5-(Phenyl)-1,3,2,4-dioxathiazole 2-oxide and its preparation
By reacting the reaction of sulfonic chloride and N-hydroxylzyamide under nitrogen protection, combined with specific solvents and reaction conditions, high-purity 5- (benzene) -1,3,2,4-composite is successfully prepared Pato 2-oxide solves the problem of preparing high-purity compounds in existing technologies, and achieves efficient and simple process processes.
Patent Information
- Application Number
- CN202010979769.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2020-09-17
- Publication Date
- 2025-01-24
- Estimated Expiration
- 2040-09-17
AI Technical Summary
There is a lack of a simple and effective method for preparing high purity 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide in the prior art.
Under the protection of nitrogen protection, the response of sulfonic chloride and N-hydroxylzyleide in a specific solvent, by controlling the reaction temperature and dripping speed, combined with the steps of filtration, washing, discoloration, and decompression drying, successfully prepared high purity 5 5 -(phenyl) -1,3,2,4-eoxidazole 2-oxides.
Realizing the simplification of the process route, the reaction is easy to control, the purity is low, and the purity of the product can reach more than 99 %.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide and its preparation. Background Art
[0002] Sulfate ester compounds have a wide range of applications and good market prospects. To this end, our company prepared 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide, which has a simple preparation method and good yield. Summary of the invention
[0003] The purpose of the present invention is to provide a 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide and a preparation method thereof.
[0004] To achieve the above object, the technical solution adopted by the present invention is: 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide, the structural formula of which is shown in Formula 1, wherein R is a halogen atom at any position on the benzene ring;
[0005]
[0006] The preparation method of 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide comprises the following steps: 1. mixing sulfonyl chloride and a first solvent under nitrogen protection, stirring and cooling; 2. controlling the reaction temperature, dripping an acid-binding agent and an N-hydroxybenzamide solution, wherein the solvent of the N-hydroxybenzamide solution is the first solvent, and cooling the reaction after the dripping is completed; the structure of N-hydroxybenzamide is shown in Formula 2:
[0007] In formula 2, R is a halogen atom at any position on the benzene ring;
[0008] 3. After the reaction is completed, the reaction solution is cooled and filtered, and then washed with water, decolorized, dehydrated, crystallized, and filtered to obtain a crude product. The crude product is dried under reduced pressure to obtain a finished product.
[0009] Furthermore, in the aforementioned method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide, the first solvent is ethyl acetate or acetonitrile, and the amount used is 10 to 15 times the mass of N-hydroxybenzamide.
[0010] Furthermore, in the aforementioned method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide, in the first step, the temperature is cooled to -15°C to -10°C with stirring.
[0011] Furthermore, in the aforementioned method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide, in the second step, the reaction temperature is controlled at -10°C to 0°C, and after the acid binding agent and N-hydroxybenzamide solution are added dropwise, the temperature is lowered to react for 5-20 hours, and the reaction temperature is controlled at -15 to -10°C.
[0012] Furthermore, in the aforementioned method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide, in the third step, the reaction solution is cooled to -20°C to -15°C and filtered, and after filtration, it is washed with potassium carbonate solution at -10 to 0°C, and then decolorized with activated carbon and dehydrated with magnesium sulfate.
[0013] Furthermore, in the aforementioned method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide, the molar ratio of N-hydroxybenzamide to sulfonyl chloride is 1:1.05-1.15.
[0014] Furthermore, in the aforementioned method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide, the molar ratio of N-hydroxybenzamide to the acid binding agent is 1:2.1-2.3.
[0015] Furthermore, in the aforementioned method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide, the acid-binding agent is an organic base, and the organic base includes triethylamine and pyridine.
[0016] Furthermore, in the aforementioned method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide, the acid binding agent is pyridine.
[0017] The advantages of the present invention are: 1. It provides a new type of sulfate compound. 2. The process route is simple, the reaction is easy to control, the purification difficulty is low, and the product purity is high, which can reach more than 99%. DETAILED DESCRIPTION
[0018] The preparation method of 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide is described in detail below through specific examples.
[0019] Example 1.
[0020] Under nitrogen protection, 14.1g sulfonyl chloride and 30g ethyl acetate were added to the reactor in sequence, and the mixture was stirred and cooled to -10°C. Subsequently, the reaction temperature was controlled between -10 and 0°C, and 33.2g pyridine and 3-fluoro-N-hydroxybenzamide solution with ethyl acetate as solvent were added dropwise simultaneously. 128g ethyl acetate and 15.8g 3-fluoro-N-hydroxybenzamide were added to the 3-fluoro-N-hydroxybenzamide-ethyl acetate solution. The reaction was cooled to -15°C and reacted for 5 hours. After the reaction, the reaction was cooled to -20°C and filtered to remove most of the hydrochloride. The filtrate was washed with potassium carbonate solution at -10°C, and the organic phase was added with activated carbon and anhydrous magnesium sulfate for decolorization and dehydration. After most of the solvent was removed, the mixture was crystallized. After suction filtration, the crude product was dried under reduced pressure to obtain the finished product. The harvested product was a white solid. The product was characterized by nuclear magnetic resonance, and the results confirmed that it was the target product 5-(3-fluorophenyl)-1,3,2,4-dioxathiazole 2-oxide with a purity of 99.4%. The structural formula of 5-(3-fluorophenyl)-1,3,2,4-dioxathiazole 2-oxide:
[0021] Example 2
[0022] Under nitrogen protection, 15.4g of sulfonyl chloride and 30g of ethyl acetate were added to the reactor in sequence, and the mixture was stirred and cooled to -10°C. Subsequently, the reaction temperature was controlled between -10 and 0°C, and 36.3g of pyridine and a 4-chloro-N-hydroxybenzamide solution with ethyl acetate as solvent were added dropwise simultaneously. 232g of ethyl acetate and 17.5g of 4-chloro-N-hydroxybenzamide were added to the 4-chloro-N-hydroxybenzamide-ethyl acetate solution. The reaction was cooled to -10°C and reacted for 20 hours. After the reaction was completed, the reaction was cooled to -20°C and filtered to remove most of the hydrochloride. The filtrate was washed with potassium carbonate solution at -5°C. The organic phase was added with activated carbon and anhydrous magnesium sulfate for decolorization and dehydration. After most of the solvent was removed, the mixture was crystallized. After suction filtration, the crude product was dried under reduced pressure to obtain the finished product. The harvested product was a white solid. The product was characterized by nuclear magnetic resonance, and the results confirmed that it was the target product 5-(4-chlorophenyl)-1,3,2,4-dioxathiazole 2-oxide with a purity of 99.2%. The structural formula of 5-(4-chlorophenyl)-1,3,2,4-dioxathiazole 2-oxide:
[0023] Example 3
[0024] Under nitrogen protection, 15.4g of sulfonyl chloride and 30g of ethyl acetate were added to the reactor in sequence, and the mixture was stirred and cooled to -10°C. Subsequently, the reaction temperature was controlled between -10 and 0°C, and 42.4g of triethylamine and 2-fluoro-N-hydroxybenzamide solution with ethyl acetate as solvent were added dropwise simultaneously. 160g of ethyl acetate and 15.8g of 2-fluoro-N-hydroxybenzamide were added to the 2-fluoro-N-hydroxybenzamide-ethyl acetate solution. The reaction was cooled to -13°C and reacted for 10 hours. After the reaction, the reaction was cooled to -25°C and filtered to remove most of the hydrochloride. The filtrate was washed with potassium carbonate solution at 0°C, and the organic phase was added with activated carbon and anhydrous magnesium sulfate for decolorization and dehydration. After most of the solvent was removed, the mixture was crystallized. After suction filtration, the crude product was dried under reduced pressure to obtain the finished product. The harvested product was a white solid. The product was characterized by nuclear magnetic resonance, and the results confirmed that it was the target product 5-(2-fluorophenyl)-1,3,2,4-dioxathiazole 2-oxide with a purity of 99.2%. The structural formula of 5-(2-fluorophenyl)-1,3,2,4-dioxathiazole 2-oxide
[0025] The advantages of the present invention are: 1. It provides a new type of sulfate compound. 2. The process route is simple, the reaction is easy to control, the purification difficulty is low, and the product purity is high, which can reach more than 99%.
Claims
1. A method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide, comprising the following steps:
1. Mix sulfonyl chloride and the first solvent under nitrogen protection, stir and cool; 2. Control the reaction temperature at -10°C to 0°C, dropwise add an acid binding agent and N-hydroxybenzamide solution, the solvent of the N-hydroxybenzamide solution is the first solvent, and after the dropwise addition is completed, cool and react for 5-20 hours, and the reaction temperature is controlled at -15 to -10°C; the molar ratio of N-hydroxybenzamide to sulfonyl chloride is 1:1.05 to 1.15; the molar ratio of N-hydroxybenzamide to the acid binding agent is 1:2.1 to 2.3; 3. After the reaction is completed, cool the reaction solution to -20°C to -15°C and filter it, and after filtering, wash it with potassium carbonate solution at -10°C to 0°C, decolorize it with activated carbon, dehydrate it with magnesium sulfate, crystallize it, and filter it to obtain a crude product, and the crude product is dried under reduced pressure to obtain a finished product; The finished product is shown in Formula 1; the structural formula of N-hydroxybenzamide is shown in Formula 2; Formula 1: , in formula 1, R is a halogen atom at any position on the benzene ring; Formula 2: In formula 2, R is a halogen atom at any position on the benzene ring.
2. The method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide according to claim 1, characterized in that: The first solvent is ethyl acetate or acetonitrile, and the usage amount is 10 to 15 times the mass of N-hydroxybenzamide.
3. The method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide according to claim 1 or 2, characterized in that: In the first step, the temperature is cooled to -15°C to -10°C with stirring.
4. The method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide according to claim 1 or 2, characterized in that: The acid binding agent is an organic base.
5. The method for preparing 5-(phenyl)-1,3,2,4-dioxathiazole 2-oxide according to claim 4, characterized in that: The acid binding agent is pyridine.
Citation Information
Patent Citations
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