Preparation method of amino sulfonyl fluoride

Abstract

The invention belongs to the technical field of material synthesis, and discloses a preparation method of amino sulfonyl fluoride, sulfuryl fluoride chloride reacts with inorganic ammonia to obtain amino sulfonyl fluoride, and the inorganic ammonia is ammonia or ammonium chloride. Active sulfur-chlorine bonds in sulfuryl fluoride chloride can be used for carrying out ammonolysis reaction with ammonia or ammonium chloride under mild conditions, sulfur-fluorine bonds are very stable and do not participate in the ammonolysis reaction, the high yield of the sulfuryl fluoride is obtained at low cost, the yield is larger than or equal to 90.5% according to sulfuryl fluoride chloride, meanwhile, the quality of the obtained sulfuryl fluoride is high, the gas phase purity is larger than or equal to 99.5%, and the method is suitable for industrial production. The method can be widely applied to construction of sulfanilamide structures in medicines and pesticides.

Description

Technical Field

[0001] This invention belongs to the field of materials synthesis technology, and specifically relates to a method for preparing aminosulfonyl fluoride. Background Technology

[0002] Sulfonamides (-SO2-NH-) structures, as a class of highly valuable functional groups, demonstrate irreplaceable application value in several core areas of modern chemical industry. In the pharmaceutical field, compounds containing sulfonamide structures, with their unique antibacterial and anti-inflammatory biological activities, have become key components of some drugs. In the pesticide field, the introduction of sulfonamide structures can significantly improve the targeting and duration of efficacy of pesticides, and they are used in products such as herbicides and fungicides. With the rapid development of the new energy industry, the application of sulfonamide structures in the field of lithium-ion batteries is becoming increasingly prominent. For example, lithium difluorosulfonylimide, as a high-performance electrolyte salt, has become a core candidate material for next-generation lithium-ion battery electrolytes due to its excellent electrochemical stability and ionic conductivity, and its molecular structure contains key sulfonamide-derived units. The performance optimization and large-scale preparation of such materials directly depend on the stable supply of high-quality sulfonamide intermediates.

[0003] Aminosulfonyl fluoride, as an important intermediate in the synthesis of various sulfonamide compounds, has long been a research hotspot in the field of chemical synthesis due to the need for efficient, safe, and low-cost preparation methods. Current techniques for synthesizing sulfonamide structures often employ a fluorosulfonation reaction between sulfuryl fluoride and the corresponding amine. This route not only suffers from low yield and high cost, but the gaseous storage, transportation, and use of sulfuryl fluoride also limit its convenience in chemical production. Currently, a common method for preparing aminosulfonyl fluoride involves the reaction of fluorosulfonic acid isocyanate with formic acid. However, fluorosulfonic acid isocyanate is typically prepared by fluorination with highly toxic and corrosive chlorosulfonyl isocyanate, resulting in a hazardous and costly process. Another reported method involves the fluorination of aminosulfonyl chloride, but aminosulfonyl chloride is also an uncommon chemical raw material, making its preparation difficult and resulting in high costs. Therefore, developing a method for preparing aminosulfonyl fluoride that uses readily available raw materials, operates under mild reaction conditions, is highly safe, and has controllable costs has significant theoretical and practical value. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a method for preparing aminosulfonyl fluoride in order to address the shortcomings of the existing technology. The method utilizes the active sulfur-chlorine bond in sulfuryl fluoride to carry out ammonolysis reaction with ammonia or ammonium chloride under mild conditions. The sulfur-fluorine bond is very stable and does not participate in the ammonolysis reaction. The prepared aminosulfonyl fluoride is of high quality and low cost.

[0005] To address the technical problem proposed in this invention, this invention provides a method for preparing aminosulfonyl fluoride, which involves reacting sulfuryl fluoride chloride with inorganic ammonia to obtain aminosulfonyl fluoride; wherein the inorganic ammonia is ammonia or ammonium chloride.

[0006] In the above scheme, when the inorganic ammonia is ammonia, the reaction equation is as follows: .

[0007] In the above scheme, when the inorganic ammonia is ammonia, the specific steps include: adding sulfuryl fluoride chloride to liquid ammonia for reaction, then filtering under normal pressure, and purifying the filtrate by distillation to obtain aminosulfonyl fluoride.

[0008] Furthermore, the molar ratio of the liquid ammonia to sulfuryl fluoride is greater than 2:1.

[0009] Preferably, the molar ratio of liquid ammonia to sulfuryl fluoride is (20~50):1.

[0010] Furthermore, the reaction temperature of the liquid ammonia with sulfuryl fluoride is -50~50℃, the reaction pressure is 0.01~1.5MPa, and the reaction time is 0.2~2h.

[0011] Preferably, the reaction temperature of the liquid ammonia with sulfuryl fluoride is -15~15℃, the reaction pressure is 0.25~0.8MPa, and the reaction time is 0.5~1h.

[0012] Furthermore, the distillation is carried out at a pressure of 20~50 Pa, and the fraction with a vapor phase temperature of 45~50°C is collected.

[0013] In the above scheme, when the inorganic ammonia is ammonium chloride, the reaction equation is as follows: .

[0014] In the above scheme, when the inorganic ammonia is ammonium chloride, the specific steps include: dispersing ammonium chloride in an inert aprotic solvent, then adding sulfuryl fluoride and heating to react, filtering, and purifying the filtrate by distillation to obtain aminosulfonyl fluoride.

[0015] Furthermore, the inert aprotic solvent is one or a combination of several of the following: hydrocarbons, esters, ethers, amides, sulfoxides, and sulfones.

[0016] Preferably, the inert aprotic solvent is one of dichloroethane, dimethyl sulfoxide, and methyl tert-butyl ether.

[0017] Furthermore, the mass of the inert aprotic solvent is 1 to 20 times the mass of ammonium chloride.

[0018] Preferably, the mass of the inert aprotic solvent is 1 to 2 times the mass of ammonium chloride.

[0019] Furthermore, the molar ratio of the sulfuryl fluoride to ammonium chloride is 1:(1.1~1.5).

[0020] Preferably, the molar ratio of the sulfuryl fluoride to ammonium chloride is 1:(1.2~1.5).

[0021] Furthermore, the reaction temperature of the sulfuryl fluoride chloride with ammonium chloride is 50~150℃, the reaction pressure is atmospheric pressure to 0.5MPa, and the reaction time is 1~12h.

[0022] Preferably, the reaction temperature of the sulfuryl fluoride chloride and ammonium chloride is 80~120℃, the reaction pressure is 0.01~0.2MPa, and the reaction time is 4~8h.

[0023] Furthermore, the distillation is carried out at a pressure of 20~50 Pa, and the fraction with a vapor phase temperature of 45~50°C is collected.

[0024] The yield of aminosulfonyl fluoride prepared by the method of the present invention is ≥90.5% based on thioyl fluoride chloride, and the gas phase purity is ≥99.5%.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows: 1) In the production of sulfuryl fluoride, the fluorination reaction is accompanied by sulfuryl fluoride chloride, which is generally disposed of as waste after alkaline washing and neutralization. This not only increases the production cost of sulfuryl fluoride, but also generates a large amount of pollutants, affecting the environment. This invention proposes a method for preparing high-value-added aminosulfonyl fluoride using sulfuryl fluoride chloride, a byproduct of sulfuryl fluoride. It can be prepared by directly reacting sulfuryl fluoride chloride with inorganic ammonia, which increases the value of the byproduct and reduces environmental pollution.

[0026] 2) This invention utilizes the active sulfur-chlorine bond in sulfuryl fluoride to undergo ammonolysis with ammonia or ammonium chloride under mild conditions. The sulfur-fluorine bond is very stable and does not participate in the ammonolysis reaction, thus obtaining a high yield of aminosulfonyl fluoride, with a yield of ≥90.5% based on sulfuryl fluoride. At the same time, the obtained aminosulfonyl fluoride is of high quality, with a gas phase purity of ≥99.5%, and can be widely used in the construction of sulfonamide structures in pharmaceuticals and pesticides. Detailed Implementation

[0027] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0028] The sulfuryl fluoride used in the following examples is derived from a sulfuryl fluoride production process. The mixed gas of sulfuryl fluoride and sulfuryl fluoride obtained from the process is passed through a serpentine condenser at -20°C. The liquid collected at the bottom of the tower is sulfuryl fluoride, and the purity of the gas phase is 99.6%. The sulfuryl fluoride gas at the top of the tower has a purity of 99.7% according to the gas phase analysis.

[0029] Example 1 20 mol of liquid ammonia was added to a high-pressure reactor, followed by 1 mol of sulfuryl fluoride. The reaction was carried out at a pressure of 0.25 MPa and a temperature of -15 °C for 1 h. The reactor was then depressurized to recover excess ammonia. The generated ammonium chloride solid was removed by filtration at room temperature and pressure. The filtrate was purified by distillation. The fraction with a gas phase temperature of 46 °C was collected at 40 Pa, yielding 97.6 g of a colorless and transparent liquid. Analyzing the liquid using NMR fluorine spectrum (59 ppm) and proton NMR (8.12 ppm), it was confirmed to be aminosulfonyl fluoride with a gas phase purity of 99.5% and a yield of 97.6% based on sulfuryl fluoride.

[0030] Example 2 30 mol of liquid ammonia was added to a high-pressure reactor, followed by 1 mol of sulfuryl fluoride. The reaction was carried out at 0.5 MPa and 0 °C for 1 h. The reactor was then depressurized to recover excess ammonia. The generated ammonium chloride solid was removed by filtration at room temperature and pressure. The filtrate was purified by distillation. The fraction with a gas phase temperature of 46 °C was collected at 40 Pa, yielding 97.8 g of a colorless and transparent liquid. Analytical analysis using NMR fluorine spectrum (59 ppm) and 1H NMR (8.12 ppm) confirmed that it was aminosulfonyl fluoride with a gas phase purity of 99.6% and a yield of 98.3% based on sulfuryl fluoride.

[0031] Example 3 40 mol of liquid ammonia was added to a high-pressure reactor, followed by 1 mol of sulfuryl fluoride. The reaction was carried out at 0.8 MPa and 15 °C for 0.5 h. The reactor was then depressurized to recover excess ammonia. The generated ammonium chloride solid was removed by filtration at room temperature and pressure. The filtrate was purified by distillation, and the fraction at 46 °C was collected at 40 Pa to obtain 97.4 g of a colorless and transparent liquid. Analytical analysis using NMR fluorine spectrum (59 ppm) and 1H NMR (8.12 ppm) confirmed that it was aminosulfonyl fluoride with a gas phase purity of 99.6% and a yield of 97.9% based on sulfuryl fluoride.

[0032] Example 4 1.2 mol of ammonium chloride was dispersed in an equal mass of dichloroethane, and then 1 mol of sulfuryl fluoride was added. The mixture was reacted at 0.2 MPa and 100 °C for 4 h to obtain a mixed solution containing solids. Excess ammonium chloride was removed by filtration at room temperature and pressure and reused to obtain a clear and transparent mixed solution. Finally, the solution was purified by distillation. The fraction with a gas phase temperature of 46 °C was collected at 40 Pa to obtain 90.2 g of aminosulfonyl fluoride. The purity of the gas phase was 99.6%, and the yield based on sulfuryl fluoride was 90.7%.

[0033] Example 5 1.3 mol of ammonium chloride was dispersed in 1.5 times its mass of dimethyl sulfoxide, and then 1 mol of thiosulfonyl fluoride was added. The mixture was reacted at 0.01 MPa and 80 °C for 8 h to obtain a mixed solution containing solids. Excess ammonium chloride was removed by filtration at room temperature and pressure and reused to obtain a clear and transparent mixed solution. Finally, the solution was purified by distillation. The fraction with a gas phase temperature of 46 °C was collected at 40 Pa to obtain 91.8 g of aminosulfonyl fluoride. The purity of the gas phase was 99.7%, and the yield based on thiosulfonyl fluoride was 92.4%.

[0034] Example 6 1.5 mol of ammonium chloride was dispersed in 2 times its mass of methyl tert-butyl ether, and then 1 mol of sulfuryl fluoride was added. The mixture was reacted at 0.1 MPa and 120 °C for 6 h to obtain a mixed solution containing solids. Excess ammonium chloride was removed by filtration at room temperature and pressure and reused to obtain a clear and transparent mixed solution. Finally, the solution was purified by distillation. The fraction with a gas phase temperature of 46 °C was collected at 40 Pa to obtain 90.8 g of aminosulfonyl fluoride. The purity of the gas phase was 99.5%, and the yield based on sulfuryl fluoride was 90.5%.

[0035] Comparative Example 1 The reaction temperature of Examples 1-3 was controlled at -55°C, and other conditions remained unchanged. The yields of aminosulfonyl fluoride were 52.3%, 50.8%, and 53.2%, respectively.

[0036] Comparative Example 2 The reaction temperature in Example 4 was controlled at 45°C, and other conditions remained unchanged. The final yield of aminosulfonyl fluoride was 51.2%.

[0037] The above embodiments are merely examples for clear illustration and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations, and any obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for preparing aminosulfonyl fluoride, characterized in that, Thionyl fluoride chloride is reacted with inorganic ammonia to obtain aminosulfonyl fluoride; the inorganic ammonia is ammonia or ammonium chloride.

2. The method for preparing aminosulfonyl fluoride according to claim 1, characterized in that, When the inorganic ammonia is ammonia, the specific steps include: adding sulfuryl fluoride chloride to liquid ammonia for reaction, then filtering under normal pressure, and purifying the filtrate by distillation to obtain aminosulfonyl fluoride.

3. The method for preparing aminosulfonyl fluoride according to claim 2, characterized in that, The molar ratio of liquid ammonia to sulfuryl fluoride is greater than 2:1, the reaction temperature is -50~50℃, the reaction pressure is 0.01~1.5MPa, and the reaction time is 0.2~2h.

4. The method for preparing aminosulfonyl fluoride according to claim 2, characterized in that, The molar ratio of liquid ammonia to sulfuryl fluoride is (20~50):1, the reaction temperature is -15~15℃, the reaction pressure is 0.25~0.8MPa, and the reaction time is 0.5~1h.

5. The method for preparing aminosulfonyl fluoride according to claim 1, characterized in that, When the inorganic ammonia is ammonium chloride, the specific steps include: dispersing ammonium chloride in an inert aprotic solvent, then adding sulfuryl fluoride and heating to react, filtering, and purifying the filtrate by distillation to obtain aminosulfonyl fluoride.

6. The method for preparing aminosulfonyl fluoride according to claim 5, characterized in that, The molar ratio of sulfuryl fluoride to ammonium chloride is 1:(1.1~1.5), the reaction temperature is 50~150℃, the reaction pressure is atmospheric pressure~0.5MPa, and the reaction time is 1~12h.

7. The method for preparing aminosulfonyl fluoride according to claim 5, characterized in that, The molar ratio of sulfuryl fluoride to ammonium chloride is 1:(1.2~1.5), the reaction temperature is 80~120℃, the reaction pressure is 0.01~0.2MPa, and the reaction time is 4~8h.

8. The method for preparing aminosulfonyl fluoride according to claim 5, characterized in that, The inert aprotic solvent is one or a combination of several of the following: hydrocarbons, esters, ethers, amides, sulfoxides, and sulfones. The mass of the inert aprotic solvent is 1 to 20 times the mass of ammonium chloride.

9. The method for preparing aminosulfonyl fluoride according to claim 5, characterized in that, The inert aprotic solvent is one of dichloroethane, dimethyl sulfoxide, and methyl tert-butyl ether, and the mass of the inert aprotic solvent is 1 to 2 times the mass of ammonium chloride.

10. The method for preparing aminosulfonyl fluoride according to claim 2 or 5, characterized in that, The distillation is carried out at a pressure of 20~50Pa, and the fraction with a vapor temperature of 45~50℃ is collected; the yield of aminosulfonyl fluoride is ≥90.5% based on sulfuryl fluoride chloride, and the vapor purity is ≥99.5%.