Synthesis method of diphenyl (p-tolyl) sulfonium perfluorobutyl-1-sulfonate and synthesis method of intermediate of diphenyl (p-tolyl) sulfonium perfluorobutyl-1-sulfonate

Abstract

The invention discloses a synthesis method of diphenyl (p-tolyl) sulfonium perfluorobutyl-1-sulfonate and a synthesis method of an intermediate of the diphenyl (p-tolyl) sulfonium perfluorobutyl-1-sulfonate, p-methylphenyl magnesium bromide and diphenyl sulfoxide are used as raw materials and are subjected to substitution reaction under the catalytic action of trimethylchlorosilane to directly synthesize diphenyl (p-tolyl) sulfonium salt, and the intermediate of the diphenyl (p-tolyl) sulfonium salt is synthesized into the intermediate of the diphenyl (p-tolyl) sulfonium perfluorobutyl-1-sulfonate. Extracting, purifying, filtering and drying to obtain the intermediate; carrying out reflux reaction on the intermediate and perfluorobutanesulfonic acid metal salt in an organic solvent, and after the reflux reaction is finished, filtering, concentrating, pulping, filtering again, washing filtrate and concentrating again to obtain a target product diphenyl (p-tolyl) sulfonium perfluorobutyl-1-sulfonate product. The intermediate prepared by the method is high in purity and low in production cost, can be used for preparing products meeting the basic requirements of electronic chemical raw materials, and is suitable for industrial use.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of electronic chemistry, and relates to a synthesis method of a resistant triphenyl sulfonium salt for photoresist, in particular to a synthesis method of diphenyl (p-tolyl) sulfonium perfluorobutyl-1-sulfonate and a synthesis method of an intermediate thereof. BACKGROUND

[0002] Sulfonium salts are often used as photo-acid generators in chemically amplified photoresists. Such substances can absorb certain wavelengths of energy in the ultraviolet or visible light region, generating free radicals, cations, etc., thereby initiating the polymerization and crosslinking of monomers to form a cured compound. However, such substances have a certain solubility in water, and when applied to immersion exposure technology, they can precipitate from the photoresist and dissolve into the deionized water filling medium, causing damage to the lens. The introduction of fluorine atoms into such substances helps to improve hydrophobicity, which can effectively improve the rear contact angle of the photoresist layer. However, if the surface contact angle of the photoresist after development is high, it is easy to produce spot defects. Therefore, hydrophilic groups such as sulfonic acid can also be introduced to effectively inhibit the generation of spot defects.

[0003] The target product of the present application, diphenyl (p-tolyl) sulfonium perfluorobutyl-1-sulfonate (structure formula as follows), is such a new type of photo-acid generator. This product can ensure high resolution and good defined pattern profile after development, and minimize defects (residues) left after development and resist removal, thus having the effects of high sensitivity, high resolution, and anti-etching, etc.

[0004] Structure formula:

[0005] One of the routes for synthesizing such substances is to react the corresponding sulfonium salt intermediate with a perfluoro metal sulfonate under heating conditions. For example, the Chinese invention patent application No. 202110289166.X “Preparation method of triphenyl sulfonium perfluorobutyl sulfonate” uses triphenyl sulfonium bromide and sodium perfluorobutyl sulfonate as raw materials, reacts in a composite solvent under heating conditions for 8-10 hours, and after the reaction is complete, the crude product of triphenyl sulfonium perfluorobutyl sulfonate is separated, and then the finished product is obtained by recrystallization. However, even after recrystallization, the purity of the obtained finished product can only reach 99.0%. This is because the process route is relatively short, and the removal rate of impurities in the process is not enough, and the impurities introduced by the starting material triphenyl sulfonium bromide are difficult to remove.

[0006] Therefore, it is necessary to further study the synthesis method of sulfonium salt to prepare high-purity target products. SUMMARY

[0007] The present application aims to overcome the deficiencies of the prior art, and optimizes the synthesis method of sulfonium salt, improves the purity of the intermediate, and then prepares the target product with high purity to meet the requirements of the product as a raw material for photoresist products.

[0008] The technical scheme adopted by the present application is a synthesis method of diphenyl(p-methylphenyl)sulfonium perfluorobutyl-1-sulfonate, and the key lies in that the synthesis method is a two-step method for preparing diphenyl(p-methylphenyl)sulfonium perfluorobutyl-1-sulfonate, and the specific steps are as follows:

[0009] S1, preparing the intermediate of diphenyl(p-methylphenyl)sulfonium perfluorobutyl-1-sulfonate: p-methylphenyl magnesium bromide and diphenyl sulfoxide are used as raw materials to occur substitution reaction under the catalysis of trimethylchlorosilane, and then diphenyl(p-methylphenyl)sulfonium salt is directly synthesized, and then the intermediate is obtained by extraction, purification, filtration and drying; the molar ratio of p-methylphenyl magnesium bromide, diphenyl sulfoxide and trimethylchlorosilane is 1:2-3:2-3; the temperature of the substitution reaction is 15-30°C; and the time of the substitution reaction is 2-3h;

[0010] S2, preparing diphenyl(p-methylphenyl)sulfonium perfluorobutyl-1-sulfonate: the intermediate and perfluorobutyl sulfonic acid metal salt are subjected to reflux reaction in an organic solvent, and then the target product diphenyl(p-methylphenyl)sulfonium perfluorobutyl-1-sulfonate is obtained by filtration, concentration, beating, re-filtering, washing the filtrate, and re-concentration after the reflux reaction is completed.

[0011] Specifically, the perfluorobutyl sulfonic acid metal salt is any one of potassium perfluorobutyl sulfonate or sodium perfluorobutyl sulfonate.

[0012] More specifically, the organic solvent used in the reflux reaction is any one of methanol, ethanol or isopropanol; the temperature of the reflux reaction is 60-80°C; and the time of the reflux reaction is 2-3h.

[0013] Further, the washing of the filtrate refers to washing with EDTA aqueous solution first, and then washing with ultrapure water.

[0014] Further, the molar ratio of the intermediate and perfluorobutyl sulfonic acid metal salt is 1:1.0-1.3.

[0015] The synthesis method of the intermediate of diphenyl(p-methylphenyl)sulfonium perfluorobutyl-1-sulfonate, and the key lies in that the synthesis method is to use p-methylphenyl magnesium bromide and diphenyl sulfoxide as raw materials to occur substitution reaction under the catalysis of trimethylchlorosilane, and then diphenyl(p-methylphenyl)sulfonium salt is directly synthesized, and then the intermediate is obtained by extraction, purification, filtration and drying.

[0016] Specifically, the molar ratio of methylphenyl magnesium bromide, diphenyl sulfoxide, and trimethylchlorosilane is 1:2-3:2-3.

[0017] More specifically, the temperature of the above substitution reaction is 15℃~30℃, and the reaction time is 2h~3h.

[0018] Furthermore, the above-mentioned extraction and purification refers to the process of separating the aqueous phase after the reaction, extracting the aqueous phase with the organic phase, retaining the organic phase, adding anhydrous sulfate to the organic phase for drying, filtering and concentrating the organic phase to obtain a concentrated solution, slurrying the concentrated solution, filtering and drying it again to obtain the intermediate.

[0019] Furthermore, the extraction and separation process is repeated 2 to 3 times, and the organic phase is either dichloromethane or dichloroethane; the concentrate is pulped 2 to 3 times, and tetrahydrofuran is added during the concentration and pulping process.

[0020] Compared with the prior art, the present invention has the following advantages:

[0021] The diphenyl sulfoxide used in this invention belongs to the aryl sulfoxide family. These substances can undergo a series of organic transformations, such as the Sonogashira reaction with terminal alkynes, borylation with B2pin2, amination with amines, phosphorylation with P(O)-H compounds, and etherification with alcohols. Aryl sulfoxides can also effectively participate in transition metal-catalyzed cross-coupling reactions with Grignard reagents. For example, Wenkert et al. reported in 1979 a nickel-catalyzed Kumada-type cross-coupling reaction of diaryl sulfoxides with Grignard reagents; in 2017, Yorimitsu's group reported a cross-coupling reaction of diaryl zinc compounds prepared by transmetallation of Grignard reagents with zinc bromide in the presence of lithium bromide with arylmethyl sulfoxides under a nickel catalyst; and in 2020, Cao, Dang, Shi, and colleagues reported a palladium-catalyzed Suzuki-type coupling reaction of diaryl sulfoxides with arylboronic acids. It is evident that the diaryl sulfoxides reported in existing technologies all undergo cross-coupling reactions with Grignard reagents under the action of transition metal catalysts such as nickel and palladium.

[0022] The p-methylphenyl magnesium bromide used in this invention is also a Grignard reagent. However, this invention discovers that by directly using p-methylphenyl magnesium bromide and diphenyl sulfoxide as raw materials, a substitution and dehydration reaction can rapidly occur at room temperature under the catalysis of trimethylchlorosilane to prepare the corresponding thioonium salt. This is because trimethylchlorosilane can activate the sulfoxy double bond in diphenyl sulfoxide, reacting with p-methylphenyl magnesium bromide to form a complex salt containing magnesium ions, bromide ions, and hydroxide ions. When the reaction is quenched with water and hydrochloric acid is added, the magnesium ions, bromide ions, and hydroxide ions in the complex salt are removed, yielding only the corresponding thioonium salt. This invention provides a short reaction time for preparing thioonium salts, can complete the reaction at normal temperatures, and yields high-purity intermediates, facilitating the preparation of high-purity target products that meet the requirements of electronic chemical raw materials.

[0023] Meanwhile, this invention does not use expensive catalysts such as transition metals, and the reagents used are all readily available and inexpensive. The first step reaction can be completed within a normal temperature range without special heating or cooling. Even when the ambient temperature is suitable, there is no need to specially control the reaction temperature of the first step. The reaction time of both steps is controlled within 3 hours, and the reaction process does not require long standing or crystal growth processes such as overnight, which greatly shortens the total production time. Therefore, the method of this invention for preparing diphenyl(p-tolyl)thionium perfluorobutyl-1-sulfonate is very suitable for industrial use. Attached Figure Description

[0024] Figure 1 This is the 1H NMR spectrum of the sample from this invention.

[0025] Figure 2 This is the NMR fluorine spectrum of the sample from this invention.

[0026] Figure 3 This is the mass spectrum of the sample liquid of this invention.

[0027] Figure 4 This is the high-performance liquid chromatography (HPLC) spectrum of the sample from this invention. Detailed Implementation

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0029] Unless otherwise specified in the examples, the procedures can be followed according to conventional conditions; unless the manufacturers of the reagents or instruments used are specified, they are all conventional products that can be purchased commercially.

[0030] Example 1

[0031] S1. Preparation of diphenyl(p-tolyl)thionium perfluorobutyl-1-sulfonate intermediate:

[0032] S1-1. Add a tetrahydrofuran solution containing 1 mol of p-methylphenyl magnesium bromide (the purchased p-methylphenyl magnesium bromide is stored in tetrahydrofuran, so this solution does not need to be prepared separately; just use the molar amount of p-methylphenyl magnesium bromide) to the reactor. Control the temperature inside the reactor at 25°C. Add 2.5 mol of diphenyl sulfoxide in 3 batches, and add 2.8 mol of trimethylchlorosilane dropwise. After the addition is complete, keep the reaction at the temperature for 2.5 h.

[0033] S1-2. When the reaction is finished, add water to quench the reaction, adjust the pH of the reaction solution to 1.7, and separate the aqueous phase.

[0034] S1-3. Add dichloromethane to the aqueous phase for two extractions and separation, retain the organic phase, add anhydrous magnesium sulfate to dry, filter and concentrate the organic phase to about 1 / 2 of the original volume.

[0035] S1-4. Add tetrahydrofuran to the concentrate and slurry three times. Filter again to obtain the filtrate. Dry the filtrate to obtain intermediate sample 1.

[0036] S2. Preparation of diphenyl(p-tolyl)thionium perfluorobutyl-1-sulfonate:

[0037] S2-1. Dissolve the intermediate obtained in step S1-4 and the perfluorobutyl sulfonate metal salt in 8 times their volume of methanol at a molar ratio of 1:1.2, and heat the reaction system to 70°C and reflux for 2.5 h.

[0038] S2-2. After the reflux reaction is completed, filter the reaction solution to remove insoluble matter, concentrate the reaction solution to about 1 / 3 of the original volume to obtain a concentrated solution, add dichloromethane to the concentrated solution for slurrying, filter again to remove insoluble matter, wash the filtrate with EDTA aqueous solution and ultrapure water respectively, and concentrate the washed filtrate again to obtain the target product diphenyl (p-tolyl)thionium perfluorobutyl-1-sulfonate sample 1.

[0039] Example 2

[0040] S1. Preparation of diphenyl(p-tolyl)thionium perfluorobutyl-1-sulfonate intermediate:

[0041] S1-1. Add a tetrahydrofuran solution containing 1 mol of p-methylphenyl magnesium bromide (same as in Example 1) to the reactor, control the temperature inside the reactor to 15°C, add 2 mol of diphenyl sulfoxide in two batches, add 3 mol of trimethylchlorosilane dropwise, and keep the reaction at the temperature for 3 hours after the addition is complete.

[0042] S1-2. When the reaction is finished, add water to quench the reaction, adjust the pH of the reaction solution to 1.1, and separate the aqueous phase.

[0043] S1-3. Add dichloroethane to the aqueous phase and perform three extractions and separations. Retain the organic phase, add anhydrous sodium sulfate to dry it, filter it, and concentrate the organic phase to about 1 / 3 of its original volume.

[0044] S1-4. Add tetrahydrofuran to the concentrate and pulp twice, then filter again to obtain the filtrate. Dry the filtrate to obtain intermediate sample 2.

[0045] S2. Preparation of diphenyl(p-tolyl)thionium perfluorobutyl-1-sulfonate:

[0046] S2-1. Dissolve the intermediate obtained in step S1-4 and the perfluorobutyl sulfonate metal salt in 10 times their volume of ethanol at a molar ratio of 1:1.0, and heat the reaction system to 80°C and reflux for 2 hours.

[0047] S2-2. After the reflux reaction is completed, filter the reaction solution to remove insoluble matter, concentrate the reaction solution to about 1 / 2 of the original volume to obtain a concentrated solution, add dichloroethane to the concentrated solution for slurrying, filter again to remove insoluble matter, wash the filtrate with EDTA aqueous solution and ultrapure water respectively, and concentrate the washed filtrate again to obtain the target product diphenyl (p-tolyl)thionium perfluorobutyl-1-sulfonate sample 2.

[0048] Example 3

[0049] S1. Preparation of diphenyl(p-tolyl)thionium perfluorobutyl-1-sulfonate intermediate:

[0050] S1-1. Add a tetrahydrofuran solution containing 1 mol of p-methylphenyl magnesium bromide (same as in Example 1) to the reactor, control the temperature inside the reactor to 30°C, add 3 mol of diphenyl sulfoxide in 3 batches, add 2 mol of trimethylchlorosilane dropwise, and keep the reaction at the temperature for 2 hours after the addition is complete.

[0051] S1-2. When the reaction is finished, add water to quench the reaction, adjust the pH of the reaction solution to 1.9, and separate the aqueous phase.

[0052] S1-3. Add dichloromethane to the aqueous phase and perform three extractions and separations. Retain the organic phase, add anhydrous magnesium sulfate to dry, filter, and concentrate the organic phase to about 1 / 2 of its original volume.

[0053] S1-4. Add tetrahydrofuran to the concentrate and pulp it three times. Filter it again to obtain the filtrate. Dry the filtrate to obtain intermediate sample 3.

[0054] S2. Preparation of diphenyl(p-tolyl)thionium perfluorobutyl-1-sulfonate:

[0055] S2-1. Dissolve the intermediate obtained in step S1-4 and the perfluorobutyl sulfonate metal salt in 5 times the volume of isopropanol at a molar ratio of 1:1.3, and heat the reaction system to 60°C and reflux for 3 hours.

[0056] S2-2. After the reflux reaction is completed, filter the reaction solution to remove insoluble matter, concentrate the reaction solution to about 1 / 3 of the original volume to obtain a concentrated solution, add dichloroethane to the concentrated solution for slurrying, filter again to remove insoluble matter, wash the filtrate with EDTA aqueous solution and ultrapure water respectively, and concentrate the washed filtrate again to obtain the target product diphenyl (p-tolyl)thionium perfluorobutyl-1-sulfonate sample 3.

[0057] Comparative Example 1

[0058] The specific preparation process is the same as in Example 1, except that in step S1-1, p-methylphenyl magnesium bromide is not used. Instead, under nitrogen protection, air is completely isolated. 2 mol of magnesium shavings and 1 mol of p-bromotoluene are added to 100 ml of ultra-dry tetrahydrofuran. The mixture is heated to 80°C and maintained for 30 seconds, then cooled to room temperature. 2.8 mol of trimethylchlorosilane is added, and the system is heated to 80°C again and maintained for 30 seconds, then cooled to room temperature again to complete the activation of the magnesium shavings. 2.5 mol of diphenyl sulfoxide, 0.3 mol of nickel bromide, and 0.3 mol of 1,2-bis(diphenylphosphine)ethane are added to the system in three batches. The reaction temperature is controlled at 50°C. After the addition is complete, the reaction is maintained at this temperature for 3 hours. Samples are taken every 0.5 hours to check the content of the raw materials. The reaction is terminated when the raw materials no longer decrease. However, after analysis, the obtained substance is not the target intermediate prepared in this invention, so no further preparation is carried out.

[0059] This is because in catalysts that produce complex structures using transition metal catalysts and phosphine ligands, the target of attack is the thiobenzene single bond of diphenyl sulfoxide, leaving only the benzene ring to undergo cross-coupling with Grignard reagents. Such reactions cannot produce the target product.

[0060] Comparative Example 2

[0061] The specific preparation process is the same as in Example 1, except that in step S1-1, instead of using 2.8 mol of trimethylchlorosilane, an equimolar amount of dimethyldichlorosilane is used. The subsequent preparation process is the same as in Example 1, and intermediate reference standard 1 is prepared, which in turn yields target product reference standard 1.

[0062] Comparative Example 3

[0063] The specific preparation process is the same as in Example 1, except that in step S2-2, instead of using EDTA aqueous solution and ultrapure water to wash the filtrate, only ultrapure water is used for washing twice. The subsequent preparation process is the same as in Example 1, and then the target product reference standard 2 is obtained.

[0064] Analysis and Testing

[0065] The sample prepared in this invention is a pale yellow liquid. Analysis using 1H NMR and HPLC-MS / MS confirmed that the sample obtained in the examples conforms to the structural characteristics of diphenyl(p-tolyl)thionium perfluorobutyl-1-sulfonate. Some of the analytical spectra are shown in the appendix. Figures 1 to 3 .

[0066] The purity of the samples was determined by high-performance liquid chromatography (HPLC), and the yield was calculated using the following formula. The results are shown in Table 1, and some test chromatograms are shown in the appendix. Figure 4 .

[0067] The yield calculation formula is:

[0068] Intermediate yield = Actual weight of the intermediate obtained (g) / Theoretical yield (g) calculated based on the amount of 2,4,6-trienylpropoxy-1,3,5-triazine used × 100%.

[0069] Product yield = Actual weight of the obtained sample (g) / Theoretical yield (g) calculated based on the amount of 2,4,6-trienylpropoxy-1,3,5-triazine used × 100%.

[0070] Table 1: Summary of Purity and Yield Results

[0071]

[0072] Impurity analysis was performed on sample 1 of diphenyl(p-tolyl)thionium perfluorobutyl-1-sulfonate, and the results are shown in Table 2.

[0073] Table 2: Sample Impurity Analysis Table

[0074]

[0075]

[0076] As can be seen from the results in Tables 1 and 2, the intermediate prepared by this invention has a purity of over 98.6%, with few types of impurities and low impurity content, and the content of the largest single impurity is less than 0.04%.

[0077] The first step yields over 93%, and the second step yields over 83%, thus increasing the overall yield to 77%. The high purity of the intermediate prepared in this invention facilitates the purification process in the second step. Therefore, recrystallization is unnecessary after the salt formation reaction in the second step, saving crystal growth time. Impurities are effectively removed through two washing cycles, yielding a high-purity product. In this invention, purification without recrystallization not only yields a high-purity product meeting electrochemical requirements but also avoids yield losses caused by excessive recrystallization, thereby increasing the yield of the second step reaction to over 83%.

[0078] In addition, EDTA aqueous solution can form complexes with metal ions in the product, which helps to remove impurities, maintain product stability, and improve product purity.

[0079] Table 3: Summary of Elemental Analysis Results for Samples and Reference Standards

[0080]

[0081]

[0082] As shown in Table 3, the metal impurity content of the product and the reference standard prepared by this invention is less than 300 ppb, while the metal impurity content is relatively higher in the product prepared without EDTA aqueous solution washing. Magnesium was not detected in either the sample or the reference standard, indicating that the process design of this invention has a good removal effect on this elemental impurity.

Claims

1. A process for the synthesis of diphenyl (p-tolyl) sulfonium perfluorobutyl-1- sulphonate, characterized in that, The synthesis method is a two-step method for preparing diphenyl (p-tolyl) sulfonium perfluorobutyl-1-sulfonic acid salt, and the specific steps are as follows: S1, preparation of diphenyl (p-tolyl) sulfonium perfluorobutyl-1-sulfonic acid salt intermediate: p-methyl phenyl magnesium bromide and diphenyl sulfoxide are used as raw materials, substitution reaction occurs under the catalysis of trimethylchlorosilane, diphenyl (p-tolyl) sulfonium salt is directly synthesized, and then the intermediate is obtained by extraction purification, filtration and drying; the molar ratio of p-methyl phenyl magnesium bromide, diphenyl sulfoxide and trimethylchlorosilane is 1:2-3:2-3; the temperature of the substitution reaction is 15-30 DEG C; and the time of the substitution reaction is 2-3 h; S2, preparation of diphenyl (p-tolyl) sulfonium perfluorobutyl-1-sulfonic acid salt: the intermediate is subjected to reflux reaction with perfluorobutyl sulfonic acid metal salt in an organic solvent, after the reflux reaction is completed, the target product diphenyl (p-tolyl) sulfonium perfluorobutyl-1-sulfonic acid salt is obtained by filtration, concentration, beating, re-filtering, washing the filtrate, and re-concentration.

2. The method of synthesis of diphenyl (p-tolyl) sulfonium perfluoro butyl-1- sulphonate according to claim 1, characterized in that, The perfluorobutyl sulfonic acid metal salt is any one of potassium perfluorobutyl sulfonate or sodium perfluorobutyl sulfonate.

3. The method of synthesis of diphenyl(p-tolyl)sulfonium perfluorobutyl-1- sulphonate according to claim 1, characterized in that, The organic solvent used in the reflux reaction is any one of methanol, ethanol or isopropanol; the temperature of the reflux reaction is 60-80 DEG C; and the time of the reflux reaction is 2-3 h.

4. The method of synthesis of diphenyl(p-tolyl)sulfonium perfluorobutyl-1- sulphonate according to claim 1, characterized in that, The washing of the filtrate refers to washing with EDTA aqueous solution first and then with ultrapure water.

5. The method of synthesis of diphenyl(p-tolyl)sulfonium perfluorobutyl-1- sulphonate according to claim 1, characterized in that, The molar ratio of the intermediate to the perfluorobutyl sulfonic acid metal salt is 1:1.0-1.

3.

6. A process for the synthesis of diphenyl (p-tolyl) sulfonium perfluorobutyl-1- sulphonate intermediate, characterized in that, The synthesis method of the intermediate is that p-methyl phenyl magnesium bromide and diphenyl sulfoxide are used as raw materials, substitution reaction occurs under the catalysis of trimethylchlorosilane, and then diphenyl (p-tolyl) sulfonium salt is directly synthesized.

7. The method of synthesis of diphenyl(p-tolyl)sulfonium perfluorobutyl-1- sulphonate intermediate according to claim 6, characterized in that, The molar ratio of p-methyl phenyl magnesium bromide, diphenyl sulfoxide and trimethylchlorosilane is 1:2-3:2-3.

8. The method of synthesis of diphenyl (p-tolyl) sulfonium perfluorobutyl-1- sulphonate intermediate according to claim 6, characterized in that, The temperature of the substitution reaction is 15-30 DEG C; and the time of the substitution reaction is 2-3 h.

9. The method of synthesis of diphenyl (p-tolyl) sulfonium perfluorobutyl-1- sulphonate intermediate according to claim 6, characterized in that, The extraction and purification refer to that after the reaction is completed, the aqueous phase is obtained by liquid separation, the aqueous phase is extracted by an organic phase, the organic phase is retained, anhydrous sulfate is added to the organic phase for drying, the organic phase is filtered and concentrated to obtain a concentrated solution, the concentrated solution is beaten, and then the intermediate is obtained by re-filtering and drying.

10. The method of synthesis of diphenyl(p-tolyl)sulfonium perfluorobutyl-1- sulphonate according to claim 9, characterized in that, The extraction and liquid separation are performed for 2-3 times; the organic phase is any one of dichloromethane or dichloroethane; and the concentrated solution is beaten for 2-3 times, and tetrahydrofuran needs to be added during the beating.

Images