A method for synthesizing diphenyl[4-(phenylthio)phenyl]perfluorobutylsulfonium sulfonium salt

Abstract

The application relates to the technical field of synthesis of photoresist initiators, and provides a synthesis method of diphenyl[4-(phenylthio)phenyl] perfluorobutyl sulfonium sulfonate, which comprises the following steps: using diphenyl sulfide, diphenyl sulfoxide and potassium perfluorobutyl sulfonate as raw materials, and performing reaction under the catalysis of anhydride and a strong inorganic acid; after the reaction is completed, the product is extracted by using an organic solvent; then aromatic solvent recrystallization is performed to obtain the diphenyl[4-(phenylthio)phenyl] perfluorobutyl sulfonium sulfonate, and the purity can reach more than 99%.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of synthesis of photoresist initiators, and particularly relates to a synthesis method of diphenyl[4-(phenylthio)phenyl] perfluorobutyl sulfonium sulfonate. BACKGROUND

[0002] Diphenyl[4-(phenylthio)phenyl] perfluorobutyl sulfonium sulfonate is used for a photoresist component, and reference is made to JP2019182813A, and a structural formula is as follows:

[0003]

[0004] Diphenyl[4-(phenylthio)phenyl] perfluorobutyl sulfonium sulfonate is an important cationic initiator and also an important photoacid generator, and the generated acid is a photocontrollable acid, which can cause decomposition or crosslinking reaction of a photosensitive substance and can be used in the field of photoresists.

[0005] The synthesis method of the compound is rarely reported in literatures, and Japanese patent JP2019182813A reports that diphenyl sulfide, diphenyl sulfoxide and sodium perfluorobutyl sulfonate are used as raw materials, and phosphorus pentoxide and methanesulfonic acid are used as catalysts, the obtained product has an impurity ratio of 11%, and needs column chromatography for purification. Japanese patent JP2002139838A reports the synthesis method of the compound, and the compound is generated in the form of a by-product, and is difficult to purify. Therefore, the application provides a synthesis method of diphenyl[4-(phenylthio)phenyl] perfluorobutyl sulfonium sulfonate, the synthesis method is more convenient than the currently reported method, industrialization is easy to realize, the yield is 80%, and the purity can reach more than 99%. SUMMARY

[0006] The application provides a synthesis method of diphenyl[4-(phenylthio)phenyl] perfluorobutyl sulfonium sulfonate.

[0007] The application adopts the following technical scheme:

[0008] The application provides a synthesis method of diphenyl[4-(phenylthio)phenyl] perfluorobutyl sulfonium sulfonate, characterized by using diphenyl sulfide, diphenyl sulfoxide and potassium perfluorobutyl sulfonate as raw materials, and performing reaction under the catalysis of anhydride and a strong inorganic acid, using an organic solvent to extract the product after the reaction is completed, and then using an aromatic solvent to recrystallize to obtain diphenyl[4-(phenylthio)phenyl] perfluorobutyl sulfonium sulfonate.

[0009] Further, the molar ratio of diphenyl sulfide to diphenyl sulfoxide is 1:1.

[0010] Further, the mass ratio of the diphenyl sulfide to the anhydride is 1:5-20, preferably the mass ratio of the diphenyl sulfide to the anhydride is 1:5-10.

[0011] Further, the amount of concentrated sulfuric acid is 1:0.7-1:1.5 by mass ratio of diphenyl sulfide.

[0012] Further, the molar ratio of the raw material diphenyl sulfide to diphenyl sulfoxide is 1:1.

[0013] Further, the reaction condition is 25-50℃, preferably the reaction is carried out for 5 hours.

[0014] Further, the recrystallization solvent is toluene.

[0015] Further, the mass ratio of the raw material diphenyl sulfide to potassium perfluorobutyl sulfonate is 1:2-3.

[0016] The present application has the following beneficial effects:

[0017] The present application provides a method for synthesizing diphenyl[4-(phenylthio)phenyl] perfluorobutyl sulfonium sulfonate. The method is simple in operation, the product is easy to purify, the purity is more than 99%, and the product yield is high. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 The figure is a nuclear magnetic hydrogen spectrum identification map;

[0019] Figure 2 The figure is a liquid phase detection map. DETAILED DESCRIPTION

[0020] The present application will be described in detail below in combination with specific examples:

[0021] Example 1

[0022] 500ml four-necked flask was added potassium perfluorobutyl sulfonate 19.62g, trifluoroacetic anhydride 40.84g, and concentrated sulfuric acid with a mass concentration of 98% 5.82g, and stirred at room temperature for 30min in the dark, 8.10g (0.04mol) of diphenyl sulfoxide was added and stirred uniformly, 7.46g (0.04mol) of diphenyl sulfide was slowly added dropwise, and the dropping was completed after 40min, and the reaction was stirred at 25℃ for 5h. 80ml of the reaction liquid was poured into 500g of water and stirred for 10min, 300g of dichloromethane was added for extraction and separation, and the organic phase was washed with 400g of 4% sodium hydroxide solution. Then, 200g of water was used for washing each time, and the washing was carried out for three times, and 33g of oil liquid was obtained by distillation under reduced pressure at 40℃, 100g of toluene was added, heated to 110℃ and refluxed for 10min, then cooled to room temperature, and white powder 20.8g was obtained by suction filtration, which was identified by nuclear magnetic resonance to be correct in structure. Figure 1 , the yield was 77.6%, and the purity was 99.65%.

[0023] Comparative Example 1

[0024] Into a 500ml four-necked flask, 19.62g of potassium perfluorobutylsulfonate, 40.84g of acetic anhydride, and 5.82g of concentrated sulfuric acid with a mass concentration of 98% were added, and stirred for 30 minutes at room temperature in the dark. 8.10g (0.04mol) of diphenyl sulfoxide was added and stirred uniformly, and 7.46g (0.04mol) of diphenyl sulfide was slowly added dropwise. After 40 minutes of dropping, it was stirred for 5 hours at 25°C. 80ml of the reaction solution was poured into 500g of water, stirred for 10 minutes, and 300g of dichloromethane was added for extraction and separation. The organic phase was washed with 400g of a sodium hydroxide solution with a mass concentration of 4%. Then, it was washed with 200g of water three times. After distillation under reduced pressure at 40°C, 29.5g of an oily liquid was obtained. 88.5g of toluene was added, heated to 110°C, and refluxed for 10 minutes. After cooling to room temperature, 15.84g of white powder (diphenyl [4-(phenylthio) phenyl] perfluorobutyl sulfonium sulfide salt) was obtained, with a yield of 59.1% and a purity of 95.10%.

[0025] Comparative Example 2

[0026] Into a 500ml four-necked flask, 19.62g of potassium perfluorobutylsulfonate, 40.84g of propionic anhydride, and 5.82g of concentrated sulfuric acid with a mass concentration of 98% were added, and stirred for 30 minutes at room temperature in the dark. 8.10g (0.04mol) of diphenyl sulfoxide was added and stirred uniformly, and 7.46g (0.04mol) of diphenyl sulfide was slowly added dropwise. After 40 minutes of dropping, it was stirred for 5 hours at 25°C. 80ml of the reaction solution was poured into 500g of water, stirred for 10 minutes, and 300g of dichloromethane was added for extraction and separation. The organic phase was washed with 400g of a sodium hydroxide solution with a mass concentration of 4%. Then, it was washed with 200g of water three times. After distillation under reduced pressure at 40°C, 28.8g of an oily liquid was obtained. 86.4g of toluene was added, heated to 110°C, and refluxed for 10 minutes. After cooling to room temperature, 14.5g of yellow solid (diphenyl [4-(phenylthio) phenyl] perfluorobutyl sulfonium sulfide salt) was obtained, with a yield of 54.1% and a purity of 87.2%.

[0027] From the comparison of the processes and results of Experimental Example 1 and Comparative Examples 1 and 2, it can be seen that trifluoroacetic anhydride has a better catalytic effect. Although acetic anhydride and propionic anhydride can catalyze the reaction, impurities will be generated.

[0028] Example 2

[0029] Add 22.38 g of potassium perfluorobutyl sulfonate, 74.6 g of trifluoroacetic anhydride, and 11.19 g of 98% concentrated sulfuric acid to a 500 ml four-necked flask. Stir at room temperature in the dark for 30 min. Add 8.91 g (0.044 mol) of diphenyl sulfoxide and stir until homogeneous. Slowly add 8.2 g (0.044 mol) of diphenyl sulfide dropwise over 40 min. Stir at 50 °C for 5 h. Pour 80 ml of the reaction solution into 500 g of water and stir for 10 min. Add 300 g of dichloromethane for extraction and separation. Wash the organic phase with 400 g of 4% sodium hydroxide solution and separate. The sample was washed three times with 200g of water each time, and then distilled under reduced pressure at 40℃ to obtain 32.4g of an oily liquid. 97.2g of benzene was added, and the mixture was heated to 80℃ and refluxed for 10 minutes. After cooling to room temperature, the mixture was filtered to obtain 18.5g of a white powder (which is diphenyl[4-(phenylthio)phenyl]perfluorobutylsulfonate sulfonate sulfonium salt). The yield was 69.32%, and the purity was 99.43%.

[0030] Example 3

[0031] In a 500ml four-necked flask, 19.2g of potassium perfluorobutyl sulfonate, 49g of trifluoroacetic anhydride, and 6.98g of 98% concentrated sulfuric acid were added. The mixture was stirred at room temperature in the dark for 30 minutes. Then, 8.10g (0.04mol) of diphenyl sulfoxide was added and stirred until homogeneous. 7.46g (0.04mol) of diphenyl sulfide was slowly added dropwise over 40 minutes. The mixture was stirred at 35℃ for 5 hours. 80ml of the reaction solution was poured into 500g of water and stirred for 10 minutes. 405g of dichloromethane was added for extraction and separation. The organic phase was washed with 400g of 4% sodium hydroxide solution. The mixture was washed three times with 300g of water each time. The mixture was then distilled under reduced pressure at 40℃ to obtain 29.2g of an oily liquid. 87.6g of xylene was added, and the mixture was heated to 110℃ and refluxed for 10 minutes. After cooling to room temperature, the mixture was filtered to obtain 16.9g of a white powder (which is sulfonium diphenyl[4-(phenylthio)phenyl]perfluorobutyl sulfonate). Yield: 63.03%, purity: 99.11%.

[0032] Example 4

[0033] In a 500ml four-necked flask, add 20.8g of potassium perfluorobutyl sulfonate, 45g of trifluoroacetic anhydride, and 7.6g of 98% concentrated sulfuric acid. Stir at room temperature in the dark for 30min. Add 8.10g (0.04mol) of diphenyl sulfoxide and stir until homogeneous. Slowly add 7.46g (0.04mol) of diphenyl sulfide dropwise over 40min. Stir at 50℃ for 5h. Pour 80ml of the reaction solution into 500g of water and stir for 10min. Add 300g of ethyl acetate and extract. Wash the organic phase with 400g of 4% sodium hydroxide solution. Wash three times with 200g of water each time. Distill under reduced pressure at 40℃ to obtain 33.4g of an oily liquid. Add 99g of toluene, heat to 110℃ and reflux for 10min. Cool to room temperature and filter to obtain 19.2g of a pale yellow powder (which is sulfonium diphenyl[4-(phenylthio)phenyl]perfluorobutyl sulfonate). Yield 71.64%, purity 99.25%.

[0034] The above description is not intended to limit the present invention, and the present invention is not limited to the examples given above. Any changes, modifications, additions, or substitutions made by those skilled in the art within the scope of the present invention should also fall within the protection scope of the present invention.

Claims

1. A method for synthesizing a diphenyl[4-(phenylthio)phenyl]perfluorobutylsulfonate sulfonate, characterized in that... Diphenyl sulfide, diphenyl sulfoxide, and potassium perfluorobutyl sulfonate were used as raw materials. The reaction was carried out under the catalysis of trifluoroacetic anhydride and an inorganic strong acid. After the reaction was completed, the product was extracted with an organic solvent and then recrystallized with an aromatic solvent to obtain diphenyl[4-(phenylthio)phenyl]perfluorobutyl sulfonate sulfonate. The inorganic strong acid was concentrated sulfuric acid with a mass concentration of 96%-98%, and the mass ratio of the concentrated sulfuric acid to diphenyl sulfide was 1:0.7-1:1.

5.

2. The synthesis method according to claim 1, characterized in that, The molar ratio of the diphenyl sulfide to the diphenyl sulfoxide is 1:0.8-1.5; The mass ratio of diphenyl sulfide to potassium perfluorobutyl sulfonate used is 1:2-3.

3. The synthesis method according to claim 2, characterized in that, The molar ratio of the diphenyl sulfide to the diphenyl sulfoxide is 1:1; The mass ratio of diphenyl sulfide to potassium perfluorobutyl sulfonate used is 1:2.5-2.

8.

4. The synthesis method according to claim 1, characterized in that, The extraction solvent is one or more of dichloromethane, dichloroethane, or ethyl acetate.

5. The synthesis method according to claim 1, characterized in that, The aromatic solvent is one or more of benzene, toluene, or xylene.

6. The synthesis method according to claim 5, characterized in that, The aromatic solvent is toluene.

7. The synthesis method according to claim 1, characterized in that, The inorganic strong acid is concentrated sulfuric acid with a mass concentration of 98%.

8. The synthesis method according to claim 1, characterized in that, The mass ratio of diphenyl sulfide to trifluoroacetic anhydride used in the reaction is 1:5-20.

9. The synthesis method according to claim 8, characterized in that, The mass ratio of diphenyl sulfide to trifluoroacetic anhydride used in the reaction is 1:5-10.

10. The synthesis method according to claim 1, characterized in that, The reaction conditions are controlled at 25-50℃ and the reaction time is 2-8 hours.

11. The synthesis method according to claim 10, characterized in that, The reaction conditions are controlled at 25-50℃ and the reaction time is 4-6 hours.

12. The synthesis method according to claim 1, characterized in that, The process of extracting the product with an organic solvent after the reaction is complete is as follows: Pour the reaction solution into water and stir for 10-15 minutes. The volume ratio of the reaction solution to water is 1:7-8.

0. Then, after adding the extraction solvent, the liquid phase was separated, and the organic phase was washed with a 3%-4% sodium hydroxide solution. The amount of extraction solvent used is 3.5-4 g / ml of reaction solution; After washing with water to remove the solvent, an oily liquid is obtained.

13. The synthesis method according to claim 1 or 12, characterized in that, The mass ratio of the extract to the recrystallized aromatic solvent is 1:2.5-3.

5. The mixture is heated to 80-110℃ and refluxed for 10-15 minutes, then cooled to room temperature to precipitate the product.

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