: the invention adopts a brand-new synthesis method with shorter steps, and isomers do not exist in the reaction process. 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride is synthesized by using 2-methylthio-3-amino benzotrifluoride as a raw material through diazotization, fluorination, etherification and chlorination. The process has the advantages of low cost, mild conditions, simple operation and high yield, and is suitable for industrial production.
Detailed Description
Example one
The invention provides a synthesis method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride, which takes 2-methylthio-3-amino benzotrifluoride as a raw material, synthesizes 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride through diazotization, etherification and chlorination,
example two
The invention provides a synthetic method of 2- (2,2-difluoroethoxy) -6-trifluoromethyl benzene sulfonyl chloride, which comprises the following steps:
s1, 110-130 g of 2-methylthio-3-aminotrifluorotoluene are added in portions to 1400-1600 g of 40% fluoroboric acid and cooled to 0 ℃; dropwise adding a mixed solution of 42-44 g of sodium nitrite and 90-110 g of water, stirring for 2 hours at 0 ℃ after the dropwise adding is finished, and filtering; sequentially washing with water, ethanol and diethyl ether; adding the obtained solid into 900-100 ml of dimethylbenzene at 130 ℃ in batches, then preserving the heat at 130 ℃ for 2 hours, cooling to 25 ℃, adding 250-350 g of water, stirring for 15 minutes, separating liquid, and pressurizing and desolventizing a dimethylbenzene layer to obtain a compound 1;
s2, adding 450-550 g of DMF, 28-30 g of 60% sodium hydrogen and 43-45 g of difluoroethanol into the compound 1 in the S1, reacting for 3 hours at 25 ℃, adding 1400-1600 ml of water and 650-750 g of dichloromethane, and separating; extracting the water layer with 450-550 g of dichloromethane for 1 time, combining dichloromethane, washing with water for 1 time, and removing the solvent by reduced pressure evaporation to obtain a compound 2;
and S3, adding 550-650 g of acetic acid and 55-65 g of water into the compound 2 in the S2, dissolving, introducing liquid chlorine at 45 ℃ for 2 hours, completely reacting, pouring into 1.5-2.5 kg of ice water, filtering, washing with water for 3 times, and drying in vacuum at 40 ℃ to obtain the 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride.
EXAMPLE III
The invention provides a synthetic method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride, which comprises the following steps:
s1, 120 g of 2-methylthio-3-amino benzotrifluoride is added into 1500 g of 40 percent fluoroboric acid in batches, the mixture is cooled to 0 ℃, 43 g of mixed solution of sodium nitrite and 100 g of water is dripped, after the dripping is finished, the mixture is stirred for 2 hours at 0 ℃, and then is filtered, and is washed by water, ethanol and ether; adding the obtained solid into 1000 ml of dimethylbenzene at 130 ℃ in batches, then preserving the heat at 130 ℃ for 2 hours, cooling to 25 ℃, adding 300 g of water, stirring for 15 minutes, separating liquid, and pressurizing and desolventizing a xylene layer to obtain 109.5 g of compound 1 with the yield of 90%;
s2, adding 500 g of DMF, 29 g of 60% sodium hydride and 44 g of difluoroethanol into the compound 1 in the S1, reacting for 3 hours at 25 ℃, adding 1500 ml of water and 700 g of dichloromethane, separating, extracting a water layer for 1 time by using 500 g of dichloromethane, combining dichloromethane, washing for 1 time, and evaporating under reduced pressure to remove the solvent to obtain 133 g of compound 2, wherein the yield is 95%;
and S3, adding 600 g of acetic acid and 60 g of water into the compound 2 in the S2, dissolving, introducing chlorine into the solution at 45 ℃ for 2 hours to react completely, pouring the solution into 2 kg of ice water, filtering and washing the solution for 3 times, and performing vacuum drying at 40 ℃ to obtain 126.6 g of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride with the yield of 86%.
The invention adopts a brand-new synthesis method with shorter steps, and isomers do not exist in the reaction process. 2-methylthio-3-amino trifluorotoluene is used as a raw material, and 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride is synthesized through diazotization, fluorination and chlorination. The process has the advantages of low cost, mild conditions, simple operation and high yield, and is suitable for industrial production.
While the embodiments of the present invention have been described in detail, the present invention is not limited thereto, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art.
Claims (3)
1. A synthetic method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride is characterized in that 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride is synthesized by diazotization, etherification and chlorination by taking 2-methylthio-3-aminobenzotrifluoride as a raw material,
2. the method for synthesizing 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride as claimed in claim 1, wherein the method comprises the following steps:
s1, 110-130 g of 2-methylthio-3-aminotrifluorotoluene are added in portions to 1400-1600 g of 40% fluoroboric acid and cooled to 0 ℃; dropwise adding a mixed solution of 42-44 g of sodium nitrite and 90-110 g of water, stirring for 2 hours at 0 ℃ after the dropwise adding is finished, and filtering; sequentially washing with water, ethanol and diethyl ether; adding the obtained solid into 900-100 ml of dimethylbenzene at 130 ℃ in batches, then preserving the heat at 130 ℃ for 2 hours, cooling to 25 ℃, adding 250-350 g of water, stirring for 15 minutes, separating liquid, and pressurizing and desolventizing a dimethylbenzene layer to obtain a compound 1;
s2, adding 450-550 g of DMF, 28-30 g of 60% sodium hydrogen and 43-45 g of difluoroethanol into the compound 1 in the S1, reacting for 3 hours at 25 ℃, adding 1400-1600 ml of water and 650-750 g of dichloromethane, and separating; extracting the water layer with 450-550 g of dichloromethane for 1 time, combining dichloromethane, washing with water for 1 time, and removing the solvent by reduced pressure evaporation to obtain a compound 2;
and S3, adding 550-650 g of acetic acid and 55-65 g of water into the compound 2 in the S2, dissolving, introducing liquid chlorine for 2 hours at 45 ℃, completely reacting, pouring into 1.5-2.5 kg of ice water, filtering, washing for 3 times, and drying in vacuum at 40 ℃ to obtain 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride.
3. The method for synthesizing 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride as claimed in claim 2, wherein the method comprises the following steps:
s1, 120 g of 2-methylthio-3-amino benzotrifluoride is added into 1500 g of 40 percent fluoroboric acid in batches, the mixture is cooled to 0 ℃, 43 g of mixed solution of sodium nitrite and 100 g of water is dripped, after the dripping is finished, the mixture is stirred for 2 hours at 0 ℃, and then is filtered, and is washed by water, ethanol and ether; adding the obtained solid into 1000 ml of dimethylbenzene at 130 ℃ in batches, then preserving the heat at 130 ℃ for 2 hours, cooling to 25 ℃, adding 300 g of water, stirring for 15 minutes, separating liquid, and pressurizing and desolventizing a dimethylbenzene layer to obtain a compound 1;
s2, adding 500 g of DMF, 29 g of 60% sodium hydride and 44 g of difluoroethanol into the compound 1 in the S1, reacting for 3 hours at 25 ℃, adding 1500 ml of water and 700 g of dichloromethane, separating, extracting a water layer for 1 time by using 500 g of dichloromethane, combining the dichloromethane, washing for 1 time, and evaporating under reduced pressure to remove the solvent to obtain a compound 2;
and S3, adding 600 g of acetic acid and 60 g of water into the compound 2 in the S2, dissolving, introducing chlorine into the solution at 45 ℃ for 2 hours to completely react, pouring the solution into 2 kg of ice water, filtering and washing the solution for 3 times, and drying the solution in vacuum at 40 ℃ to obtain the 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211115153.1A CN115340479A (en) | 2022-09-14 | 2022-09-14 | Synthetic method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211115153.1A CN115340479A (en) | 2022-09-14 | 2022-09-14 | Synthetic method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115340479A true CN115340479A (en) | 2022-11-15 |
Family
ID=83956204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211115153.1A Pending CN115340479A (en) | 2022-09-14 | 2022-09-14 | Synthetic method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115340479A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020037811A1 (en) * | 2000-09-26 | 2002-03-28 | Gonzalez Michael Allen | Process for the preparation of 2-alkoxy-6-trifluoromethyl-N-([1,2,4]triazolo[1,5-c]pyrimidin-2-yl)benzenesulfonamides |
| CN104693080A (en) * | 2013-12-04 | 2015-06-10 | 南京正荣医药化学有限公司 | Preparation method of 6-substituted-2-trifluoromethylbenzenesulfonyl chloride |
| CN105801454A (en) * | 2014-12-31 | 2016-07-27 | 沈阳中化农药化工研发有限公司 | Method for preparation of 2-(2,2-difluoroethoxy)-6-(trifluoromethyl)benzene-1-sulfonyl chloride |
| CN114539103A (en) * | 2022-03-21 | 2022-05-27 | 佳木斯黑龙农药有限公司 | Synthesis method of 2-difluoroethoxy-6-trifluoromethylbenzenesulfonyl chloride |
-
2022
- 2022-09-14 CN CN202211115153.1A patent/CN115340479A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020037811A1 (en) * | 2000-09-26 | 2002-03-28 | Gonzalez Michael Allen | Process for the preparation of 2-alkoxy-6-trifluoromethyl-N-([1,2,4]triazolo[1,5-c]pyrimidin-2-yl)benzenesulfonamides |
| CN104693080A (en) * | 2013-12-04 | 2015-06-10 | 南京正荣医药化学有限公司 | Preparation method of 6-substituted-2-trifluoromethylbenzenesulfonyl chloride |
| CN105801454A (en) * | 2014-12-31 | 2016-07-27 | 沈阳中化农药化工研发有限公司 | Method for preparation of 2-(2,2-difluoroethoxy)-6-(trifluoromethyl)benzene-1-sulfonyl chloride |
| CN114539103A (en) * | 2022-03-21 | 2022-05-27 | 佳木斯黑龙农药有限公司 | Synthesis method of 2-difluoroethoxy-6-trifluoromethylbenzenesulfonyl chloride |
Non-Patent Citations (1)
| Title |
|---|
| （英）马奇（MARCH，J）: "《高等有机化学 上 反应、机理和结构》", pages: 542 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111285884A (en) | Preparation method of pentaerythritol sulfate | |
| CN107778183B (en) | Preparation method of 2,4, 6-trifluorobenzylamine | |
| KR101126825B1 (en) | Method for producing z-1-phenyl-1-diethylaminocarbonyl-2-aminomethyl cyclopropane hydrochloride | |
| TWI775753B (en) | Process for preparing boscalid | |
| CN107176929B (en) | Method for preparing 1H-tebuconazole | |
| CN115340479A (en) | Synthetic method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride | |
| CN106916068B (en) | A kind of simple and convenient benzalkonium chloride production method | |
| DE69826845T2 (en) | PROCESS FOR PREPARING ARYLSULFONYL CHLORIDE | |
| CN110461840A (en) | The method for preparing 1- (4- mesyl -2- romethyl-benzy) -2- methyl-1 H- pyrrolo- [2,3-b] pyridin-3-yl-acetic acid | |
| CN106748796B (en) | The method for preparing the fluoro- 2,4- dinitrobenzene of 1,5- bis- | |
| CN110668952B (en) | Preparation method of benzphetamine hydrochloride | |
| CN110003023B (en) | Preparation method of environment-friendly N, N-dimethylformamide dimethyl acetal | |
| CN113563266A (en) | Process for continuously synthesizing prochloraz and intermediate acylate of prochloraz raw material | |
| CN113292456A (en) | Preparation method of N-fluorenylmethoxycarbonyl-L-aspartic acid-4-tert-butyl ester | |
| CN106243029A (en) | The method preparing Boscalid | |
| CN110835323A (en) | Production method of important intermediate for synthesizing mesotrione | |
| CN110683992A (en) | Method for synthesizing econazole nitrate by one-pot method | |
| CN109134455A (en) | A kind of preparation method of 3 β -ol of 6,6,9- trimethyl -9- azabicyclic [3,3,1] nonyl- and its salt | |
| CN101168532B (en) | Method for synthesizing N-methylpiperazine substituted anilin | |
| JP4500983B2 (en) | 6-alkoxy-2-naphthalenethiol and process for producing the same | |
| JP4406294B2 (en) | Process for producing tert-butyl N- (2-bromoethyl) carbamate | |
| CN112341406A (en) | Synthesis method of trans-4- [4- (3-methoxy-4-nitrophenyl) -1-piperazinyl ] adamantane-1-ol | |
| CN106380466B (en) | A kind of synthetic method of 2- (2- thiophene) pyridine | |
| CN118026854A (en) | Preparation method of 2-chloro-6-trifluoromethyl aniline | |
| JP3069810B2 (en) | Method for producing (3-fluoropyridin-2-yloxy) phenoxypropionic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |