Synthesis method and synthesis device of benzenesulfonyl fluoride

Abstract

The invention belongs to the technical field of synthesis of organic intermediates, and particularly relates to a synthesis method and a synthesis device of benzenesulfonyl fluoride. The synthesis method of the benzenesulfonyl fluoride comprises the following steps: firstly, adding hydrogen fluoride and sulfuryl chloride into a premixer, enabling the hydrogen fluoride and the sulfuryl chloride to sequentially pass through tubular reactors a, b and c, enabling the hydrogen fluoride and the sulfuryl chloride to enter a terminal reaction kettle for mixing reaction, controlling gas-liquid two-phase mixing reaction through the terminal reaction kettle and a vertical condenser a to prepare sulfuryl fluoride chloride, then mixing the sulfuryl fluoride chloride, benzene and a catalyst, and finally adding the benzenesulfonyl fluoride into the premixer to obtain the benzenesulfonyl fluoride. The method comprises the following steps: adding benzenesulfonyl fluoride into a sulfonation reaction kettle for reaction, controlling the sulfonation reaction through the sulfonation reaction kettle and a vertical filler b to obtain a mixed reaction solution, finally distilling the mixed reaction solution, and collecting fractions to obtain benzenesulfonyl fluoride. The synthesis method of the benzenesulfonyl fluoride provided by the invention is low in reaction condition requirement, stable, easy to control, low in unit consumption and easy in subsequent treatment, and the prepared benzenesulfonyl fluoride is high in yield and high in purity. The invention also provides a synthesis device adopted by the synthesis method of benzenesulfonyl fluoride.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic intermediate synthesis, and particularly relates to a synthesis method and a synthesis device for benzenesulfonyl fluoride. Background Art

[0002] Benzenesulfonyl fluoride , is an organic compound, a colorless liquid with a strong pungent odor. Benzenesulfonyl fluoride is generally used as a chemical reagent, fine chemical, pharmaceutical intermediate, material intermediate, etc. Benzenesulfonyl fluoride can participate in the fluorination reactions of organic compounds such as esters, amides, ethers, and olefins to introduce fluorine atoms and change the molecular structure.

[0003] The preparation method of benzenesulfonyl fluoride is mainly prepared by reacting benzenesulfonyl chloride with hydrogen fluoride. For example, in Example 2 of CN109734633A, benzenesulfonyl chloride is added to polytetrafluoroethylene, and sulfamic acid is used as a catalyst. The temperature is raised to 120°C, and anhydrous hydrogen fluoride gas is uniformly introduced. The reaction temperature is maintained at 120±5°C, and benzenesulfonyl fluoride is prepared by reaction, with a purity of 98.3% and a yield of 80.6%. However, the synthesis temperature of this reaction is too high, the amount of hydrogen fluoride used is large, and the yield is low.

[0004] As disclosed in CN101585787A, a benzenesulfonyl fluoride compound, its preparation method and application are disclosed. The preparation is carried out by a fluorination reaction of a precursor compound benzenesulfonyl chloride and a metal fluoride in acetonitrile. The fluorination reaction of sulfonyl chloride substances is carried out through a fluoride salt. Although the danger of fluorination is reduced, this reaction requires a large amount of organic matter as a solvent, and the process is complex, making it difficult to achieve industrialization. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the above-mentioned defects existing in the prior art, and provide a synthesis method for benzenesulfonyl fluoride with low reaction condition requirements, stability, easy control, low unit consumption, easy post-treatment, and high yield and high purity of the prepared benzenesulfonyl fluoride. The present invention also provides a synthesis device adopted by the synthesis method of benzenesulfonyl fluoride.

[0006] The synthesis method of benzenesulfonyl fluoride according to the present invention includes the following steps: First, hydrogen fluoride and thionyl chloride are added to a premixer, and successively pass through tubular reactor a, tubular reactor b, and tubular reactor c, and enter the terminal reaction kettle for mixing reaction. The gas-liquid two-phase mixing reaction is controlled by the terminal reaction kettle and the vertical condenser a at the upper end to prepare thionyl fluoride chloride. Then, thionyl fluoride chloride, benzene, and a catalyst are mixed and enter the sulfonation reaction kettle for reaction. The sulfonation reaction is controlled by the sulfonation reaction kettle and the vertical packing b at the upper end to obtain a mixed reaction solution. Finally, the mixed reaction solution is rectified, and the fractions are collected to obtain benzenesulfonyl fluoride.

[0007] The catalyst is a mixture of aluminum chloride and 4-dimethylaminopyridine.

[0008] The molar ratio of hydrogen fluoride to thionyl chloride is 1:2.5 - 3.5.

[0009] The molar ratio of thionyl fluorochloride to benzene is 1:1.05 - 1.2.

[0010] The mass ratio of thionyl fluorochloride, aluminum chloride, and 4 - dimethylaminopyridine is 1:0.001 - 0.003:0.001 - 0.003.

[0011] The purity of thionyl chloride ≥ 99%, the purity of benzene ≥ 99.5%, and the purity of hydrogen fluoride ≥ 99.5%.

[0012] Control the temperature of tubular reactor a at 50 - 60 °C, the temperature of tubular reactor b at 65 - 75 °C, and the temperature of tubular reactor c at 50 - 60 °C.

[0013] Control the temperature of the terminal reaction kettle at 35 - 45 °C, and the temperature of vertical condenser a at - 5 - 3 °C.

[0014] Control the temperature of the sulfonation reaction kettle at 40 - 55 °C, and the temperature of vertical filler b at - 5 - 3 °C.

[0015] The flow rate of hydrogen fluoride added to the premixer is 0.3 kg / h - 0.37 kg / h, and the flow rate of thionyl chloride added to the premixer is 5.15 kg / h - 8.8 kg / h.

[0016] The synthesis device used in the described method for synthesizing benzenesulfonyl fluoride includes a premixer, tubular reactor a, tubular reactor b, tubular reactor c, terminal reaction kettle, vertical condenser a, sulfonation reaction kettle, and vertical filler b; the outlet of the premixer is connected to the inlet of tubular reactor a, the outlet of tubular reactor a is connected to the inlet of tubular reactor b, the outlet of tubular reactor b is connected to the inlet of tubular reactor c, the outlet of tubular reactor c is connected to the inlet of the terminal reaction kettle, a vertical condenser a is arranged at the top of the terminal reaction kettle, vertical condenser a is connected to vertical filler a, vertical filler a is connected to the thionyl fluorochloride condensation and collection device, the thionyl fluorochloride condensation and collection device is connected to the thionyl fluorochloride storage tank, the thionyl fluorochloride storage tank is connected to the sulfonation reaction kettle, and a vertical filler b is arranged at the upper end of the sulfonation reaction kettle.

[0017] Vertical filler b is connected to vertical condenser b, and vertical condenser b is connected to the hydrogen chloride treatment device. Vertical filler a is connected to the hydrogen chloride treatment device.

[0018] The described premixer is connected to the hydrogen fluoride tank and thionyl chloride tank for loading raw materials as a raw material supply.

[0019] Specifically, the method for synthesizing benzenesulfonyl fluoride includes the following steps: (1) Adjust the tubular reactor a, tubular reactor b, tubular reactor c, vertical condenser a, and terminal reaction kettle to temperatures of 50 - 60 °C, 65 - 75 °C, 50 - 60 °C, -5 - 3 °C, and 35 - 45 °C respectively. Open the pipeline between the vertical filler a and the hydrogen chloride treatment device. Add hydrogen fluoride and thionyl chloride from the hydrogen fluoride tank and thionyl chloride tank to the pre - mixer at speeds of 0.3 kg / h to 0.37 kg / h and 5.15 kg / h to 8.8 kg / h respectively. After adding to half of the process, turn on the circulation pump of the terminal reaction kettle. After the addition is completed, continue the reaction for 1 - 2 h. The hydrogen chloride gas generated during the reaction enters the hydrogen chloride treatment device. After the reaction is completed, cut the connection pipeline of the vertical filler a to the thionyl fluorochloride condensation and collection device, and at the same time stop the heat exchange of the vertical condenser a. Keep the temperature of the terminal reaction kettle, separate the thionyl fluorochloride gas to the thionyl fluorochloride condensation and collection device, and then introduce it into the thionyl fluorochloride storage tank.

[0020] (2) Add the catalyst to the sulfonation reaction kettle, and adjust the sulfonation reaction kettle and the vertical filler b to temperatures of 40 - 55 °C and -5 - 3 °C respectively. Cut the connection pipeline of the hydrogen chloride treatment device to the vertical condenser b, and then pump thionyl fluorochloride from the thionyl fluorochloride storage tank into the sulfonation reaction kettle at a speed of 1.7 - 2.2 kg / h through a metering pump for reaction, with a total addition time of 2 - 3 h. After the addition is completed, continue the reaction for 1 - 2 h. The hydrogen chloride gas generated during the reaction enters the hydrogen chloride treatment device. After the reaction is completed, introduce the reaction product into the distillation system for distillation treatment.

[0021] (3) Evaporate benzene and benzenesulfonyl fluoride in the mixed liquid to be distilled in turn, and finally obtain the target product benzenesulfonyl fluoride in total. Detect its purity and calculate the yield based on HF.

[0022] In the present invention, an excessive amount of thionyl chloride reacts continuously under a multi - stage gradient temperature tubular reactor to generate a thionyl fluorochloride intermediate. Under these process conditions, the generation of thionyl fluorochloride does not require a catalyst to promote the reaction. And under the conditions of different temperatures in the three - stage tubular reactor, the reaction process proceeds more stably and efficiently, fully ensuring the conversion rate and selectivity of the reaction. Then, thionyl fluorochloride reacts with benzene. The exposed chlorine atoms of thionyl fluoride have good reactivity with the benzene ring, and only a small amount of catalyst is needed to promote the reaction, avoiding the problem of a large amount of solid waste by - products caused by the promotion of a large amount of aluminum chloride.

[0023] The process route of the reaction in the present invention is: 。

[0024] Compared with the prior art, the beneficial effects of the present invention are: (1) The synthesis method of benzenesulfonyl fluoride in the present invention has stable process conditions, few side reactions, less catalyst consumption, and simple solid waste treatment.

[0025] (2)The synthesis method of benzenesulfonyl fluoride of the present invention has a high yield, high purity and good quality of the synthesized benzenesulfonyl fluoride.

[0026] (3)The synthesis device adopted by the synthesis method of benzenesulfonyl fluoride of the present invention is simple to operate, easy to control, and easy to realize industrialization. Description of the Drawings

[0027] Figure 1 It is a synthesis device diagram adopted by the synthesis method of benzenesulfonyl fluoride of the present invention.

[0028] In the figure: 1, hydrogen fluoride tank; 2, thionyl chloride tank; 3, premixer; 4, tubular reactor a; 5, tubular reactor b; 6, tubular reactor c; 7, terminal reaction kettle; 8, vertical condenser a; 9, vertical packing device a; 10, hydrogen chloride treatment device; 11, sulfuryl fluoride chloride condensation and collection device; 12, sulfuryl fluoride chloride storage tank; 13, sulfonation reaction kettle; 14, vertical packing device b; 15, vertical condenser b. Detailed Embodiments

[0029] The present invention will be further described below in conjunction with specific embodiments.

[0030] The synthesis device adopted by the synthesis method of the described benzenesulfonyl fluoride is as Figure 1 shown, including a premixer 3, a tubular reactor a 4, a tubular reactor b 5, a tubular reactor c 6, a terminal reaction kettle 7, a vertical condenser a 8, a sulfonation reaction kettle 13, and a vertical packing device b 14; the outlet of the premixer 3 is connected to the inlet of the tubular reactor a 4, the outlet of the tubular reactor a 4 is connected to the inlet of the tubular reactor b 5, the outlet of the tubular reactor b 5 is connected to the inlet of the tubular reactor c 6, the outlet of the tubular reactor c 6 is connected to the inlet of the terminal reaction kettle 7, a vertical condenser a 8 is arranged at the top of the terminal reaction kettle 7, the vertical condenser a 8 is connected to a vertical packing device a 9, the vertical packing device a 9 is connected to a sulfuryl fluoride chloride condensation and collection device 11, the sulfuryl fluoride chloride condensation and collection device 11 is connected to a sulfuryl fluoride chloride storage tank 12, the sulfuryl fluoride chloride storage tank 12 is connected to the sulfonation reaction kettle 13, and a vertical packing device b 14 is arranged at the upper end of the sulfonation reaction kettle 13.

[0031] The vertical packing device b 14 is connected to a vertical condenser b 15, the vertical condenser b 15 is connected to a hydrogen chloride treatment device 10, and the vertical packing device a 9 is connected to the hydrogen chloride treatment device 10.

[0032] The premixer 3 is connected to a hydrogen fluoride tank 1 and a thionyl chloride tank 2 for loading raw materials as a raw material supply.

[0033] The mass content of hydrogen fluoride used in the following examples is 99.5%, the mass content of thionyl chloride is 99.0%, and the mass content of benzene is 99.5%.

[0034] Example 1 The described synthesis method of benzenesulfonyl fluoride includes the following steps: (1) Adjust the tubular reactor a4, tubular reactor b5, tubular reactor c6, vertical condenser a8, and terminal reaction kettle 7 to temperatures of 50 °C, 65 °C, 50 °C, -5 °C, and 45 °C respectively. Open the pipeline between the vertical packing device a9 and the hydrogen chloride treatment device 10. Add hydrogen fluoride and thionyl chloride from the hydrogen fluoride tank 1 and thionyl chloride tank 2 to the premixer 3 at speeds of 0.304 kg / h and 5.154 kg / h respectively. After adding to half of the process, turn on the circulation pump of the terminal reaction kettle 7. Finally, a total of 1.52 kg of hydrogen fluoride and 25.774 kg of thionyl chloride are added. After the addition is completed, continue the reaction for 2 h. The hydrogen chloride gas generated during the reaction process enters the hydrogen chloride treatment device 10. After the reaction ends, cut the connection pipeline of the vertical packing device a9 to the sulfuryl fluoride chloride condensation and collection device 11, and at the same time shut down the circulating refrigeration of the vertical condenser a8. Keep the temperature of the terminal reaction kettle 7. The sulfuryl fluoride chloride gas is separated into the sulfuryl fluoride chloride condensation and collection device 11, and then introduced into the sulfuryl fluoride chloride storage tank 12, obtaining a total of 8.731 kg of sulfuryl fluoride chloride (the yield is 95% and the purity is 98% calculated by HFmol).

[0035] (2) Add 5.921 kg of benzene, 26.193 g of aluminum chloride, and 26.193 g of 4-dimethylaminopyridine to the sulfonation reaction kettle 13. Adjust the sulfonation reaction kettle 13 and the vertical packing device b14 to temperatures of 40 °C and 3 °C respectively. Cut the connection pipeline of the hydrogen chloride treatment device 10 to the vertical condenser b15, and then pump the sulfuryl fluoride chloride from the sulfuryl fluoride chloride storage tank 12 into the sulfonation reaction kettle 13 at a rate of 2.182 kg / h through a metering pump for reaction, with a total addition time of 4 h. After the addition is completed, continue the reaction for 2 h. The hydrogen chloride gas generated during the reaction process enters the hydrogen chloride treatment device 10, and then after the reaction ends, introduce the reaction product into the distillation system for distillation treatment.

[0036] (3) Distill benzene and benzenesulfonyl fluoride in the mixed liquid to be distilled under normal pressure and -0.1 MPa conditions respectively. Finally, a total of 10.971 kg of the target product benzenesulfonyl fluoride is obtained. The detected purity is 99%, and the yield calculated based on sulfuryl fluoride chloride is 95%.

[0037] Example 2 The described synthesis method of benzenesulfonyl fluoride includes the following steps: (1) Adjust the tube reactors a4, b5, and c6, the vertical condenser a8, and the terminal reaction kettle 7 to temperatures of 55°C, 70°C, 55°C, 0°C, and 40°C respectively. Open the pipeline between the vertical filler a9 and the hydrogen chloride treatment device 10. Add hydrogen fluoride and thionyl chloride from the hydrogen fluoride tank 1 and the thionyl chloride tank 2 to the pre - mixer 3 at speeds of 0.37 kg / h and 8.801 kg / h respectively. After adding for half of the total amount, turn on the circulation pump of the terminal reaction kettle 7. Finally, a total of 1.483 kg of hydrogen fluoride and 35.205 kg of thionyl chloride are added. After the addition is completed, continue the reaction for 1.5 h. The hydrogen chloride gas generated during the reaction enters the hydrogen chloride treatment device 10. After the reaction ends, cut the connecting pipeline of the vertical filler a9 to the thionyl fluorochloride condensation and collection device 11, and at the same time shut down the circulating refrigeration of the vertical condenser a8. Keep the temperature of the terminal reaction kettle 7. The thionyl fluorochloride gas is separated into the thionyl fluorochloride condensation and collection device 11, and then introduced into the thionyl fluorochloride storage tank 12, obtaining a total of 8.543 kg of thionyl fluorochloride (yield 96.2% and purity 98.4% based on HFmol).

[0038] (2) Add 6.128 kg of benzene, 17.086 g of aluminum chloride, and 17.086 g of 4 - dimethylaminopyridine to the sulfonation reaction kettle 13. Adjust the sulfonation reaction kettle 13 and the vertical filler b14 to temperatures of 48°C and 0°C respectively. Cut the connecting pipeline of the hydrogen chloride treatment device 10 to the vertical condenser b15, and then use a metering pump to pump thionyl fluorochloride from the thionyl fluorochloride storage tank 12 into the sulfonation reaction kettle 13 at a rate of 1.709 kg / h for reaction, with a total addition time of 5 h. After the addition is completed, continue the reaction for 1 h. The hydrogen chloride gas generated during the reaction enters the hydrogen chloride treatment device 10. Then, after the reaction ends, introduce the reaction product into the distillation system for distillation treatment.

[0039] (3) Distill benzene and benzenesulfonyl fluoride in the mixed liquid to be distilled under normal pressure and - 0.1 MPa conditions respectively. Finally, a total of 10.998 kg of the target product benzenesulfonyl fluoride is obtained. The detected purity is 98.5%, and the yield based on thionyl fluorochloride is 95.3%.

[0040] Example 3 The method for synthesizing benzenesulfonyl fluoride described above includes the following steps: (1) Adjust the tubular reactor a4, tubular reactor b5, tubular reactor c6, vertical condenser a8, and terminal reaction kettle 7 to temperatures of 60°C, 75°C, 60°C, 3°C, and 35°C respectively. Open the pipeline between the vertical filler a9 and the hydrogen chloride treatment device 10. Add hydrogen fluoride and thionyl chloride from the hydrogen fluoride tank 1 and thionyl chloride tank 2 to the premixer 3 at speeds of 0.332 kg / h and 5.633 kg / h respectively. After adding for half of the process, turn on the circulation pump of the terminal reaction kettle 7. Finally, a total of 1.495 kg of hydrogen fluoride and 25.349 kg of thionyl chloride are added. After the addition is completed, continue the reaction for 1 h. The hydrogen chloride gas generated during the reaction enters the hydrogen chloride treatment device 10. After the reaction ends, cut the connection pipeline of the vertical filler a9 to the sulfuryl fluoride chloride condensation and collection device 11, and at the same time shut down the circulating refrigeration of the vertical condenser a8. Keep the temperature of the terminal reaction kettle 7. Separate the sulfuryl fluoride chloride gas to the sulfuryl fluoride chloride condensation and collection device 11, and then introduce it into the sulfuryl fluoride chloride storage tank 12, obtaining a total of 8.777 kg of sulfuryl fluoride chloride (the yield is 97% and the purity is 97.4% based on HFmol).

[0041] (2) Add 6.796 kg of benzene, 8.777 g of aluminum chloride, and 8.777 g of 4-dimethylaminopyridine to the sulfonation reaction kettle 13. Adjust the sulfonation reaction kettle 13 and the vertical filler b14 to temperatures of 55°C and -5°C respectively. Cut the connection pipeline of the hydrogen chloride treatment device 10 to the vertical condenser b15, and then use a metering pump to pump the sulfuryl fluoride chloride from the sulfuryl fluoride chloride storage tank 12 into the sulfonation reaction kettle 13 at a rate of 1.755 kg / h for reaction, with a total addition time of 5 h. After the addition is completed, continue the reaction for 1.5 h. The hydrogen chloride gas generated during the reaction enters the hydrogen chloride treatment device 10. Then, after the reaction ends, introduce the reaction product into the distillation system for distillation treatment.

[0042] (3) Evaporate benzene and benzenesulfonyl fluoride in the mixed liquid to be distilled under normal pressure and -0.1 MPa conditions respectively. Finally, a total of 10.994 kg of the target product benzenesulfonyl fluoride is obtained. Detect its purity to be 99.3%, and the yield based on sulfuryl fluoride chloride is 94.8%.

[0043] Example 4 The method for synthesizing benzenesulfonyl fluoride as described above includes the following steps: (1) Adjust the tubular reactor a4, tubular reactor b5, tubular reactor c6, vertical condenser a8, and terminal reaction kettle 7 to temperatures of 57 °C, 72 °C, 57 °C, 0 °C, and 41 °C respectively. Open the pipeline between the vertical packer a9 and the hydrogen chloride treatment device 10. Add hydrogen fluoride and thionyl chloride from the hydrogen fluoride tank 1 and thionyl chloride tank 2 to the premixer 3 at speeds of 0.333 kg / h and 6.791 kg / h respectively. After adding for half the process, turn on the circulation pump of the terminal reaction kettle 7. Finally, a total of 1.502 kg of hydrogen fluoride and 30.562 kg of thionyl chloride are added. After the addition is complete, continue the reaction for 1.5 h. The hydrogen chloride gas generated during the reaction enters the hydrogen chloride treatment device 10. After the reaction ends, cut the connection pipeline of the vertical packer a9 to the sulfuryl fluoride chloride condensation and collection device 11, and at the same time shut down the circulating refrigeration of the vertical condenser a8. Keep the temperature of the terminal reaction kettle 7. Separate the sulfuryl fluoride chloride gas to the sulfuryl fluoride chloride condensation and collection device 11, and then introduce it into the sulfuryl fluoride chloride storage tank 12. A total of 8.791 kg of sulfuryl fluoride chloride is obtained (the yield is 97.3% and the purity is 98% calculated by HFmol).

[0044] (2) Add 5.993 kg of benzene, 17.582 g of aluminum chloride, and 13.186 g of 4-dimethylaminopyridine to the sulfonation reaction kettle 13. Adjust the sulfonation reaction kettle 13 and the vertical packer b14 to temperatures of 47 °C and 0 °C respectively. Cut the connection pipeline of the hydrogen chloride treatment device 10 to the vertical condenser b15, and then use a metering pump to pump the sulfuryl fluoride chloride from the sulfuryl fluoride chloride storage tank 12 into the sulfonation reaction kettle 13 at a rate of 2.182 kg / h for reaction, with a total addition time of 4.5 h. After the addition is complete, continue the reaction for 1.5 h. The hydrogen chloride gas generated during the reaction enters the hydrogen chloride treatment device 10, and then after the reaction ends, introduce the reaction product into the distillation system for distillation treatment.

[0045] (3) Distill benzene and benzenesulfonyl fluoride in the mixed liquid to be distilled at normal pressure and -0.1 MPa respectively. Finally, a total of 11.27 kg of the target product benzenesulfonyl fluoride is obtained, with a detected purity of 99.5% and a yield of 96.3% calculated based on sulfuryl fluoride chloride.

[0046] Comparative Example 1 This comparative example is the same as Example 1, except that the tubular reactor in step (1) is removed, and other preparation conditions are the same. Finally, a total of 4.21 kg of the target product benzenesulfonyl fluoride is obtained, and its yield is 25.61% calculated according to the mol amount of HF. The detected purity is 70%.

[0047] Comparative Example 2 This comparative example is the same as Example 1. The temperatures of the three-stage tubular reactor in step (1) were set at 20 °C, 30 °C, and 20 °C respectively, and other preparation conditions were the same. Finally, a total of 5.35 kg of the target product benzenesulfonyl fluoride was obtained. Its yield was calculated to be 33.47% based on the molar amount of HF. Its purity was detected to be 72%.

[0048] Comparative Example 3 This comparative example is the same as Example 1. The addition amount of benzene in step (2) was adjusted to 2 times the molar amount of sulfuryl fluoride chloride, and other preparation conditions were the same. Finally, a total of 4.113 kg of the target product benzenesulfonyl fluoride was obtained. Its yield was calculated to be 17.51% based on the molar amount of HF. Its purity was detected to be 49%.

[0049] Comparative Example 4 This comparative example is the same as Example 1. The aluminum chloride and 4-dimethylaminopyridine catalysts in step (2) were removed, and other preparation conditions were the same. Finally, a total of 2.15 kg of the target product benzenesulfonyl fluoride was obtained. Its yield was calculated to be 11.21% based on the molar amount of HF. Its purity was detected to be 60%.

[0050] Comparative Example 5 This comparative example is the same as Example 1. The 4-dimethylaminopyridine catalyst in step (2) was removed, and other preparation conditions were the same. Finally, a total of 5.4 kg of the target product benzenesulfonyl fluoride was obtained. Its yield was calculated to be 31.91% based on the molar amount of HF. Its purity was detected to be 68%.

[0051] Comparative Example 6 This comparative example is the same as Example 1. The temperature of the sulfonation reactor in step (2) was lowered to 20 °C, and other preparation conditions were the same. Finally, a total of 4.113 kg of the target product benzenesulfonyl fluoride was obtained. Its yield was calculated to be 17.51% based on the molar amount of HF. Its purity was detected to be 49%.

Claims

1. A method for synthesizing benzenesulfonyl fluoride, characterized in that, It includes the following steps: First, hydrogen fluoride and thionyl chloride are added to a premixer and sequentially pass through tubular reactor a, tubular reactor b, and tubular reactor c, and then enter the terminal reaction kettle for mixing reaction. The gas-liquid two-phase mixing reaction is controlled by the terminal reaction kettle and the vertical condenser a at the upper end to obtain thionyl fluorochloride. Then, thionyl fluorochloride, benzene, and a catalyst are mixed and enter the sulfonation reaction kettle for reaction. The sulfonation reaction is controlled by the sulfonation reaction kettle and the vertical filler b at the upper end to obtain a mixed reaction solution. Finally, the mixed reaction solution is rectified, and the fraction is collected to obtain benzenesulfonyl fluoride.

2. The synthesis method of benzenesulfonyl fluoride according to claim 1, characterized in that: The catalyst is aluminum chloride and 4-dimethylaminopyridine.

3. The synthesis method of benzenesulfonyl fluoride according to claim 1, characterized in that: The molar ratio of hydrogen fluoride to thionyl chloride is 1:2.5 - 3.

5.

4. The synthesis method of benzenesulfonyl fluoride according to claim 2, characterized in that: The molar ratio of thionyl fluorochloride to benzene is 1:1.05 - 1.2, and the mass ratio of thionyl fluorochloride, aluminum chloride, and 4-dimethylaminopyridine is 1:0.001 - 0.003:0.001 - 0.

003.

5. The synthesis method of benzenesulfonyl fluoride according to claim 1, characterized in that: Control the temperature of tubular reactor a at 50 - 60 °C, the temperature of tubular reactor b at 65 - 75 °C, and the temperature of tubular reactor c at 50 - 60 °C.

6. The synthesis method of benzenesulfonyl fluoride according to claim 5, characterized in that: Control the temperature of the terminal reaction kettle at 35 - 45 °C, and the temperature of the vertical condenser a at -5 - 3 °C.

7. The method for synthesizing benzenesulfonyl fluoride according to claim 6, wherein: Control the temperature of the sulfonation reaction kettle at 40 - 55 °C, and the temperature of the vertical filler b at -5 - 3 °C.

8. The synthesis method of benzenesulfonyl fluoride according to claim 1, characterized in that: The flow rate of hydrogen fluoride added to the premixer is 0.3 kg / h - 0.37 kg / h, and the flow rate of thionyl chloride added to the premixer is 5.15 kg / h - 8.8 kg / h.

9. The synthesis apparatus used in the synthesis method of benzenesulfonyl fluoride according to any one of claims 1-8, characterized in that: It includes a premixer (3), tubular reactor a (4), tubular reactor b (5), tubular reactor c (6), terminal reaction kettle (7), vertical condenser a (8), sulfonation reaction kettle (13), and vertical filler b (14); the outlet of the premixer (3) is connected to the inlet of tubular reactor a (4), the outlet of tubular reactor a (4) is connected to the inlet of tubular reactor b (5), the outlet of tubular reactor b (5) is connected to the inlet of tubular reactor c (6), the outlet of tubular reactor c (6) is connected to the inlet of the terminal reaction kettle (7), the vertical condenser a (8) is arranged at the top of the terminal reaction kettle (7), the vertical condenser a (8) is connected to the vertical filler a (9), the vertical filler a (9) is connected to the thionyl fluorochloride condensation and collection device (11), the thionyl fluorochloride condensation and collection device (11) is connected to the thionyl fluorochloride storage tank (12), the thionyl fluorochloride storage tank (12) is connected to the sulfonation reaction kettle (13), and the vertical filler b (14) is arranged at the upper end of the sulfonation reaction kettle (13).

10. The synthesis device used in the method for synthesizing benzenesulfonyl fluoride according to claim 9, characterized in that: The vertical filler b (14) is connected to the vertical condenser b (15), the vertical condenser b (15) is connected to the hydrogen chloride treatment device (10), and the vertical filler a (9) is connected to the hydrogen chloride treatment device (10).

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