CN112760672A - Method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride - Google Patents
Method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride Download PDFInfo
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Abstract
The invention relates to a method for electrochemically preparing trifluoromethyl sulfuryl fluoride from methylsulfonyl chloride, belonging to the field of fine chemical engineering; the method comprises the following steps: adding methylsulfonyl chloride, a conductive agent and anhydrous hydrogen fluoride into an electrolytic bath to form an electrolyte; under the conditions that the temperature is minus 10 ℃ to 20 ℃ and the voltage is 3V to 4.5V, the electrolyte is electrolyzed and dehydrated for 2h to 10 h; electrolyzing at the temperature of-10-20 ℃ and under the voltage of 5-7.5V to obtain electrolytic gas, wherein the electrolytic gas contains trifluoromethyl sulfonyl fluoride; according to the method, methylsulfonyl chloride is used as a raw material, a conductive agent and anhydrous hydrogen fluoride are added, electrochemical fluorination reaction is carried out at constant pressure, and then trifluoromethyl sulfuryl fluoride is obtained, wherein the anhydrous hydrogen fluoride is used as a solvent of electrolyte and a fluorinating agent; the electrochemical preparation method of the trifluoromethyl sulfuryl fluoride provided by the invention is simple and convenient to operate, low in cost and suitable for large-scale application.
Description
Technical Field
The invention relates to a method for electrochemically preparing trifluoromethyl sulfuryl fluoride from methylsulfonyl chloride, and belongs to the field of fine chemical engineering.
Background
Trifluoromethyl sulfonyl fluoride (CF)3SO2F) Is an important raw material for fine chemical synthesis, can be used for preparing products in related fields such as medical intermediates, ionic liquids, lithium ion electrolytes and the like, and has wide application prospect. At present, the trifluoromethyl sulfonyl fluoride is mainly prepared by methyl sulfonyl chloride, and the preparation method comprises the following steps: step 1) carrying out chemical fluorination on methylsulfonyl chloride in a potassium fluoride aqueous solution to generate methylsulfonyl fluoride, and step 2) carrying out electrochemical fluorination on methylsulfonyl fluoride in anhydrous hydrogen fluoride to generate trifluoromethyl sulfonyl fluoride.
The preparation method has the following disadvantages:
(1) the preparation method is complex: because the market does not have the methanesulfonyl fluoride product, if the methanesulfonyl fluoride is used for preparing the trifluoromethanesulfonyl fluoride, the methanesulfonyl fluoride product must be prepared firstly, and then the methanesulfonyl fluoride is used for preparing the trifluoromethanesulfonyl fluoride product; the preparation method comprises the steps of preparing trifluoromethyl sulfonyl fluoride from methylsulfonyl chloride through two-step reaction; wherein, the purity of the methylsulfonyl fluoride prepared in the step 1) is low, the methylsulfonyl fluoride needs to be further purified to be used in the reaction for preparing the trifluoromethyl sulfuryl fluoride in the step 2), the reaction is complex, and the cost is high.
(2) The preparation method can generate a large amount of three wastes: a small amount of potassium fluoride and impurities generated by hydrolysis of methylsulfonyl chloride exist in the potassium chloride aqueous solution generated in the step 1), and the impurities cannot be directly recycled.
(3) The safety is low: the methanesulfonyl fluoride prepared in the step 1) contains water, and the methanesulfonyl fluoride prepared in the step 1) generates oxygen difluoride (OF) during electrolysis in the step 2)2) The explosion of the electrolytic cell can be caused, and potential safety hazards exist.
(4) The electrolysis energy consumption is high: the preparation method completely removes the water in the electrolyte, needs long-time electrolysis for removing water, and consumes a large amount of electric energy.
Disclosure of Invention
In view of the above, the present invention provides a method for electrochemically preparing trifluoromethanesulfonyl fluoride from methylsulfonyl chloride, in which methylsulfonyl chloride is used as a raw material, a conductive agent and anhydrous hydrogen fluoride are added, and electrochemical fluorination reaction is performed at constant pressure to obtain trifluoromethanesulfonyl fluoride, where the anhydrous hydrogen fluoride is used as a solvent and a fluorinating agent for an electrolyte; the electrochemical preparation method of the trifluoromethyl sulfuryl fluoride provided by the invention has the advantages of easily obtained raw materials, simple and convenient operation and low cost, and is suitable for large-scale application.
In order to achieve the purpose of the invention, the following technical scheme is provided.
A method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride, comprising the following steps:
(1) adding methylsulfonyl chloride, a conductive agent and anhydrous hydrogen fluoride into an electrolytic bath to form an electrolyte;
(2) under the conditions that the temperature is minus 10 ℃ to 20 ℃ and the voltage is 3V to 4.5V, the electrolyte is electrolyzed and dehydrated for 2h to 10 h;
(3) electrolyzing at the temperature of minus 10-20 ℃ and under the voltage of 5-7.5V to obtain electrolytic gas, wherein the electrolytic gas contains trifluoromethyl sulfonyl fluoride.
Preferably, the anode material used for electrolysis is nickel or nickel alloy, and the cathode material is nickel, nickel alloy or carbon steel.
Preferably, the mass fraction of the methylsulfonyl chloride is 10-30%, the mass fraction of the conductive agent is 3-7%, and the balance is anhydrous hydrogen fluoride, wherein the mass fraction of the electrolyte is 100%.
Preferably, the conductive agent is one or more of lithium fluoride, nickel fluoride, antimony pentafluoride, antimony trifluoride, potassium fluoride, and potassium hydrogen fluoride.
Preferably, the temperature in the step (2) is-7 ℃ to 13 ℃.
Preferably, the voltage in step (2) is 3.0V to 4.0V.
Preferably, the temperature in step (3) is-7 ℃ to 13 ℃.
Preferably, the voltage in step (3) is 5.0V to 6.5V.
Has the advantages that:
(1) the invention provides a method for electrochemically preparing trifluoromethyl sulfuryl fluoride from methylsulfonyl chloride, which comprises the steps of taking methylsulfonyl chloride as a raw material, adding a conductive agent and anhydrous hydrogen fluoride, wherein the anhydrous hydrogen fluoride is used as a solvent and a fluorinating agent of electrolyte, and performing electrochemical fluorination reaction at constant pressure at a set temperature; generating trifluoromethyl sulfonyl fluoride at the anode and hydrogen at the cathode; the method has the advantages of easily obtained raw materials, simple and convenient operation, low cost and suitability for large-scale application.
(2) Compared with the prior art, the method for electrochemically preparing the trifluoromethyl sulfuryl fluoride from the methyl sulfuryl chloride provided by the invention has the advantages that the methyl sulfuryl chloride is used as a raw material, the trifluoromethyl sulfuryl fluoride can be prepared through one-step electrolysis, the methyl sulfuryl fluoride is not required to be prepared through the methyl sulfuryl chloride, and then the trifluoromethyl sulfuryl fluoride is prepared through the methyl sulfuryl fluoride to generate the trifluoromethyl sulfuryl fluoride; the method has the advantages of easily available raw materials, simple preparation method and convenient operation.
(3) The water content of the methylsulfonyl chloride, the conductive agent and the anhydrous hydrogen fluoride used in the method is little, and only the trace water impurities of the raw materials are used; in addition, the dehydration step of the method can remove a small amount of moisture in the raw materials, and the energy consumption is low; in addition, the invention can complete the dehydration operation by one step, and the method is simple; thirdly, in the dehydration process, if the dehydration voltage is higher, oxygen difluoride is generated, and the safety is poor, so the dehydration voltage value is controlled, so the dehydration voltage is controlled to be 3V-4.5V, and the safety is better when the dehydration voltage is 3.0V-4.0V; therefore, the dehydration step of the invention has lower energy consumption, thereby leading the dehydration cost to be lower; meanwhile, after dehydration, the reaction of the invention is carried out under anhydrous condition, and the safety is good.
(4) In the electrolytic reaction, the conductive agent is added, and the suitable conductive agent can reduce the voltage value required by electrolysis and the electrolytic reaction temperature, thereby reducing the energy consumption cost of the electrolytic reaction; and the volatilization of the hydrogen fluoride is less at a lower electrolysis reaction temperature, so that the loss of materials is reduced.
(5) The byproducts in the preparation process of the method are hydrogen generated by a cathode and hydrogen chloride generated in the reaction process, and no three wastes are generated; wherein, the recovered hydrogen chloride can be used as a raw material for preparing high-purity (the purity is more than 5N) hydrogen chloride electronic gas.
Detailed Description
The invention will be described in more detail with reference to specific examples, which should not be construed as limiting the scope of the invention.
In the following examples:
gas chromatography testing using Shimadzu GC-2014
And (3) qualitatively judging the hydrogen chloride by adopting a chemical method, namely, the hydrogen chloride gas reacts with the silver nitrate acid solution to generate precipitate.
Example 1
(1) 1kg of methylsulfonyl chloride, 0.30kg of lithium fluoride and 8.7kg of anhydrous hydrogen fluoride are added into an electrolytic bath to form electrolyte, wherein the anode material adopted by electrolysis is nickel, and the cathode material is carbon steel;
(2) controlling the temperature at-10 ℃, and carrying out electrolytic dehydration for 10h under the voltage of 3.0V;
(3) carrying out electrolysis at the temperature of-10 ℃ and the voltage of 5.5V to carry out electrochemical fluorination reaction to obtain electrolytic gas, analyzing by gas chromatography, wherein the electrolytic gas generated at the anode contains trifluoromethyl sulfonyl fluoride, the yield is 90%, and hydrogen is generated at the cathode; judging that hydrogen chloride is generated in the electrolytic reaction by a chemical method; the volume fraction of trifluoromethanesulfonyl fluoride obtained in this example was 18%, based on 100% of the total volume of the electrolytic gas.
Example 2
(1) Adding 1kg of methylsulfonyl chloride, 0.25kg of antimony pentafluoride and 2.2kg of anhydrous hydrogen fluoride into an electrolytic bath to form electrolyte, wherein the anode material adopted by electrolysis is nickel alloy, and the cathode material is nickel;
(2) controlling the temperature at 5 ℃, and carrying out electrolytic dehydration for 5h under the voltage of 4.0V;
(3) carrying out electrolysis at the temperature of 10 ℃ and the voltage of 6.2V to carry out electrochemical fluorination reaction to obtain electrolytic gas, analyzing by gas chromatography, wherein the electrolytic gas generated at the anode contains trifluoromethyl sulfonyl fluoride, the yield is 89%, hydrogen is generated at the cathode, and hydrogen chloride generated in the electrolysis reaction is judged by a chemical method; the volume fraction of trifluoromethanesulfonyl fluoride obtained in this example was 17.8% based on 100% of the total volume of the electrolytic gas.
Example 3
(1) 1kg of methylsulfonyl chloride, 0.3kg of potassium fluoride and 3.7kg of anhydrous hydrogen fluoride are added into an electrolytic bath to form electrolyte, wherein the anode material adopted by electrolysis is nickel alloy, and the cathode material is nickel alloy;
(2) controlling the temperature at 20 ℃, and carrying out electrolytic dehydration for 2h under the voltage of 4.5V;
(3) carrying out electrolysis at the temperature of 20 ℃ and the voltage of 7.5V to carry out electrochemical fluorination reaction to obtain electrolytic gas, analyzing by gas chromatography, wherein the electrolytic gas generated at the anode contains trifluoromethyl sulfonyl fluoride, the yield is 91%, hydrogen is generated at the cathode, and hydrogen chloride generated in the electrolysis reaction is judged by a chemical method; the volume fraction of trifluoromethanesulfonyl fluoride obtained in this example was 18.2% based on 100% of the total volume of the electrolytic gas.
The present invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the principle of the spirit of the present invention should be considered as being within the scope of the present invention.
Claims (9)
1. A method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride is characterized by comprising the following steps: the method comprises the following steps:
(1) adding methylsulfonyl chloride, a conductive agent and anhydrous hydrogen fluoride into an electrolytic bath to form an electrolyte;
(2) under the conditions that the temperature is minus 10 ℃ to 20 ℃ and the voltage is 3V to 4.5V, the electrolyte is electrolyzed and dehydrated for 2h to 10 h;
(3) electrolyzing at the temperature of minus 10-20 ℃ and under the voltage of 5-7.5V to obtain electrolytic gas, wherein the electrolytic gas contains trifluoromethyl sulfonyl fluoride.
2. The method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride according to claim 1, wherein: the anode material used for electrolysis is nickel or nickel alloy, and the cathode material is nickel, nickel alloy or carbon steel.
3. The method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride according to claim 1, wherein: based on 100% of the electrolyte, the mass fraction of the methylsulfonyl chloride is 10% -30%, the mass fraction of the conductive agent is 3% -7%, and the balance is anhydrous hydrogen fluoride.
4. The method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride according to claim 1, wherein: the conductive agent is more than one of lithium fluoride, nickel fluoride, antimony pentafluoride, antimony trifluoride, potassium fluoride and potassium bifluoride.
5. The method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride according to claim 1, wherein: in the step (2), the temperature is-7 ℃ to 13 ℃.
6. The method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride according to claim 1, wherein: the voltage in the step (2) is 3.0V-4.0V.
7. The method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride according to claim 1, wherein: in the step (3), the temperature is-7 ℃ to 13 ℃.
8. The method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride according to claim 1, wherein: the voltage in the step (3) is 5.0V-6.5V.
9. The method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride according to claim 1, wherein: the anode material used for electrolysis is nickel or nickel alloy, and the cathode material is nickel, nickel alloy or carbon steel;
based on 100% of the electrolyte, the mass fraction of the methylsulfonyl chloride is 10% -30%, the mass fraction of the conductive agent is 3% -7%, and the balance is anhydrous hydrogen fluoride;
the conductive agent is more than one of lithium fluoride, nickel fluoride, antimony pentafluoride, antimony trifluoride, potassium fluoride and potassium bifluoride;
the temperature in the step (2) is-7 ℃ to 13 ℃;
the voltage in the step (2) is 3.0V-4.0V;
the temperature in the step (3) is-7 ℃ to 13 ℃;
the voltage in the step (3) is 5.0V-6.5V.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113862707A (en) * | 2021-10-29 | 2021-12-31 | 中船重工（邯郸）派瑞特种气体有限公司 | Method for preparing trifluoromethyl sulfuryl fluoride by medium-temperature electrolysis method |
| CN114436292A (en) * | 2022-02-21 | 2022-05-06 | 中船(邯郸)派瑞特种气体股份有限公司 | Treatment method of organic sylvite wastewater |
| US11680041B1 (en) | 2021-12-07 | 2023-06-20 | Ses Holdings Pte. Ltd. | Processes for producing high-purity N,N-dialkyl perfluoroalkylsulfonamide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113862707A (en) * | 2021-10-29 | 2021-12-31 | 中船重工（邯郸）派瑞特种气体有限公司 | Method for preparing trifluoromethyl sulfuryl fluoride by medium-temperature electrolysis method |
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| US11680041B1 (en) | 2021-12-07 | 2023-06-20 | Ses Holdings Pte. Ltd. | Processes for producing high-purity N,N-dialkyl perfluoroalkylsulfonamide |
| CN114436292A (en) * | 2022-02-21 | 2022-05-06 | 中船(邯郸)派瑞特种气体股份有限公司 | Treatment method of organic sylvite wastewater |
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