Sulfonium sulfonate-derived photoacid generators, methods of preparation, and photoresists

Abstract

Disclosed are a sulfonium sulfonate-derived photoacid generator, a preparation method and a photoresist. The photoacid generator has a structure as shown in A6, and the photoacid generator can be used as a high-purity electronic-grade photoacid generator. A6:

Description

Technical Field

[0001] This invention relates to the field of photoacid generators for semiconductor photoresists, and particularly to a thioonium sulfonate-derived photoacid generator, its preparation method, and a photoresist. Background Technology

[0002] Photoacid generators are key components of semiconductor photoresists, significantly impacting the yield, quality, and processing precision of photoresists and lithography products. Photoacid generators mainly include two types: onium salt-based acid generators and sulfonate ester-based acid generators.

[0003] Onium salts are used relatively early, have mature processes, high acid production efficiency, fast photoinitiation rate, good thermal stability, and high acid strength, which helps to promote chemical reactions in photoresists. However, their poor solubility, complex synthesis steps, and low product purity limit their application range.

[0004] With the rapid development of new materials science, green chemistry and biotechnology, the application prospects of thioonium sulfonate technology in energy, environmental protection, medicine and other fields are becoming more apparent. With its unique chemical properties and multifunctionality, thioonium sulfonate technology is becoming one of the key technologies in many fields. Summary of the Invention

[0005] The purpose of this invention is to provide a novel thioonium sulfonate-derived photoacid generator, its preparation method, and a photoresist, which can be used as a high-purity electronic-grade photoacid generator.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] A thioonium sulfonate-derived photoacid-generating agent having a structure as shown in A6.

[0008] A6: .

[0009] A method for preparing the photoacid-generating agent as described in claim 1, comprising the following steps:

[0010] ,

[0011] The compound shown in A3 reacts with the compound shown in A5 to give a photoacid-producing agent as shown in A6.

[0012] In an optional embodiment, in the preparation method of the photoacid generator shown in A6, the compound shown in A3 and the compound shown in A5 are mixed with dichloromethane and reacted to obtain the photoacid generator shown in A6.

[0013] The molar ratio of the compound shown in A3 to the compound shown in A5 is 1:(1-2.5), and the volume ratio of the compound shown in A3 to dichloromethane is 1:(8-10).

[0014] In an optional embodiment, the compound shown in A3 is obtained by the following preparation method:

[0015] ,

[0016] Step S5: Stir the compound shown in A1 with chloroform, cool to 0 to -10°C, add acid dropwise, and after the addition is complete, maintain the internal temperature at 5 to -5°C, add brominating agent dropwise, and after the addition is complete, maintain the internal temperature at 20 to 30°C to obtain the compound shown in A2.

[0017] Step S6: Mix the compound shown in A2 with dichloromethane, add 1-oxo-1,4-thiaoxane, cool to -20 to -30°C, add trifluoroacetic anhydride dropwise, and after the addition is complete, keep the internal temperature below -10°C to obtain the compound shown in A3.

[0018] In one alternative embodiment,

[0019] Step S5 specifically includes: stirring the compound shown in A1 with chloroform, cooling to -5°C, adding glacial acetic acid dropwise, maintaining the internal temperature at 0°C after the addition is complete, adding bromine dropwise, maintaining the internal temperature at 25°C after the addition is complete, and reacting for 3-5 hours to obtain the compound shown in A2; and / or,

[0020] Step S6 specifically includes: mixing the compound shown in A2 with dichloromethane, adding 1-oxo-1,4-thiaoxane, cooling to -23°C, adding trifluoroacetic anhydride dropwise, and after the addition is complete, maintaining the internal temperature at -20°C and stirring for 2-3 hours to obtain the compound shown in A3; and / or,

[0021] In step S5, the brominating agent is selected from any one or more of bromine, hydrobromic acid, NBS, DBH, copper bromide, and PyHBz; and / or,

[0022] In step S5, the acid is selected from any one or more of glacial acetic acid, hydrobromic acid, and TsOH; and / or,

[0023] In step S5, the molar ratio of the compound shown in A1, the acid, and the brominating agent is 1:(1.5-2.5):(1.0-1.5), and the volume ratio of the compound shown in A1 to chloroform is 1:(5-20); and / or,

[0024] In step S6, the molar ratio of the compound shown in A2, 1-oxo-1,4-thiaoxane, and trifluoroacetic anhydride is 1:(1.1-2.0):(1.5-2.5), and the volume ratio of the compound shown in A2 to dichloromethane is 1:(8-15).

[0025] In an optional embodiment, the compound shown in A3 is obtained by the following preparation method:

[0026] ,

[0027] Step S2: Cool the first solvent to below -60°C, add the second base, keep the reaction temperature below -50°C, add N,N-dimethylpropenylurea, keep the reaction temperature below -50°C, add the compound shown in A1, after the addition is complete, keep the reaction temperature below -50°C, add trimethylchlorosilane, keep the reaction temperature below -30°C, and obtain the compound shown in B2.

[0028] Step S3: Mix the compound shown in B2 with the second solvent, add 1-oxo-1,4-thiaoxane, cool to below -20°C, add trifluoroacetic anhydride dropwise, and after the addition is complete, keep the internal temperature below -10°C to obtain the compound shown in A3.

[0029] In one alternative embodiment,

[0030] Step S2 specifically includes: cooling tetrahydrofuran to -65°C, adding a second base dropwise while maintaining the reaction temperature at -60°C, adding N,N-dimethylpropenylurea dropwise while maintaining the reaction temperature at -60°C, adding the compound shown in A1 dropwise, maintaining the reaction temperature at -60°C after the addition is complete, stirring for 30-60 minutes while maintaining the reaction temperature at -40°C, and stirring for 2-4 hours to obtain the compound shown in B2; and / or,

[0031] Step S3 specifically includes: mixing the compound shown in B2 with dichloromethane, adding 1-oxo-1,4-thiaoxane, cooling to -23°C, adding trifluoroacetic anhydride dropwise, and after the addition is complete, maintaining the internal temperature at -20°C and stirring for 1-3 hours to obtain the compound shown in A3; and / or,

[0032] In step S2, the molar ratio of the compound shown in A1, the second base, N,N-dimethylpropenylurea, and trimethylchlorosilane is 1:(1.1-1.5):(1.1-2):(1.1-2), and the volume ratio of the compound shown in A1 to the first solvent is 1:(2-3); and / or,

[0033] The second base is selected from any one or more of sodium bis(trimethylsilyl)amino, lithium bis(trimethylsilyl)amino, and potassium bis(trimethylsilyl)amino; and / or,

[0034] In step S3, the molar ratio of the compound shown in B2, 1-oxo-1,4-thiaoxane and trifluoroacetic anhydride is 1:(0.9-1.5):(1.0-2), and the volume ratio of the compound shown in B2 to dichloromethane is 1:(8-15).

[0035] In an optional embodiment, the compound shown in A5 is obtained using the following preparation method:

[0036] ,

[0037] Step S1: 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride is reacted with the compound shown in S1 in the presence of the first base to obtain the compound shown in A4, and then reacted with an aqueous sodium hydroxide solution to obtain the compound shown in A5.

[0038] In step S1, the first base is selected from any one or more of triethylamine, potassium carbonate, cesium carbonate, and sodium hydride.

[0039] In one alternative embodiment,

[0040] Step S1 specifically includes: mixing 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride and a third solvent, cooling to 0 to -10°C, adding the compound shown in S1, maintaining the internal temperature at 0 to -10°C, adding triethylamine dropwise, and after the reaction, adding an aqueous sodium hydroxide solution to obtain the compound shown in A5 in one step.

[0041] The third solvent is selected from any one or more of acetonitrile, tetrahydrofuran, triethylamine, dichloromethane, and N,N-dimethylformamide; and / or,

[0042] In step S1, the molar ratio of the compound shown in S1, 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride, the first base, and sodium hydroxide is 1:(1-2):(1.5-2):(1.2-2), the concentration of the sodium hydroxide aqueous solution is 15wt%-25wt%, and the volume ratio of the compound shown in S1 to the third solvent is 1:(10-30).

[0043] A photoresist comprising the aforementioned photoacid-generating agent. The photoresist may include a photosensitive resin, a photosensitizer, a photoacid-generating agent, and a solvent, etc., and the components and proportions of the photoresist can be formulated using known techniques.

[0044] Compared with the prior art, the beneficial effects of the present invention include at least the following:

[0045] 1. Step S1 uses a one-step synthesis method to obtain a compound with the structure shown in A5, with a yield of over 90%. No by-products are produced during the reaction, simplifying the production process and reducing raw material costs.

[0046] 2. In the post-processing step S2, silica gel quenching is used to avoid the problem of silane hydrolysis upon contact with water, which can improve the yield.

[0047] 3. During the reaction process in step S2, the reaction temperature is strictly controlled to be below -40℃, which can effectively avoid product hydrolysis.

[0048] 4. During the reaction in step S3, the reaction temperature is strictly controlled to be below -20℃. Trifluoroacetic anhydride is added dropwise instead of trifluoroacetic anhydride activator, which improves the reaction rate. At the same time, by controlling the dropping rate, silane hydrolysis can be effectively avoided.

[0049] 5. In the post-treatment water washing process of step S3, controlling the volume ratio of dichloromethane to water to be 10:1 or 12:1 can effectively prevent the product from dissolving in water and improve the yield.

[0050] 6. In the purification process of step S3, controlling the volume ratio of petroleum ether to ethyl acetate to be 50:1 or 30:1 can effectively prevent the product from dissolving in water, effectively remove impurities, effectively improve the purity of the product, and avoid a large loss of product during the purification process.

[0051] 7. In the reaction process of step S4, the feeding ratio of A5 and A3 is controlled at 1:2, which can effectively avoid A5 residue, which would lead to the product containing A5 that cannot be purified. The excess A3 can be completely removed in the post-treatment water washing, effectively improving the purity of the product. Attached Figure Description

[0052] Figure 1 This is the HNMR spectrum of the compound shown in embodiment B2 of the present invention.

[0053] Figure 2 This is the HNMR spectrum of the compound shown in embodiment A3 of the present invention.

[0054] Figure 3 This is the FNMR spectrum of the compound shown in embodiment A3 of the present invention.

[0055] Figure 4 This is the HNMR spectrum of the compound shown in embodiment A5 of the present invention.

[0056] Figure 5 This is the FNMR spectrum of the compound shown in embodiment A5 of the present invention.

[0057] Figure 6 This is the HNMR spectrum of the compound shown in embodiment A6 of the present invention.

[0058] Figure 7 This is the FNMR spectrum of the compound shown in embodiment A6 of the present invention.

[0059] Figure 8 This is the HPLC spectrum of the compound shown in embodiment A6 of the present invention. Detailed Implementation

[0060] The exemplary embodiments will now be described more fully. However, the exemplary embodiments can be implemented in many forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided to make the invention more comprehensive and complete, and to fully convey the concept of the exemplary embodiments to those skilled in the art.

[0061] The photo-induced acid-producing agent of the present invention can be prepared by two preparation routes, route A and route B.

[0062] Route A is as follows:

[0063]

[0064] Route B is as follows:

[0065]

[0066] The difference between Route A and Route B lies in the preparation method of the compound shown in A3; the rest of the process is the same. Specifically, in Route A, the compound shown in A1 generates the compound shown in A2, and then the compound shown in A3; in Route B, the compound shown in A1 generates the compound shown in B2, and then the compound shown in A3.

[0067] The detailed preparation process of route B includes steps S1-S4.

[0068] Step S1: 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride is reacted with the compound shown in S1 (decahydroisoquinoline) in the presence of a first base to obtain the compound shown in A4, which is then reacted with an aqueous sodium hydroxide solution to obtain the compound shown in A5.

[0069] In one embodiment, the first base is selected from any one or more of triethylamine, potassium carbonate, cesium carbonate, and sodium hydride.

[0070] Step S1 may specifically include: mixing 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride and a third solvent, cooling to 0 to -10°C, adding the compound shown in S1, maintaining the internal temperature at 0 to -10°C, adding triethylamine dropwise, and after the reaction, adding an aqueous sodium hydroxide solution to obtain the compound shown in A5 in one step. The third solvent is selected from any one or more of acetonitrile, tetrahydrofuran, triethylamine, dichloromethane, and N,N-dimethylformamide. In one embodiment, the third solvent is selected from acetonitrile.

[0071] In one embodiment, the molar ratio of the compound shown in S1, 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride, the first base, and sodium hydroxide is 1:(1-2):(1.5-2):(1.2-2), for example, 1:1.5:1.7:1.7. The concentration of the aqueous sodium hydroxide solution is 15wt%-25wt%. The volume ratio (g / ml) of the compound shown in S1 (g) to the third solvent (ml) is 1:(10-30), for example, 1:10, 1:15, 1:20, or 1:25.

[0072] Step S2: Cool the first solvent to below -60°C, add the second base, keep the reaction temperature below -50°C, add N,N-dimethylpropenylurea, keep the reaction temperature below -50°C, add the compound shown in A1, after the addition is complete, keep the reaction temperature below -50°C, add trimethylchlorosilane, keep the reaction temperature below -30°C, and obtain the compound shown in B2.

[0073] In one embodiment, the molar ratio of the compound shown in A1, the second base, N,N-dimethylpropenylurea, and trimethylchlorosilane is 1:(1.1-1.5):(1.1-2):(1.1-2), for example, 1:1.2:1.2:1.2, 1:1.3:1.4:1.5, or 1:1.4:1.5:1.7, and the volume ratio (g / ml) of the compound shown in A1 (g) to the first solvent (ml) is 1:(2-3). The second base is selected from any one or more of sodium bis(trimethylsilyl)amino, lithium bis(trimethylsilyl)amino, and potassium bis(trimethylsilyl)amino. In use, the second base can be a THF solution of sodium bis(trimethylsilyl)amino, a THF solution of lithium bis(trimethylsilyl)amino, or a THF solution of potassium bis(trimethylsilyl)amino.

[0074] Step S2 may specifically include: cooling tetrahydrofuran to -65°C, adding a second base dropwise while maintaining the reaction temperature at -60°C, adding N,N-dimethylpropenylurea dropwise while maintaining the reaction temperature at -60°C, adding the compound shown in A1 dropwise, maintaining the reaction temperature at -60°C after the addition is complete, stirring for 30-60 minutes, adding trimethylchlorosilane dropwise while maintaining the reaction temperature at -40°C, and stirring for 2-4 hours to obtain the compound shown in B2.

[0075] Step S3: Mix the compound shown in B2 with the second solvent, add 1-oxo-1,4-thiaoxane, cool to below -20°C, add trifluoroacetic anhydride dropwise, and after the addition is complete, keep the internal temperature below -10°C to obtain the compound shown in A3.

[0076] In one embodiment, the molar ratio of the compound shown in B2, 1-oxo-1,4-thiaoxane, to trifluoroacetic anhydride is 1:(0.9-1.5):(1.0-2), for example, 1:1:1.1, 1:1.1:1.5, 1:1.4:1.8, and the volume ratio (g / ml) of the compound shown in B2 to dichloromethane is 1:(8-15), for example, 1:10.

[0077] Step S3 may specifically include: mixing the compound shown in B2 with dichloromethane, adding 1-oxo-1,4-thiaoxane, cooling to -23°C, adding trifluoroacetic anhydride dropwise, and after the addition is complete, maintaining the internal temperature at -20°C and stirring for 1-3 hours to obtain the compound shown in A3.

[0078] Step S4: The compound shown in A3 reacts with the compound shown in A5 to obtain the photoacid-producing agent shown in A6.

[0079] Step S2 may specifically include: mixing the compound shown in A3 and the compound shown in A5 with dichloromethane, and reacting to obtain a photo-induced acid-producing agent as shown in A6.

[0080] In one embodiment, the molar ratio of the compound shown in A3 to the compound shown in A5 is 1:(1-2.5), for example, 1:1.5, 1:2, and the volume ratio (g / ml) of the compound shown in A3 (g) to dichloromethane (ml) is 1:(8-20), for example, 1:10, 1:15.

[0081] The method of route A for the compound shown in A3 may include steps S5-S6.

[0082] Step S5: Stir the compound shown in A1 with chloroform, cool to 0 to -10°C, add acid dropwise, and after the addition is complete, maintain the internal temperature at 5 to -5°C, add brominating agent dropwise, and after the addition is complete, maintain the internal temperature at 20 to 30°C to obtain the compound shown in A2.

[0083] In one embodiment, the brominating agent may be selected from any one or more of bromine, hydrobromic acid, NBS, DBH, copper bromide, and PyHBz. The acid may be selected from any one or more of glacial acetic acid, hydrobromic acid, and TsOH. The molar ratio of the compound, acid, and brominating agent shown in A1 is 1:(1.5-2.5):(1.0-1.5), for example, 1:1.8:1.1, 1:2:1.2, and the volume ratio (g / ml) of the compound (g) shown in A1 to chloroform (ml) is 1:(5-20), for example, 1:10, 1:15.

[0084] Step S5 may specifically include: stirring the compound shown in A1 with chloroform, cooling to -5°C, adding glacial acetic acid dropwise, maintaining the internal temperature at 0°C after the addition is complete, adding bromine dropwise, maintaining the internal temperature at 25°C after the addition is complete, and reacting for 3-5 hours to obtain the compound shown in A2.

[0085] Step S6: Mix the compound shown in A2 with dichloromethane, add 1-oxo-1,4-thiaoxane, cool to -20 to -30°C, add trifluoroacetic anhydride dropwise, and after the addition is complete, keep the internal temperature below -10°C to obtain the compound shown in A3.

[0086] Step S6 may specifically include: mixing the compound shown in A2 with dichloromethane, adding 1-oxo-1,4-thiaoxane, cooling to -23°C, adding trifluoroacetic anhydride dropwise, and after the addition is complete, maintaining the internal temperature at -20°C and stirring for 2-3 hours to obtain the compound shown in A3.

[0087] In one embodiment, the molar ratio of the compound shown in A2, 1-oxo-1,4-thiaoxane, to trifluoroacetic anhydride is 1:(1.1-2.0):(1.5-2.5), for example, 1:1.5:1.8, 1:1.8:2.0, and the volume ratio (g / ml) of the compound shown in A2 to dichloromethane is 1:(8-15), for example, 1:10.

[0088] Example 1:

[0089] Step S1: Add 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride (10 g, 31.63 g) to the solution. Mix 100 mL of acetonitrile (1 mmol) and 100 mL of dichloromethane, cool to -3 °C, and under nitrogen protection, add decahydroisoquinoline (3.96 g, 28.47 mmol), maintain the internal temperature at -3 °C, and add triethylamine (4.32 g, 42.71 mmol) dropwise. After the addition is complete, under nitrogen protection, maintain the internal temperature at -3 °C for 5 h to carry out the substitution reaction. For post-treatment, add 25 wt% sodium hydroxide (1.71 g, 42.71 mmol) aqueous solution. After the reaction is complete, add water with a volume ratio of dichloromethane to water of 10:1, wash three times with water, add saturated brine, maintain the volume ratio of dichloromethane to saturated brine of 15:1, wash twice with saturated brine, collect the organic phase, evaporate to dryness, add methyl ether with a volume ratio of 1:5, slurry overnight, discard the supernatant, evaporate to dryness to obtain a compound with the structure shown in A5 (12.44 g, 27.33 mmol), with a yield of 96%. 1 HNMR spectrum (400MHz, CDCl3) and 19 FNMR spectrum (400MHz, CDCl3) see Figure 4 and Figure 5 .

[0090] (A5)

[0091] Comparative Example 1:

[0092] Step S1 was modified as follows: 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride (10 g, 31.63 mmol) and tetrahydrofuran (100 mL) were mixed, cooled to -3 °C, and decahydroisoquinoline (3.96 g, 28.47 mmol) was added. Triethylamine (4.32 g, 42.71 mmol) was added dropwise. After the addition was complete, the mixture was reacted at room temperature for 6 h to carry out the substitution reaction. 25% sodium hydroxide (1.71 g, 42.71 mmol) was added as a post-treatment. After the reaction was completed, the mixture was washed three times with saturated brine, and the organic phase was collected and evaporated to dryness to obtain a compound with the structure shown in A5 (9.08 g, 19.93 mmol), with a yield of 63%.

[0093] Comparison results:

[0094] Example 1 added nitrogen protection and the reaction was carried out at low temperature, which effectively avoided the generation of by-products. The reaction yield was as high as 96% and the purity was 91%. Comparative Example 1, due to the lack of nitrogen protection and the reaction being carried out at room temperature, resulted in the production of by-products, resulting in a darker product with a purity of 75%.

[0095] Example 2:

[0096] Step S2: Stir 16 mL of tetrahydrofuran and cool to -65°C under nitrogen protection. Add a THF solution of sodium bis(trimethylsilyl)aminosodium (42.66 mL, 42.66 mmol), maintaining the internal temperature at -60°C. Add 7.46 g of N,N-dimethylpropenylurea (58.17 mmol). The compound A1 (bis-1-(4-methoxyphenyl)-3,3-methylbutane-1-one) (8 g, 38.78 mmol) was added dropwise while maintaining an internal temperature of -60 °C. After the addition was complete, the internal temperature was maintained at -60 °C and the mixture was stirred for 40 minutes. Trimethylchlorosilane (6.32 g, 58.17 mmol) was then added dropwise. After the addition was complete, the internal temperature was maintained below -40 °C and the reaction was allowed to proceed for 3 hours. Once the reaction was complete, petroleum ether was added at a volume ratio of 1:1 to the reaction solution. The internal temperature was maintained below 40 °C. Silica gel containing sodium bis(trimethylsilyl)aminosodium and silica gel in an equivalent ratio of 1:2 was added, and the mixture was stirred for 30 minutes. The mixture was filtered, the filtrate was evaporated to dryness, and the solution was subjected to chromatography. The column was flushed with petroleum ether to obtain a compound with the structure shown in B2 (8.64 g, 31.02 mmol), with a yield of 80%. 1 The HNMR spectrum (400MHz, CDCl3) is shown below. Figure 1 .

[0097] (B2)

[0098] Comparative Example 2:

[0099] Step S2 is modified as follows: A solution of sodium bis(trimethylsilyl)amino (10.67 mL, 10.67 mmol) in 4 mL of THF is cooled to -78 °C under nitrogen protection. N,N-dimethylpropenylurea (1.86 g, 14.55 mmol) is added, followed by the compound shown in A1 (1-(4-methoxyphenyl)-3,3-dimethylbutane-1-one) (2 g, 9.70 mmol) (dissolved in 5 mL THF). After 20 minutes, trichlorosilane (1.58 g, 14.55 mmol) (dissolved in 1 mL THF) is added. The reaction mixture becomes viscous. After maintaining at -78 °C for 30 minutes, the mixture is warmed to room temperature and stirred for 2–4 hours. The reaction mixture is partitioned between pentane and phosphate buffer at pH 7. The organic layer is washed with phosphate buffer at pH 7, 5% cold HCl aqueous solution, saturated NaHCO3 aqueous solution, and brine, and then with Na2SO4. The material was dried and concentrated under vacuum. The unpurified material was passed through a SiO2 or Florisil (2-inch, first equilibrated with 100% Et2O, then equilibrated with the desired solvent system) column, eluted with 2-5% Et2O / pentane, to give a compound with the structure shown in B2 (0.81 g, 2.91 mmol), which was cured after several months.

[0100] Comparison results:

[0101] In Example 2, the reaction process was carried out at a temperature below -40°C under nitrogen protection, which effectively prevented the hydrolysis of the deprotonating agent and the product. In the post-processing, silica gel was used to quench the deprotonating agent, which effectively prevented the product from contacting water and hydrolyzing, resulting in a yield of 80%. In Comparative Example 2, the reaction at room temperature caused the product to hydrolyze simultaneously with the reaction, resulting in 50% raw material residue. In the post-processing, contact with water resulted in complete or partial hydrolysis of the product, and the reaction yield was only 30%.

[0102] Example 3:

[0103] Step S3: Mix the compound shown in B2 prepared in S2 (5 g, 17.96 mmol) with dichloromethane (50 mL), add 1-oxo-1,4-thiaoxane (2.16 g, 17.96 mmol), cool to -23 °C, under nitrogen protection, add trifluoroacetic anhydride (4.15 g, 19.76 mmol) dropwise. After the addition is complete, maintain the internal temperature at -20 °C and stir for 2 h. When the reaction is complete, add deionized water at a volume ratio of 10:1, wash three times with deionized water, collect the organic phase, and add the organic phase to a 1% citric acid aqueous solution at a volume ratio of 1:1. The organic phase was washed three times with citric acid at a ratio of 0:1, and collected. Then, deionized water (organic phase to deionized water volume ratio of 10:1) was added, and the mixture was washed three times. The organic phase was collected again, and saturated brine (organic phase to saturated brine volume ratio of 8:1) was added. The organic phase was collected, dried over anhydrous sodium sulfate, and evaporated to dryness. A mixture of petroleum ether and ethyl acetate (volume ratio of 50:1) was added, and the mixture was stirred and slurried at -20°C. The mixture was filtered to obtain a compound with the structure shown in A3 (6.83 g, 16.16 mmol), with a yield of 90%. 1 HNMR spectrum (400MHz, CDCl3) and 19 FNMR spectrum (400MHz, CDCl3) see Figure 2 and Figure 3 .

[0104] (A3)

[0105] Comparative Example 3:

[0106] Step S3 is modified as follows: Prepare a dichloromethane solution containing [(1-(4-methoxyphenyl)-3,3-dimethylbut-1-en-1-yl)oxy]trimethylsilane (the compound shown in B2) and 1,4-dioxane as the raw material mixture solution. Prepare a dichloromethane solution containing trifluoroacetic anhydride as the activator solution. Set the thermostat to -15°C (reaction temperature is -15°C). Use a pump to feed the raw material mixture solution into flow path (1) from inlet (Ia) at a flow rate of 3.43 mL / min. Use a pump to feed the activator solution into flow path (2) from inlet (Ib) at a flow rate of 2.34 mL / min. The residence time (reaction time) under the above conditions is 180 seconds. After being fully replaced by the above solution or mixture in the system, the reaction liquid discharged from the reaction flow path (4) is collected into the sample container.

[0107] Comparison results:

[0108] Example 3 mainly uses reaction flasks and has a complete post-processing purification process. Comparative Example 3 uses channel reactions, which involves more complex equipment and has unclear post-processing.

[0109] Example 4:

[0110] Step S4: The compound A3 (10 g, 23.67 mmol) prepared in S3 was mixed with dichloromethane (100 mL), and the compound A5 (21.56 g, 47.34 mmol) prepared in S1 was added. The mixture was stirred for 2 h while maintaining an internal temperature of 25 °C until the reaction was complete. A 1% citric acid aqueous solution (volume ratio of reaction solution to 1% citric acid aqueous solution) was added, and the mixture was washed three times with acid. Deionized water (volume ratio of organic phase to deionized water) (volume ratio of organic phase to deionized water) was added, and the mixture was washed three times with water. The mixture was then evaporated to dryness. A mixed solvent of petroleum ether and dichloromethane (volume ratio of 20:1) was added, and the mixture was stirred at 10 V for 2 h. The supernatant was discarded, and a mixed solvent of methyl ether and methanol (volume ratio of 20:1) was added, and the mixture was stirred at 3 V for 2 h. The mixture was filtered to obtain a compound with the structure shown in A6 (15.27 g, 20.59 mmol), with a yield of 87%. 1 HNMR spectrum (400MHz, CDCl3) 19 The FNMR spectrum (400MHz, CDCl3) and HPLC spectrum are shown below. Figure 6 , Figure 7 and Figure 8 .

[0111] (A6)

[0112] Comparative Example 4:

[0113] Step S4 is modified as follows: The compound A3 (5g, 11.84mmol) prepared in S3 is mixed with methanol (100mL), and anion exchange resin (BAMB140) (50mL) is added. The mixture is stirred for 2h while maintaining an internal temperature of 25℃. After filtration, the filtrate is collected and added to anion exchange resin (BAMB140) (10mL). The mixture is stirred for 2h and then filtered. The filtrate is collected and added to the compound A5 (10.78g, 23.68mmol) prepared in S1. After the reaction is complete, the mixture is filtered, evaporated to dryness, and then stirred for 2h at 10V with a mixed solvent of petroleum ether and dichloromethane in a volume ratio of 20:1. The supernatant is discarded, and then stirred for 2h at 3V with a mixed solvent of methyl ether and methanol in a volume ratio of 20:1. The mixture is then filtered to obtain a compound with the structure shown in A6 (5.53g, 7.46mmol).

[0114] Comparison results:

[0115] In Example 4, during the reaction process, A3 and A5 were dissolved in dichloromethane for ion exchange, which effectively prevented the anion exchange resin from adsorbing A3 and causing a large loss of raw materials, resulting in a yield of 87%. In Comparative Example 4, due to the large amount of anion exchange resin used, the raw material A3 was inevitably adsorbed, affecting the purity of A3 and thus affecting the yield, which was only 63%.

[0116] Example 5:

[0117] Step S5: The compound shown in A1 (1-(4-methoxyphenyl)-3,3-dimethylbutane-1-one) (5 g, 24.24 mmol) was stirred with chloroform (50 mL), cooled to -5 °C, and glacial acetic acid (2.91 g, 48.48 mmol) was added dropwise. After the addition was complete, the internal temperature was maintained at -0 °C, and bromine (4.26 g, 26.66 mmol) was added dropwise. After the addition was complete, the internal temperature was maintained at 25 °C, and the reaction was carried out for 4 h to obtain the compound with the structure shown in A2 (5.05 g, 17.70 mmol), with a yield of 73%.

[0118] (A2)

[0119] Example 6:

[0120] Step S6: Mix the compound shown in A2 prepared in S5 (10 g, 35.07 mmol) with dichloromethane (100 mL), add 1-oxo-1,4-thiaoxane (6.32 g, 52.60 mmol), cool to -23 °C, under nitrogen protection, add trifluoroacetic anhydride (14.72 g, 70.10 mmol) dropwise. After the addition is complete, maintain the internal temperature at -20 °C and stir for 2 h. When the reaction is complete, add deionized water at a volume ratio of 10:1, wash three times with deionized water, collect the organic phase, and add the organic phase to a 1% citric acid aqueous solution at a volume ratio of... The organic phase was washed three times with citric acid at a ratio of 10:1, and the organic phase was collected. Deionized water at a volume ratio of 10:1 was added, and the mixture was washed three times. The organic phase was collected again, and saturated brine at a volume ratio of 8:1 was added. The organic phase was collected, dried over anhydrous sodium sulfate, and evaporated to dryness. A mixture of petroleum ether and ethyl acetate at a volume ratio of 50:1 (5V) was added, and the mixture was stirred and slurried. The supernatant was discarded, and the process was repeated three times. The mixture was evaporated to dryness, and isopropyl ether at 3V was added. The mixture was stirred and slurried at -20°C, and filtered to obtain the compound with the structure shown in A3 (8.30 g, 19.64 mmol), with a yield of 56%.

[0121] (A3)

[0122] Example 7:

[0123] Step S1: Mix 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride (5 g, 15.82 mmol) and triethylamine (100 mL), cool to -3 °C, and under nitrogen protection, add decahydroisoquinoline (1.98 g, 14.24 mmol). Maintain the internal temperature at -3 °C. After the addition is complete, continue the reaction under nitrogen protection at -3 °C for 5 hours to carry out the substitution reaction. Once the reaction is complete, evaporate to dryness. For post-treatment, add 25 wt% sodium hydroxide (0.86 g, 21.36 mmol) aqueous solution. Once the reaction is complete, add dichloromethane. The mixture was washed three times with water at a volume ratio of 10:1 for alkane and water. Then, a 10:1 volume ratio of dichloromethane to 5% citric acid aqueous solution was added, followed by three acid washes. This process was repeated three times with water at the same volume ratio. Saturated brine was added, maintaining a 15:1 volume ratio of dichloromethane to saturated brine. The mixture was washed twice with saturated brine, and the organic phase was collected and evaporated to dryness. A 1:5 volume ratio of evaporated organic phase to tertiary methyl ether was added, and the mixture was stirred overnight. The supernatant was discarded, and the mixture was evaporated to dryness to obtain a compound with the structure shown in A5 (4.98 g, 10.94 mmol), in 77% yield.

[0124] (A5)

[0125] Example 8:

[0126] Step S1: Mix 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride (8 g, 25.30 mmol) and acetonitrile (80 mL), cool to -3°C, and under nitrogen protection, add decahydroisoquinoline (3.17 g, 25.30 mmol). Maintain the internal temperature at -3°C, and dropwise add cesium carbonate (12.36 g, 37.95 mmol). After the addition is complete, maintain the internal temperature at -3°C under nitrogen protection for 5 hours to carry out the substitution reaction. For post-treatment, add a 25 wt% sodium hydroxide aqueous solution (1.37 g, 34.17 mmol). After the reaction is complete... The organic phase was prepared by adding dichloromethane to water at a volume ratio of 10:1, washing three times with water, adding dichloromethane to 5% citric acid aqueous solution at a volume ratio of 10:1, washing three times with acid, adding dichloromethane to water at a volume ratio of 10:1, washing three times with water, adding saturated brine, maintaining a dichloromethane to saturated brine volume ratio of 15:1, washing twice with saturated brine, collecting the organic phase, evaporating to dryness, adding the evaporated organic phase to methyl tert-methyl ether at a volume ratio of 1:5, stirring overnight, discarding the supernatant, and evaporating to dryness to obtain a compound with the structure shown in A5 (8.06 g, 17.71 mmol), with a yield of 70%.

[0127] (A5)

[0128] Example 9:

[0129] Step S2: Stir 16 mL of tetrahydrofuran and cool to -65 °C under nitrogen protection. Add 42.66 mL (42.66 mmol) of bis(trimethylsilyl)aminolithium dropwise. The THF solution was kept at -60°C, and N,N-dimethylpropenylurea (7.46 g, 58.17 mmol) was added dropwise. The internal temperature was maintained at -60°C, and then compound A1 (bis-1-(4-methoxyphenyl)-3,3-dimethylbutane-1-one) (8 g, 38.78 mmol) was added dropwise. After the addition was complete, the internal temperature was maintained at -60°C, and the mixture was stirred for 40 minutes. Trimethylchlorosilane (6.32 g, 58.17 mmol) was added dropwise. After the addition was complete, the internal temperature was maintained below -40°C, and the reaction was allowed to proceed for 3 hours. The reaction solution was then diluted with petroleum ether at a volume ratio of 1:1, and the internal temperature was maintained below 40°C. Silica gel containing sodium bis(trimethylsilyl)aminosodium and silica gel in a 1:2 equivalent ratio was added, and the mixture was stirred for 30 minutes. The mixture was filtered, the filtrate was evaporated to dryness, and the solution was subjected to chromatography. The column was flushed with petroleum ether to obtain the compound with the structure shown in B2 (7.78 g, 27.92 mmol), with a yield of 72%.

[0130] (B2)

[0131] Example 10:

[0132] Step S2: Stir 10 mL of tetrahydrofuran and cool to -65 °C under nitrogen protection. Add 27.66 mL (27.66 mmol) of bis(trimethylsilyl)aminopotassium dropwise. The THF solution was kept at -60°C, and N,N-dimethylpropenylurea (4.66 g, 36.36 mmol) was added dropwise. The internal temperature was maintained at -60°C. Then, compound A1 (bis-1-(4-methoxyphenyl)-3,3-dimethylbutane-1-one) (5 g, 24.24 mmol) was added dropwise. After the addition was complete, the internal temperature was maintained at -60°C, and the mixture was stirred for 40 minutes. Trimethylchlorosilane (3.95 g, 36.36 mmol) was added dropwise. After the addition was complete, the internal temperature was maintained below -40°C, and the reaction was allowed to proceed for 3 hours. The reaction solution was then diluted with petroleum ether at a volume ratio of 1:1, and the internal temperature was maintained below 40°C. Silica gel containing sodium bis(trimethylsilyl)aminosodium and silica gel in a 1:2 equivalent ratio was added, and the mixture was stirred for 30 minutes. The mixture was filtered, the filtrate was evaporated to dryness, and the solution was subjected to chromatography. The column was flushed with petroleum ether to obtain the compound with the structure shown in B2 (4.38 g, 15.71 mmol), with a yield of 65%.

[0133] (B2)

[0134] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the invention without departing from the principles and spirit of the invention, and all such changes should fall within the protection scope of the claims of the present invention.

Claims

1. A photoacid-generating agent derived from thioonium sulfonate, characterized in that, The photo-induced acid-producing agent has the structure shown in A6. A6： 。 2. A method for preparing the photoacid-producing agent as described in claim 1, characterized in that, Includes the following steps: ， The compound shown in A3 reacts with the compound shown in A5 to give a photoacid-producing agent as shown in A6.

3. The preparation method of the photoacid-producing agent as described in claim 2, characterized in that, In the preparation method of the photoacid generator shown in A6, the compounds shown in A3 and A5 are mixed with dichloromethane and reacted to obtain the photoacid generator shown in A6. The molar ratio of the compound shown in A3 to the compound shown in A5 is 1:(1-2.5), and the volume ratio of the compound shown in A3 to dichloromethane is 1:(8-10).

4. The method for preparing the photoacid-producing agent as described in claim 2, characterized in that, The compound shown in A3 was obtained using the following preparation method: ， Step S5: Stir the compound shown in A1 with chloroform, cool to 0 to -10°C, add acid dropwise, and after the addition is complete, maintain the internal temperature at 5 to -5°C, add brominating agent dropwise, and after the addition is complete, maintain the internal temperature at 20 to 30°C to obtain the compound shown in A2. Step S6: Mix the compound shown in A2 with dichloromethane, add 1-oxo-1,4-thiaoxane, cool to -20 to -30°C, add trifluoroacetic anhydride dropwise, and after the addition is complete, keep the internal temperature below -10°C to obtain the compound shown in A3.

5. The preparation method of the photoacid-producing agent as described in claim 4, characterized in that, Step S5 specifically includes: stirring the compound shown in A1 with chloroform, cooling to -5°C, adding glacial acetic acid dropwise, maintaining the internal temperature at 0°C after the addition is complete, adding bromine dropwise, maintaining the internal temperature at 25°C after the addition is complete, and reacting for 3-5 hours to obtain the compound shown in A2; and / or, Step S6 specifically includes: mixing the compound shown in A2 with dichloromethane, adding 1-oxo-1,4-thiaoxane, cooling to -23°C, adding trifluoroacetic anhydride dropwise, and after the addition is complete, maintaining the internal temperature at -20°C and stirring for 2-3 hours to obtain the compound shown in A3; and / or, In step S5, the brominating agent is selected from any one or more of bromine, hydrobromic acid, NBS, DBH, copper bromide, and PyHBz; and / or, In step S5, the acid is selected from any one or more of glacial acetic acid, hydrobromic acid, and TsOH; and / or, In step S5, the molar ratio of the compound shown in A1, the acid, and the brominating agent is 1:(1.5-2.5):(1.0-1.5), and the volume ratio of the compound shown in A1 to chloroform is 1:(5-20); and / or, In step S6, the molar ratio of the compound shown in A2, 1-oxo-1,4-thiaoxane and trifluoroacetic anhydride is 1: (1.1-2.0): (1.5-2.5), and the volume ratio of the compound shown in A2 to dichloromethane is 1: (8-15).

6. The method for preparing the photoacid-producing agent as described in claim 2, characterized in that, The compound shown in A3 was obtained using the following preparation method: ， Step S2: Cool the first solvent to below -60°C, add the second base, keep the reaction temperature below -50°C, add N,N-dimethylpropenylurea, keep the reaction temperature below -50°C, add the compound shown in A1, after the addition is complete, keep the reaction temperature below -50°C, add trimethylchlorosilane, keep the reaction temperature below -30°C, and obtain the compound shown in B2. Step S3: Mix the compound shown in B2 with the second solvent, add 1-oxo-1,4-thiaoxane, cool to below -20°C, add trifluoroacetic anhydride dropwise, and after the addition is complete, keep the internal temperature below -10°C to obtain the compound shown in A3.

7. The method for preparing the photoacid-producing agent as described in claim 6, characterized in that, Step S2 specifically includes: cooling tetrahydrofuran to -65°C, adding a second base dropwise while maintaining the reaction temperature at -60°C, adding N,N-dimethylpropenylurea dropwise while maintaining the reaction temperature at -60°C, adding the compound shown in A1 dropwise, maintaining the reaction temperature at -60°C after the addition is complete, stirring for 30-60 minutes while maintaining the reaction temperature at -40°C, and stirring for 2-4 hours to obtain the compound shown in B2; and / or, Step S3 specifically includes: mixing the compound shown in B2 with dichloromethane, adding 1-oxo-1,4-thiaoxane, cooling to -23°C, adding trifluoroacetic anhydride dropwise, and after the addition is complete, maintaining the internal temperature at -20°C and stirring for 1-3 hours to obtain the compound shown in A3; and / or, In step S2, the molar ratio of the compound shown in A1, the second base, N,N-dimethylpropenylurea, and trimethylchlorosilane is 1:(1.1-1.5):(1.1-2):(1.1-2), and the volume ratio of the compound shown in A1 to the first solvent is 1:(2-3); and / or, The second base is selected from any one or more of sodium bis(trimethylsilyl)amino, lithium bis(trimethylsilyl)amino, and potassium bis(trimethylsilyl)amino; and / or, In step S3, the molar ratio of the compound shown in B2, 1-oxo-1,4-thiaoxane and trifluoroacetic anhydride is 1: (0.9-1.5): (1.0-2), and the volume ratio of the compound shown in B2 to dichloromethane is 1: (8-15).

8. The method for preparing the photoacid-producing agent as described in claim 2, characterized in that, The compound shown in A5 was obtained using the following preparation method: ， Step S1: 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride is reacted with the compound shown in S1 in the presence of the first base to obtain the compound shown in A4, and then reacted with an aqueous sodium hydroxide solution to obtain the compound shown in A5. In step S1, the first base is selected from any one or more of triethylamine, potassium carbonate, cesium carbonate, and sodium hydride.

9. The method for preparing the photoacid-producing agent as described in claim 8, characterized in that, Step S1 specifically includes: mixing 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride and a third solvent, cooling to 0 to -10°C, adding the compound shown in S1, maintaining the internal temperature at 0 to -10°C, adding triethylamine dropwise, and after the reaction, adding an aqueous sodium hydroxide solution to obtain the compound shown in A5 in one step. The third solvent is selected from any one or more of acetonitrile, tetrahydrofuran, triethylamine, dichloromethane, and N,N-dimethylformamide; and / or, In step S1, the molar ratio of the compound shown in S1, 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride, the first base, and sodium hydroxide is 1:(1-2):(1.5-2):(1.2-2), the concentration of the sodium hydroxide aqueous solution is 15wt%-25wt%, and the volume ratio of the compound shown in S1 to the third solvent is 1:(10-30).

10. A photoresist, characterized in that, The photoresist includes the photoacid generator as described in claim 1.

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