CN112592353A - Industrial preparation method of cyclic sulfate - Google Patents
Industrial preparation method of cyclic sulfate Download PDFInfo
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- CN112592353A CN112592353A CN202011519416.6A CN202011519416A CN112592353A CN 112592353 A CN112592353 A CN 112592353A CN 202011519416 A CN202011519416 A CN 202011519416A CN 112592353 A CN112592353 A CN 112592353A
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- cyclic sulfate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
- C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D497/10—Spiro-condensed systems
Abstract
The invention discloses an industrial preparation method of cyclic sulfate, belonging to the technical field of new energy material synthesis. Firstly, the method for producing sulfoxide by adopting thionyl chloride is adopted for the pentaerythritol A, so that the use of organic base or inorganic base used in the existing literature is avoided, and a key intermediate sulfoxide B is obtained; and secondly, adopting chlorine as a source of an oxidant, avoiding oxidation of noble metals, Oxone with low available oxygen and high-concentration hydrogen peroxide, and obtaining the cyclic sulfate C. The invention successfully develops a process for preparing the cyclic sulfate with simple operation and high yield on the basis of the prior literature, reduces the requirements on production equipment and improves the product competitiveness.
Description
Technical Field
The invention relates to the technical field of new energy material synthesis, in particular to a method for synthesizing cyclic sulfate, and the cyclic sulfate prepared by the method can be used as an additive of lithium ion battery electrolyte and also can be used as a drug synthesis intermediate.
Background
Along with the enhancement of environmental protection consciousness and the progress of science and technology, novel green energy technology is increasingly valued by people, and particularly lithium ion secondary batteries have the advantages of high working voltage, small volume, light weight, high energy density, small environmental pollution, small self-discharge, long cycle service life and no memory effect, so that the lithium ion secondary batteries receive the attention of the battery industry and are widely applied.
The cyclic sulfate is used as an additive of a lithium ion electrolyte, is particularly suitable for an electrolyte additive of a high-power lithium ion battery of a ternary system anode material, can effectively avoid the reduction of the initial capacity of the lithium ion battery, increase the initial discharge capacity, improve the charge and discharge performance and cycle times of the battery, and improve the high-low temperature cycle performance.
The literature reports that the synthesis method of cyclic sulfate ester mainly comprises four methods, namely acylation, substitution, addition and oxidation.
Acylation method: prepared by reacting sulfuryl chloride or sulfuryl fluoride with vicinal diols (cf. CN 107629032A). The method has low yield, strong corrosivity and great environmental pollution, and is not suitable for industrial production.
Substitution method: the method adopts dibromoethane and silver sulfate to react, has low yield and expensive materials, and is obviously not suitable for strict limit of industrialization on cost.
An addition method comprises the following steps: the use of sulfur trioxide with high corrosiveness is involved, and has strict requirements on equipment, so that the method is not suitable for industrial production.
An oxidation method: the relative literature reports are more. Compared with the classical operation, the sulfoxide is oxidized under the action of sodium periodate and a metal catalyst, and the reaction equation is as follows:
however, the price of noble metal and sodium periodate is high, and the noble metal and the sodium periodate are difficult to be comprehensively recovered, so that the industrial application can not be realized (J.org.chem.,1998,63, 5240-; patents CN103012386A and CN104744427A report mild oxidation with Oxone, but the available oxygen content is too low and the amount of by-product sulfate is large, which causes difficulties in production. CN110386916A adopts high-concentration hydrogen peroxide as an oxidant, and is not suitable to be used as a preferred method for production due to explosion hazard in the production, use, storage and transportation processes of the high-concentration hydrogen peroxide.
After sufficient market research and comparative analysis of process cost, the spiro-cyclic sulfate as the lithium ion battery additive has wide market space in the future and huge market potential, so that a evasive patent is determined to be rapidly developed, and the development of a process suitable for future industrial production is strived to meet market requirements and compete for market first chance in the future.
Disclosure of Invention
In order to overcome the technical defects, the invention adopts the technical scheme that: the first step, a sulfoxide generation mode by using thionyl chloride is adopted, so that the use of organic base or inorganic base used in the existing literature is avoided, and a key intermediate sulfoxide B is obtained; and secondly, adopting chlorine as a source of an oxidant, avoiding oxidation of noble metals, Oxone with low available oxygen and high-concentration hydrogen peroxide, and obtaining the cyclic sulfate C.
The industrial preparation method of the cyclic sulfate comprises the following steps of:
firstly, reacting pentaerythritol A with thionyl chloride to generate intermediate sulfoxide B; and secondly, reacting the intermediate sulfoxide B with chlorine to obtain cyclic sulfate C.
Further, in the above-mentioned embodiment, the first reaction is carried out in a toluene solvent without adding an organic base such as Et3N, pyridine, and the like.
Further, in the above technical scheme, in the first step of reaction, the mole ratio of the pentaerythritol A to the thionyl chloride is 1: 2-4.
Further, in the above technical scheme, after the first step of reaction is completed, the reaction solution is cooled to room temperature, a solid is precipitated, and the intermediate sulfoxide B is obtained by filtration.
Further, in the above technical scheme, in the second step of reaction, the sulfoxide B is dissolved in a mixture of acetonitrile and an aqueous alkali solution, and chlorine gas is introduced into the mixture for reaction in a TEMPO catalyst.
Further, in the above technical solution, the aqueous alkali solution is selected from an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution.
Further, in the above technical scheme, the molar ratio of sulfoxide B, aqueous alkali and TEMPO is 1: 1-5: 0.001 to 0.005.
Further, in the above technical scheme, after the second step of reaction, standing for layering, concentrating to dryness, adding acetone, and stirring at room temperature to obtain cyclic sulfate C.
The invention has the beneficial effects
In the invention, a sulfoxide generation mode by using thionyl chloride is adopted in the first step, so that the use of organic base or inorganic base used in the existing literature is avoided; and in the second step, chlorine is used as the source of the oxidant, so that oxidation of noble metals, Oxone with low available oxygen and high-concentration hydrogen peroxide is avoided, the operation is simple, and the process is relatively safe and reliable.
The invention successfully develops a process for preparing the cyclic sulfate with simple operation and high yield on the basis of the prior literature, reduces the requirements on production equipment and improves the product competitiveness.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions. The reagents and starting materials used in the present invention are commercially available.
Example 1
The first step is as follows: preparation of sulfoxide B
In a 500mL reaction flask, pentaerythritol (30.0g,220.5mmol), toluene (195.0 g) and thionyl chloride (63.0g,529mmol) were added and, after stirring well, the reaction was slowly raised to 75-80 ℃ and the reaction was continued at that temperature for 24 hours with TLC to check the completion of the starting material reaction. Stopping the reaction, reducing the temperature of the reaction system to 0-5 ℃, precipitating a large amount of solid, carrying out suction filtration, and drying to obtain a white-like solid 48.0g, wherein the yield is 95.4%. HNMR (Acetone-d)6,400MHz):4.96(d,J＝12.0,2H),4.63(d,J＝12.0Hz,2H),4.43(dd,2H),3.96(dd,2H).
Step two: preparation of cyclic sulfate C
A500 mL reaction flask was charged with sulfoxide B (10.0g,43.8mmol), acetonitrile 50.0g, and 10% aqueous sodium carbonate solution 50g, cooled to 0-10 ℃ with stirring, charged with TEMPO (10.0mg), and then charged with chlorine gas (6.2 g, 87.3mmol), and the mixture was ventedAnd (4) after the reaction is finished, continuously stirring for reacting for 1-2 hours, and detecting the completion of the reaction of the raw materials by TLC. And introducing nitrogen for 10 minutes, adding 2M hydrochloric acid to adjust the pH to be 4-5, and standing for layering. Drying the organic phase, filtering and concentrating to dryness to obtain a crude product, adding 50g of acetone, heating to dissolve, filtering, removing mechanical impurities, concentrating the filtrate to obtain the residual 10mL of solvent, cooling to room temperature, filtering to obtain a white solid, and drying in vacuum to constant weight to obtain 10.1g of the white solid with the yield of 88%. HNMR (Acetone-d)6,400MHz):5.0(s,8H).
Example 2
The first step is as follows: preparation of sulfoxide B
In a 500mL reaction flask, pentaerythritol (30.0g,220.5mmol), toluene (195.0 g) and thionyl chloride (52.5g,441.0mmol) were added and, after stirring well, the reaction slowly rose to 75-80 ℃ and continued at that temperature for 24 hours, with TLC to check the completion of the starting material reaction. Stopping the reaction, reducing the temperature of the reaction system to 0-5 ℃, precipitating a large amount of solid, carrying out suction filtration, and drying to obtain 40.5g of off-white solid with the yield of 80.5%.
Step two: preparation of cyclic sulfate C
Adding sulfoxide B (20.0g,87.6mmol), acetonitrile 100.0g and 10% sodium carbonate aqueous solution 200g into a 500mL reaction bottle, cooling to 0-10 ℃ under stirring, adding TEMPO (10.0mg), introducing 12.5g of chlorine (176mmol), continuing to stir for 1-2 hours after the gas introduction is finished, and detecting the completion of the raw material reaction by TLC. And introducing nitrogen for 10 minutes, adding 2M hydrochloric acid to adjust the pH to be 4-5, and standing for layering. Drying the organic phase, filtering and concentrating to dryness to obtain a crude product, adding 100g of acetone, heating to dissolve, filtering, removing mechanical impurities, concentrating the filtrate to obtain the residual 20mL of solvent, cooling to room temperature, filtering to obtain a white solid, and drying in vacuum to constant weight to obtain 20.8g of the white solid with the yield of 91.2%.
Example 3
The first step is as follows: preparation of sulfoxide B
In a 500mL reaction flask, pentaerythritol (30.0g,220.5mmol), toluene (195.0 g) and thionyl chloride (131.2g,1.1mol) were added and, after stirring well, the reaction slowly rose to 75-80 ℃ and the reaction was continued at that temperature for 24 hours with TLC to check the completion of the starting material reaction. Stopping the reaction, reducing the temperature of the reaction system to 0-5 ℃, precipitating a large amount of solid, performing suction filtration, and drying to obtain 47.5g of off-white solid with the yield of 94.4%.
Step two: preparation of cyclic sulfate C
A500 mL reaction flask was charged with sulfoxide B (10.0g,43.8mmol), acetonitrile 50.0g, and 10% aqueous sodium carbonate 200g, cooled to 0-10 ℃ with stirring, charged with TEMPO (10.0mg), charged with 6.2g of chlorine (87.3mmol), and after the completion of the aeration, the reaction was continued for 1-2 hours with stirring, and the completion of the reaction of the starting materials was detected by TLC. And introducing nitrogen for 10 minutes, adding 2M hydrochloric acid to adjust the pH to be 4-5, and standing for layering. Drying the organic phase, filtering and concentrating to dryness to obtain a crude product, adding 50g of acetone, heating to dissolve, filtering, removing mechanical impurities, concentrating the filtrate to obtain the residual 20mL of solvent, cooling to room temperature, filtering to obtain a white solid, and drying in vacuum to constant weight to obtain 10.2g of the white solid with the yield of 89.5%.
The foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (8)
1. The preparation method of the cyclic sulfate comprises the following steps, and is characterized in that the reaction equation is as follows:
firstly, reacting pentaerythritol A with thionyl chloride to generate intermediate sulfoxide B; and secondly, reacting the intermediate sulfoxide B with chlorine to obtain cyclic sulfate C.
2. The process for producing a cyclic sulfate according to claim 1, wherein: in the first reaction step, the reaction is carried out in a toluene solvent.
3. The process for producing a cyclic sulfate according to claim 1, wherein: in the first step, the mole ratio of the pentaerythritol A to the thionyl chloride is 1: 2 to 4.
4. The process for producing a cyclic sulfate according to claim 1, wherein: and after the first-step reaction is finished, cooling the reaction liquid to room temperature, separating out a solid, and filtering to obtain an intermediate sulfoxide B.
5. The process for producing a cyclic sulfate according to claim 1, wherein: in the second step of reaction, sulfoxide B is dissolved in a mixture of acetonitrile and alkali water solution, and chlorine gas is introduced into the mixture to react in a TEMPO catalyst.
6. The process for producing a cyclic sulfate according to claim 1, wherein: the aqueous alkali solution is selected from sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
7. The process for producing a cyclic sulfate according to claim 1, wherein: the mol ratio of the sulfoxide B, the alkaline water solution and TEMPO is 1: 1-5: 0.001 to 0.005.
8. The process for producing a cyclic sulfate according to claim 1, wherein: and after the second step of reaction, standing for layering, concentrating to be dry, adding acetone, and stirring at room temperature to obtain cyclic sulfate C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114478570A (en) * | 2021-12-28 | 2022-05-13 | 湖北澳格森化工有限公司 | Preparation method of pentaerythritol sulfate |
| KR20230012771A (en) * | 2021-07-16 | 2023-01-26 | (주)덕산테코피아 | A method for producing cyclic sulfate by oxidation |
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| CN110386916A (en) * | 2019-07-23 | 2019-10-29 | 常熟市常吉化工有限公司 | A kind of synthetic method of cyclic sulfates |
| CN111285884A (en) * | 2018-12-10 | 2020-06-16 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of pentaerythritol sulfate |
| CN111909129A (en) * | 2020-09-03 | 2020-11-10 | 常熟市常吉化工有限公司 | Method for preparing cyclic sulfate by direct oxidation of hydrogen peroxide |
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| CN104788361A (en) * | 2015-04-21 | 2015-07-22 | 杭州科巢生物科技有限公司 | Synthetic method for 5-azaspiro[2.4]heptane-6-formic acid derivative |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230012771A (en) * | 2021-07-16 | 2023-01-26 | (주)덕산테코피아 | A method for producing cyclic sulfate by oxidation |
| KR102581237B1 (en) * | 2021-07-16 | 2023-09-21 | (주)덕산테코피아 | A method for producing cyclic sulfate by oxidation |
| CN114478570A (en) * | 2021-12-28 | 2022-05-13 | 湖北澳格森化工有限公司 | Preparation method of pentaerythritol sulfate |
| CN114478570B (en) * | 2021-12-28 | 2024-04-05 | 湖北澳格森化工有限公司 | Preparation method of pentaerythritol sulfate |
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