Triphenylsulfonium 1-[[(3-hydroxy-1-adamantyl) oxy] carbonyl]-2, 2-difluoroethane sulfonate and preparation method and application thereof
By preparing triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate, the problems of insufficient solubility and processing flexibility of photoacid generators in the field of semiconductor photolithography were solved, and efficient and environmentally friendly photoresist resolution improvement was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-11
- Publication Date
- 2026-03-17
AI Technical Summary
Existing photoacid generators suffer from insufficient solubility and processing flexibility in the field of semiconductor photolithography. In particular, sulfonium thionate photoacid generators containing adamantane structures have poor acid diffusion suppression effects during chip etching, which affects the resolution of the photoresist.
Triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate was used as a photo-induced acid-producing agent and prepared via a four-step reaction method, including transesterification, substitution, oxidation and coordination reactions. The preparation process is highly selective and environmentally friendly, and is carried out under inert gas protection.
A high-yield, low-cost preparation of triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate was achieved, which is suitable for semiconductor chip etching and improves the resolution and processing precision of photoresists.
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Figure CN121673210A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic chemistry, and in particular to a triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate, its preparation method, and its application. Background Technology
[0002] Photoacid generators (PAGs) are a class of substances that can decompose and generate specific acids under radiation such as light, rays, and plasma. The generated specific acids can decompose or cross-link acid-sensitive resins, thereby creating differences in the solubility and affinity properties of the illuminated and unilluminated parts, which are then developed into images.
[0003] Photoacid generators (PAGs) are key components of high-end semiconductor photoresists, and have a significant impact on the yield, quality, and processing precision of photoresists and photolithography products.
[0004] Photoacid generators can be classified into nonionic and ionic types based on their structure. Ionic photoacid generators are further divided into iodonium salts, thiodonium salts, and ammonium salts. Among them, thiodonium salt photoacid generators have seen rapid development in the field of semiconductor photochemistry due to their good solubility in solvents and resin systems, ease of processing, flexibility, and wide applicability.
[0005] Ionic photoacid generators, particularly those containing adamantane-based sulfonium thioate salts, possess large alicyclic structures that effectively suppress acid diffusion during the post-baking process of chip etching, thereby improving photoresist resolution. Therefore, photoacid generators containing adamantane-based sulfonium thioate salts have become a hot research topic. Summary of the Invention
[0006] To address at least one of the aforementioned technical problems, this invention provides a triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate, its preparation method, and its application; a novel triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate, and its preparation method is simple and has a high yield.
[0007] In one aspect, the present invention provides a triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate, the structural formula of which is shown in formula (I): Formula (I).
[0008] In another aspect, the present invention provides a method for preparing the above-mentioned triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate, comprising: In an inert gas atmosphere, a first reaction is carried out in a first reaction system consisting of an acid catalyst, ethyl 3-bromo-2,2-difluoropropionate, 1,3-adamantanediol and a first solvent to prepare the compound shown in formula (II); Formula (II) In an inert gas atmosphere, a second reaction is carried out in a second reaction system consisting of the compound shown in formula (II), sodium dithionite, water, and a second solvent to prepare the compound shown in formula (III); Formula (III) The compound shown in formula (III), 30% hydrogen peroxide, water and a third solvent are used to carry out a third reaction to prepare the compound shown in formula (IV); Formula (IV) The compound of formula (I) is prepared by a fourth reaction system consisting of the compound shown in formula (IV), triphenylsulfonium chloride, water and a fourth solvent.
[0009] In some embodiments of the present invention, in the first reaction, the molar ratio of ethyl 3-bromo-2,2-difluoropropionate, 1,3-adamantanediol, and acid catalyst is 1.0:(1.1~3.0):(0.05~1.0); and / or, the temperature of the first reaction is 50~60°C, and the time is 4~6h; for example, the temperature of the first reaction can be 51°C, 53°C, 54°C, 56°C, 58°C, etc., and the time can be 4.2h, 4.6h, 5.3h, 5.6h, 5.9h, etc.
[0010] In some embodiments of the present invention, the acid catalyst includes at least one of trifluoroacetic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; and / or the first solvent includes at least one of acetone, acetonitrile, tetrahydrofuran, dioxane, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, and toluene.
[0011] In some embodiments of the present invention, in the second reaction, the molar ratio of the compound represented by formula (II) to sodium dithionite is 1.0:(1.1~3.0); and / or, the temperature of the second reaction is 35~45°C, and the time is 9~11h; for example, the temperature of the second reaction can be 37°C, 39°C, 41°C, 43°C, 44°C, etc., and the time can be 9.2h, 9.6h, 10.3h, 10.6h, 10.9h, etc.; and / or, the second solvent includes at least one of methanol, ethanol, acetone, isopropanol, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, and dioxane.
[0012] In some embodiments of the present invention, in the third reaction, the molar ratio of the compound represented by formula (Ⅲ) to 30% hydrogen peroxide is 1.0:(2.0~5.0); and / or, the temperature of the third reaction is 10~20°C, and the time is 2~4h; for example, the temperature of the third reaction can be 11°C, 13°C, 14°C, 16°C, 18°C, etc., and the time can be 2.4h, 2.6h, 3.3h, 3.6h, 3.9h, etc.; and / or, the third solvent includes at least one of acetone, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, and dioxane.
[0013] In some embodiments of the present invention, in the fourth reaction, the molar ratio of the compound represented by formula (IV) to triphenylsulfonium chloride is 1.0:(1.1~2.0); and / or, the temperature of the fourth reaction is 20~30°C, and the time is 4~6h; for example, the temperature of the fourth reaction can be 21°C, 23°C, 24°C, 26°C, 28°C, etc., and the time can be 4.3h, 4.7h, 5.2h, 5.4h, 5.8h, etc.; and / or, the fourth solvent includes at least one selected from dichloromethane, 1,2-dichloroethane, trichloromethane, 2-methyltetrahydrofuran, and ethyl acetate.
[0014] In some embodiments of the present invention, the inert gas is at least one of nitrogen and argon.
[0015] In another aspect, the present invention provides the application of triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate in the field of semiconductor chip etching, wherein the triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate includes at least one of the above-mentioned triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate or the triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate obtained by the above-mentioned preparation method.
[0016] In some embodiments of the present invention, triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate is a photoacid-generating agent.
[0017] The technical solution provided by this invention has the following advantages: This invention relates to triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate, its preparation method, and its applications. Using ethyl 3-bromo-2,2-difluoropropionate and 1,3-adamantanediol as starting materials, triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate is obtained through transesterification, substitution, oxidation, and coordination reactions. The preparation method is simple, safe, easy to implement, and uses environmentally friendly reaction conditions, resulting in high yield and few side reactions. Therefore, the preparation method of triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate in this invention is novel, selective, environmentally friendly, low-cost, and has a high yield, making it suitable for industrial production.
[0018] Furthermore, the triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate of the present invention can be used as a photo-induced acid generator in the field of semiconductor chip etching, such as ArF lithography, KrF lithography, electron beam (EB) lithography, extreme ultraviolet (EUV) lithography, etc. Attached Figure Description
[0019] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.
[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, those skilled in the art can obtain other drawings based on these drawings without creative effort.
[0021] Figure 1 The HPLC chromatogram of triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate prepared in Example 2 of this invention is shown. Detailed Implementation
[0022] To better understand the above-mentioned objectives, features, and advantages of the present invention, the solutions of the present invention will be further described below. It should be noted that, unless otherwise specified, the embodiments of the present invention and the features thereof can be combined with each other.
[0023] Many specific details are set forth in the following description in order to provide a full understanding of the invention, but the invention may also be practiced in other ways different from those described herein; obviously, the embodiments in the specification are only some embodiments of the invention, and not all embodiments.
[0024] According to embodiments of the present invention, a triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate is provided, the structural formula of which is shown in formula (I): Formula (I).
[0025] According to embodiments of the present invention, a method for preparing triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate is provided, comprising the following steps: Step S1: In an inert gas atmosphere, ethyl 3-bromo-2,2-difluoropropionate, 1,3-adamantanediol and the first solvent are mixed evenly, an acid catalyst is added, and the mixture is refluxed at 50-60°C for 4-6 hours. After the reaction is completed by TLC, the mixture is cooled, concentrated, quenched with ice water, filtered, washed with water, and vacuum dried to obtain the compound shown in formula (II). By using excess 1,3-adamantanediol and an acid catalyst, incomplete transesterification is avoided to the greatest extent.
[0026] Step S2: Mix the compound shown in formula (II), sodium dithionite, water and the second solvent evenly, replace the inert gas under vacuum three times, keep warm and stir, and react at 35~45℃ for 9~11h. After the reaction is completed by TLC detection, cool down, filter, concentrate the filtrate to dryness, and obtain the compound shown in formula (III); by using excess sodium dithionite, incomplete substitution is avoided to the greatest extent.
[0027] Step S3: Mix the compound shown in formula (III), water, and the third solvent evenly, add 30% hydrogen peroxide dropwise under controlled temperature, keep warm and stir, and react at 10~20℃ for 2~4h. After the reaction is detected by TLC, cool down, quench with 10% sodium sulfite until the starch potassium iodide test paper does not change color, concentrate to dryness, dissolve in acetonitrile, filter, concentrate the filtrate to dryness, and obtain the compound shown in formula (IV). By adding hydrogen peroxide dropwise and controlling the temperature, the occurrence of side reactions is avoided to the greatest extent.
[0028] Step S4: Mix the compound shown in formula (IV), triphenyl sulfonium chloride, water and the fourth solvent evenly, keep warm and stir, and react at 20~30℃ for 4~6h. After the reaction is completed by HPLC detection, separate the liquid, wash with water, concentrate the organic phase, crystallize, filter, and vacuum dry to obtain the compound shown in formula (I); by using excess triphenyl sulfonium chloride, incomplete coordination reaction is avoided to the greatest extent.
[0029] The specific synthesis routes from steps S1 to S4 are as follows: In some embodiments of the present invention, in step S1, the molar ratio of ethyl 3-bromo-2,2-difluoropropionate, 1,3-adamantanediol, and the acid catalyst is 1.0:(1.1~3.0):(0.05~1.0). Within this range, the reaction between ethyl 3-bromo-2,2-difluoropropionate and 1,3-adamantanediol is most complete, resulting in the highest yield.
[0030] In some embodiments of the present invention, in step S1, the first solvent includes at least one selected from acetone, acetonitrile, tetrahydrofuran, dioxane, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, and toluene.
[0031] In some embodiments of the present invention, in step S1, the acid catalyst includes at least one of trifluoroacetic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.
[0032] In some embodiments of the present invention, in step S2, the molar ratio of the compound represented by formula (II) to sodium dithionite is 1.0:(1.1~3.0). Within this range, the compound represented by formula (II) reacts most completely with sodium dithionite.
[0033] In some embodiments of the present invention, in step S2, the second solvent is at least one of methanol, ethanol, acetone, isopropanol, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, and dioxane.
[0034] In some embodiments of the present invention, in step S3, the molar ratio of the compound represented by formula (III) to 30% hydrogen peroxide is 1.0:(2.0~5.0). Within this range, the compound represented by formula (III) reacts most completely with 30% hydrogen peroxide.
[0035] In some embodiments of the present invention, in step S3, the third solvent is at least one of acetone, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, and dioxane.
[0036] In some embodiments of the present invention, in step S4, the molar ratio of the compound represented by formula (IV) to triphenylsulfonium chloride is 1.0:(1.1~2.0). Within this range, the compound represented by formula (IV) reacts most completely with triphenylsulfonium chloride, resulting in the highest yield.
[0037] In some embodiments of the present invention, in step S4, the fourth solvent includes at least one of dichloromethane, 1,2-dichloroethane, trichloromethane, 2-methyltetrahydrofuran, and ethyl acetate.
[0038] In some embodiments of the present invention, in steps S1 and S2, the inert gas includes at least one of nitrogen and argon.
[0039] The following detailed description and explanation are provided through specific examples.
[0040] Example 1 A method for preparing triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate includes the following steps: Step S1: The molar ratio of ethyl 3-bromo-2,2-difluoropropionate and 1,3-adamantanediol was 1:1.1. Under nitrogen protection, ethyl 3-bromo-2,2-difluoropropionate (100.0 g, 1.0 eq), 1,3-adamantanediol (85.3 g, 1.1 eq), trifluoroacetic acid (2.6 g, 0.05 eq), and acetone (500 mL) were added to a 2 L four-necked flask, stirred until homogeneous, and heated to 55 °C for 5 h. After the reaction was complete as detected by TLC, the mixture was concentrated, quenched with 500 mL of water, filtered, washed with water, and dried under vacuum to obtain 144.7 g of the compound shown in formula (II), yield: 92.6%.
[0041] In the above transesterification reaction, in order to ensure that the substrates ethyl 3-bromo-2,2-difluoropropionate, 1,3-adamantanediol and acid can be fully dissolved and participate in the reaction, the first solvent used should be a polar aprotic solvent. Therefore, acetone can also be replaced by acetonitrile, tetrahydrofuran, dioxane, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether or toluene.
[0042] Trifluoroacetic acid acts as a catalyst. To ensure its full dissolution in the first solvent and participation in the reaction, common acids can be selected. Therefore, trifluoroacetic acid can also be replaced by hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, or trifluoromethanesulfonic acid.
[0043] Step S2: The molar ratio of the compound shown in formula (II) to sodium dithionite is 1:1.1. To a 2L four-necked flask, add the compound shown in formula (II) (100.0 g, 1.0 eq), sodium dithionite (56.5 g, 1.1 eq), water (300 mL), and methanol (300 mL). Purge the mixture with nitrogen three times under vacuum, stir and heat to 40°C, maintain the temperature and stir for 10 h. After the reaction is complete as detected by TLC, cool, filter, and concentrate the filtrate to dryness to obtain 100.0 g of the compound shown in formula (III), yield: 97.9%.
[0044] In the above substitution reaction, in order to fully dissolve the compound shown in formula (II) and sodium dithionite to participate in the reaction, the second solvent used should be a water-soluble organic solvent. Therefore, methanol can also be replaced by ethanol, acetone, isopropanol, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether or dioxane.
[0045] Step S3: The molar ratio of the compound shown in formula (III) to 30% hydrogen peroxide is 1:2.0. Add the compound shown in formula (III) (100.0 g, 1.0 eq), water (300 mL), and acetone (300 mL) to a 2 L four-necked flask, stir well, and add 30% hydrogen peroxide (65.5 g, 2.0 eq) dropwise at a controlled temperature of 10-20 °C. The addition is completed in about 1-2 hours. Keep the temperature at 10-20 °C for 3 hours. After the reaction is completed as detected by TLC, cool the reaction solution to 10 °C, add 10% sodium sulfite aqueous solution to quench until the starch-potassium iodide test paper does not change color, concentrate to dryness, dissolve in acetonitrile, filter, concentrate the filtrate to dryness, and obtain 97.4 g of the compound shown in formula (IV), yield: 93.1%.
[0046] In the above oxidation reaction, in order to make the compound shown in formula (Ⅲ) fully contact and react with 30% hydrogen peroxide, the solvent used should be a water-soluble organic solvent. Therefore, acetone can also be replaced by acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether or dioxane.
[0047] Step S4: The molar ratio of the compound shown in formula (IV) to triphenylsulfonium chloride is 1:1.1. Under nitrogen protection, the compound shown in formula (III) (100.0 g, 1.0 eq), triphenylsulfonium chloride (90.7 g, 1.1 eq), ultrapure water (500 mL), and dichloromethane (500 mL) are added to a 2 L four-necked flask, and stirred at 20-30 °C for 5 h. After the reaction is complete as detected by TLC, the mixture is allowed to stand, separated, extracted with dichloromethane, and the organic phases are combined, washed with water, concentrated under reduced pressure to dryness, crystallized with methyl ether, filtered, and dried under vacuum to obtain 161.0 g of the compound shown in formula (IV), triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate, with a yield of 96.8%.
[0048] In the coordination reaction described above, in order to ensure that the compound shown in formula (IV) and triphenylsulfonium chloride can fully contact and participate in the reaction and are easy to post-process, the solvent used should be a non-water-soluble polar organic solvent. Therefore, dichloromethane can also be replaced by 1,2-dichloroethane, trichloromethane, 2-methyltetrahydrofuran or ethyl acetate.
[0049] Example 2 A method for preparing triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate includes the following steps: Step S1: The molar ratio of ethyl 3-bromo-2,2-difluoropropionate and 1,3-adamantanediol was 1:2.0. Under nitrogen protection, ethyl 3-bromo-2,2-difluoropropionate (100.0 g, 1.0 eq), 1,3-adamantanediol (155.1 g, 2.0 eq), sulfuric acid (9.0 g, 0.2 eq), and acetonitrile (500 mL) were added to a 2 L four-necked flask, stirred until homogeneous, and heated to 55 °C for 5 h. After the reaction was complete as detected by TLC, the mixture was concentrated, quenched with 500 mL of water, filtered, washed with water, and dried under vacuum to obtain 152.4 g of the compound shown in formula (II), yield: 97.5%.
[0050] Step S2: The molar ratio of the compound shown in formula (II) to sodium dithionite is 1:2.0. To a 2L four-necked flask, add the compound shown in formula (II) (100.0 g, 1.0 eq), sodium dithionite (102.7 g, 2.0 eq), water (300 mL), and acetonitrile (300 mL). Purge the mixture with nitrogen three times under vacuum, stir and heat to 40°C, maintain the temperature and stir for 10 h. After the reaction is complete as detected by TLC, cool, filter, and concentrate the filtrate to obtain 101.0 g of the compound shown in formula (III), yield: 98.9%.
[0051] Step S3: The molar ratio of the compound shown in formula (III) to 30% hydrogen peroxide is 1:3.0. Add the compound shown in formula (III) (100.0 g, 1.0 eq), water (300 mL), and tetrahydrofuran (300 mL) to a 2 L four-necked flask, stir well, and add 30% hydrogen peroxide (98.2 g, 3.0 eq) dropwise at a controlled temperature of 10-20 °C over approximately 1-2 hours. Maintain the temperature at 10-20 °C for 3 hours. After the reaction is complete as detected by TLC, cool the reaction solution to 10 °C, quench with 10% sodium sulfite aqueous solution until the starch-potassium iodide test paper does not change color, concentrate to dryness, dissolve in acetonitrile, filter, and concentrate the filtrate to dryness to obtain 102.1 g of the compound shown in formula (IV), yield: 97.6%.
[0052] Step S4: The molar ratio of the compound shown in formula (IV) to triphenylsulfonium chloride is 1:1.5. Under nitrogen protection, the compound shown in formula (IV) (100.0 g, 1.0 eq), triphenylsulfonium chloride (123.7 g, 1.5 eq), ultrapure water (500 mL), and chloroform (500 mL) are added to a 2 L four-necked flask and stirred at 20-30 °C for 5 h. After the reaction is complete as detected by TLC, the mixture is allowed to stand, separated, extracted with chloroform, and the organic phases are combined, washed with water, concentrated under reduced pressure to dryness, crystallized with methyl ether, filtered, and dried under vacuum to obtain 164.0 g of the compound shown in formula (I), triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate, with a yield of 98.6%.
[0053] Example 3 A method for preparing triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate includes the following steps: Step S1: The molar ratio of ethyl 3-bromo-2,2-difluoropropionate and 1,3-adamantanediol was 1:3.0. Under nitrogen protection, ethyl 3-bromo-2,2-difluoropropionate (100.0 g, 1.0 eq), 1,3-adamantanediol (232.6 g, 3.0 eq), p-toluenesulfonic acid (63.5 g, 0.8 eq), and toluene (500 mL) were added to a 2 L four-necked flask, stirred until homogeneous, and heated to 55 °C for 5 h. After the reaction was complete as detected by TLC, the mixture was concentrated, quenched with 500 mL of water, filtered, washed with water, and dried under vacuum to obtain 143.5 g of the compound shown in formula (II), yield: 91.8%.
[0054] Step S2: The molar ratio of the compound shown in formula (II) to sodium dithionite is 1:3.0. Add the compound shown in formula I (100.0 g, 1.0 eq), sodium dithionite (154.0 g, 3.0 eq), water (300 mL), and dioxane (300 mL) to a 2 L four-necked flask. Purge the mixture with nitrogen three times under vacuum, stir and heat to 40 °C, maintain the temperature and stir for 10 h. After the reaction is complete as detected by TLC, cool, filter, and concentrate the filtrate to dryness to obtain 97.2 g of the compound shown in formula (III), yield: 95.2%.
[0055] Step S3: The molar ratio of the compound shown in formula (III) to 30% hydrogen peroxide is 1:5.0. Add the compound shown in formula (III) (100.0 g, 1.0 eq), water (300 mL), and dioxane (300 mL) to a 2 L four-necked flask, stir well, and add 30% hydrogen peroxide (163.7 g, 5.0 eq) dropwise at a controlled temperature of 10-20 °C over approximately 1-2 hours. Maintain the temperature at 10-20 °C for 3 hours. After the reaction is complete as detected by TLC, cool the reaction solution to 10 °C, quench with 10% sodium sulfite aqueous solution until the starch-potassium iodide test paper does not change color, concentrate to dryness, dissolve in acetonitrile, filter, and concentrate the filtrate to dryness to obtain 99.5 g of the compound shown in formula (IV), yield: 95.1%.
[0056] Step S4: The molar ratio of the compound shown in formula (IV) to triphenylsulfonium chloride is 1:2.0. Under nitrogen protection, the compound shown in formula (IV) (100.0 g, 1.0 eq), triphenylsulfonium chloride (165.0 g, 2.0 eq), ultrapure water (500 mL), and ethyl acetate (500 mL) are added to a 2 L four-necked flask, and stirred at 20-30 °C for 5 h. After the reaction is complete as detected by TLC, the mixture is allowed to stand, separated, extracted with ethyl acetate, and the organic phases are combined, washed with water, concentrated under reduced pressure to dryness, crystallized with methyl ether, filtered, and dried under vacuum to obtain 156.5 g of the compound shown in formula (I), triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate, with a yield of 94.1%.
[0057] The specific process for obtaining triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate by the preparation methods in Examples 1-3 is as follows: (1) Ethyl 3-bromo-2,2-difluoropropionate and 1,3-adamantanediol were transesterified under sulfuric acid catalysis to give the compound shown in formula (II); (2) The compound shown in formula (II) undergoes a substitution reaction with sodium dithionite in acetonitrile and water to give the compound shown in formula (III); (3) The compound shown in formula (III) undergoes an oxidation reaction with 30% hydrogen peroxide in tetrahydrofuran and an aqueous solvent to obtain the compound shown in formula (IV); (4) The compound shown in formula (IV) undergoes a coordination reaction with triphenylsulfonium chloride in chloroform and water solvent to give the compound shown in formula (I) triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate.
[0058] The HPLC chromatogram of triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate prepared in Example 2 is shown below. Figure 1 As shown.
[0059] In summary, the preparation method of triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate according to the embodiments of the present invention includes the following steps: ethyl 3-bromo-2,2-difluoropropionate undergoes an acid-catalyzed transesterification reaction with 1,3-adamantanediol to obtain the compound shown in formula (I); the compound shown in formula (II) undergoes a substitution reaction with sodium dithionite to obtain the compound shown in formula (III); the compound shown in formula (III) undergoes an oxidation reaction with 30% hydrogen peroxide to obtain the compound shown in formula (IV); and the compound shown in formula (IV) undergoes a coordination reaction with triphenylsulfonium chloride to obtain the compound shown in formula (I), triphenylthionium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate. The preparation method of the embodiments of the present invention is simple, the reaction system is green and environmentally friendly, has good selectivity, and the overall preparation cost is low and the yield is high.
[0060] It should be noted that, in this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.
[0061] The above description is merely a specific embodiment of the present invention, enabling those skilled in the art to understand or implement the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments described herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A triphenylsulfonium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate, characterized in that, The structure of the triphenylsulfonium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonate is shown as formula (I): Formula (I).
2. A process for the preparation of triphenylsulfonium l-[[(3-hydroxy-l- adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonic acid salt according to claim 1, characterized in that, Comprise: A first reaction system comprising an acid catalyst, ethyl 3-bromo-2,2-difluoropropionate, 1,3-adamantanediol and a first solvent in an inert gas atmosphere is carried out to prepare a compound shown as formula (II); Formula (II) A second reaction system comprising the compound shown as formula (II), sodium hydrosulfite, water and a second solvent in an inert gas atmosphere is carried out to prepare a compound shown as formula (III); Formula (III) A third reaction system comprising the compound shown as formula (III), 30% hydrogen peroxide, water and a third solvent is carried out to prepare a compound shown as formula (IV); Formula (IV) A fourth reaction system comprising the compound shown as formula (IV), triphenylsulfonium chloride, water and a fourth solvent is carried out to prepare the compound shown as formula (I).
3. The preparation method according to claim 2, characterized in that, In the first reaction, The molar ratio of ethyl 3-bromo-2,2-difluoropropionate, 1,3-adamantanediol and the acid catalyst is 1.0:(1.1-3.0):(0.05-1.0); And / or, the temperature of the first reaction is 50-60°C, and the time is 4-6h.
4. The preparation method of claim 2 or 3, characterized in that, The acid catalyst comprises at least one of trifluoroacetic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid; And / or, the first solvent comprises at least one of acetone, acetonitrile, tetrahydrofuran, dioxane, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether and toluene.
5. The method according to any one of claims 2 to 4, wherein the compound of formula (I) is prepared by the process of claim 1. In the second reaction, The molar ratio of the compound shown as formula (II) and sodium hydrosulfite is 1.0:(1.1-3.0); And / or, the temperature of the second reaction is 35-45°C, and the time is 9-11h; And / or, the second solvent comprises at least one of methanol, ethanol, acetone, isopropanol, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether and dioxane.
6. The method of any one of claims 2 to 5, wherein the compound of formula (I) is prepared by the process of claim 1. In the third reaction, The molar ratio of the compound shown as formula (III) and 30% hydrogen peroxide is 1.0:(2.0-5.0); And / or, the temperature of the third reaction is 10-20°C, and the time is 2-4h; And / or, the third solvent comprises at least one of acetone, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether and dioxane.
7. The method of any one of claims 2 to 6, wherein the method further comprises the step of: In the fourth reaction, The molar ratio of the compound shown as formula (IV) and triphenylsulfonium chloride is 1.0:(1.1-2.0); And / or, the temperature of the fourth reaction is 20-30°C, and the time is 4-6h; And / or, the fourth solvent comprises at least one of dichloromethane, 1,2-dichloroethane, chloroform, 2-methyltetrahydrofuran and ethyl acetate.
8. The preparation method of any one of claims 2-7, characterized in that, The inert gas is at least one of nitrogen and argon.
9. Use of triphenylsulfonium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonic acid salt in the field of semiconductor chip etching, characterized in that, the triphenylsulfonium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonic acid salt comprises at least one of the triphenylsulfonium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonic acid salt according to claim 1 or the triphenylsulfonium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonic acid salt obtained by the preparation method according to any one of claims 2 to 8.
10. Use according to claim 9, characterized in that, the triphenylsulfonium 1-[[(3-hydroxy-1-adamantyl)oxy]carbonyl]-2,2-difluoroethane sulfonic acid salt is a photoacid generator.