CN115368377A - Preparation method of cyclic sulfate - Google Patents

Abstract

The invention relates to the technical field of chemical synthesis, in particular to a preparation method of cyclic sulfate, which comprises the following steps: s1, reaction process: uniformly dispersing the raw material A or the raw material B into an organic solvent, controlling the reaction temperature, introducing sulfonyl fluoride gas into a reaction system, and obtaining a cyclic sulfate reaction solution after the reaction is finished; wherein the reaction temperature is-10 ℃ to 50 ℃, and the reaction time is 7 to 12 hours; s2, purification process: recrystallizing to obtain the fine target product of the cyclic sulfate. The preparation method of the cyclic sulfate provided by the invention does not need noble metal catalysis, has no wastewater and no hydrogen fluoride escape risk in the post-treatment process, has low requirement on equipment, can use the by-product fluorine-containing silane as a fluorosilicone rubber raw material, does not generate organic amine hydrofluoride, is safer and more environment-friendly, and is suitable for large-scale industrial production.

Description

A kind of preparation method of cyclic sulfuric acid ester

technical field

The invention relates to a preparation method of cyclic sulfuric acid ester, which belongs to the technical field of organic synthesis.

Background technique

Cyclic sulfate ester materials have been known for a long time and have received great attention in organic synthesis. In recent years, a large number of literatures have introduced substances with such similar structures as intermediates of medicine and surfactants, which have broad application prospects. In recent years, cyclic sulfate ester materials have been gradually used as electrolyte additives for lithium-ion batteries, which can effectively suppress side reactions on the electrode surface.

At present, the main synthetic route of this type of compound is as follows: (CN109485633A, CN109369609A, CN108707095A, CN102241662A, CN107086324A):

This route requires a two-step reaction. First, diol compounds and thionyl chloride are used to react to obtain sulfite, and further, under the catalysis of noble metal ruthenium trichloride, sodium hypochlorite is used to oxidize to obtain the target product.

In addition, Chinese patent CN109988145A discloses using ethylene glycol and thionyl chloride as raw materials to synthesize sulfite, and then vinyl sulfite is mixed with air or Oxygen oxidizes to produce vinyl sulfate, and after filtration, washing with water, concentration and crystallization, the finished product of vinyl sulfate is obtained.

The main problems of this route are: (1) the use of thionyl chloride produces a large amount of corrosive gas hydrogen chloride; (2) the second oxidation reaction requires the use of ruthenium trichloride as a catalyst, which is expensive and difficult to recycle. At the same time, sodium hypochlorite is used as the oxidant, the reaction is exothermic violently, it is difficult to control, and the energy consumption is high; (3) using sodium hypochlorite as the oxidant produces a large amount of saline wastewater, which increases the cost of wastewater treatment; (4) due to the ring The sulfuric acid ester material has poor solubility and needs a large amount of solvent to participate in the reaction, so that the production efficiency of this method is particularly low.

Even if the Chinese patent CN109988145A uses air or oxygen as the oxidant instead, the reaction must occur in the presence of palladium chloride and cupric chloride catalysts, which are expensive, especially in recent years when the price of palladium-containing catalysts has increased by 4 times. Moreover, it is difficult to recover the catalyst in this process, which does not meet the development requirements of green chemistry.

In recent years, patents CN107629032A and CN110818674A have reported a method of cyclizing a diol compound and a sulfonyl fluoride to obtain a cyclic sulfate in the presence of an organic base. Even in the presence of an acid-binding agent, this method will still escape highly corrosive and highly toxic hydrogen fluoride during the reaction preparation process, the reaction safety risk is relatively high, and the requirements for equipment materials are relatively high. At the same time, the by-product organic amine hydrogen Fluorate cannot be recycled, nor can it be harmlessly disposed of through incineration or other methods.

Contents of the invention

The present invention provides a cyclic sulfuric acid for the problems of large amount of acid gas, serious equipment corrosion, large amount of waste water, large salt content, uncontrollable reaction heat release, low production efficiency and high cost in the existing process for synthesizing cyclic sulfuric acid esters. The preparation method of ester, the method adopts cheap silicon ether and sulfonyl fluoride as raw materials, and prepares cyclic sulfuric acid ester in one step.

The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of preparation method of cyclic sulfuric acid ester, the preparation method of described cyclic sulfuric acid ester is:

，原料B为

，环状硫酸酯为

；Prepare cyclic sulfate by reacting raw material A with sulfonyl fluoride gas, or prepare cyclic sulfate by reacting raw material B with sulfonyl fluoride gas. Raw material A is:

, raw material B is

, the cyclic sulfate is

;

Wherein, R ₁ ~ R ₅ are selected from one of methyl, ethyl, propyl, isopropyl and vinyl;

Described preparation method comprises the steps:

S1. Reaction process:

uniformly disperse raw material A or raw material B in an organic solvent, control the reaction temperature, feed sulfonyl fluoride gas into the reaction system, and complete the reaction to obtain a cyclic sulfuric acid ester reaction liquid;

S2, purification process:

Recrystallization was used to obtain the refined target object of cyclic sulfate.

Further, in step S1, the reaction temperature is -10°C-50°C, and the reaction time is 7-12 hours.

，所述的原料B为

、

中的任意一种。Further, the raw material A is

, the raw material B is

,

any of the.

Further, in step S1, the molar ratio of raw material A or raw material B to sulfonyl fluoride is 1:2.4~5, and the amount of the organic solvent used is 4.9-8.05 times the mass of raw material A or raw material B.

Further, in step S1, the organic solvent is selected from dichloromethane, dichloroethane, chloroform, acetonitrile, bis(2,2,2-trifluoroethyl) ether, dimethyl carbonate, diethyl carbonate One or a combination of esters.

Further, in step S2, the operation of the purification process is: recrystallize the crude cyclic sulfate in the cyclic sulfate reaction solution, heat and dissolve the crude cyclic sulfate in a good solvent, and then slowly add Poor solvent, cooling and filtering to obtain the cyclic sulfuric acid ester fine target.

Further, the good solvent is selected from one or more combinations of chloroform, acetonitrile, bis(2,2,2-trifluoroethyl)ether, dimethyl carbonate, and diethyl carbonate. When the good solvent heats and dissolves the crude cyclic sulfate, the heating temperature is 1-10°C below the boiling point of the good solvent.

Further, the poor solvent is selected from one or more combinations of dichloroethane, dichloromethane, n-hexane, cyclohexane, petroleum ether, n-heptane or n-octane.

Further, the amount of the good solvent is 1 to 8 times the mass of the raw material A or raw material B, the amount of the poor solvent is 1 to 4 times the mass of the good solvent, and the cooling and filtering temperature is -10 to 20°C .

Further, when the crude cyclic sulfate ester is dissolved in a good solvent, an adsorption filler is first added for decolorization and adsorption treatment, and the adsorption filler is filtered out after the decolorization and adsorption treatment. The adsorption filler is basic alumina or activated clay, but not limited to these two. Decolorization and adsorption treatment is beneficial to reduce the acid value of the product and improve product quality.

When the organic solvent used in step S1 is a good solvent, the purification process of step S2 can be as follows: after adding adsorption filler to the cyclic sulfuric acid ester reaction solution for decolorization and adsorption, filter the adsorption filler, and then carry out vacuum distillation. Part of the organic solvent, when the solids start to precipitate in the system, stop the distillation, heat the system to 1~10°C below the boiling point of the organic solvent, until the solids precipitated in the system are dissolved, slowly add the poor solvent dropwise, and make a slurry treatment, and finally carry out cooling crystallization and filtration to obtain the cyclic sulfuric acid ester fine target product.

When the organic solvent used in step S1 is a poor solvent, there will be solid precipitation directly in the cyclic sulfuric acid ester reaction solution, and the purification process of step S2 can be: the cyclic sulfuric acid ester reaction solution is filtered, and the obtained filter cake is Crude cyclic sulfate, then add the crude cyclic sulfate into a good solvent, heat to dissolve, the heating temperature is 1~10°C below the boiling point of the good solvent, then add adsorption filler for decolorization and adsorption treatment, filter out the adsorption filler , slowly drop a poor solvent, and beating, and finally carry out cooling crystallization, filtration, and obtain the cyclic sulfuric acid ester fine target product.

The beneficial effects of the present invention are:

(1) The present invention uses cheap silicon ether and sulfonyl fluoride as raw materials, and develops a new process for preparing cyclic sulfate by metathesis exchange method.

(2) The preparation method of cyclic sulfate provided by the present invention does not require precious metal catalysis, and there is no waste water in the post-treatment process, no risk of hydrogen fluoride escape, low requirements on equipment, and the by-product fluorine-containing silane can be used as fluorosilicone rubber The raw material is free of organic amine hydrofluoride, which is safer and more environmentally friendly, and is suitable for large-scale process production.

The preparation method provided by the invention avoids the problems of large amount of waste water, large amount of solvent used, cumbersome operation, low yield and especially low production efficiency caused by the poor solubility of the cyclic sulfate ester.

(3) In the preparation method of the cyclic sulfate provided by the present invention, the by-product is fluorine-containing silane, and the fluorine-containing silane is a gas at normal temperature, and the cyclic sulfate is a solid product. Fluorine-containing silane can escape from the reaction system, so it is more conducive to the purification of cyclic sulfate, so as to obtain high-quality cyclic sulfate products.

(4) In the preparation method of the present invention, chromaticity <10 Hazen (10% acetonitrile solution), acid value <10ppm (calculated as HF), water content <30ppm, chloride ion content <5ppm, no sulfate exists, and GC purity >99.9% of the products meet the requirements of high-voltage lithium ion batteries and sodium iron sulfate system sodium ion batteries.

Description of drawings

Fig. 1 is the synthetic route of cyclic sulfuric acid ester described in the present invention;

Fig. 2 is the ¹ H NMR spectrogram of the cyclic sulfuric acid ester compound that makes in embodiment 1;

Fig. 3 is the ¹³ C NMR spectrogram of the cyclic sulfuric acid ester compound that makes in embodiment 1;

Fig. 4 is the MS-ESI mass spectrogram of the cyclic sulfate ester compound prepared in embodiment 1.

Detailed ways

Specific embodiments of the present invention will be described in detail below. The present invention can be implemented in many ways other than those described here, and those skilled in the art can make similar improvements without departing from the connotation of the present invention, so the present invention is not limited by the disclosed specific embodiments.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used are for describing specific embodiments only, not for limiting the invention.

A kind of preparation method of cyclic sulfuric acid ester, the synthetic route of described cyclic sulfuric acid ester is as shown in Figure 1, and the preparation method of described cyclic sulfuric acid ester is:

，原料B为

，环状硫酸酯为

；Prepare cyclic sulfate by reacting raw material A with sulfonyl fluoride gas, or prepare cyclic sulfate by reacting raw material B with sulfonyl fluoride gas. Raw material A is:

, raw material B is

, the cyclic sulfate is

;

Wherein, R ₁ ~ R ₅ are selected from one of methyl, ethyl, propyl, isopropyl and vinyl;

Described preparation method comprises the steps:

S1. Reaction process:

uniformly disperse raw material A or raw material B in an organic solvent, control the reaction temperature, feed sulfonyl fluoride gas into the reaction system, and complete the reaction to obtain a cyclic sulfuric acid ester reaction solution;

S2, purification process:

Recrystallization was used to obtain the refined target object of cyclic sulfate.

In step S1, the reaction temperature is -10°C-50°C, and the reaction time is 7-12 hours.

In step S1, the molar ratio of raw material A or raw material B to sulfonyl fluoride is 1:2.4-5, and the amount of the organic solvent used is 4.9-8.05 times the mass of raw material A or raw material B.

In step S1, the organic solvent is selected from dichloromethane, dichloroethane, chloroform, acetonitrile, bis(2,2,2-trifluoroethyl) ether, dimethyl carbonate, diethyl carbonate one or a combination of several.

In step S2, the operation of the purification process is as follows: recrystallize the crude cyclic sulfate in the cyclic sulfate reaction solution, select a good solvent to heat and dissolve the crude cyclic sulfate, and then slowly add a poor solvent, Cool down and filter to obtain the cyclic sulfuric acid ester fine target product.

The good solvent is selected from one or more combinations of chloroform, acetonitrile, bis(2,2,2-trifluoroethyl)ether, dimethyl carbonate and diethyl carbonate.

The poor solvent is selected from one or more combinations of dichloroethane, dichloromethane, n-hexane, cyclohexane, petroleum ether, n-heptane or n-octane.

The amount of the good solvent is 1-8 times the mass of the raw material A or raw material B, the amount of the poor solvent is 1-4 times the mass of the good solvent, and the cooling and filtering temperature is -10-20°C.

When the crude cyclic sulfate ester is dissolved in a good solvent, first add an adsorption filler for decolorization and adsorption treatment, and filter out the adsorption filler after the decolorization and adsorption treatment. The adsorption filler is basic alumina or activated clay.

When the organic solvent used in step S1 is a good solvent, the purification process of step S2 can be as follows: after adding adsorption filler to the cyclic sulfuric acid ester reaction solution for decolorization and adsorption, filter the adsorption filler, and then carry out vacuum distillation. Part of the organic solvent, when solids start to precipitate in the system, stop the distillation, heat the system to 1~19°C below the boiling point of the organic solvent, until the solids precipitated in the system are dissolved, slowly add the poor solvent dropwise, and make a slurry treatment, and finally carry out cooling crystallization and filtration to obtain the cyclic sulfuric acid ester fine target product.

When the organic solvent used in step S1 is a poor solvent, there will be solid precipitation directly in the cyclic sulfuric acid ester reaction solution, and the purification process of step S2 can be: the cyclic sulfuric acid ester reaction solution is filtered, and the obtained filter cake is Crude cyclic sulfate, then add the crude cyclic sulfate into a good solvent, heat to dissolve, the heating temperature is 1~10°C below the boiling point of the good solvent, then add adsorption filler for decolorization and adsorption treatment, filter out the adsorption filler , slowly drop a poor solvent, and beating, and finally carry out cooling crystallization, filtration, and obtain the cyclic sulfuric acid ester fine target product.

Wherein the preparation method references of raw material A or raw material B: EP3366137A1, CN104710456A, CN104710459A.

Example 1

1000mL three-necked pressure-resistant flask, weigh 62.1g (0.25mol) raw material 1 and 500g acetonitrile into the 1000mL three-necked flask, stir magnetically, replace with N ₂ (10mL/min), control the internal temperature of the system at 20~30℃, slowly Sulfonyl fluoride gas was introduced into the system, and when the system pressure reached 0.05Mpa, the air intake was stopped, the reaction was kept for 2.0 hours, and the nitrogen gas was vented. Continue to feed sulfonyl fluoride gas into the system until the system pressure is 0.05Mpa, hold the reaction for 2.0h, and vent the nitrogen until the GC is followed by sampling. After confirming that the reaction is complete, stop feeding sulfonyl fluoride, and feed a total of 66.2g of sulfonyl fluoride into the reaction. The total reaction time is 12.0h.

After confirming that the reaction is complete, add 10g of basic alumina to the above system, and stir at 20~30°C for 2.0h, filter with suction to remove basic alumina, and the obtained colorless and clear filtrate is desolvated under reduced pressure until the system has a slight solid Precipitate.

Control the internal temperature of the system at 65-70°C, heat the above system until it is fully dissolved, slowly add 500g of n-heptane to the system, a large amount of white solids will precipitate out of the system, beat and stir at this temperature for 30min, cool down to 0-5°C, pump The white solid was obtained by filtration, and further dried under reduced pressure to obtain 59.19 g of cyclic sulfuric acid ester product, yield 90.98%, GC purity 99.92%, chromaticity 6 Hazen (10% acetonitrile solution), acid value: 7 ppm (calculated as HF), chlorine The ion content is less than 5ppm, no sulfate radical is detected, and ^{the 1} H NMR, ¹³ C NMR and MS-ESI mass spectrometry detection of the fine cyclic sulfate ester is shown in Figure 2, Figure 3 and Figure 4.

Example 2

1000mL three-necked pressure-resistant flask, weigh 42.5g (0.1mol) of raw material 2 and 280g of dichloromethane into the 1000mL three-necked flask, stir magnetically, replace with N ₂ (10mL/min), control the internal temperature of the system at 0~10℃, Under normal pressure, slowly feed sulfonyl fluoride gas into the system until GC tracking and sampling. After confirming that the reaction is complete, stop feeding sulfonyl fluoride. A total of 51.0 g of sulfonyl fluoride was fed into the reaction, and the total reaction time was 8.0 h.

After confirming that the reaction is complete, filter under reduced pressure, add 104g of bis(2,2,2-trifluoroethyl)ether to the obtained filter cake, heat to 45~50°C, the system is completely dissolved, and add 5g of active clay, and stirred at 40~50°C for 1.0h, filtered with suction to remove activated clay, and obtained a colorless and clear filtrate.

Control the internal temperature of the system at 50-60°C, slowly add 200g of n-hexane to the above filtrate, a large amount of white solids are precipitated in the system, beating and stirring at this temperature for 30min, cooling down to -10~-5°C, suction filtering to obtain white solids, further After drying under reduced pressure, 23.4g of fine cyclic sulfate ester was obtained, yield 90.00%, GC purity 99.96%, chromaticity 8 Hazen (10% acetonitrile solution), acid value: 5ppm (calculated as HF), chloride ion content < 5ppm, sulfuric acid Root not detected.

Example 3

In a 1000mL three-necked pressure-resistant flask, weigh 60.9g (0.2mol) of raw material 3 and 300g of bis(2,2,2-trifluoroethyl) ether into a 1000mL three-necked flask, stir magnetically, and replace with N ₂ (10mL/min) , control the internal temperature of the system at -10~10°C, slowly feed sulfonyl fluoride gas into the system, stop the gas flow when the system pressure reaches 0.1Mpa, keep the reaction for 1.0h, and vent the nitrogen. Continue to feed sulfonyl fluoride gas into the system until the system pressure is 0.1Mpa, hold the reaction for 1.0h, and vent the nitrogen until the GC is followed by sampling. After confirming that the reaction is complete, stop feeding sulfonyl fluoride, and feed a total of 60.3g of sulfonyl fluoride into the reaction. The total reaction time is 8.0h.

After confirming that the reaction is complete, add 5 g of activated clay to the above system, stir at 20-30°C for 2.0 h, filter with suction to remove the activated clay, and obtain a colorless and clear filtrate.

Control the internal temperature of the system at 55-60°C, slowly add 300g of dichloroethane to the above filtrate, the system precipitates a large amount of white solid, beating and stirring at this temperature for 30min, cool down to 0-5°C, and obtain a white solid by suction filtration, further After drying under reduced pressure, 46.1g of fine cyclic sulfate ester was obtained, with a yield of 88.57%, a GC purity of 99.90%, a chromaticity of 9 Hazen (10% acetonitrile solution), an acid value: 7ppm (calculated as HF), and a chloride ion content <5ppm. Root not detected.

Example 4

1000mL three-necked pressure-resistant flask, weigh 62.1g (0.25mol) of raw material 1 and 350g of dichloroethane into the three-necked flask, stir magnetically, replace with N ₂ (10mL/min), control the internal temperature of the system at 40~50℃, Slowly feed sulfonyl fluoride gas into the system. When the system pressure reaches 0.1Mpa, stop the gas flow, keep the reaction for 2.0 hours, and vent the nitrogen gas. Continue to feed sulfonyl fluoride gas into the system until the system pressure is 0.1Mpa, hold the reaction for 2.0h, and vent the nitrogen gas until the GC is tracking and sampling. After confirming that the reaction is complete, stop feeding sulfonyl fluoride, and feed a total of 61.2g of sulfonyl fluoride into the reaction. The total reaction time is 7.0h.

After confirming that the reaction is complete, filter under reduced pressure, add 300g of acetonitrile to the obtained filter cake, heat to 75~80°C, the system is completely dissolved, cool down to 40~50°C, add 5g of activated clay to the above system, and Stir at 50°C for 30 minutes, filter with suction to remove activated clay, and obtain a colorless and clear filtrate. The obtained colorless and clear filtrate was desolventized under reduced pressure until a slight solid precipitated out of the system.

Control the internal temperature of the system at 75-80°C, heat the above system until it is fully dissolved, slowly add 500g of n-heptane to the system, a large amount of white solids will precipitate out of the system, beating and stirring at this temperature for 30min, cool down to 0-5°C, pump The white solid was obtained by filtration, and further dried under reduced pressure to obtain 60.2 g of fine cyclic sulfate ester, with a yield of 92.53%, a GC purity of 99.94%, a chromaticity of 6 Hazen (10% acetonitrile solution), an acid value: 8 ppm (calculated as HF), and chlorine Ion content <5ppm, no sulfate was detected.

Comparative example 1

With reference to the reaction principle proposed by the patent CN110818674A, the preparation of cyclic sulfuric acid ester is carried out, and ethylene glycol is replaced with pentaerythritol, and dichloromethane is used as a solvent. The specific conditions are:

Add 27.2g (0.20mol) of pentaerythritol and 300g of dichloromethane into a 1000mL three-necked pressure-resistant flask, add 85g (0.84mol) of triethylamine, stir and mix evenly, magnetic stirring, N ₂ (10mL/min) replacement, control The internal temperature of the system is 30~40°C. Slowly feed sulfuryl fluoride gas into the system. When the system pressure reaches 0.1Mpa, stop the gas flow, keep the reaction for 2.0h, and vent the nitrogen. Continue to feed sulfonyl fluoride gas to the system until the system pressure is 0.1Mpa, heat preservation reaction for 2.0h, and vent the nitrogen gas. During the reaction, pentaerythritol cannot be dissolved, and the system is white and turbid. No product is obtained after GC tracking; further feed sulfonyl fluoride gas to The system pressure was 0.3Mpa, and the reaction was kept for 2.0 hours, but there was still no product after GC tracking.

During the reaction process, the raw materials could not be completely dissolved, and no product was obtained after GC tracking.

Comparative example 2

The reaction principle proposed with reference to patent CN110818674A carries out the preparation of cyclic sulfuric acid ester, replaces ethylene glycol with pentaerythritol, takes acetonitrile as solvent, and specific conditions are:

Add 27.2g (0.20mol) of pentaerythritol and 250g of acetonitrile into a 1000mL three-necked pressure-resistant flask, the system is colorless and clear, add 58.1g (0.50mol) of tetramethylethylenediamine, stir and mix evenly, magnetic stirring, N ₂ ( 10mL/min) replacement, control the internal temperature of the system at 60~70°C, slowly introduce sulfonyl fluoride gas into the system, stop the gas flow when the system pressure reaches 0.1Mpa, keep the reaction for 2.0h, and vent the nitrogen. Continue to feed sulfuryl fluoride gas into the system until the system pressure is 0.1Mpa, keep the reaction for 2.0h, vent the nitrogen gas, and GC traces no product; further feed sulfuryl fluoride gas to the system pressure of 0.3Mpa, keep the reaction for 2.0h, and GC traces still No product.

During the reaction, the raw materials could be completely dissolved, but no product was obtained by GC tracking.

Comparative example 3

Refer to the reaction principle proposed by the patent CN107629032A to prepare cyclic sulfuric acid esters, use pentaerythritol instead of ethylene glycol, and use dichloromethane as the solvent. The difference from the comparative example 1 of this application is to add 6.0eq potassium hydroxide (compared to pentaerythritol) and 0.02eq tetrabutylammonium fluoride, the specific conditions are:

Add 27.2g (0.20mol) of pentaerythritol and 300g of dichloromethane into a 1000mL three-necked pressure-resistant flask, add 67.3g (1.2mol) of potassium hydroxide and 1.1g (0.0042mol) of tetrabutylammonium fluoride, and stir and mix well , magnetic stirring, N ₂ (10mL/min) replacement, control the internal temperature of the system at 0~10°C, slowly introduce sulfuryl fluoride gas into the system, wait until the system pressure reaches 0.1Mpa, stop the gas flow, keep warm for 2.0h, nitrogen empty. Continue to feed sulfonyl fluoride gas to the system until the system pressure is 0.1Mpa, heat preservation reaction for 2.0h, and vent the nitrogen gas. During the reaction, pentaerythritol cannot be dissolved, and the system is white and turbid. No product is obtained after GC tracking; further feed sulfonyl fluoride gas to The system pressure was 0.3Mpa, and the reaction was kept for 2.0 hours, but there was still no product after GC tracking.

During the reaction process, the raw materials could not be completely dissolved, and no product was obtained after GC tracking.

Comparative example 4

Refer to the reaction principle proposed by patent CN107629032A to prepare cyclic sulfuric acid ester, replace ethylene glycol with pentaerythritol, and use acetonitrile as solvent. The difference from Comparative Example 1 of this application is that 6.0eq potassium hydroxide (compared to pentaerythritol) and 0.02 eq tetrabutylammonium fluoride, specific conditions are:

Add 27.2g (0.20mol) of pentaerythritol and 250g of acetonitrile to a 1000mL three-necked pressure-resistant flask, the system is colorless and clear, after adding 67.3g (1.2mol) of potassium hydroxide and 1.1g (0.0042mol) of tetrabutylammonium fluoride Stir and mix evenly, magnetically stir, replace with N ₂ (10mL/min), control the internal temperature of the system at 0~10°C, and slowly introduce sulfonyl fluoride gas into the system, and stop the gas flow when the system pressure reaches 0.1Mpa, and keep warm for 2.0 h, nitrogen venting. Continue to feed sulfonyl fluoride gas into the system until the system pressure is 0.1Mpa, keep the heat for 2.0h, vent the nitrogen gas, the potassium hydroxide is not completely dissolved, the system is white and turbid, and no product is obtained after GC tracking; further feed the sulfonyl fluoride gas to The system pressure was 0.3Mpa, and the reaction was kept for 2.0 hours, but there was still no product after GC tracking.

During the reaction, the raw materials were all dissolved, but potassium hydroxide could not be completely dissolved, and no product was obtained after GC tracking.

Comparative example 5

With reference to the reaction principle proposed by the patent CN109776487A, the preparation of cyclic sulfuric acid ester is carried out. Pentaerythritol is used instead of ethylene glycol, chloroform is used as a solvent, and sulfuryl chloride is used instead of sulfuryl fluoride for the reaction. The specific conditions are:

Add 27.2g (0.20mol) of pentaerythritol and 300g of chloroform into a 1000mL three-necked pressure-resistant flask. The system is white and turbid. Stir with magnetic force and replace with N ₂ (10mL/min). Feed sulfonyl fluoride gas, wait for the system pressure to reach 0.1Mpa, stop the air intake, keep the reaction for 2.0h, and release the nitrogen gas. Continue to feed sulfonyl fluoride gas to the system until the system pressure is 0.1Mpa, heat preservation reaction for 2.0h, and vent the nitrogen gas. During the reaction, pentaerythritol cannot be dissolved, and the system is white and turbid. No product is obtained after GC tracking; further feed sulfonyl fluoride gas to The system pressure was 0.3Mpa, and the reaction was kept for 2.0 hours, but there was still no product after GC tracking.

During the reaction process, the raw materials could not be completely dissolved, and no product was obtained after GC tracking.

It can be clearly seen from comparative examples 1 to 5 that the current existing methods for preparing cyclic sulfates cannot obtain the cyclic sulfates described in formula I of the present invention. This is due to the special structure of pentaerythritol, just as the diol compound with strong electron-withdrawing groups described in the document Chem. Get cyclic sulfate esters, but diols without strong electron-withdrawing groups, such as 5,6-decanediol, 1,2-decanediol, 1-adamantane-1,2-ethanediol, etc. , with the participation of sulfuryl chloride and imidazole, a complex mixture was obtained, and the cyclic sulfate could not be obtained.

Comparative example 6

Adopt the same method as in Example 1 to prepare cyclic sulfuric acid esters, the difference is that raw material 1 and acetonitrile are added to a 1000mL three-necked flask, magnetically stirred, and after _N2 replacement, the internal temperature of the control system is 60~70°C, and then the into the sulfuryl fluoride gas for the reaction.

Using the same method as in Example 1 for purification, the yield of the finally obtained cyclic sulfate was 60.5%, and the GC purity was 97.48%.

As can be seen from the experimental results of Comparative Example 6 and Example 1, increasing the reaction temperature can cause the yield and the purity of the cyclic sulfuric acid ester product to decline greatly, so adopting the reaction temperature of the present invention is more conducive to obtaining high yield and high yield. The pure cyclic sulfate product, because after the reaction temperature rises, chain polymerization side reactions between multiple molecules are prone to occur. The metathesis reaction is carried out to generate chain polymer impurities, which leads to a decrease in yield. The chain polymer impurities are as follows:

The various technical features of the above-mentioned embodiments can be combined arbitrarily. For the sake of concise description, all possible combinations of the various technical features in the above-mentioned embodiments are not listed exhaustively. However, as long as there is no contradiction in the combination of these technical features, all It should be regarded as the scope described in this specification.

For those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, which all belong to the protection scope of the present invention, and the protection scope of the present invention is based on the appended claims .

Claims (10)

1. a preparation method of cyclic sulfuric acid ester, is characterized in that, described preparation method is: Prepare cyclic sulfate by reacting raw material A with sulfonyl fluoride gas, or prepare cyclic sulfate by reacting raw material B with sulfonyl fluoride gas. Raw material A is:

, raw material B is

, the cyclic sulfate is

; Wherein, R ₁ ~ R ₅ are selected from one of methyl, ethyl, propyl, isopropyl and vinyl; Described preparation method comprises the steps: S1. Reaction process: uniformly disperse raw material A or raw material B in an organic solvent, control the reaction temperature, feed sulfonyl fluoride gas into the reaction system, and complete the reaction to obtain a cyclic sulfuric acid ester reaction solution; S2, purification process: Recrystallization was used to obtain the refined target object of cyclic sulfate. 2. The method for preparing a cyclic sulfuric acid ester according to claim 1, characterized in that, in step S1, the reaction temperature is -10°C-50°C, and the reaction time is 7-12 hours. 3. according to the preparation method of a kind of cyclic sulfuric acid ester described in claim 1, it is characterized in that, described raw material A is

, the raw material B is

,

any of the. 4. the preparation method of a kind of cyclic sulfuric acid ester according to claim 1 is characterized in that, in step S1, the molar ratio of raw material A or raw material B and sulfuryl fluoride is 1:2.4～5, and the mol ratio of described organic solvent The dosage is 4.9-8.05 times of the mass of raw material A or raw material B. 5. the preparation method of a kind of cyclic sulfuric acid ester according to claim 1 is characterized in that, in step S1, described organic solvent is selected from methylene dichloride, ethylene dichloride, chloroform, acetonitrile, bis(2, One or a combination of 2,2-trifluoroethyl) ether, dimethyl carbonate, and diethyl carbonate. 6. according to the preparation method of a kind of cyclic sulfuric acid ester described in claim 1, it is characterized in that, in step S2, described purifying process operation is: the crude product of cyclic sulfuric acid ester in the cyclic sulfuric acid ester reaction liquid is carried out heavy For crystallization treatment, a good solvent is selected to heat and dissolve the crude cyclic sulfate, and then a poor solvent is slowly added, and the cyclic sulfate target is obtained by cooling and filtering. 7. according to the preparation method of a kind of cyclic sulfuric acid ester described in claim 6, it is characterized in that, described good solvent is to select chloroform, acetonitrile, two (2,2,2-trifluoroethyl) ether, biscarbonate One or more combinations of methyl ester and diethyl carbonate. 8. according to the preparation method of a kind of cyclic vitriol ester described in claim 6, it is characterized in that, described poor solvent selects ethylene dichloride, methylene dichloride, normal hexane, hexanaphthene, sherwood oil, normal heptane Or one or more combinations of n-octane. 9. according to the preparation method of a kind of cyclic sulfuric acid ester described in claim 6, it is characterized in that, described good solvent consumption is 1～8 times of raw material A or raw material B quality, and described poor solvent consumption is good solvent 1 to 4 times the mass, and the cooling and filtering temperature is -10 to 20°C. 10. according to the preparation method of a kind of cyclic sulfuric acid ester described in claim 6, it is characterized in that, when the cyclic sulfuric acid ester crude product is dissolved in good solvent, add adsorption filler earlier and carry out decolorization adsorption treatment, filter out adsorption after decolorization adsorption treatment filler.

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