Ultrasonic-promoted tembotrione acid preparation method
The ultrasonic-promoted preparation method for cyclosulfonic acid solves the problems of long reaction time and many impurities, and achieves efficient and low-cost production of cyclosulfonic acid.
Patent Information
- Application Number
- CN202511558993.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-29
- Publication Date
- 2026-01-23
AI Technical Summary
The existing process for preparing cyclosulfonic acid has problems such as long reaction time and many product impurities, resulting in low yield.
An ultrasound-promoted substitution hydrolysis reaction is employed, combining an inorganic base with a specific organic solvent. An ultrasound generator is inserted into the reaction vessel or external circulation pipeline to optimize the separation and purification steps, thereby improving the reaction rate and selectivity.
Shorten reaction time, reduce impurity formation, improve reaction yield, simplify process flow, and reduce costs.
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Abstract
Description
TECHNICAL FIELD
[0001] The application relates to the technical field of chemical engineering, in particular to a preparation method of sulfentrazone acid promoted by ultrasonic waves. BACKGROUND
[0002] Sulfentrazone is a triketone herbicide belonging to the HPPD inhibitor type, and has the characteristics of wide weed spectrum, wide use period, high safety, excellent prevention and treatment effect and the like. Sulfentrazone is mainly used for corn, one of the three major staple foods in China, and can be used for almost all corn varieties, and can also be used for non-field crops such as sunflower, and has hydrophobicity and rainwater washing resistance, and its importance is increasingly prominent. Sulfentrazone acid is a key intermediate in the production of sulfentrazone, and the preparation method of sulfentrazone acid is the key and difficulty of the improvement of the sulfentrazone process technology, and directly determines the quality and cost of the sulfentrazone product, and the preparation route (see: Miga, Synthesis of Sulfentrazone, Master's Thesis of Hebei University of Science and Technology, 2021-12-31) is as follows:
[0003] At present, the above preparation process route is adopted in industrial production, and the last step of the sulfentrazone acid preparation process is the bromide substitution hydrolysis reaction process, which has the problems of long reaction time and high impurity content of the product, resulting in low yield, and therefore needs to be improved. SUMMARY
[0004] The purpose of the application is to provide a preparation method of sulfentrazone acid promoted by ultrasonic waves to solve the problems in the background art.
[0005] In order to achieve the above-mentioned purpose, the application provides the following technical scheme: A preparation method of sulfentrazone acid promoted by ultrasonic waves, comprising the following steps: S1, the raw material bromide (compound 4 in the background art) and trifluoroethanol are subjected to substitution hydrolysis in the presence of inorganic base in organic solvent A under the promotion of ultrasonic waves; S2, after the reaction is completed, the organic solvent A is recovered by distillation, if the organic solvent B is the same as A, the distillation step is omitted; water and organic solvent B are added to the reaction product after distillation, if the organic solvent B is the same as A, the organic solvent B is not added, and the water layer is extracted with organic solvent B after standing and separating; S3, the organic phase is combined and recovered by distillation; the water phase is combined, the pH value is adjusted to 1-2 with hydrochloric acid, and the product sulfentrazone acid (compound 5 in the background art) is obtained by filtration and water washing.
[0006] Further, under the promotion of ultrasonic waves, at least one ultrasonic wave generator is inserted into the reaction kettle to generate ultrasonic waves; Or, an external circulation pipeline is arranged and at least one ultrasonic generator is inserted in the external circulation pipeline to generate ultrasonic waves; Or, at least one ultrasonic generator is inserted in the reaction kettle to generate ultrasonic waves, and at the same time, an external circulation pipeline is arranged and at least one ultrasonic generator is inserted in the external circulation pipeline to generate ultrasonic waves.
[0007] Further, the inorganic base is a mixture of one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
[0008] Further, the organic solvent A is any one of dichloromethane, dichloroethane, chlorobenzene, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, acetone, 2-butanone, N-methyl pyrrolidone, cyclopentanone, cyclohexanone, methyl tert-butyl ether, tetrahydrofuran, methyl tetrahydrofuran, and ethylene glycol dimethyl ether.
[0009] Further, the organic solvent B is any one of dichloromethane, dichloroethane, cyclohexane, petroleum ether, toluene, xylene, chlorobenzene, ethyl acetate, dimethyl carbonate, and methyl tert-butyl ether.
[0010] Compared with the prior art, the application has the following beneficial effects: The ultrasonic-promoted preparation method of the cyclic sulfentrazone acid is characterized by improving the reaction speed to shorten the reaction time, improving the reaction selectivity, reducing the generation of impurities to improve the reaction yield. The preparation method is simple, does not need to add any additional reaction raw materials, does not need to increase additional processing steps, and only needs to be simply modified on the equipment to be implemented, so the method has great practical value for the preparation of the cyclic sulfentrazone acid. DETAILED DESCRIPTION
[0011] The technical solutions in the embodiments of the application will be described below clearly and completely. Obviously, the described embodiments are only part of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the application.
[0012] The application provides a technical solution: An ultrasonic-promoted preparation method of a cyclic sulfentrazone acid, comprising the following steps: S1, the raw material bromide (compound 4 in the background art) and trifluoroethanol are subjected to substitution hydrolysis in an inorganic base in an organic solvent A under the promotion of ultrasonic waves; S2, after the reaction is completed, distill to recover the organic solvent A, if the organic solvent B and A are the same, then omit this distillation step; add water and organic solvent B to the reaction product after distillation, if the organic solvent B and A are the same, then do not add organic solvent B, stand to separate layers and extract the water layer with organic solvent B; S3, combine the organic phase, distill to recover and reuse; combine the water phase, adjust the pH value to 1-2 with hydrochloric acid, filter and wash with water to obtain the product mesotrione acid (compound 5 in the background art).
[0013] Further, under the promotion of ultrasonic waves means inserting at least one ultrasonic generator in the reaction kettle to generate ultrasonic waves; Or, set up an external circulation pipeline and insert at least one ultrasonic generator in the external circulation pipeline to generate ultrasonic waves; Or, insert at least one ultrasonic generator in the reaction kettle to generate ultrasonic waves, and at the same time set up an external circulation pipeline and insert at least one ultrasonic generator in the external circulation pipeline to generate ultrasonic waves.
[0014] In this application, under the promotion of ultrasonic waves, the preferred scheme is to insert at least one ultrasonic generator in the reaction kettle to generate ultrasonic waves, and at the same time set up an external circulation pipeline and insert at least one ultrasonic generator in the external circulation pipeline to generate ultrasonic waves.
[0015] Further, the inorganic base is a mixture of one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.
[0016] Further, the organic solvent A is any one of dichloromethane, dichloroethane, chlorobenzene, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, acetone, 2-butanone, N-methyl pyrrolidone, cyclopentanone, cyclohexanone, methyl tert-butyl ether, tetrahydrofuran, methyl tetrahydrofuran, and ethylene glycol dimethyl ether.
[0017] Further, the organic solvent B is any one of dichloromethane, dichloroethane, cyclohexane, petroleum ether, toluene, xylene, chlorobenzene, ethyl acetate, dimethyl carbonate, and methyl tert-butyl ether.
[0018] Specifically, the bromide (compound 4 in the background art) used in the following examples of the present application has a content of 98%, the trifluoroethanol has a content of 99%, the sodium hydroxide has a content of 99%, and the solvent has a content of 99% or more.
[0019] Example 1
[0020] Put 2000g dichloroethane, 768g (19mol) sodium hydroxide into the reaction kettle with ultrasonic generator and circulation pipeline, open the circulation pipeline and the reaction kettle stirring, heating to 40-50℃, 1h drop 1818g (18mol) trifluoroethanol under ultrasonic conditions, 1h after the drop continue to drop 4183g bromide (12mmol) dissolved in 6000g dichloroethane solution, 1h drop continue to heat the reaction 1.5h, sample analysis to get ring sulfone acid content of 95%, the main impurity content of 3%, the raw material bromide content is less than 0.5%. In the kettle 6000g water, stirring 0.5h, static stratification, 1000g dichloroethane extraction of water, combined organic phase distillation recovery dichloroethane for use. The water phase is adjusted to pH 1-2 with hydrochloric acid, filtration, 200g water washing, get wet ring sulfone acid, drying to get ring sulfone acid product 3863g (content more than 98%, molar yield 91%).
[0021] Put 2000g dichloroethane, 768g (19mol) sodium hydroxide into the reaction kettle, open the reaction kettle stirring, heating to 40-50℃, 1h drop 1818g (18mol) trifluoroethanol, 1h after the drop continue to heat to 55-60℃ drop 4183g bromide (12mmol) dissolved in 6000g dichloroethane solution, 1h drop continue to heat the reaction 4h, sample analysis to get ring sulfone acid content of 88%, the main impurity content of 8%, the raw material bromide content is less than 0.5%. In the kettle 6000g water, stirring 0.5h, static stratification, 1000g dichloroethane extraction of water, combined organic phase distillation recovery dichloroethane for use. The water phase is adjusted to pH 1-2 with hydrochloric acid, filtration, 200g water washing, get wet ring sulfone acid, drying to get ring sulfone acid product 3517g (content more than 97%, molar yield 82%).
[0022] Example 2
[0023] Put 2000g acetonitrile, 768g (19mol) sodium hydroxide into the reaction kettle with ultrasonic generator and circulation pipeline, open the circulation pipeline and the reaction kettle stirring, heating to 40-50℃, ultrasonic conditions 1h drop 1818g (18mol) trifluoroethanol, 1h after the drop is completed, continue to drop 4183g bromide (12mmol) dissolved in 6000g acetonitrile solution, 1h drop, continue to heat for 1h, sample analysis obtained ring sulfone acid content of 95%, the main impurity content of 2%, the raw material bromide content is less than 0.5%. After recovering acetonitrile by distillation under reduced pressure, 6000g water and 3000g dichloroethane were added to the kettle, stirred for 0.5h, and then separated into layers. The organic phase was extracted with 1000g dichloroethane, and the combined organic phase was distilled to recover dichloroethane for reuse. The water phase was adjusted to pH 1-2 with hydrochloric acid, filtered, washed with 200g water, and the wet product ring sulfone acid was obtained. After drying, 3906g of ring sulfone acid product was obtained (content more than 98%, molar yield 92%).
[0024] Put 2000g acetonitrile, 768g (19mol) sodium hydroxide into the reaction kettle, open the reaction kettle stirring, heating to 40-50℃, 1h drop 1818g (18mol) trifluoroethanol, 1h after the drop is completed, continue to heat to 55-60℃ drop 4183g bromide (12mmol) dissolved in 6000g acetonitrile solution, 1h drop, continue to heat for 3h, sample analysis obtained ring sulfone acid content of 90%, the main impurity content of 7%, the raw material bromide content is less than 0.5%. After recovering acetonitrile by distillation under reduced pressure, 6000g water and 3000g dichloroethane were added to the kettle, stirred for 0.5h, and then separated into layers. The organic phase was extracted with 1000g dichloroethane, and the combined organic phase was distilled to recover dichloroethane for reuse. The water phase was adjusted to pH 1-2 with hydrochloric acid, filtered, washed with 200g water, and the wet product ring sulfone acid was obtained. After drying, 3906g of ring sulfone acid product was obtained (content more than 98%, molar yield 92%).
[0025] Example 3
[0026] Into a reaction kettle with ultrasonic generator and circulation pipeline, 2000g tetrahydrofuran, 768g (19mol) sodium hydroxide were put, the circulation pipeline and the reaction kettle were opened, and stirring was started, and the temperature was raised to 40-50°C, 1818g (18mol) trifluoroethanol was added dropwise under ultrasonic condition for 1h, and after the dropwise addition was completed, the temperature was kept for 1h, and then 4183g bromide (12mmol) dissolved in 6000g tetrahydrofuran was added dropwise for 1h, and the reaction was kept for 1.5h, and the sample analysis showed that the content of cyclo sulfone acid was 94%, the content of main impurities was 3%, and the content of raw material bromide was less than 0.5%. After recovering tetrahydrofuran by distillation under reduced pressure, 6000g water and 3000g dichloroethane were added to the kettle, stirring was started for 0.5h, and then the kettle was kept still to separate the layers, 1000g dichloroethane was used to extract the water phase, and the combined organic phase was distilled to recover dichloroethane for reuse. The water phase was adjusted to pH 1-2 by hydrochloric acid, and then filtration was started, and 200g water was used for washing, so as to obtain wet cyclo sulfone acid, and after drying, 3821g of cyclo sulfone acid product was obtained (the content was more than 98%, and the molar yield was 90%).
[0027] Into a reaction kettle with ultrasonic generator and circulation pipeline, 2000g tetrahydrofuran, 768g (19mol) sodium hydroxide were put, the circulation pipeline and the reaction kettle were opened, and stirring was started, and the temperature was raised to 40-50°C, 1818g (18mol) trifluoroethanol was added dropwise under ultrasonic condition for 1h, and after the dropwise addition was completed, the temperature was kept for 1h, and then 4183g bromide (12mmol) dissolved in 6000g tetrahydrofuran was added dropwise for 1h, and the reaction was kept for 1.5h, and the sample analysis showed that the content of cyclo sulfone acid was 94%, the content of main impurities was 3%, and the content of raw material bromide was less than 0.5%. After recovering tetrahydrofuran by distillation under reduced pressure, 6000g water and 3000g dichloroethane were added to the kettle, stirring was started for 0.5h, and then the kettle was kept still to separate the layers, 1000g dichloroethane was used to extract the water phase, and the combined organic phase was distilled to recover dichloroethane for reuse. The water phase was adjusted to pH 1-2 by hydrochloric acid, and then filtration was started, and 200g water was used for washing, so as to obtain wet cyclo sulfone acid, and after drying, 3821g of cyclo sulfone acid product was obtained (the content was more than 98%, and the molar yield was 90%).
[0028] Example 4
[0029] Other steps were the same as in Example 1, the organic solvent B was replaced by toluene instead of dichloroethane, and after drying, 3778g of cyclo sulfone acid product was obtained (the content was more than 98%, and the molar yield was 89%).
[0030] Example 5
[0031] Other steps were the same as in Example 1, the organic solvent B was replaced by methyl tert-butyl ether instead of dichloroethane, and after drying, 3948g of cyclo sulfone acid product was obtained (the content was more than 98%, and the molar yield was 93%).
[0032] The above examples are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and to implement it, and cannot limit the protection scope of the present application. Any equivalent changes or modifications made according to the spirit and essence of the present application shall be covered within the protection scope of the present application.
Claims
1. A process for the preparation of ultrasonically promoted cyclic sulfonamide acid, characterized by, Specifically comprising the following steps: S1, the raw material bromide and trifluoroethanol are subjected to substitution hydrolysis in the presence of inorganic base in organic solvent A under the promotion of ultrasonic wave; S2, after the reaction is completed, the organic solvent A is recovered by distillation, if the organic solvent B is the same as A, this distillation step is omitted; water and organic solvent B are added to the reaction product after distillation, if the organic solvent B is the same as A, the organic solvent B is not added, the layers are separated by standing and the water layer is extracted with organic solvent B; S3, the organic phase is combined and recovered by distillation for reuse; the water phase is combined, the pH value is adjusted to 1-2 with hydrochloric acid, and the product is obtained by filtering and washing with water.
2. A process for the preparation of an ultrasonic promoted cyclic sulfone acid according to claim 1, characterized by: The promotion of ultrasonic wave refers to inserting at least one ultrasonic wave generator in the reaction kettle to generate ultrasonic wave; Or, an external circulation pipeline is arranged and at least one ultrasonic wave generator is inserted in the external circulation pipeline to generate ultrasonic wave; Or, at least one ultrasonic wave generator is inserted in the reaction kettle to generate ultrasonic wave, and at the same time, an external circulation pipeline is arranged and at least one ultrasonic wave generator is inserted in the external circulation pipeline to generate ultrasonic wave.
3. The process for the preparation of an ultrasonic promoted cyclic sulfone acid according to claim 1, characterized by: The inorganic base is a mixture of one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
4. The process for the preparation of an ultrasonic promoted cyclic sulfone acid according to claim 1, characterized by: The organic solvent A is any one of dichloromethane, dichloroethane, chlorobenzene, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, acetone, 2-butanone, N-methyl pyrrolidone, cyclopentanone, cyclohexanone, methyl tert-butyl ether, tetrahydrofuran, methyl tetrahydrofuran and dimethyl ether.
5. The process for the preparation of an ultrasonic promoted cyclic sulfone acid according to claim 1, characterized by: The organic solvent B is any one of dichloromethane, dichloroethane, cyclohexane, petroleum ether, toluene, xylene, chlorobenzene, ethyl acetate, dimethyl carbonate and methyl tert-butyl ether.