CN114805240B - Method for synthesizing fluoro-olefine sulfone by one-pot method - Google Patents
Method for synthesizing fluoro-olefine sulfone by one-pot method Download PDFInfo
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- CN114805240B CN114805240B CN202210737832.6A CN202210737832A CN114805240B CN 114805240 B CN114805240 B CN 114805240B CN 202210737832 A CN202210737832 A CN 202210737832A CN 114805240 B CN114805240 B CN 114805240B
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- sulfone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/36—Sulfur atoms
Abstract
The invention discloses a method for synthesizing a fluoro-olefine sulfone by a one-pot method, which comprises the following steps: taking 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole as an initial raw material, taking an alcohol-water mixed system as a reaction solvent, reacting dropwise hydrogen peroxide and concentrated hydrochloric acid to generate low-concentration chlorine, performing thiazole ring chlorination reaction on the low-concentration chlorine and the 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole, oxidizing hydrogen peroxide and thioether into sulfone, completing dropwise addition of hydrogen peroxide and concentrated hydrochloric acid, and adding sodium hydrosulfite into the system to perform dehalogenation reaction to prepare the fluoroolefin sulfone. The method has the advantages of simple process, mild reaction conditions, high yield and low raw material cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to a method for synthesizing fluoroolefin sulfone by a one-pot method, belonging to the technical field of organic synthesis.
Background
Fluoroolefinsulfones, the fluoroolefm nematicide developed by makhtesim Chemical Works (now avemai), was the only new Chemical nematicide developed in more than 20 recent years, had contact activity, and enabled growers to get rid of dependence on fumigant-type nematicides for many years, while avoiding some of the adverse consequences of fumigant application. The fluoroolefin sulfone has low toxicity, low environmental risk and simple use, and has good development prospect in the aspect of preventing and controlling nematodes. At present, the product is registered in the United states for preventing and treating nematode damage of fruit and vegetable crops such as tomatoes, hot peppers, okra, eggplants, cucumbers, watermelons, hami melons, pumpkins and the like.
CAS registry number [318290-98-1]. Its relative molecular mass is 291.7; the molecular formula is C7H5ClF3NO2S 2. The structure is shown as the following formula:
。
european patent EP1200418B1 discloses a method for preparing a fluoroalkene sulfone by using 2- ((3,4, 4-trifluorobutyl) thio) thiazole as a starting material, performing chlorination reaction of N-chlorosuccinimide and thiazole ring, oxidizing thioether with m-chloroperoxybenzoic acid as an oxidant to synthesize sulfoxide, and finally oxidizing the sulfoxide with hydrogen peroxide under the condition of acetic acid as a solvent. The raw materials N-chlorosuccinimide and m-chloroperoxybenzoic acid used in the synthetic route are expensive, and simultaneously generate a large amount of difficultly separated by-products succimide and m-chloroperoxybenzoic acid, so that the synthetic route is not suitable for industrial production.
European patent EP1519928B1 discloses an oxidation process from thioether to sulfoxide to sulfone using potassium hydrogen peroxysulphate starting from 5-chloro-2- ((3,4, 4-trifluoro-3-butenyl) sulfinyl) thiazole at different pH conditions. This patent only describes the synthesis of the sulfone from the thioether and does not show the obvious advantages of this method for the synthesis of fluoroalkene sulfones. In addition, the raw material potassium hydrogen peroxysulfate is expensive, the requirements on storage and transportation are high, a large amount of solid waste can be generated in the oxidation process, the environmental protection pressure is increased, and the industrial production is not facilitated.
World patent WO2020065652A1 discloses a method for preparing a fluoroalkene sulfone by taking 2-mercaptothiazole and 1, 4-dibromo-2-chloro-1, 1, 2-trifluorobutane as starting materials and performing a thioetherification reaction, thiazole ring chlorination, an oxidation reaction and a dehalogenation reaction. The synthetic route has long steps, needs to purify intermediates for many times, has complex and tedious process operation, and is not suitable for industrialization. In addition, the synthesis process generates a large amount of wastewater, and dehalogenation reaction generates a large amount of zinc salt, thereby causing potential risks to the environment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for synthesizing fluoro-olefine sulfone by a one-pot method, and the invention provides the following technical scheme:
2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole is taken as a starting material, an alcohol-water mixed system is taken as a reaction solvent, under the action of a catalyst, dropwise added hydrogen peroxide and concentrated hydrochloric acid react to generate low-concentration chlorine which is subjected to thiazole ring chlorination reaction with 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole, meanwhile, hydrogen peroxide and thioether are oxidized into sulfone, hydrogen peroxide and concentrated hydrochloric acid are dropped, the temperature is reduced, sodium hydrosulfite is added into a reaction system to perform dehalogenation reaction, after the reaction is finished, the pH of the system is regulated to be = 8-9 by saturated sodium bicarbonate aqueous solution, the reaction solution is extracted twice by using methylbenzene, organic phases are combined, the organic phases are washed once by using water, and a light yellow oily product is obtained by negative pressure distillation.
Preferably, the alcohol solvent in the technical scheme is selected from one of methanol, ethanol and isopropanol, the dosage of the alcohol solvent is 10-20% of the mass of water, and the dosage of the water is 3 times of the mass of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole.
Preferably, the catalyst in the technical scheme is selected from one of ferric trichloride, aluminum trichloride and zinc chloride, and the dosage of the catalyst is 0.1-0.5% of the mass of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole.
Preferably, in the technical scheme, the reaction temperature of the thiazole ring chlorination reaction and the oxidation of hydrogen peroxide and thioether into sulfone is 60-65 ℃.
Preferably, the molar ratio of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole to hydrogen peroxide in the technical scheme is 1: 3.5-4.0.
Preferably, the molar ratio of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole to concentrated hydrochloric acid in the technical scheme is 1: 1.5-2.0.
Preferably, the molar ratio of the 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole to the sodium hydrosulfite in the technical scheme is 1: 2.5-3.0.
Preferably, the dehalogenation reaction temperature in the technical scheme is 20-30 ℃.
Detailed Description
The invention is further described in the following description and specific preferred embodiments, without thereby limiting the scope of protection of the invention.
Example 1
100.0g of water, 10.0g of methanol, 34.0g of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole and 0.034g of FeCl3 were added in this order to a 250mL four-necked flask equipped with a mechanical stirrer, a condenser and a thermometer. Heating to 62 ℃, simultaneously dripping 45.3g of 30% hydrogen peroxide and 24.3g of 30% hydrochloric acid, reacting for 3 hours, stirring for 2 hours, sampling, cooling to 20 ℃ after the reaction of the raw materials is finished by liquid chromatography, and adding 52.2g of sodium hydrosulfite for three times. And (3) continuing the reaction for 1h, adjusting the pH of the system to be 8-9 by using a saturated sodium bicarbonate aqueous solution, extracting the reaction solution twice by using 100.0g of toluene, combining organic phases, washing the organic phase once by using 100.0g of water, and distilling the organic phase at the temperature of 62 ℃ under negative pressure to obtain 25.6g of a light yellow oily substance with the content of 96.5% (by a liquid chromatography external standard method) and the yield of 85.2%.
Example 2
100.0g of water, 14.0g of methanol, 34.0g of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole and 0.102g of FeCl3 were added in this order to a 250mL four-necked flask equipped with a mechanical stirrer, a condenser and a thermometer. Heating to 60 ℃, simultaneously dripping 40.8g of 30% hydrogen peroxide and 15.2g of 36% hydrochloric acid, reacting for 3 hours, stirring for 2 hours, sampling, cooling to 28 ℃ after the reaction of the raw materials is finished by liquid chromatography, and adding 43.5g of sodium hydrosulfite for three times. And (3) continuing the reaction for 1h, adjusting the pH of the system to be 8-9 by using a saturated sodium bicarbonate aqueous solution, extracting the reaction solution twice by using 100.0g of toluene, combining organic phases, washing the organic phase once by using 100.0g of water, and distilling the organic phase at the temperature of 62 ℃ under negative pressure to obtain 25.8g of a light yellow oily substance with the content of 96.8% (by a liquid chromatography external standard method), wherein the yield is 86.1%.
Example 3
100.0g of water, 20.0g of methanol, 34.0g of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole and 0.034g of AlCl3 were added in this order to a 250mL four-necked flask equipped with mechanical stirring, a condenser and a thermometer. Heating to 65 ℃, simultaneously dripping 23.8g of 50% hydrogen peroxide and 19.5g of 30% hydrochloric acid, reacting for 3 hours, stirring for 2 hours, sampling, cooling to 24 ℃ after the reaction of the raw materials is finished by liquid chromatography, and adding 45.3g of sodium hydrosulfite for three times. And (3) continuing the reaction for 1h, adjusting the pH of the system to be 8-9 by using a saturated sodium bicarbonate aqueous solution, extracting the reaction solution twice by using 100.0g of toluene, combining organic phases, washing the organic phase once by using 100.0g of water, and distilling the organic phase at the temperature of 60 ℃ under negative pressure to obtain 25.7g of a light yellow oily substance with the content of 96.5% (by using a liquid chromatography external standard method), wherein the yield is 86.3%.
Example 4
100.0g of water, 18.0g of methanol, 34.0g of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole and 0.170g of ZnCl2 were charged in this order into a 250mL four-necked flask equipped with a mechanical stirrer, a condenser and a thermometer. Heating to 61 ℃, simultaneously dripping 25.8g of 50% hydrogen peroxide and 18.3g of 36% hydrochloric acid, reacting for 3 hours, stirring for 2 hours, sampling, cooling to 30 ℃ after the reaction of the raw materials is finished by liquid chromatography, and adding 48.7g of sodium hydrosulfite for three times. And (3) continuing the reaction for 1h, adjusting the pH of the system to be 8-9 by using a saturated sodium bicarbonate aqueous solution, extracting the reaction solution twice by using 100.0g of toluene, combining organic phases, washing the organic phase once by using 100.0g of water, and distilling the organic phase at the temperature of 60 ℃ under negative pressure to obtain 25.8g of a light yellow oily substance with the content of 97.0% (liquid chromatography external standard method) and the yield of 85.5%.
The foregoing is considered as illustrative of the preferred embodiments of the invention and is not to be construed as limiting the invention in any way. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall fall within the protection scope of the technical solution of the present invention, unless the technical essence of the present invention departs from the content of the technical solution of the present invention.
Claims (8)
1. A method for synthesizing fluoroalkene sulfone by a one-pot method is characterized in that 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole is used as an initial raw material, an alcohol-water mixed system is used as a reaction solvent, one of ferric trichloride, aluminum trichloride and zinc chloride is used as a catalyst, dropwise hydrogen peroxide and concentrated hydrochloric acid react to generate low-concentration chlorine, the low-concentration chlorine and the 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole undergo a thiazole ring chlorination reaction, hydrogen peroxide and thioether are oxidized into sulfone, the hydrogen peroxide and the concentrated hydrochloric acid are dropwise added, the temperature is reduced, sodium hydrosulfite is added into the system to undergo a dehalogenation reaction, after the reaction is finished, the pH of the system is adjusted to be = 8-9 by using a sodium bicarbonate aqueous solution, a toluene extraction reaction solution is used, a toluene layer is washed once, negative pressure distillation gave a pale yellow oily product of the formula:
2. the method for synthesizing fluoroolefinsuline sulfone according to claim 1, wherein the alcohol solvent is selected from one of methanol, ethanol, and isopropanol, the amount of the alcohol solvent is 10-20% of the mass of water, and the amount of the water is 3 times of the mass of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole.
3. The method for synthesizing fluoroalkene sulfone according to claim 1, wherein the amount of the catalyst is 0.1-0.5% by mass of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole.
4. The method for synthesizing fluoroolefin sulfone according to claim 1, wherein the temperature of the chlorination reaction of thiazole ring and the oxidation reaction of hydrogen peroxide and thioether into sulfone is 60-65 ℃.
5. The method for synthesizing fluoroalkene sulfone according to claim 1, wherein the molar ratio of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole to hydrogen peroxide is 1: 3.5-4.0.
6. The method for synthesizing fluoroalkene sulfone according to claim 1, wherein the molar ratio of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole to concentrated hydrochloric acid is 1: 1.5-2.0.
7. The one-pot method for synthesizing fluoroalkene sulfone according to claim 1, wherein the molar ratio of 2- ((4-bromo-3-chloro-3, 4, 4-trifluorobutyl) thio) thiazole to sodium hydrosulfite is 1: 2.5-3.0.
8. The method for synthesizing fluoroolefin sulfone by one-pot process according to claim 1, wherein the dehalogenation reaction temperature is 20-30 ℃.
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Citations (8)
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| WO1998047884A1 (en) * | 1997-04-24 | 1998-10-29 | Zeneca Limited | Process for the production of 5-chloro-2- (4,4-difluorobut-3-enylsulphonyl) thiazole and intermediates therefor |
| CN1224420A (en) * | 1997-03-24 | 1999-07-28 | 道农业科学公司 | 1-alkyl-4-benzoyl-5-hydroxypyrazole compounds and their use as herbicides |
| CN101066944A (en) * | 2007-06-08 | 2007-11-07 | 浙江工业大学 | Synthesis process of sulcoatrione |
| CN102702133A (en) * | 2012-01-10 | 2012-10-03 | 山东省联合农药工业有限公司 | Trifluoro-butylene insecticide containing thiazole |
| CN105152852A (en) * | 2015-09-16 | 2015-12-16 | 湖南城市学院 | Preparation method of 1-bromo-1-chloro-2,2-difluoroethylene |
| CN111233785A (en) * | 2020-03-17 | 2020-06-05 | 河北师范大学 | Method for synthesizing fluensulfone |
| WO2021024253A1 (en) * | 2019-08-04 | 2021-02-11 | Yeda Research And Development Co. Ltd. | Process for the preparation of fluensulfone |
| CN112930342A (en) * | 2018-09-26 | 2021-06-08 | 阿达玛马克西姆有限公司 | Process and intermediates for preparing difluoride sulfones |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224420A (en) * | 1997-03-24 | 1999-07-28 | 道农业科学公司 | 1-alkyl-4-benzoyl-5-hydroxypyrazole compounds and their use as herbicides |
| WO1998047884A1 (en) * | 1997-04-24 | 1998-10-29 | Zeneca Limited | Process for the production of 5-chloro-2- (4,4-difluorobut-3-enylsulphonyl) thiazole and intermediates therefor |
| CN101066944A (en) * | 2007-06-08 | 2007-11-07 | 浙江工业大学 | Synthesis process of sulcoatrione |
| CN102702133A (en) * | 2012-01-10 | 2012-10-03 | 山东省联合农药工业有限公司 | Trifluoro-butylene insecticide containing thiazole |
| CN105152852A (en) * | 2015-09-16 | 2015-12-16 | 湖南城市学院 | Preparation method of 1-bromo-1-chloro-2,2-difluoroethylene |
| CN112930342A (en) * | 2018-09-26 | 2021-06-08 | 阿达玛马克西姆有限公司 | Process and intermediates for preparing difluoride sulfones |
| WO2021024253A1 (en) * | 2019-08-04 | 2021-02-11 | Yeda Research And Development Co. Ltd. | Process for the preparation of fluensulfone |
| CN111233785A (en) * | 2020-03-17 | 2020-06-05 | 河北师范大学 | Method for synthesizing fluensulfone |
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