Preparation of furan[3,4-d]-1,3,2-dithiol-4(3aH)-one, dihydro-, 2-oxide

Abstract

This invention discloses the preparation of furan[3,4-d]-1,3,2-dioxathiol-4(3aH)-one, dihydro-,2-oxide, comprising the following steps: 1. Dissolving D-isoascorbic acid in water and adding sodium carbonate; 2. Adding 40 μL of 50% H2O2 aqueous solution dropwise. o C. Stir the reaction, then heat to 80°C. o C. Stir the reaction, filter while hot, wash with water to obtain a colorless and clear filtrate; 2. Quench the reaction with hydrochloric acid dropwise to acidity, evaporate to dryness under high vacuum to obtain a white solid; reflux with ethyl acetate, filter, evaporate the filtrate by rotary evaporation to obtain a crude intermediate, which is then processed to obtain a white needle-like crystalline intermediate; 3. Dissolve the white needle-like crystalline intermediate in acetonitrile, add thionyl chloride dropwise, and stir the reaction; 4. Pour the reaction solution into ice water, extract with dichloromethane, dry, filter, and evaporate by rotary evaporation to obtain a yellow solid crude product; further processing yields the product. The advantages of this invention are: simple process route, mild and easy-to-control reaction, low purification difficulty, few by-products, and high yield and purity.

Description

Technical Field

[0001] This invention relates to the field of sulfite compound synthesis technology, specifically to a method for preparing furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide. Background Technology

[0002] Cyclic sulfites are important chemical materials that can be used as electrolyte additives in the battery field, especially in lithium-ion batteries, to improve battery performance.

[0003] Adding cyclic sulfites to the electrolyte can prevent lithium ions from dissolving excessively or forming lithium dendrites. At the same time, cyclic sulfites participate in the formation of the solid electrolyte interphase (SEI) film, improving the battery's initial discharge capacity and cycle performance. This is of great significance in improving the overall performance of the battery and extending its lifespan.

[0004] Besides their applications in the battery field, cyclic sulfites have other uses, such as: some cyclic sulfites can be used as preservatives in black and white developers or as antioxidants in chemical reactions.

[0005] This demonstrates the promising economic prospects of cyclic sulfites. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide. This method uses readily available raw materials, has a simple preparation process, high yield, and is suitable for industrial production.

[0007] To achieve the above objectives, the technical solution adopted in this invention is: the preparation of furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide, comprising the following steps: 1. Dissolve D-isoascorbic acid in water and add sodium carbonate. The molar ratio of D-isoascorbic acid to sodium carbonate is 1:(2~2.5). 2. Add a 50% (w / w) H₂O₂ aqueous solution dropwise, maintaining a temperature of 40°C initially. o C. Stir the reaction, then heat to 80°C. o C. Stir the reaction until no hydrogen peroxide residue remains, filter while hot, wash with water, and obtain a colorless and clear filtrate. 3. Add hydrochloric acid dropwise to the filtrate to quench the reaction until it becomes acidic, evaporate to dryness under high vacuum to obtain a white solid; reflux with ethyl acetate, filter, evaporate the filtrate to obtain a crude intermediate, wash the crude intermediate in dichloromethane, filter, and dry to obtain a white needle-like crystalline intermediate; IV. Dissolve the white needle-like crystalline intermediate in acetonitrile, 20 oAdd thionyl chloride dropwise at C~25℃, and after the addition is complete, 20 o The reaction mixture was stirred at 25°C; the reaction solution was poured into ice water, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and rotary evaporated to obtain a yellow crude solid. V. The final product is obtained through post-processing of the crude solid product.

[0008] The above reaction process is illustrated in the following formula: .

[0009] Furthermore, in the preparation of the aforementioned furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide, in the first step, the mass ratio of D-isoascorbic acid to water is 1:(5-10).

[0010] Furthermore, in the preparation of the aforementioned furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide, in the second step, the molar ratio of D-isoascorbic acid to 50% H2O2 aqueous solution is 1:(5-7).

[0011] Furthermore, in the preparation of the aforementioned furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide, the temperature is controlled at 0–15°C when adding a 50% (w / w) H2O2 aqueous solution.

[0012] Furthermore, in the preparation of the aforementioned furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide, in the third step, the reaction is quenched until the acidic pH is 1-2.

[0013] Furthermore, in the preparation of the aforementioned furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide, in the fourth step, after the addition of thionyl chloride, the stirring reaction time is 1 h to 2 h.

[0014] Furthermore, in the preparation of the aforementioned furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide, the mass ratio of the white needle-like crystalline intermediate to acetonitrile in the fourth step is 1:(8-12).

[0015] Furthermore, in the preparation of the aforementioned furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide, the molar ratio of the white needle-like crystalline intermediate to thionyl chloride in the fourth step is 1:(1.6~2.2).

[0016] Furthermore, in the preparation of the aforementioned furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide, the post-treatment steps of the crude solid product include: adding dichloromethane and activated carbon and stirring, filtering to obtain a colorless and clear filtrate, adding n-hexane dropwise to precipitate a white solid, filtering, taking the white powder filtrate, and drying to obtain the final product.

[0017] The advantages of this invention are: 1. The process route is very simple, the reaction conditions are mild and easy to control, the purification difficulty is low, and the yield and purity are high. 2. There are few by-products, the generated waste is easy to treat, and it is environmentally friendly. 3. The raw materials are readily available and can be purchased directly, thereby effectively reducing production costs. Attached Figure Description

[0018] Figure 1 This is the hydrogen NMR spectrum of the product in Example 1.

[0019] Figure 2 This is the carbon NMR spectrum of the product in Example 1. Detailed Implementation

[0020] The preparation of furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide according to the present invention will be described in detail below through specific embodiments.

[0021] Example 1: Dissolve 100g of D-isoascorbic acid in 500g of water, and add 120g of sodium carbonate in batches. Adding sodium carbonate in batches is to control the reaction process and prevent the reaction from being too violent.

[0022] In 0 o Add 193g of a 50% H2O2 aqueous solution dropwise at a temperature of C~15℃, initially maintaining a temperature of 40℃. o Stir and heat to 80°C. o Stir at C for 0.5 h, and chlorine test paper shows no hydrogen peroxide residue. Filter while hot, wash with water, and obtain a colorless and clear filtrate.

[0023] The reaction was quenched by adding 6M HCl to the filtrate until the pH reached 1. The solution was then evaporated under high vacuum to obtain 186g of white solid. The solid was refluxed with ethyl acetate, filtered, and the filtrate was evaporated to obtain 62g of white needle-like crystalline intermediate.

[0024] The white needle-like crystalline intermediate was dissolved in 500g of acetonitrile, 20 o Add 101g of thionyl chloride dropwise at C~25℃, and after the addition is complete, 20 o The reaction mixture was stirred at 25°C for 1 hour. The reaction solution was then poured into ice water, extracted twice with dichloromethane, dried over anhydrous sodium sulfate, filtered, and rotary evaporated to obtain a yellow crude solid.

[0025] The crude yellow solid was added to dichloromethane and activated carbon and stirred. The mixture was filtered to obtain a colorless, clear filtrate. Hexane was added dropwise, resulting in the precipitation of a white solid. The filtrate was filtered, and the white powder was collected and dried to obtain 79 g of the final product (yield: 85%, purity: 98%). The product's 1H NMR spectrum is shown below. Figure 1 As shown, see the carbon NMR spectrum. Figure 2 As shown.

[0026] Example 2: Dissolve 100g of D-isoascorbic acid in 1000g of water, and add 132g of sodium carbonate in batches. Adding sodium carbonate in batches is to control the reaction process and prevent the reaction from being too violent.

[0027] In 0 o Add 193g of a 50% (w / w) H₂O₂ aqueous solution dropwise at a temperature of C~15℃, and maintain for 40℃. o Stir and heat to 80°C. o Stir at C for 0.5 h; chlorine test paper shows no hydrogen peroxide residue. Filter while hot, wash with water, and obtain a colorless, clear filtrate.

[0028] The reaction was quenched by adding 6M HCl to the filtrate until the pH reached 2. The solution was evaporated under high vacuum to obtain 180g of white solid. The solution was refluxed with ethyl acetate, filtered, and the filtrate was evaporated to obtain 60g of white needle-like crystalline intermediate.

[0029] The white needle-like crystalline intermediate was dissolved in 700g of acetonitrile, 20 o Add 101g of thionyl chloride dropwise at C~25℃, and after the addition is complete, 20 o Stir at 25°C for 1 hour. Pour the reaction solution into ice water, extract twice with dichloromethane, dry with anhydrous sodium sulfate, filter, and rotary evaporate to obtain a yellow crude solid.

[0030] The crude yellow solid was added to dichloromethane and activated carbon and stirred. After filtration, a colorless and clear filtrate was obtained. When n-hexane was added dropwise, a white solid precipitated out. After filtration, the white powder was collected and dried to obtain 75g of the final product (yield: 81%, purity: 98%).

[0031] Example 3: Dissolve 100g of D-isoascorbic acid in 700g of water, and add 120g of sodium carbonate in batches. Adding sodium carbonate in batches is to control the reaction process and prevent the reaction from being too violent.

[0032] In 0 o Add 270g of a 50% (w / w) H₂O₂ aqueous solution dropwise at a temperature of C~15℃, and maintain for 40 minutes. o Stir and heat to 80°C. o Stir at C for 2 hours. Chlorine test paper showed no hydrogen peroxide residue. Filter while hot, wash with water, and obtain a colorless and clear filtrate.

[0033] The reaction was quenched by adding 6M HCl to the filtrate until the pH reached 2. The solution was evaporated under high vacuum to obtain 178g of white solid. The solution was refluxed with ethyl acetate, filtered, and the filtrate was evaporated to obtain 62g of white needle-like crystalline intermediate.

[0034] The white needle-like crystalline intermediate was dissolved in 600g of acetonitrile, 20 o Add 101g of thionyl chloride dropwise at C~25℃, and after the addition is complete, 20 o Stir at 25°C for 2 hours. Pour the reaction solution into ice water, extract twice with dichloromethane, dry with anhydrous sodium sulfate, filter, and rotary evaporate to obtain a yellow crude solid.

[0035] The yellow crude solid was added to dichloromethane and activated carbon and stirred. After filtration, a colorless and clear filtrate was obtained. When n-hexane was added dropwise, a white solid precipitated out. After filtration, the white powder was collected and dried to obtain 77g of the final product (yield: 83%, purity: 98%).

[0036] Example 4: Dissolve 100g of D-isoascorbic acid in 500g of water, and add 120g of sodium carbonate in batches. Adding sodium carbonate in batches is to control the reaction process and prevent the reaction from being too violent.

[0037] In 0 o Add 193g of a 50% (w / w) H₂O₂ aqueous solution dropwise at a temperature of C~15℃, and maintain for 40℃. o Stir and heat to 80°C. o Stir at C for 0.5 h, and chlorine test paper shows no hydrogen peroxide residue. Filter while hot, wash with water, and obtain a colorless and clear filtrate.

[0038] The reaction was quenched by adding 6M HCl to the filtrate until the pH reached 1. The solution was evaporated under high vacuum to obtain 190g of white solid. The solution was refluxed with ethyl acetate, filtered, and the filtrate was evaporated to obtain 60g of white needle-like crystalline intermediate.

[0039] The white needle-like crystalline intermediate was dissolved in 500g of acetonitrile, 20 o Add 135g of thionyl chloride dropwise at C~25℃. After the addition is complete, 20... o Stir at 25°C for 4 hours. Pour the reaction solution into ice water, extract twice with dichloromethane, dry with anhydrous sodium sulfate, filter, and rotary evaporate to obtain a yellow crude solid.

[0040] The yellow crude solid was added to dichloromethane and activated carbon and stirred. After filtration, a colorless and clear filtrate was obtained. When n-hexane was added dropwise, a white solid precipitated out. After filtration, the white powder was collected and dried to obtain 76g of the final product (yield: 82%, purity: 98%).

[0041] Example 5: Dissolve 100g of D-isoascorbic acid in 500g of water, add 150g of sodium carbonate, and add sodium carbonate at a rate that ensures obvious bubbles emerge without significant exothermic reaction.

[0042] In 0 o 270g of a 50% H2O2 aqueous solution was prepared at a temperature of C~15℃ and maintained for 40 minutes. o Stir and heat to 80°C. o Stir at C for 1 hour, and the chlorine test paper shows no hydrogen peroxide residue. Filter while hot, and wash with water to obtain a colorless and clear filtrate.

[0043] The reaction was quenched by adding 6M HCl to the filtrate until the pH reached 1. The solution was evaporated under high vacuum to obtain 183g of white solid. The solution was refluxed with ethyl acetate, filtered, and the filtrate was evaporated to obtain 63g of white needle-like crystalline intermediate.

[0044] The white needle-like crystalline intermediate was dissolved in 500g of acetonitrile, 20 o Add 135g of thionyl chloride dropwise at C~25℃, and after the addition is complete, 20 o Stir at 25°C for 1 hour. Pour the reaction solution into ice water, extract twice with dichloromethane, dry with anhydrous sodium sulfate, filter, and rotary evaporate to obtain a yellow crude solid.

[0045] The yellow crude solid was added to dichloromethane and activated carbon and stirred. After filtration, a colorless and clear filtrate was obtained. When n-hexane was added dropwise, a white solid precipitated out. After filtration, the white powder was collected and dried to obtain 77g of the final product (yield: 83%, purity: 98%).

[0046] The advantages of this invention are: 1. The process route is very simple, the reaction conditions are mild and easy to control, the purification difficulty is low, and the yield and purity are high. 2. There are few by-products, the generated waste is easy to treat, and it is environmentally friendly. 3. The raw materials are readily available and can be purchased directly, thereby effectively reducing production costs.

Claims

1. Preparation of furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide, comprising the following steps:

1. Dissolve D-isoascorbic acid in water and add sodium carbonate. The molar ratio of D-isoascorbic acid to sodium carbonate is 1:(2~2.5).

2. Add a 50% (w / w) H₂O₂ aqueous solution dropwise, maintaining a temperature of 40°C initially. o C. Stir the reaction, then heat to 80°C. o C. Stir the reaction until no hydrogen peroxide residue remains, filter while hot, wash with water, and obtain a colorless and clear filtrate.

3. Add hydrochloric acid dropwise to the filtrate to quench the reaction until it becomes acidic, then evaporate to dryness under high vacuum to obtain a white solid; Ethyl acetate was refluxed, filtered, and the filtrate was rotary evaporated to obtain a crude intermediate. The crude intermediate was washed in dichloromethane, filtered, and dried to obtain a white needle-like crystalline intermediate. IV. Dissolve the white needle-like crystalline intermediate in acetonitrile, 20 o Add thionyl chloride dropwise at C~25℃, and after the addition is complete, 20 o The reaction mixture was stirred at 25°C; the reaction solution was poured into ice water, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and rotary evaporated to obtain a yellow crude solid. V. The final product is obtained through post-processing of the crude solid product.

2. The preparation of furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide according to claim 1, characterized in that: In the first step, the mass ratio of D-isoascorbic acid to water is 1:(5-10).

3. The preparation of furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide according to claim 1, characterized in that: In the second step, the molar ratio of D-isoascorbic acid to 50% H2O2 aqueous solution is 1:(5-7).

4. The preparation of furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide according to claim 1, characterized in that: When adding a 50% (w / w) H2O2 aqueous solution, the temperature should be controlled between 0 and 15°C.

5. The method for preparing a furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide according to claim 1, characterized in that: In the third step, the reaction is quenched until the acidic pH is 1-2.

6. The method for preparing a furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide according to claim 1, characterized in that: In the fourth step, after the thionyl chloride is added dropwise, the stirring reaction time is 1 h to 2 h.

7. The method for preparing a furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide according to claim 1, characterized in that: In the fourth step, the mass ratio of the white needle-like crystalline intermediate to acetonitrile is 1:(8-12).

8. A method for preparing a furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide according to claim 1 or 8, characterized in that: In the fourth step, the molar ratio of the white needle-like crystal intermediate to thionyl chloride is 1:(1.6~2.2).

9. The method for preparing a furan[3,4-d]-1,3,2-dioxothiol-4(3aH)-one, dihydro-,2-oxide according to claim 1, characterized in that: The steps for post-processing the crude solid product include: adding dichloromethane and activated carbon and stirring, filtering to obtain a colorless and clear filtrate, adding n-hexane dropwise to precipitate a white solid, filtering, taking the white powder filtrate, and drying to obtain the final product.

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