CN115368377A - Preparation method of cyclic sulfate - Google Patents
Preparation method of cyclic sulfate Download PDFInfo
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- CN115368377A CN115368377A CN202211321738.9A CN202211321738A CN115368377A CN 115368377 A CN115368377 A CN 115368377A CN 202211321738 A CN202211321738 A CN 202211321738A CN 115368377 A CN115368377 A CN 115368377A
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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
Technical Field
The invention relates to a preparation method of cyclic sulfate, belonging to the technical field of organic synthesis.
Background
Cyclic sulfate materials have long been known and have received great attention in organic synthesis. In recent years, a large number of documents introduce substances with similar structures as intermediates of medicines and surfactants, and have wide application prospects. In recent years, cyclic sulfate materials have been used as additives for lithium ion battery electrolytes, and can effectively suppress side reactions on the electrode surface.
The main synthetic route of the compounds at present is as follows: (CN 109485633A, CN109369609A, CN108707095A, CN102241662A, CN 107086324A):
the method needs two steps of reaction, firstly, diol compound and thionyl chloride are used for reaction to obtain sulfite, and further, under the catalysis of noble metal ruthenium trichloride, sodium hypochlorite is used for oxidation to obtain a target object.
In addition, chinese patent CN109988145A discloses that ethylene glycol and thionyl chloride are used as raw materials to synthesize sulfite, then ethylene sulfite and air or oxygen are subjected to oxidation reaction under the action of catalysts (palladium chloride complex catalyst and copper chloride catalyst) to generate ethylene sulfate, and the ethylene sulfate is filtered, washed with water, concentrated and crystallized to obtain the finished product of ethylene sulfate.
The main problems with this route are: (1) Using thionyl chloride to generate a large amount of corrosive gas hydrogen chloride; (2) Ruthenium trichloride is used as a catalyst in the second oxidation reaction, the catalyst is expensive and is not easy to recover and reuse, and meanwhile, sodium hypochlorite is used as an oxidant, so that the reaction is violent in heat release, difficult to control and high in energy consumption; (3) Sodium hypochlorite is used as an oxidant to generate a large amount of salt-containing wastewater, so that the wastewater treatment cost is increased; (4) Because of the poor solubility of some cyclic sulfate materials, a large amount of solvent is needed for the reaction, so that the production efficiency of the method is particularly low.
Even though the Chinese patent CN109988145A uses air or oxygen as an oxidant instead, the reaction can only be carried out in the presence of palladium chloride and copper chloride catalysts, the catalysts are expensive, particularly the price of the palladium-containing catalysts is increased by 4 times in recent years, and the catalyst recovery of the process is difficult and does not meet the development requirement of green chemistry.
In recent years, patent nos. CN107629032A and CN110818674A report methods in which a diol compound and sulfonyl fluoride are cyclized in the presence of an organic base to obtain a cyclic sulfate ester. Even in the presence of an acid binding agent, the method still can release highly corrosive and highly toxic hydrogen fluoride in the reaction preparation process, has high reaction safety risk and high requirement on equipment materials, and simultaneously can not recycle the organic amine hydrofluoride as a byproduct of the reaction, and can not be subjected to harmless treatment by methods such as incineration and the like.
Disclosure of Invention
The invention provides a preparation method of cyclic sulfate, aiming at the problems of large amount of acidic gas, serious equipment corrosion, large amount of waste water, large salt content, difficult control of reaction heat release, low production efficiency, high cost and the like in the existing cyclic sulfate synthesis process.
The technical scheme for solving the technical problems is as follows: a method for preparing cyclic sulfate, which comprises the following steps:
the method is characterized in that a raw material A is adopted to react with sulfuryl fluoride gas to prepare cyclic sulfate, or a raw material B is adopted to react with sulfuryl fluoride gas to prepare cyclic sulfate, wherein the raw material A is as follows:
the raw material B is
Cyclic sulfates
；
Wherein R is 1 ~R 5 One selected from methyl, ethyl, propyl, isopropyl and vinyl;
the preparation method 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;
s2, purification process:
and recrystallizing to obtain the refined target product of the cyclic sulfate.
Further, in the step S1, the reaction temperature is-10 ℃ to 50 ℃, and the reaction time is 7 to 12 hours.
Further, the raw material A is
The raw material B is
、
Any one of them.
Further, in step S1, the molar ratio of the raw material a or the raw material B to the sulfonyl fluoride is 1:2.4 to 5, wherein the dosage of the organic solvent is 4.9 to 8.05 times of the mass of the raw material A or the raw material B.
Further, in step S1, the organic solvent is one or a combination of several selected from dichloromethane, dichloroethane, chloroform, acetonitrile, bis (2, 2-trifluoroethyl) ether, dimethyl carbonate, and diethyl carbonate.
Further, in step S2, the purification process is operated as follows: recrystallizing the cyclic sulfate crude product in the cyclic sulfate reaction liquid, heating and dissolving the cyclic sulfate crude product by using a good solvent, slowly adding a poor solvent, cooling and filtering to obtain the cyclic sulfate fine product target.
Further, the good solvent is one or a combination of chloroform, acetonitrile, bis (2, 2-trifluoroethyl) ether, dimethyl carbonate and diethyl carbonate. When the good solvent is used for heating and dissolving the cyclic sulfate crude product, the heating temperature is 1 to 10 ℃ below the boiling temperature of the good solvent.
Furthermore, the poor solvent is selected from one or more of dichloroethane, dichloromethane, n-hexane, cyclohexane, petroleum ether, n-heptane or n-octane.
Further, the using amount of the good solvent is 1 to 8 times of the mass of the raw material A or the raw material B, the using amount of the poor solvent is 1 to 4 times of the mass of the good solvent, and the temperature for cooling and filtering is-10 to 20 ℃.
Furthermore, when the cyclic sulfate crude product is dissolved in a good solvent, firstly adding an adsorption filler for decoloring adsorption treatment, and filtering the adsorption filler after the decoloring adsorption treatment. The adsorption filler is alkaline alumina or activated clay, but not limited to the two. The decoloring adsorption treatment is beneficial to reducing the acid value of the product and improving the quality of the product.
When the organic solvent used in step S1 is a good solvent, then the purification process of step S2 may be: adding an adsorption filler into the cyclic sulfate reaction liquid for decoloring and adsorption treatment, filtering the adsorption filler, then distilling under reduced pressure to evaporate part of the organic solvent, stopping distillation when a solid begins to be separated out from the system, heating the system to 1-10 ℃ below the boiling temperature of the organic solvent until the separated solid is dissolved, slowly dropwise adding a poor solvent, pulping, finally cooling, crystallizing and filtering to obtain a fine cyclic sulfate target product.
When the organic solvent used in step S1 is a poor solvent, a solid is directly precipitated in the cyclic sulfate reaction solution, and the purification process in step S2 may be: filtering the cyclic sulfate reaction liquid to obtain a filter cake, namely a cyclic sulfate crude product, adding the cyclic sulfate crude product into a good solvent, heating to dissolve at the temperature of 1-10 ℃ below the boiling point of the good solvent, adding an adsorption filler to perform decolorization adsorption treatment, filtering the adsorption filler, slowly dropwise adding a poor solvent, performing pulping treatment, and finally performing cooling crystallization and filtration to obtain a cyclic sulfate fine product target.
The beneficial effects of the invention are:
(1) The invention develops a new process for preparing cyclic sulfate by a double decomposition exchange method by taking cheap silyl ether and sulfonyl fluoride as raw materials.
(2) 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.
The preparation method provided by the invention avoids the problems of large wastewater amount, large solvent consumption, complex operation, low yield and particularly low production efficiency caused by poor solubility of the cyclic sulfate.
(3) According to the preparation method of the cyclic sulfate provided by the invention, the by-product is fluorine-containing silane which is a gas at normal temperature, the cyclic sulfate is a solid product, and the fluorine-containing silane can escape from a reaction system in the reaction process, so that the purification of the cyclic sulfate is facilitated, and a high-quality cyclic sulfate product is obtained.
(4) The preparation method can obtain the product with the chroma less than 10Hazen (10% acetonitrile solution), the acid value less than 10ppm (calculated by HF), the water content less than 30ppm, the chloride ion content less than 5ppm, no sulfate radical and the GC purity more than 99.9%, and meets the requirements of a high-voltage lithium ion battery and a sodium ion battery of a sodium ferric sulfate system.
Drawings
FIG. 1 is a scheme for the synthesis of cyclic sulfates according to the present invention;
FIG. 2 is a drawing showing a process for preparing a cyclic sulfate compound obtained in example 1 1 H NMR spectrum;
FIG. 3 is a drawing showing the preparation of the cyclic sulfate compound obtained in example 1 13 C NMR spectrum;
FIG. 4 is a MS-ESI mass spectrum of the cyclic sulfate compound prepared in example 1.
Detailed Description
The following is a detailed description of specific embodiments of the invention. This invention can be embodied in many different forms than those herein described and many modifications may be made by those skilled in the art without departing from the spirit of the invention and the scope of the invention is therefore not limited to the specific embodiments disclosed.
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 terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The preparation method of the cyclic sulfate is as shown in figure 1, and comprises the following steps:
the method is characterized in that a raw material A is adopted to react with sulfuryl fluoride gas to prepare cyclic sulfate, or a raw material B is adopted to react with sulfuryl fluoride gas to prepare cyclic sulfate, wherein the raw material A is as follows:
the raw material B is
The cyclic sulfate ester
；
Wherein R is 1 ~R 5 One selected from methyl, ethyl, propyl, isopropyl and vinyl;
the preparation method 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;
s2, purification process:
and recrystallizing to obtain the refined target product of the cyclic sulfate.
In the step S1, the reaction temperature is-10-50 ℃, and the reaction time is 7-12 hours.
In step S1, the molar ratio of the raw material a or the raw material B to the sulfonyl fluoride is 1:2.4 to 5, wherein the dosage of the organic solvent is 4.9 to 8.05 times of the mass of the raw material A or the raw material B.
In the step S1, the organic solvent is one or a combination of more of dichloromethane, dichloroethane, chloroform, acetonitrile, bis (2, 2-trifluoroethyl) ether, dimethyl carbonate and diethyl carbonate.
In step S2, the purification process is operated as follows: recrystallizing the cyclic sulfate crude product in the cyclic sulfate reaction liquid, heating and dissolving the cyclic sulfate crude product by using a good solvent, slowly adding a poor solvent, cooling and filtering to obtain the cyclic sulfate fine product target.
The good solvent is one or a combination of chloroform, acetonitrile, bis (2, 2-trifluoroethyl) ether, dimethyl carbonate and diethyl carbonate.
The poor solvent is one or a combination of dichloroethane, dichloromethane, n-hexane, cyclohexane, petroleum ether, n-heptane or n-octane.
The dosage of the good solvent is 1 to 8 times of the mass of the raw material A or the raw material B, the dosage of the poor solvent is 1 to 4 times of the mass of the good solvent, and the temperature for cooling and filtering is-10 to 20 ℃.
When the cyclic sulfate crude product is dissolved in the good solvent, firstly adding the adsorption filler for decoloring adsorption treatment, and filtering the adsorption filler after the decoloring adsorption treatment. The adsorption filler is alkaline alumina or activated clay.
When the organic solvent used in step S1 is a good solvent, then the purification process of step S2 may be: adding an adsorption filler into the cyclic sulfate reaction solution for decoloring and adsorption treatment, filtering the adsorption filler, then distilling under reduced pressure to evaporate part of the organic solvent, stopping distillation when a solid begins to be separated out from the system, heating the system to a temperature 1 to 19 ℃ below the boiling temperature of the organic solvent until the separated solid is dissolved, slowly dropwise adding a poor solvent, pulping, finally cooling, crystallizing and filtering to obtain a fine cyclic sulfate target.
When the organic solvent used in step S1 is a poor solvent, a solid is directly precipitated in the cyclic sulfate reaction solution, and the purification process in step S2 may be: filtering the cyclic sulfate reaction liquid to obtain a filter cake, namely a cyclic sulfate crude product, adding the cyclic sulfate crude product into a good solvent, heating to dissolve at the temperature of 1-10 ℃ below the boiling point of the good solvent, adding an adsorption filler to perform decolorization adsorption treatment, filtering the adsorption filler, slowly dropwise adding a poor solvent, performing pulping treatment, and finally performing cooling crystallization and filtration to obtain a cyclic sulfate fine product target.
Wherein the preparation method of the raw material A or the raw material B is disclosed in the reference literature: EP3366137A1, CN104710456A, CN104710459A.
Example 1
A1000 mL three-neck pressure-resistant flask was prepared by adding 62.1g (0.25 mol) of raw material 1 and 500g of acetonitrile to a 1000mL three-neck flask, magnetically stirring, and N 2 Replacing (10 mL/min), controlling the internal temperature of the system to be 20-30 ℃, slowly introducing sulfonyl fluoride gas into the system, stopping gas introduction when the system pressure reaches 0.05Mpa, reacting for 2.0h under heat preservation, and exhausting nitrogen. And (3) continuously introducing sulfonyl fluoride gas into the system until the system pressure is 0.05Mpa, keeping the temperature for reaction for 2.0h, exhausting nitrogen until GC tracking sampling is finished, stopping introducing sulfonyl fluoride after the reaction is confirmed to be finished, introducing the sulfonyl fluoride for the reaction for 66.2g in total, and taking 12.0h in total for the reaction.
And after the reaction is confirmed to be finished, adding 10g of alkaline alumina into the system, stirring for 2.0h at 20-30 ℃, performing suction filtration, filtering out the alkaline alumina, and performing reduced pressure desolventization on the obtained colorless clear filtrate until a solid is slightly precipitated from the system.
Controlling the internal temperature of the system to be 65-70 ℃, heating the system to be completely dissolved, adding 500g of n-heptane slowly into the system, separating out a large amount of white solid from the system, pulping and stirring for 30min at the temperature, cooling to 0-5 ℃, filtering to obtain white solid, and further drying under reduced pressure to obtain 59.19g of refined cyclic sulfate, wherein the yield is 90.98%, the GC purity is 99.92%, the chroma is 6Hazen (10% acetonitrile solution), and the acid value is as follows: 7ppm (calculated as HF), chloride ion content < 5ppm, no sulfate radical detected, and refined cyclic sulfate 1 H NMR、 13 C NThe detection of MR and MS-ESI mass spectra is shown in FIGS. 2, 3 and 4.
Example 2
A1000 mL three-neck pressure-resistant flask was prepared by charging 42.5g (0.1 mol) of starting material 2 and 280g of methylene chloride into a 1000mL three-neck flask, magnetically stirring, and N 2 (10 mL/min), controlling the internal temperature of the system to be 0-10 ℃, slowly introducing sulfonyl fluoride gas into the system under normal pressure until GC tracking sampling is carried out, stopping introducing sulfonyl fluoride after the reaction is confirmed to be finished, introducing the sulfonyl fluoride into the reaction for 51.0g in total, and taking 8.0h in total.
And after the completion of the reaction is confirmed, carrying out vacuum filtration, adding 104g of bis (2, 2-trifluoroethyl) ether into the obtained filter cake, heating to 45-50 ℃, fully dissolving the system, adding 5g of activated clay into the system, stirring for 1.0h at 40-50 ℃, carrying out vacuum filtration, filtering out the activated clay, and obtaining colorless clear filtrate.
Controlling the internal temperature of the system to be 50-60 ℃, adding slow 200g of normal hexane into the filtrate to separate out a large amount of white solid from the system, pulping and stirring for 30min at the temperature, cooling to-10 to-5 ℃, performing suction filtration to obtain the white solid, and further performing reduced pressure drying to obtain 23.4g of a refined cyclic sulfate product with the yield of 90.00 percent, the GC purity of 99.96 percent, the chroma of 8Hazen (10 percent acetonitrile solution), the acid value: 5ppm (calculated as HF), chloride content < 5ppm, no sulfate was detected.
Example 3
A1000 mL three-neck pressure-resistant flask was prepared by adding 60.9g (0.2 mol) of starting material 3 and 300g of bis (2, 2-trifluoroethyl) ether to a 1000mL three-neck flask, and stirring with magnetic force, N 2 And (10 mL/min) replacement, controlling the internal temperature of the system to be minus 10 to 10 ℃, slowly introducing sulfonyl fluoride gas into the system, stopping gas introduction when the system pressure reaches 0.1Mpa, reacting for 1.0h under heat preservation, and exhausting nitrogen. Continuing to introduce sulfonyl fluoride into the systemKeeping the pressure of the system at 0.1Mpa, reacting for 1.0h, exhausting nitrogen until GC tracking sampling, stopping introducing sulfonyl fluoride after confirming that the reaction is finished, and introducing the total amount of 60.3g of sulfonyl fluoride in the reaction, wherein the total amount of time of the reaction is 8.0h.
And after the completion of the reaction is confirmed, adding 5g of activated clay into the system, stirring for 2.0h at the temperature of 20-30 ℃, carrying out suction filtration, and filtering out the activated clay to obtain colorless clear filtrate.
Controlling the internal temperature of the system to be 55-60 ℃, adding 300g of dichloroethane into the filtrate slowly to separate out a large amount of white solid from the system, pulping and stirring for 30min at the temperature, cooling to 0-5 ℃, performing suction filtration to obtain the white solid, and further performing reduced pressure drying to obtain 46.1g of refined cyclic sulfate, wherein the yield is 88.57%, the GC purity is 99.90%, the chroma is 9Hazen (10% acetonitrile solution), and the acid value is: 7ppm (calculated as HF), chloride content < 5ppm, no sulfate was detected.
Example 4
A1000 mL three-necked pressure-resistant flask was charged with 62.1g (0.25 mol) of raw material 1 and 350g of dichloroethane by magnetic stirring, and subjected to N 2 And (10 mL/min) replacement, controlling the internal temperature of the system to be 40-50 ℃, slowly introducing sulfonyl fluoride gas into the system, stopping gas introduction when the pressure of the system reaches 0.1MPa, carrying out heat preservation reaction for 2.0h, and exhausting nitrogen. And (3) continuously introducing the sulfonyl fluoride gas into the system until the system pressure is 0.1Mpa, carrying out heat preservation reaction for 2.0h, emptying nitrogen until GC tracking sampling is carried out, stopping introducing the sulfonyl fluoride after the reaction is confirmed to be finished, introducing 61.2g of the sulfonyl fluoride in total for the reaction, and taking 7.0h in total for the reaction.
And after the reaction is confirmed to be completed, carrying out vacuum filtration, adding 300g of acetonitrile into the obtained filter cake, heating to 75-80 ℃, fully dissolving the system, cooling to 40-50 ℃, adding 5g of activated clay into the system, stirring for 30min at 40-50 ℃, carrying out vacuum filtration, and filtering out the activated clay to obtain colorless clear filtrate. The obtained colorless clear filtrate is desolventized under reduced pressure until a system slightly precipitates solids.
Controlling the internal temperature of the system to be 75-80 ℃, heating the system to be completely dissolved, adding 500g of n-heptane slowly into the system, separating out a large amount of white solid from the system, pulping and stirring for 30min at the temperature, cooling to 0-5 ℃, filtering to obtain white solid, and further drying under reduced pressure to obtain 60.2g of refined cyclic sulfate, wherein the yield is 92.53%, the GC purity is 99.94%, the chroma is 6Hazen (10% acetonitrile solution), and the acid value is: 8ppm (calculated as HF), chloride content < 5ppm, sulfate was not detected.
Comparative example 1
The preparation of cyclic sulfate is carried out by referring to the reaction principle proposed by patent CN110818674A, pentaerythritol is used for replacing glycol, methylene dichloride is used as solvent, and the specific conditions are as follows:
into a 1000mL three-necked pressure-resistant flask, 27.2g (0.20 mol) of pentaerythritol and 300g of methylene chloride were added, 85g (0.84 mol) of triethylamine was added, and the mixture was stirred and mixed well, magnetically stirred, and N was added 2 And (10 mL/min) replacement, controlling the internal temperature of the system to be 30-40 ℃, slowly introducing sulfonyl fluoride gas into the system, stopping gas introduction when the pressure of the system reaches 0.1MPa, carrying out heat preservation reaction for 2.0h, and exhausting nitrogen. Continuously introducing sulfonyl fluoride gas into the system until the system pressure is 0.1Mpa, carrying out heat preservation reaction for 2.0h, emptying nitrogen, wherein pentaerythritol cannot be dissolved in the reaction process, the system is white turbid, and a product is not obtained by GC tracking; further introducing sulfuryl fluoride gas to the system pressure of 0.3Mpa, carrying out heat preservation reaction for 2.0h, and keeping no product after GC tracking.
During the reaction, the raw materials can not be completely dissolved, and no product is obtained by GC tracking.
Comparative example 2
The preparation of cyclic sulfate is carried out by referring to the reaction principle proposed by patent CN110818674A, pentaerythritol is used for replacing glycol, acetonitrile is used as solvent, and the specific conditions are as follows:
into a 1000mL three-neck pressure-resistant flask, 27.2g (0.20 mol) of pentaerythritol and 250 g of acetonitrile were added to make the system colorless and clear, and 58.1g (0.50 mol) of tetramethylethylenediamine was added thereto, followed by stirring and mixing uniformly, magnetic stirring, and N 2 Replacing (10 mL/min), controlling the internal temperature of the system to be 60-70 ℃, slowly introducing sulfonyl fluoride gas into the system, stopping gas introduction when the system pressure reaches 0.1Mpa, reacting for 2.0h under heat preservation, and exhausting nitrogen. Continuously introducing into the systemSulfuryl fluoride gas is added until the system pressure is 0.1Mpa, the reaction is carried out for 2.0h under the condition of heat preservation, nitrogen is vented, and a product is not obtained after GC tracking; further introducing sulfuryl fluoride gas to the system pressure of 0.3Mpa, carrying out heat preservation reaction for 2.0h, and keeping no product after GC tracking.
The starting material was completely soluble during the reaction, but no product was obtained by GC trace.
Comparative example 3
With reference to the reaction principle proposed in patent CN107629032A, the preparation of cyclic sulfate is carried out by replacing ethylene glycol with pentaerythritol and dichloromethane as solvent, which is different from the comparative example 1 of the present application by adding 6.0eq of potassium hydroxide (compared to pentaerythritol) and 0.02eq of tetrabutylammonium fluoride, with the specific conditions:
into a 1000mL three-necked pressure-resistant flask, 27.2g (0.20 mol) of pentaerythritol and 300g of methylene chloride were charged, 67.3g (1.2 mol) of potassium hydroxide and 1.1g (0.0042 mol) of tetrabutylammonium fluoride were added, followed by stirring and mixing uniformly, magnetic stirring, and N 2 And (10 mL/min) replacement, controlling the internal temperature of the system to be 0-10 ℃, slowly introducing sulfonyl fluoride gas into the system, stopping gas introduction when the pressure of the system reaches 0.1MPa, carrying out heat preservation reaction for 2.0h, and exhausting nitrogen. Continuously introducing sulfonyl fluoride gas into the system until the system pressure is 0.1Mpa, carrying out heat preservation reaction for 2.0h, exhausting nitrogen, wherein pentaerythritol cannot be dissolved in the reaction process, the system is white and turbid, and a product is not obtained by GC tracking; further introducing sulfuryl fluoride gas until the system pressure is 0.3Mpa, reacting for 2.0h under heat preservation, and keeping no product after GC tracking.
During the reaction, the raw materials cannot be completely dissolved, and no product is obtained by GC tracking.
Comparative example 4
The preparation of cyclic sulfates is carried out by reference to the reaction principle proposed in patent CN107629032A, replacing ethylene glycol with pentaerythritol and acetonitrile as solvent, with the difference from the present comparative example 1 that 6.0eq potassium hydroxide (compared to pentaerythritol) and 0.02eq tetrabutylammonium fluoride are added, with the specific conditions:
into a 1000mL three-necked pressure-resistant flask, 27.2g (0.20 mol) of pentaerythritol and 250 g of acetonitrile were added to make the system colorless and clear, and 67.3g (1.2 mol) of potassium hydroxide and 1.1g (0.0042 mol) of tetrabutylammonium fluoride were added and mixed by stirring to mix them uniformly, followed by magnetic forceStirring, N 2 And (10 mL/min) replacement, controlling the internal temperature of the system to be 0-10 ℃, slowly introducing sulfonyl fluoride gas into the system, stopping gas introduction when the pressure of the system reaches 0.1MPa, carrying out heat preservation reaction for 2.0h, and exhausting nitrogen. Continuously introducing sulfonyl fluoride gas into the system until the system pressure is 0.1Mpa, carrying out heat preservation reaction for 2.0h, emptying nitrogen, not completely dissolving potassium hydroxide, enabling the system to be white turbid, and carrying out GC tracking to obtain no product; further introducing sulfuryl fluoride gas to the system pressure of 0.3Mpa, carrying out heat preservation reaction for 2.0h, and keeping no product after GC tracking.
In the reaction process, the raw materials are completely dissolved, the potassium hydroxide cannot be completely dissolved, and the product is not obtained by GC tracking.
Comparative example 5
The preparation of cyclic sulfate is carried out by referring to the reaction principle proposed by patent CN109776487A, pentaerythritol is used to replace ethylene glycol, chloroform is used as solvent, sulfuryl chloride is used to replace sulfuryl fluoride, and the specific conditions are as follows:
into a 1000mL three-necked pressure-resistant flask, 27.2g (0.20 mol) of pentaerythritol and 300g of chloroform were added to make the system white and turbid, and the mixture was magnetically stirred, and N was added 2 And (10 mL/min) replacement, controlling the internal temperature of the system to be 20-30 ℃, slowly introducing sulfonyl fluoride gas into the system, stopping gas introduction when the pressure of the system reaches 0.1MPa, carrying out heat preservation reaction for 2.0h, and exhausting nitrogen. Continuously introducing sulfonyl fluoride gas into the system until the system pressure is 0.1Mpa, carrying out heat preservation reaction for 2.0h, exhausting nitrogen, wherein pentaerythritol cannot be dissolved in the reaction process, the system is white and turbid, and a product is not obtained by GC tracking; further introducing sulfuryl fluoride gas to the system pressure of 0.3Mpa, carrying out heat preservation reaction for 2.0h, and keeping no product after GC tracking.
During the reaction, the raw materials can not be completely dissolved, and no product is obtained by GC tracking.
As is evident from comparative examples 1 to 5, the cyclic sulfate of the formula I of the present invention cannot be obtained by the existing methods for preparing the cyclic sulfate. This is due to the specific structure of pentaerythritol, as described in chem. Eur. J1997.3, no. 4, 517-522, diol compounds with strong electron-withdrawing groups can directly give cyclic sulfates from sulfonyl chloride and imidazole, but diols without strong electron-withdrawing groups, such as 5, 6-decanediol, 1, 2-decanediol, 1-adamantane-1, 2-ethanediol, etc., give complex mixtures in the presence of sulfonyl chloride and imidazole, and cannot give cyclic sulfates.
Comparative example 6
A cyclic sulfate was prepared by the same procedure as in example 1, except that the raw material 1 and acetonitrile were charged into a 1000mL three-necked flask, and magnetic stirring was performed, and N was used 2 After replacement, controlling the internal temperature of the system to be 60-70 ℃, and then introducing sulfonyl fluoride gas for reaction.
The cyclic sulfate ester was purified by the same method as in example 1, and the yield of the cyclic sulfate ester was 60.5% and the GC purity was 97.48%.
It can be seen from the experimental results of comparative example 6 and example 1 that increasing the reaction temperature greatly reduces the yield and purity of the cyclic sulfate ester product, so the use of the reaction temperature of the present invention is more beneficial to obtaining a cyclic sulfate ester product with high yield and high purity, because the reaction temperature is increased, a side reaction of chain polymerization among multiple molecules is easily generated, and because the reaction temperature is high, after the completion of the mono-sulfonic acid esterification, the double decomposition reaction with another molecule of raw material 1 is further performed to generate chain polymerization impurities, thereby reducing the yield. The chain polymerization impurities are as follows:
any combination of the technical features of the above embodiments may be performed, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not exhaustive, but should be considered as being within the scope of the present disclosure as long as no contradiction exists between the combinations of the technical features.
It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention as defined in the following claims.
Claims (10)
1. A preparation method of cyclic sulfate is characterized by comprising the following steps:
the method is characterized in that a raw material A is adopted to react with sulfuryl fluoride gas to prepare cyclic sulfate, or a raw material B is adopted to react with sulfuryl fluoride gas to prepare cyclic sulfate, wherein the raw material A is as follows:
the raw material B is
Cyclic sulfates
；
Wherein R is 1 ~R 5 One selected from methyl, ethyl, propyl, isopropyl and vinyl;
the preparation method 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;
s2, purification process:
recrystallizing to obtain the fine target product of the cyclic sulfate.
2. The process according to claim 1, wherein the reaction temperature in step S1 is-10 ℃ to 50 ℃ and the reaction time is 7 to 12 hours.
3. The process according to claim 1, wherein the raw material A is selected from the group consisting of
The raw material B is
、
Any one of them.
4. The method for preparing cyclic sulfate according to claim 1, wherein in step S1, the molar ratio of the raw material a or raw material B to the sulfonyl fluoride is 1:2.4 to 5, wherein the dosage of the organic solvent is 4.9 to 8.05 times of the mass of the raw material A or the raw material B.
5. The method according to claim 1, wherein in step S1, the organic solvent is selected from one or more of dichloromethane, dichloroethane, chloroform, acetonitrile, bis (2, 2-trifluoroethyl) ether, dimethyl carbonate, and diethyl carbonate.
6. The process of claim 1, wherein in step S2, the purification process is performed by: recrystallizing the cyclic sulfate crude product in the cyclic sulfate reaction liquid, selecting a good solvent to heat and dissolve the cyclic sulfate crude product, slowly adding a poor solvent, cooling and filtering to obtain the cyclic sulfate fine product target.
7. The method of claim 6, wherein the good solvent is selected from chloroform, acetonitrile, bis (2, 2-trifluoroethyl) ether, dimethyl carbonate, and diethyl carbonate.
8. The method of claim 6, wherein the poor solvent is selected from one or more of dichloroethane, dichloromethane, n-hexane, cyclohexane, petroleum ether, n-heptane and n-octane.
9. The method of claim 6, wherein the amount of the good solvent is 1 to 8 times of the mass of the raw material A or B, the amount of the poor solvent is 1 to 4 times of the mass of the good solvent, and the temperature of the filtration is-10 to 20 ℃.
10. The process of claim 6, wherein the crude cyclic sulfate is dissolved in a good solvent, and the adsorption filler is added to decolorize and adsorb, and the adsorption filler is filtered after the decolorization and adsorption.
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