4-methoxynaphthol-1-yl diphenyl sulfonium trifluoromethanesulfonate, and preparation method and application thereof
The one-pot synthesis of 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate solves the problems of environmental unfriendliness and high cost in existing technologies, and achieves a high-yield preparation method suitable for semiconductor chip etching.
Patent Information
- Application Number
- CN202511358659.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-23
- Publication Date
- 2026-01-02
AI Technical Summary
Existing technologies make it difficult to synthesize 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate, which is suitable for semiconductor photoresists, efficiently and at low cost, and the synthesis process is not environmentally friendly.
Using 1-methoxynaphthol, diphenyl sulfide, and trifluoromethanesulfonic anhydride as raw materials, oxidative coupling and coordination reactions were carried out in an organic solvent to prepare 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate via a one-pot method. The reaction conditions were controlled to improve the yield and environmental friendliness.
A high-yield, low-cost, and environmentally friendly preparation method has been achieved, which is suitable for industrial production and the product is applicable to the field of semiconductor chip etching.
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Figure CN121248459A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of organic chemical synthesis, in particular to a 4-methoxynaphthol-1-yl diphenyl sulfonium triflate, a preparation method and an application. BACKGROUND
[0002] Photoacid generator (PAG) is a key component of high-end semiconductor photoresist, which has important influence on the yield, quality, processing precision and other aspects of photoresist and photoetching product. Photoacid generators can be divided into non-ionic and ionic types according to the structure type, and the ionic type photoacid generator is divided into iodonium salt, sulfonium salt and ammonium salt. Among them, the sulfonium salt type photoacid generator has good solubility in solvent and resin system, is easy to be processed, is flexible and variable, has a wide range of application, and has developed rapidly in the field of semiconductor photochemistry. The sulfonic acid sulfonium salt type photoacid generator is applied early, has good acid generating performance and thermal stability, can quickly start electron transfer, so that it can quickly produce more stable active substances during photolysis, reduces the possibility of electron reverse transfer in polymerization reaction, and has a significant advantage in cationic polymerization.
[0003] Therefore, through molecular design, the 4-methoxynaphthol-1-yl diphenyl sulfonium triflate is synthesized efficiently, simply and at low cost, which has high theoretical significance and practical application value.
[0004] Therefore, the application is proposed. SUMMARY
[0005] The application aims to provide a 4-methoxynaphthol-1-yl diphenyl sulfonium triflate, a preparation method and an application. The 4-methoxynaphthol-1-yl diphenyl sulfonium triflate can be applied to the field of semiconductor chip etching, the preparation method has a simple synthesis route, green and environmentally friendly reaction conditions, and high product yield, and is suitable for industrial production.
[0006] In order to achieve the above-mentioned purpose of the application, the following technical scheme is adopted:
[0007] The application provides a 4-methoxynaphthol-1-yl diphenyl sulfonium triflate, and the structural formula of the 4-methoxynaphthol-1-yl diphenyl sulfonium triflate is as follows:
[0008] The application further provides a preparation method of the above-mentioned 4-methoxynaphthol-1-yl diphenyl sulfonium triflate, including the following steps:
[0009] Under the protection of the gas, 1-methoxynaphthol, diphenyl sulfide and an organic solvent are uniformly mixed, and trifluoromethanesulfonic anhydride is added dropwise under temperature control, and the reaction is carried out after heat preservation. After the reaction is completed, the 4-methoxynaphthol-1-yl diphenyl sulfonium triflate is obtained after post-treatment.
[0010] Preferably, the molar ratio of 1-methoxynaphthol, diphenyl sulfide and triflic anhydride is 1.0:(1.1-3.0):(1.1-3.0).
[0011] Preferably, the temperature of the dropwise temperature-controlled reaction is 10-20℃; and the time of the dropwise addition is 1-2h.
[0012] Preferably, the organic solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, dioxane, dichloroethane, ethylene glycol dimethyl ether, chloroform and toluene.
[0013] Preferably, the protective gas is nitrogen.
[0014] Preferably, the specific steps of the post-treatment are as follows:
[0015] After the reaction is completed, water is quenched, concentrated, filtered, washed with ultrapure water, washed with methyl tert-butyl ether, and vacuum dried to obtain 4-methoxynaphthol-1-yl diphenyl sulfonium triflate.
[0016] The application also provides a use of 4-methoxynaphthol-1-yl diphenyl sulfonium triflate in the field of semiconductor chip etching.
[0017] Preferably, the use of 4-methoxynaphthol-1-yl diphenyl sulfonium triflate is in the process of ArF, KrF, electron beam exposure lithography or extreme ultraviolet exposure lithography.
[0018] Compared with the prior art, the application has the following beneficial effects:
[0019] The application uses 1-methoxynaphthol, diphenyl sulfide and triflic anhydride as main raw materials, uses an organic solvent as a reaction solvent, and obtains 4-methoxynaphthol-1-yl diphenyl sulfonium triflate through one-pot oxidative coupling and coordination reaction. The reaction steps are simple and safe, the preparation method is easy to implement, the reaction conditions are green and environmentally friendly, the reaction yield is high, and the side reactions are few. Therefore, the preparation method is novel, has good selectivity, is environmentally friendly, has low overall preparation cost, high yield, and is suitable for industrial production. BRIEF DESCRIPTION OF DRAWINGS
[0020] Figure 1 : HPLC spectrum of 4-methoxynaphthol-1-yl diphenyl sulfonium triflate prepared in Example 2 of the application. DETAILED DESCRIPTION
[0021] The technical solutions of the present application will be described clearly and completely in combination with specific embodiments, but those skilled in the art will understand that the following described embodiments are part of the embodiments of the present application, not all the embodiments, and are only used to illustrate the present application, and should not be regarded as limiting the scope of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application. The specific conditions not specified in the embodiments are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, which are conventional products that can be purchased on the market.
[0022] The synthesis route of 4-methoxynaphthol-1-yl diphenyl sulfonium triflate is as follows:
[0023]
[0024] Example 1
[0025] The molar ratio of 1-methoxynaphthalene, diphenyl sulfide and trifluoromethanesulfonic anhydride was set to 1.0:1.1:1.1. Under nitrogen protection, 1-methoxynaphthalene (100.0 g, 1.0 eq) and diphenyl sulfide (129.5 g, 1.1 eq) were added to a 3L four-necked flask with stirring. Trifluoromethanesulfonic anhydride (196.2 g, 1.1 eq) was added dropwise at a temperature of 20°C. After the dropwise addition was completed, the reaction was stirred at 20°C for 1.5 hours. After the reaction was completed by HPLC detection, water was added for quenching, concentrated, cooled, filtered, and the filter cake was washed with ultrapure water, methyl tert-butyl ether, and vacuum dried at 40°C for 24 hours to obtain compound 4-methoxynaphthol-1-yl diphenyl sulfonium triflate 289.9 g, yield: 93.1%. Water content: 0.05%.
[0026] In the above reaction, in order to make the substrate 1-methoxynaphthalene react completely, diphenyl sulfide and trifluoromethanesulfonic anhydride are in excess and the reaction temperature is controlled between 10-20°C, so as to maximize the complete reaction of the raw materials.
[0027] Example 2
[0028] The molar ratio of methoxynaphthalene, diphenyl sulfide and triflic anhydride is 1.0:1.5:1.5, under nitrogen protection, methylene chloride 600 mL was added into a 3L four-necked flask, 1-methoxynaphthalene (100.0 g, 1.0 eq) and diphenyl sulfide (176.6 g, 1.5 eq) were added under stirring, triflic anhydride (267.5 g, 1.5 eq) was added dropwise at 20°C, after the dropwise addition was completed, the reaction was stirred at 20°C for 1.5 hours, after the reaction was completed as detected by HPLC, water was added for quenching, concentrated, cooled, filtered, the filter cake was washed with ultrapure water, washed with methyl tert-butyl ether, and vacuum dried at 40°C for 24 hours to obtain compound 4-methoxynaphthol-1- yldiphenyl sulfonium triflate 307.9 g, yield: 98.9%. Water content: 0.02%. The HPLC spectrum of 4-methoxynaphthol-1-yl diphenyl sulfonium triflate synthesized in this example is shown in Figure 1 .
[0029] Example 3
[0030] The molar ratio of methoxynaphthalene, diphenyl sulfide and triflic anhydride is 1.0:2.0:2.0, under nitrogen protection, ethylene glycol dimethyl ether 600 mL was added into a 3L four-necked flask, 1-methoxynaphthalene (100.0 g, 1.0 eq) and diphenyl sulfide (235.5 g, 2.0 eq) were added under stirring, triflic anhydride (356.7 g, 2.0 eq) was added dropwise at 10°C, after the dropwise addition was completed, the reaction was stirred at 10°C for 1.5 hours, after the reaction was completed as detected by HPLC, water was added for quenching, concentrated, cooled, filtered, the filter cake was washed with ultrapure water, washed with methyl tert-butyl ether, and vacuum dried at 40°C for 24 hours to obtain compound 4-methoxynaphthol-1- yldiphenyl sulfonium triflate 294.2 g, yield: 94.5%. Water content: 0.06%.
[0031] Example 4
[0032] The molar ratio of methoxynaphthalene, diphenyl sulfide and triflic anhydride is 1.0:2.5:2.5, under nitrogen protection, chloroform 600 mL was added into a 3L four-necked flask, 1-methoxynaphthalene (100.0 g, 1.0 eq) and diphenyl sulfide (294.4 g, 2.5 eq) were added under stirring, triflic anhydride (445.8 g, 2.5 eq) was added dropwise at 20°C, after the dropwise addition was completed, the reaction was stirred at 20°C for 1.5 hours, after the reaction was completed as detected by HPLC, water was added for quenching, concentrated, cooled, filtered, the filter cake was washed with ultrapure water, washed with methyl tert-butyl ether, and vacuum dried at 40°C for 24 hours to obtain compound 4-methoxynaphthol-1- yldiphenyl sulfonium triflate 286.4 g, yield: 92.0%. Water content: 0.02%.
[0033] Example 5
[0034] 1-methoxynaphthalene, diphenyl sulfide and triflic anhydride in a molar ratio of 1.0:2.5:2.5, under nitrogen protection, a 3L four-necked flask was charged with toluene 600mL, 1-methoxynaphthalene (100.0g, 1.0eq) and diphenyl sulfide (353.2g, 3.0eq) were added under stirring, triflic anhydride (535.0g, 3.0eq) was added dropwise at 10-20℃, after the addition was completed, the reaction was stirred at 10-20℃ for 1.5h, after the reaction was completed by HPLC detection, water was added for quenching, concentrated, cooled, filtered, the filter cake was washed with ultrapure water, methyl tert-butyl ether, and vacuum dried at 40℃ for 24h to obtain compound 4-methoxynaphthol-1-yl diphenyl sulfonium triflate 280.8g, yield: 90.2%. Water content: 0.04%.
[0035] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, and not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.
Claims
1. A 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate, characterized in that, The structural formula of the 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate is:
2. A method for preparing 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate as described in claim 1, characterized in that, Includes the following steps: Under a protective atmosphere, 1-methoxynaphthol, diphenyl sulfide, and an organic solvent were mixed evenly, and trifluoromethanesulfonic anhydride was added dropwise under controlled temperature. The reaction was maintained at this temperature, and after post-treatment, 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate was obtained.
3. The method for preparing 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate according to claim 2, characterized in that, The molar ratio of 1-methoxynaphthol, diphenyl sulfide, and trifluoromethanesulfonic anhydride is 1.0:(1.1–3.0):(1.1–3.0).
4. The method for preparing 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate according to claim 2, characterized in that, The reaction temperature for the dropwise addition is 10℃-20℃; the dropwise addition time is 1h-2h.
5. The method for preparing 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate according to claim 2, characterized in that, The organic solvent is one or more selected from tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, dioxane, dichloroethane, ethylene glycol dimethyl ether, chloroform, and toluene.
6. The method for preparing 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate according to claim 2, characterized in that, The protective gas is nitrogen.
7. The method for preparing 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate according to claim 2, characterized in that, The specific steps of the post-processing are as follows: After the reaction was completed, the solution was quenched with water, concentrated, filtered, washed with ultrapure water and methyl tert-butyl ether, and dried under vacuum to obtain 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate.
8. The application of 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate as described in claim 1 in the field of semiconductor chip etching.
9. The application of 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate according to claim 8 in the field of semiconductor chip etching, characterized in that, Application of the 4-methoxynaphthol-1-yldiphenylthionium trifluoromethanesulfonate in ArF, KrF, electron beam lithography or extreme ultraviolet lithography processes.