Synthesis process of (4-tert-butylphenyl) diphenyl sulfonium chloride
By adopting new solvents and reaction conditions in the synthesis process of (4-tert-butylphenyl)diphenylsulfonium chloride salt, the problems of difficult production of format reagents and introduction of metal ion impurities in the existing process are solved, and the production and energy consumption of high-purity products are achieved.
Patent Information
- Application Number
- CN202411894106.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-20
- Publication Date
- 2025-03-25
AI Technical Summary
In the prior art, the synthesis process of (4-tert-butylphenyl)diphenylsulfonium chloride salt has problems such as difficult production of format reagents, low atomic utilization rate, introduction of metal ion impurities, and energy waste and waste.
Using dichloromethane as a solvent, diphenyl sulfoxide and tert-butylbenzene were mixed, and trifluoromethanesulfonic anhydride was dripped at low temperature. After quenching, liquid separation, rotary distillation, recrystallization and filtration, a high-purity (4-tert-butylphenyl)diphenylsulfonium chloride salt was finally obtained under acidic conditions.
This process avoids the use of format reagents, improves the atomic utilization rate of raw materials, reduces energy consumption and waste generation, is suitable for large-scale continuous production, and obtains high-purity products.
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Figure FT_1 
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Figure BDA0005201288170000061
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic compound synthesis, in particular to a synthesis process of (4-tert-butylphenyl)diphenylsulfonium chloride. Background Art
[0002] Photoresist is a photosensitive thin film material. It is a key basic processing material for micro-processing technology in the optoelectronic information industry and is mainly used for fine graphic processing of integrated circuits and discrete semiconductor devices.
[0003] Photo acid generator (PAG) refers to a compound that can generate acid under the action of light of appropriate energy. In the chemically amplified photoresist system, the acid generator generates a small amount of acid under the action of a special light source. This acid acts as a catalyst to cause an acidolysis reaction in the illuminated area, thereby making the exposed area and the non-exposed area have a large solubility difference, and the required image can be obtained by development. At present, the acid generator in the chemically amplified imaging system is mainly onium salt. The anion in the salt can abstract hydrogen to form acid under the irradiation of ultraviolet light. Currently, sulfonium salts and iodonium salts are more commonly used. Since sulfonium salts are more stable than iodonium salts, more research has been done on sulfonium salts.
[0004] (4-tert-butylphenyl) diphenyl sulfonium chloride is a PAG with excellent performance and has important application value in the field of photoresists. In the prior art, the conventional synthesis process of (4-tert-butylphenyl) diphenyl sulfonium chloride is: p-tert-butyl chlorobenzene is made into a corresponding Grignard reagent, reacted with diphenyl sulfoxide under the action of trimethylsilyl chloride (TMSCl), and ionized under acidic conditions (prepared with concentrated hydrochloric acid) to obtain (4-tert-butylphenyl) diphenyl sulfonium chloride. However, when synthesizing (4-tert-butylphenyl) diphenyl sulfonium chloride by this conventional synthesis process, it has the following technical defects:
[0005] The preparation of the Grignard reagent for tert-butylchlorobenzene is relatively difficult, the atomic utilization rate of the raw materials is low, metal ion impurities are introduced, and a large amount of energy is wasted, and a large amount of solid and liquid waste is generated. Summary of the invention
[0006] The purpose of the present invention is to overcome the deficiencies in the prior art and provide a synthesis process of (4-tert-butylphenyl) diphenyl sulfonium chloride. The process overcomes the shortcomings of the prior art, such as low activity of the reagent and introduction of metal ion impurities, and improves the conversion rate of the raw materials. After simple treatment, (4-tert-butylphenyl) diphenyl sulfonium chloride with extremely high purity can be obtained, and the process is suitable for large-scale continuous production.
[0007] The purpose of the present invention is achieved through the following technical solutions:
[0008] S1. Using dichloromethane (DCM) as solvent, diphenyl sulfoxide and tert-butylbenzene are mixed, and trifluoromethanesulfonic anhydride (Tf2O) is dropped into the mixture at low temperature while keeping stirring;
[0009] S2. The reaction solution obtained in S1 was quenched, separated, evaporated, and recrystallized, and then a solvent was added to mix and stirred;
[0010] S3. The reaction solution obtained in S2 is filtered, and concentrated hydrochloric acid is added and stirred evenly, followed by separation, rotary evaporation, beating and filtering steps to obtain (4-tert-butylphenyl) diphenylsulfonium chloride.
[0011] The specific synthetic route of the present invention is as follows:
[0012]
[0013] The present invention proposes a novel synthesis route of (4-tert-butylphenyl) diphenyl sulfonium chloride, which does not need to introduce metal ion impurities and greatly improves the atomic utilization rate of raw materials. While obtaining high-purity (4-tert-butylphenyl) diphenyl sulfonium chloride, it reduces energy consumption, optimizes costs, and reduces the emission of toxic and harmful substances. The (4-tert-butylphenyl) diphenyl sulfonium chloride prepared by the present invention is an important chemical and semiconductor material auxiliary agent, and is particularly suitable for the synthesis and processing of KrF and ArF photoresists. Such monomers and their derivative resins have important applications and market prospects in fine graphic processing industries such as display panels, integrated circuits and semiconductor discrete devices.
[0014] As one possible embodiment of the present application, in step S1, in step S1, diphenyl sulfoxide can be replaced by any one of 3-methyldiphenyl sulfoxide, 4,4'-dimethyldiphenyl sulfoxide, and 4-tert-butyldiphenyl sulfoxide; tert-butylbenzene can be replaced by 2,6-dimethylphenol or phenol; trifluoromethanesulfonic anhydride can be replaced by trifluoromethanesulfonic acid or methanesulfonic acid.
[0015] As one possible embodiment of the present application, in step S1, when Tf2O is added dropwise, the system temperature is maintained between -10 and 0°C.
[0016] As one of the possible embodiments of the present application, in step S1, the feed equivalent ratio of diphenyl sulfoxide, tert-butylbenzene and trifluoromethanesulfonic anhydride is (1.0:1.1:1.1) to (1.0:2.0:2.0); the feed ratio of diphenyl sulfoxide and dichloromethane is (100 g:300 mL) to (100 g:500 mL).
[0017] As one possible embodiment of the present application, in step S2, the solvent is any one or more of methanol, ethanol, and acetonitrile.
[0018] As one possible embodiment of the present application, in steps S2 and S3, the solvents used for recrystallization and slurrying are one or a mixture of toluene, n-hexane, diethyl ether, methyl tert-butyl ether, ethyl acetate, and isopropanol.
[0019] As one possible embodiment of the present application, in steps S2 and S3, the solvent used for recrystallization is a mixture of toluene (Tol) and n-hexane (Hex), and the volume ratio of the two is (1.0:0.5) to (1.0:1.5).
[0020] As one possible embodiment of the present application, in step S3, after adding concentrated hydrochloric acid, the reaction temperature is controlled between 10 and 30° C., and the stirring time is 3 to 8 hours.
[0021] As one possible embodiment of the present application, in step S3, the concentration of the concentrated hydrochloric acid is 36% to 38%.
[0022] As one possible embodiment of the present application, in step S3, the amount of concentrated hydrochloric acid added is concentrated hydrochloric acid: the recrystallized solid ratio obtained in S2 = 100 ml: (166 g ~ 200 g).
[0023] As one possible embodiment of the present application, in step S3, concentrated hydrochloric acid can be replaced by hydrobromic acid, hydrofluoric acid or an acid with similar properties.
[0024] As one possible embodiment of the present application, the atmosphere of the entire synthesis process is air or an inert gas; the inert gas is one or more of nitrogen, argon, and helium. The use of an inert atmosphere can slightly improve the reaction efficiency.
[0025] Compared with the prior art, the present invention has the following beneficial effects:
[0026] 1. The synthesis route of the present invention avoids the use of Grignard reagent, does not introduce additional metal ion impurities, avoids the use of Grignard reagent for synthesizing p-tert-butylchlorobenzene, and effectively improves the atomic utilization rate of the raw materials.
[0027] 2. The preparation process of the present invention is simple and suitable for large-scale continuous production. All raw materials are common chemical products that are easy to purchase and inexpensive, with high utilization rate of raw materials, less waste generated and simple treatment, and environmentally friendly. The produced (4-tert-butylphenyl) diphenylsulfonium chloride has high economic value and has an inspiring effect on the synthesis of similar photoacid generators.
[0028] 3. The present invention changes the synthesis route and optimizes the processing technology, so that the comprehensive yield of (4-tert-butylphenyl) diphenyl sulfonium chloride salt is not less than 49%, and the purity is relatively stable, and the liquid phase purity can reach more than 99.0%. BRIEF DESCRIPTION OF THE DRAWINGS
[0029] Figure 1 : NMR spectrum of the product. DETAILED DESCRIPTION
[0030] The synthesis process of (4-tert-butylphenyl)diphenylsulfonium chloride described in the present application is further described in detail below in conjunction with specific embodiments.
[0031] Example 1
[0032] In a 5L four-necked reaction bottle, diphenyl sulfoxide (300g, 1.0eq) and tert-butylbenzene (246g, 1.2eq) were mixed, and 1.3L DCM was added as solvent. The mixture was stirred and the internal temperature was controlled at -10 to 0°C. Tf2O (502g, 1.2eq) was slowly dropped in. During the addition, the dropping rate was controlled to keep the internal temperature at -10 to 0°C. After the addition was completed, the mixture was stirred for about 2h.
[0033] Slowly add 1L of deionized water and stir for 30min, separate the liquids, collect the DCM phase, wash the DCM phase twice with deionized water, separate the liquids, collect the DCM phase, spin dry until viscous, recrystallize with a mixture of Tol and Hex (500ml Tol, 500ml Hex), filter, and obtain 630g of a white powdery solid.
[0034] Take 264 g of the above white solid powder and 1500 ml of methanol, mix them evenly at room temperature, and then filter them. Add 150 ml of concentrated hydrochloric acid to the filtrate, and stir at room temperature for 4 hours.
[0035] The liquid was dried by spin drying, 1000 ml of DCM was added, and the mixture was stirred and washed twice with 1000 ml of deionized water each time, and the liquid was separated, and the DCM phase was collected, and the mixture was dried by spin drying, and the mixture was drained to a viscous state, and a mixture of Tol and Hex (400 ml: 400 ml) was added to slurry, and filtered to obtain 101 g of a white powder product, namely (4-tert-butylphenyl) diphenylsulfonium chloride, with a yield of 50.5% and a liquid phase purity of more than 99.0%. Among them, the nuclear magnetic resonance spectrum of the product is as follows Figure 1 As shown, 1 H NMR (400MHz, CDCl3) δ7.77-7.64(m,14H),1.33(s,9H).
[0036] Example 2
[0037] In a 5L four-necked reaction bottle, diphenyl sulfoxide (300g, 1.0eq) and tert-butylbenzene (225.5g, 1.1eq) were mixed, and 1.2L DCM was added as solvent. The mixture was stirred and the internal temperature was controlled at -10 to 0°C. Tf2O (460.2g, 1.1eq) was slowly dropped in. During this period, the dropping rate was controlled to keep the internal temperature at -10 to 0°C. After the dropwise addition, the mixture was stirred for about 2h.
[0038] Slowly add 1L of deionized water and stir for 30min, separate the liquids, collect the DCM phase, wash the DCM phase twice with deionized water, separate the liquids, collect the DCM phase, spin dry until viscous, recrystallize with a mixture of Tol and Hex (500ml Tol, 500ml Hex), filter, and obtain 585g of a white powdery solid.
[0039] Take 264 g of the above white solid powder and 1584 ml of methanol, mix them evenly at room temperature, then filter, add 150 ml of concentrated hydrochloric acid to the filtrate, and stir at room temperature for 4 hours.
[0040] The liquid was spin-dried, 1000 ml of DCM was added, and the mixture was stirred and washed twice with 1000 ml of deionized water each time. The liquid was separated, the DCM phase was collected, spin-dried, and drained until viscous. A mixed solution of Tol and Hex (400 ml: 400 ml) was added for slurrying, and filtered to obtain 107 g of a white powder product, namely (4-tert-butylphenyl) diphenylsulfonium chloride, with a yield of 53.5%, and the liquid phase purity was above 99.0%.
[0041] Example 3
[0042] In a 5L four-necked reaction bottle, diphenyl sulfoxide (400g, 1.0eq) and tert-butylbenzene (307.5g, 1.5eq) were mixed, and 1.2L DCM was added as solvent. The mixture was stirred and the internal temperature was controlled at -10 to 0°C. Tf2O (627.5g, 1.5eq) was slowly dropped in. During this period, the dropping rate was controlled to keep the internal temperature at -10 to 0°C. After the dropwise addition, the mixture was stirred for about 1.5h.
[0043] Slowly add 1L of deionized water and stir for 30min, separate the liquids, collect the DCM phase, wash the DCM phase twice with deionized water, separate the liquids, collect the DCM phase, spin dry until viscous, recrystallize with a mixture of Tol and Hex (600ml Tol, 600ml Hex), filter, and obtain 660g of a white powdery solid.
[0044] Take 300 g of the above white solid powder and 1800 ml of methanol, mix them evenly at room temperature, then filter, add 170.5 ml of concentrated hydrochloric acid to the filtrate, and stir at room temperature for 5 hours.
[0045] The liquid was spin-dried, 1100 ml of DCM was added, and the mixture was stirred and washed twice with 1100 ml of deionized water each time. The liquid was separated, the DCM phase was collected, spin-dried, and drained until viscous. A mixed solution of Tol and Hex (500 ml: 500 ml) was added for slurrying, and filtered to obtain 127 g of a white powder product, namely (4-tert-butylphenyl) diphenylsulfonium chloride, with a yield of 55.9% and a liquid phase purity of more than 99.0%.
[0046] Example 4
[0047] In a 3L four-necked reaction bottle, diphenyl sulfoxide (200g, 1.0eq) and tert-butylbenzene (218.6g, 1.6eq) were mixed, and 600ml of DCM was added as solvent. The mixture was stirred and the internal temperature was controlled at -10 to 0°C. Tf2O (446.3g, 1.6eq) was slowly dropped in. During this period, the dropping rate was controlled to keep the internal temperature at -10 to 0°C. After the dropwise addition, the mixture was stirred for about 1.5h.
[0048] Slowly add 600 ml of deionized water and stir for 30 min, separate the liquids, collect the DCM phase, wash the DCM phase twice with deionized water, separate the liquids, collect the DCM phase, spin dry until viscous, recrystallize with a mixture of Tol and Hex (300 ml Tol, 300 ml Hex), filter, and obtain 325 g of a white powdery solid.
[0049] Take 200 g of the above white solid powder and 1200 ml of methanol, mix them evenly at room temperature, then filter, add 113.7 ml of concentrated hydrochloric acid to the filtrate, and stir at room temperature for 5 hours.
[0050] The liquid was dried by spin drying, 733 ml of DCM was added, and the mixture was stirred and washed twice with 740 ml of deionized water each time. The mixture was separated, and the DCM phase was collected and dried by spin drying. The mixture was drained until it became viscous. A mixture of Tol and Hex (340 ml: 340 ml) was added for slurrying. The mixture was filtered to obtain 84.8 g of a white powder product, namely (4-tert-butylphenyl) diphenylsulfonium chloride, with a yield of 56.0% and a liquid phase purity of more than 99.0%.
[0051] Example 5
[0052] In a 3L four-necked reaction bottle, diphenyl sulfoxide (200g, 1.0eq) and tert-butylbenzene (177.6g, 1.3eq) were mixed, and 600ml DCM was added as solvent. The mixture was stirred and the internal temperature was controlled at -10 to 0°C. Tf2O (362.6g, 1.3eq) was slowly dropped in. During this period, the dropping rate was controlled to keep the internal temperature at -10 to 0°C. After the dropwise addition, the mixture was stirred for about 1.5h.
[0053] Slowly add 600 ml of deionized water and stir for 30 min, separate the liquids, collect the DCM phase, wash the DCM phase twice with deionized water, separate the liquids, collect the DCM phase, spin dry until viscous, recrystallize with a mixture of Tol and Hex (300 ml Tol, 300 ml Hex), filter, and obtain 290 g of a white powdery solid.
[0054] Take 260 g of the above white solid powder and 1430 ml of methanol, mix them evenly at room temperature, then filter, add 153 ml of concentrated hydrochloric acid to the filtrate, and stir at room temperature for 5 hours.
[0055] The liquid was spin-dried, 950 ml of DCM was added, and the mixture was stirred and washed twice with 950 ml of deionized water each time. The mixture was separated, and the DCM phase was collected and spin-dried. It was drained until it became viscous. A mixture of Tol and Hex (380 ml: 380 ml) was added for slurrying. The mixture was filtered to obtain 96.5 g of a white powder product, namely (4-tert-butylphenyl) diphenylsulfonium chloride, with a yield of 49.0%, and the liquid phase purity was above 99.0%.
[0056] It is worth mentioning that:
[0057] In the above examples, the water used was UP grade, TOC < 10 ppb, resistivity (25°C) 18.25 MΩ.cm;
[0058] In the above embodiments, the reaction may be carried out in air or an inert gas (for example, nitrogen, argon, helium, etc., which may be one of nitrogen, argon, helium or a mixture of two or more thereof) environment;
[0059] In the above embodiments, eq is the abbreviation of equivalent.
[0060] Comparative Example 1
[0061] Add 7.1 g of magnesium chips and 150 ml of ultra-dry tetrahydrofuran (THF) to the reaction bottle, exhaust the air to fill the bottle with N2, stir under reflux, and slowly drop 50 g of p-tert-butylchlorobenzene, keep reflux stirring and react for about 12 h;
[0062] After cooling, add 30 g of diphenyl sulfoxide to the reaction bottle, and then slowly add 32.2 g of TMSCl dropwise, controlling the dropwise rate so that the internal temperature is not higher than 35°C. After completion, stir at room temperature for 3 h;
[0063] 150 ml of ultrapure water was added to the reaction solution, and an appropriate amount of concentrated hydrochloric acid was added to adjust the pH to about 4. The mixture was stirred for 30 min, and the liquid was separated and the aqueous phase was collected. The aqueous phase was extracted with a mixed solution of MeOH and DCM (MeOH 70 ml, DCM 210 ml), and the liquid was separated and the organic phase was collected and spin-dried to obtain 8 g of white powder, i.e. (4-tert-butylphenyl) diphenylsulfonium chloride, with a total yield of about 9.0%.
[0064] Among them, Comparative Example 1 is a commonly used synthetic route, and its synthetic route is as follows:
[0065]
[0066] It can be seen from Examples 1 to 5 and Comparative Example 1 that the present invention (Examples 1 to 5) can make the comprehensive yield of (4-tert-butylphenyl) diphenylsulfonium chloride not less than 49% by changing the synthesis route and optimizing the treatment process, which is much higher than the yield of 9.0% in Comparative Example 1, while avoiding the introduction of metal ions, and the purity is relatively stable, and the liquid phase purity can reach more than 99.0%.
Claims
1. A synthesis process for (4-tert-butylphenyl) diphenylsulfonium chloride, characterized in that: The steps include: S1. Using dichloromethane as solvent, diphenyl sulfoxide and tert-butylbenzene are mixed, and trifluoromethanesulfonic anhydride is dropped into the mixture at low temperature, and stirring is maintained; S2. The reaction solution obtained in S1 was quenched, separated, evaporated, and recrystallized, and then a solvent was added to mix and stirred; S3. The reaction solution obtained in S2 is filtered, and concentrated hydrochloric acid is added and stirred evenly, followed by separation, rotary evaporation, beating and filtering steps to obtain (4-tert-butylphenyl) diphenylsulfonium chloride.
2. A synthesis process for (4-tert-butylphenyl) diphenylsulfonium chloride according to claim 1, characterized in that: In step S1, diphenyl sulfoxide can be replaced by any one of 3-methyldiphenyl sulfoxide, 4,4'-dimethyldiphenyl sulfoxide, and 4-tert-butyldiphenyl sulfoxide; tert-butylbenzene can be replaced by 2,6-dimethylphenol or phenol; and trifluoromethanesulfonic anhydride can be replaced by trifluoromethanesulfonic acid or methanesulfonic acid.
3. A synthesis process for (4-tert-butylphenyl) diphenylsulfonium chloride according to claim 1, characterized in that: In step S1, when trifluoromethanesulfonic anhydride is added dropwise, the system temperature is maintained between -10 and 0°C.
4. A synthesis process for (4-tert-butylphenyl) diphenylsulfonium chloride according to claim 1, characterized in that: In step S1, the feed equivalent ratio of diphenyl sulfoxide, tert-butylbenzene and trifluoromethanesulfonic anhydride is (1.0:1.1:1.1) to (1.0:2.0:2.0); the feed equivalent ratio of diphenyl sulfoxide and dichloromethane is (100 g:300 mL) to (100 g:500 mL).
5. A synthesis process for (4-tert-butylphenyl) diphenylsulfonium chloride according to claim 1, characterized in that: In step S2, the solvent is any one or more of methanol, ethanol, and acetonitrile.
6. A synthesis process for (4-tert-butylphenyl) diphenylsulfonium chloride according to claim 1, characterized in that: In steps S2 and S3, the solvents used for recrystallization and slurrying are toluene, n-hexane, ethyl ether, methyl tert-butyl ether, ethyl acetate, isopropanol or a mixture of several thereof.
7. A synthesis process for (4-tert-butylphenyl) diphenylsulfonium chloride according to claim 6, characterized in that: In the steps S2 and S3, the solvent used for recrystallization is a mixture of toluene and n-hexane, and the volume ratio of the two is 1.0:0.5 to 1.0:1.
5.
8. A process for synthesizing (4-tert-butylphenyl)diphenylsulfonium chloride according to claim 1, characterized in that: In step S3, after adding concentrated hydrochloric acid, the reaction temperature is controlled between 10 and 30° C., and the stirring time is 3 to 8 hours.
9. A process for synthesizing (4-tert-butylphenyl)diphenylsulfonium chloride according to claim 1, characterized in that: In step S3, the dosage of the concentrated hydrochloric acid is concentrated hydrochloric acid: the recrystallized solid obtained in S2 = 100 ml: (166 g to 200 g).
10. A process for synthesizing (4-tert-butylphenyl)diphenylsulfonium chloride according to claim 1, characterized in that: In step S3, concentrated hydrochloric acid can be replaced by hydrobromic acid, hydrofluoric acid or an acid with similar properties.