Preparation method of 2-((adamantane-1-carbonyl) oxy)-3, 3, 3-trifluoropropane-1-sulfonate triphenyl sulfonium salt

Abstract

The invention relates to the technical field of preparation of organic compounds, in particular to a preparation method of 2-((adamantane-1-carbonyl) oxy)-3, 3, 3-trifluoropropane-1-sulfonate triphenyl sulfonium salt. The preparation method comprises the following steps: slowly dropwise adding trifluoroepoxypropane into hydrobromic acid at a low temperature, so as to prepare 3-bromo-trifluoro-2-propanol; the preparation method comprises the following steps: carrying out esterification reaction on 1-adamantanecarboxylic acid and 1-adamantanecarboxylic acid under the catalysis of DMAP (Dimethylamino Phosphate) and EDCIHCl (Ethylenedicarboxylicacid) to prepare 3-bromine-1, 1, 1-trifluoropropyl-2-adamantane-1-carboxylic ester; carrying out heating reaction on the ester under the action of sodium hydrosulfite and sodium bicarbonate, and sulfonating to obtain sulfinate; oxidizing the sulfinate with hydrogen peroxide to obtain sulfonate of an anion part; the preparation method comprises the following steps: stirring sulfonate and triphenyl sulfonium chloride salt in an organic solvent to obtain a catalytic reaction solution, and carrying out post-treatment on the catalytic reaction solution to obtain the 2-((adamantane-1-carbonyl) oxy)-3, 3, 3-trifluoropropane-1-sulfonate triphenyl sulfonium salt. The preparation method disclosed by the invention is relatively short in synthetic route, has the characteristics of low cost and high efficiency, and is favorable for realizing industrial synthesis.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of organic compound preparation, and particularly relates to a preparation method of 2-((adamantan-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium. BACKGROUND

[0002] Photoresist, also known as photoresist, is a core material for microelectronic microfabrication, mainly composed of polymer, photosensitive component (such as photoacid generator), sensitizer, solvent and the like. Its principle is similar to that of a "chip picture negative", which is first uniformly coated on a substrate, and then the light area undergoes photochemical reaction after exposure to cause solubility change; then the soluble part is removed by development, and the remaining resist film forms a mask; finally, the substrate is processed by etching and the like relying on the mask, to realize pattern transfer.

[0003] Photoacid generator (PAG) is a kind of photosensitive compound that can decompose to produce acidic substances (usually protons H+) under the action of light, radiation, plasma and the like, and is the "photosensitive core" and "chemical reaction switch" of photoresist. Its core function is to accurately convert light energy into chemical reactivity, and to realize "light-controlled chemistry" through the acid catalysis of the target reaction.

[0004] The core mechanism of PAG is a three-step cascade reaction of "photoexcitation-acid generation-catalytic amplification", and its essence is to convert light energy into acid catalytic activity to realize precise light-controlled chemical response. The specific process is as follows: the photosensitive group (such as the aromatic ring of onium salt, the oxime group of oxime sulfonate) in the PAG molecule specifically absorbs photons of a specific wavelength (such as EUV 13.5 nm, ArF 193 nm, KrF 248 nm), causing the intramolecular electron to jump from the ground state to the excited state. At this time, the PAG molecule is in a high-energy unstable state, and the chemical bond is easy to break, preparing for subsequent acid generation. Depending on the type of PAG, the acid generation path is slightly different, but the core is to generate a free-moving acidic species. The generated acid acts as a catalyst to initiate subsequent target reactions (such as deprotection, crosslinking or degradation of photoresist resin), and the reaction has a "chemical amplification effect", that is, one photon triggers the generation of 1 acid molecule, and 1 acid molecule can catalyze the reaction of hundreds of resin molecules, greatly improving the light response sensitivity, and ultimately forming a significant solubility difference between the exposed area and the non-exposed area, laying a foundation for pattern transfer.

[0005] PAGs are divided into two categories according to chemical structure, namely ionic PAGs (onium salts) and non-ionic PAGs. Ionic PAGs (onium salts) include sulfonium salts (such as triaryl sulfonium salts, diaryl sulfonium salts) and iodonium salts (such as diaryl iodonium salts), which are characterized by high thermal stability, adjustable acid types (determined by anions) and low solvent solubility. Non-ionic PAGs include imide sulfonate and oxime sulfonate, which are characterized by high solvent solubility, low thermal stability and only produce sulfonic acid.

[0006] In practical applications, considering the chemical stability of the compound, onium salt compounds are often used as photoacid generators, among which sulfonium salts and iodonium salts are more prominent. The 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt of the present application belongs to sulfonium salts, which is widely used in the fields of photoresist and semiconductor and has high commercial potential. However, in the prior art, there are few reports on the preparation method of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt, and the reaction steps involved are complex, the yield is low, and the cost is high, which leads to difficulties in industrial production. Therefore, how to develop a more efficient and economical method to produce 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt has become a difficult problem for the industry. SUMMARY

[0007] The present application aims to provide a preparation method of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt, in order to solve the technical problem of how to develop a more efficient and economical method to produce 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt. The preparation method of the present application can synthesize high-purity compound 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt through a shorter synthesis route, at low cost and high efficiency, and the compound is suitable for application in the field of photoacid generator.

[0008] The present application provides a preparation method of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt, which comprises the following steps: S1, slowly adding trifluoroepoxypropane to hydrobromic acid for reaction, and obtaining intermediate product 1 through post-treatment of the reaction solution; S2, esterification of the intermediate product 1 obtained in step S1 with 1-adamantane carboxylic acid under the catalysis of DMAP and EDCI•HCl, and obtaining intermediate product 2 through post-treatment of the reaction solution; S3, the intermediate product 2 obtained in step S2 is dissolved in a mixture of organic solvent and pure water, sodium hydrosulfite and sodium bicarbonate are added, and a heating reaction is carried out, and the reaction solution is treated to obtain intermediate product 3; S4, the intermediate product 3 obtained in step S3 is dissolved in a mixture of organic solvent and pure water, and is oxidized by hydrogen peroxide to obtain an oily liquid anion; S5, the oily liquid anion obtained in step S4 is stirred with triphenylsulfonium chloride in an organic solvent and pure water to obtain a crude product, and the crude product is purified to obtain a pure product, i.e. 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium.

[0009] Optionally, in step S1, the temperature for dropping the trifluoroepoxypropane is -5~5℃; and / or the molar ratio of the trifluoroepoxypropane and hydrobromic acid is 1:(1~2), and the reaction time is 2~4 h.

[0010] Optionally, in step S2, the molar ratio of the intermediate product 1 obtained in step S1 to the 1-adamantane carboxylic acid, DMAP and EDCI•HCl is (1~1.1):1:(1~1.2):0.2.

[0011] Optionally, in step S3, the molar ratio of the intermediate product 2 obtained in step S2 to NaHCO3 and Na2S2O4 is 1:(2~4):(1.5~2.5), the reaction temperature is 56~65℃, and the reaction time is 2~6 h.

[0012] Optionally, in step S4, the hydrogen peroxide oxidation process is: drop H2O2 under ice water bath, heat the reaction after the reaction exothermic ends, cool the reaction solution to room temperature after the reaction is completed, and slowly add NaHSO3 in batches under ice water bath, and after the reaction solution is non-oxidizing, the oily liquid anion is obtained after treatment.

[0013] Optionally, in step S4, the molar ratio of the intermediate product 3 obtained in step S3 to H2O2 is 1:(0.5~1.5), the reaction temperature is 45~55℃, and the reaction time is 2~4 h.

[0014] Optionally, in step S5, the molar ratio of the triphenylsulfonium chloride to the oily liquid anion obtained in step S4 is (0.8~1):1.

[0015] Optionally, in step S5, the purification step of the crude product is: adding a beating solvent to the crude product to beat, and filtering to obtain white solid product 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium; and the beating solvent is one of n-hexane, methyl tert-butyl ether, diethyl ether, and isopropyl ether.

[0016] Optionally, in step S1, the post-treatment process is diluting the reaction solution, adjusting pH, organic solvent extraction, and spin-drying the solvent to obtain an oily liquid intermediate product 1; and / or in step S2, the post-treatment process is adding pure water to quench the reaction solution, standing and separating, adding DCM to extract the water phase once, washing the combined organic phase with 5% dilute hydrochloric acid for 3 times, washing with pure water once, and spin-drying the solvent to obtain an oily liquid intermediate product 2; and / or in step S3, the post-treatment process is standing and separating the reaction solution, and spin-drying the organic phase to obtain an oily liquid intermediate product 3.

[0017] Optionally, in step S3, the organic solvent is acetonitrile, and the volume ratio of acetonitrile to pure water is 1: (1-3); and / or in step S4, the organic solvent is acetonitrile, and the volume ratio of acetonitrile to pure water is 1: (1-3); and / or in step S5, the organic solvent is DCM, and the volume ratio of DCM to pure water is 1: (1-2).

[0018] Compared with the prior art, the above technical scheme provided by the embodiments of the present application has the following advantages: 1. The preparation method of the present application first slowly drops 1,1,1-trifluoro-2,3-epoxypropane (trifluoro epoxy propane) into hydrobromic acid at low temperature to prepare 3-bromo-trifluoro-2-propanol; then, the esterification reaction of 3-bromo-trifluoro-2-propanol and 1-adamantane carboxylic acid occurs under the catalysis of DMAP and EDCI•HCl to prepare 3-bromo-1,1,1-trifluoroprop-2-yl adamantan-1-carboxylate; the ester is heated and reacted under the action of sodium hydrosulfite and sodium bicarbonate to perform sulfonation to obtain a sulfinate salt; the sulfinate salt is oxidized by hydrogen peroxide to obtain a sulfonate salt of an anion part; the sulfonate salt and triphenylsulfonium chloride are stirred in an organic solvent to obtain a crude product of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt, and a pure product is obtained by purification, thereby realizing low-cost and efficient preparation of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt; The 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate sodium prepared by the present application has good photosensitivity and chemical stability, and is also stable to temperature, suitable for long-term storage and use, and has good commercial value. The compound has important market value and development prospect as a photo initiator of photoresist in fine pattern working operations such as semiconductor devices and microelectronic fields, and is widely used in the fields of photoresist and semiconductors; The preparation process of the application is simple, the yield is high, the reaction condition is mild, the post-treatment and purification are simple, the reproducibility is good, the raw materials are easy to obtain and cheap, and the application has good industrial production potential. BRIEF DESCRIPTION OF DRAWINGS

[0019] The accompanying drawings, which are incorporated into and form a part of the specification, illustrate an embodiment consistent with the present application and, together with the description, serve to explain the principles of the application.

[0020] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the accompanying drawings needed to be used in the embodiments or prior art description will be briefly introduced as follows. Obviously, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.

[0021] Figure 1 A flowchart of a preparation method of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium onium salt of the present application; Figure 2 A schematic diagram of a preparation method principle of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium onium salt of the present application; DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without any creative effort fall within the scope of protection of the present application.

[0023] The range descriptions described in the present application, such as numerical range, ratio range, etc., include all possible sub-ranges and single values within the range, for example, the range description of "1 to 6" or "1~6" covers all sub-ranges (such as 1 to 3, 2 to 5, etc.) and single numbers (such as 1, 2, 3, 4, 5, 6) between 1 and 6. Unless otherwise specified, the terms "comprise" and the like used herein mean "include, but not limited to"; the relationship terms "first", "second" and the like are only used to distinguish different entities or operations, and do not imply actual sequence or relationship; "and / or" means that multiple cases can exist or coexist; "at least one", "multiple", "at least one" and the like refer to any combination of the corresponding objects, including single or multiple combinations of objects. The proportional relationship involved in the present application, such as mass ratio, molar ratio, etc., should be understood as the corresponding relationship between the front and the back of the ratio according to the description order. The raw materials, reagents, instruments and equipment used in the present application can be purchased or prepared by existing methods.

[0024] As shown in Figure 1 and Figure 2 The preparation method of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt provided by the embodiments of the present application comprises the following steps: S1, slowly drop trifluoroepoxypropane into hydrobromic acid for reaction, and the reaction solution is treated to obtain intermediate product 1; S2, the intermediate product 1 obtained in step S1 is subjected to esterification reaction with 1-adamantane carboxylic acid under the catalysis of DMAP and EDCI•HCl, and the reaction solution is treated to obtain intermediate product 2; S3, the intermediate product 2 obtained in step S2 is dissolved in a mixed liquid of organic solvent and pure water, sodium hydrosulfite and sodium bicarbonate are added, and heating reaction is carried out, and the reaction solution is treated to obtain intermediate product 3; S4, the intermediate product 3 obtained in step S3 is dissolved in a mixed liquid of organic solvent and pure water, and is oxidized by hydrogen peroxide to obtain an oily liquid anion; S5, the oily liquid anion obtained in step S4 is stirred with triphenyl chlorosulfonium salt in an organic solvent and pure water to obtain a crude product, and the crude product is purified to obtain a pure product, i.e. 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt.

[0025] It should be noted that, Figure 2The preparation method principle of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt provided for the embodiments of the present application, the present application slowly drops 1,1,1-trifluoro-2,3-epoxypropane (trifluoro epoxy propane) into hydrobromic acid to obtain 3-bromo-trifluoro-2-propanol; then the esterification reaction of 3-bromo-trifluoro-2-propanol and 1-adamantane carboxylic acid occurs under the catalysis of DMAP and EDCI•HCl to form 3-bromo-1,1,1-trifluoropropan-2-adamantane-1-carboxylate; the ester is heated and reacted under the action of sodium dithionite and sodium bicarbonate to perform sulfonation to obtain a sulfinic acid salt; the sulfinic acid salt is oxidized by hydrogen peroxide to obtain a sulfonate anion; the sulfonate anion is stirred with triphenyl chlorosulfonium salt in an organic solvent to obtain a crude product of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt, and a pure product is obtained by purification, realizing low-cost and efficient preparation of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt.

[0026] The existing preparation method often depends on expensive raw materials and reagents, and the steps are complicated (multi-step protection / deprotection), and the raw materials and reagents of the preparation method of the present application are commonly used and easy to obtain, and the preparation is completed in 5 steps of “ring opening → esterification → sulfonation → oxidation → ion exchange”, the preparation method has simple steps, the raw materials are easy to obtain, the yield is high, and the cost and production cycle are greatly reduced.

[0027] The specific mechanism is as follows: 1, Br⁻ dissociated from hydrobromic acid acts as a nucleophile to occur a nucleophilic ring-opening reaction to generate 3-bromo-trifluoro-2-propanol.

[0028] 2, esterification reaction: EDCI•HCl acts as a condensing agent to activate the carboxyl group to generate an active ester intermediate, and DMAP (nucleophilic catalyst) acts as a Lewis base to coordinate with the active ester intermediate to promote the nucleophilic addition of the hydroxyl group to the active ester, and finally complete the acylation (esterification) reaction; EDCI•HCl is responsible for “activating the substrate” (converting the carboxyl group into a highly active intermediate), and DMAP is responsible for “accelerating the reaction” (reducing the energy barrier of nucleophilic attack and inhibiting side reactions), and EDCI•HCl and DMAP greatly improve the esterification reaction rate and yield through the “activation-catalysis” synergistic mechanism.

[0029] 3. Sulfonylation reaction: in the weak alkaline environment of NaHCO3, sodium dithionite (Na2S2O4) dissociates, and the dissociated free radicals attack the Br atom in the ester molecule (C-Br bond is easy to break, and Br is a good leaving group), a nucleophilic substitution reaction occurs, and a sulfite is generated; wherein the core role of sodium bicarbonate (NaHCO3) is to provide a weak alkaline reaction environment, and by adjusting the pH value of the system, the efficiency, selectivity and stability of the sulfonylation reaction are ensured.

[0030] 4. Oxidation reaction: hydrogen peroxide (H2O2) has strong oxidizing property, which can quantitatively oxidize sulfite (-SO 2- ) to sulfonic acid (-SO 3- ), realizing accurate conversion of functional groups (without over-oxidation).

[0031] 5. The anion (-SO 3- ) of sulfonate and the cation of triphenylsulfonium chloride salt undergo ion exchange reaction to combine to generate the target sulfonium salt, which can be removed and purified by simple filtration, replacing the traditional complex refining, greatly reducing the purification cost and product loss, and at the same time improving the final purity.

[0032] In summary, the preparation method of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt provided by the embodiment of the application has the core advantages of simple process, high yield, mild reaction conditions, simple post-treatment and purification, good reproducibility, easy-to-obtain and inexpensive raw materials, and good industrial production potential compared with the traditional preparation method of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt.

[0033] It should be noted that in step S1, HBr (48%) is used to ensure reaction efficiency. At the same time, in step S1, the post-treatment process is: diluting the reaction liquid, adjusting the pH, extracting with an organic solvent, and drying the solvent to obtain an oily liquid intermediate product 1. Preferably, the reaction liquid is diluted with ice water; preferably, the number of times of organic solvent extraction can be 1, 2 or 3; preferably, the organic solvent is one of dichloromethane, dichloroethane and ethyl acetate; preferably, saturated NaHCO3 is used to adjust the pH to 7-8.

[0034] It should be noted that in step S2, the esterification reaction is: the intermediate product 1 obtained in step S1 is dissolved in 100 mL of DCM, 1-adamantane carboxylic acid and DMAP are added, EDCI•HCl is added portionwise under stirring, and the reaction is carried out at room temperature overnight to obtain a reaction liquid; and the post-treatment process is: the reaction liquid is quenched by adding pure water, and is allowed to stand and separate, the aqueous phase is extracted once with DCM, the organic phases are combined, washed with 5% dilute hydrochloric acid for 3 times, washed with pure water for 1 time, and the solvent is rotary evaporated to obtain an oily liquid intermediate product 2. It should be noted that in step S3, the post-treatment process is: the reaction liquid is allowed to stand and separate, and the organic phase is rotary evaporated to obtain an oily liquid intermediate product 3.

[0035] In some optional embodiments, in step S1, the temperature for dropping the trifluoropropylene oxide is -5~5℃; and / or the molar ratio of the trifluoropropylene oxide to the hydrobromic acid is 1: (1~2), and the reaction time is 2~4 h.

[0036] In these embodiments, the temperature for dropping the trifluoropropylene oxide is controlled at -5~5℃, which can avoid side reactions of the trifluoropropylene oxide at high temperature (such as self-polymerization of the epoxy ring and generation of polysubstituted products), and low temperature can reduce the reaction rate, avoid over-reaction, and improve the regioselectivity of the ring-opening reaction. In addition, the evaporation of HBr can be avoided, and the effective concentration of HBr in the reaction system can be ensured.

[0037] The temperature for dropping the trifluoropropylene oxide can be -5℃, -4℃, -3℃, -2℃, -1℃, 0℃, 1℃, 2℃, 3℃, 4℃ or 5℃, and is preferably 0℃.

[0038] In these embodiments, the molar ratio of the trifluoropropylene oxide to the hydrobromic acid is 1: (1~2), which is conducive to ensuring the complete reaction of the trifluoropropylene oxide, reducing the residue of raw materials, and improving the yield of the target product.

[0039] The molar ratio of the trifluoropropylene oxide to the hydrobromic acid can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2.

[0040] In some optional embodiments, in step S2, the molar ratio of the intermediate product 1 obtained in step S1 to the 1-adamantane carboxylic acid, DMAP and EDCI•HCl is (1~1.1):1: (1~1.2):0.2.

[0041] In these embodiments, the molar ratio of intermediate product 1 to 1-adamantane carboxylic acid, DMAP and EDCI•HCl is (1-1.1):1:(1-1.2):0.2, which is conducive to ensuring that 1-adamantane carboxylic acid (carboxylic acid) is fully reacted, reducing the residue of carboxylic acid, DMAP can fully activate the carboxylic acid (cooperating with EDCI to form a highly active intermediate), accelerating the esterification reaction rate, while inhibiting the self-condensation side reaction of carboxylic acid, EDCI can efficiently activate the carboxyl group (combined with the catalytic effect of DMAP), reducing the impurities brought by excessive condensate. Alternatively, the molar ratio of intermediate product 1 to 1-adamantane carboxylic acid, DMAP and EDCI•HCl can be 1:1:1:0.2, 1.1:1:1:0.2, 1:1:1.1:0.2, 1:1:1.2:0.2, 1.1:1:1.1:0.2 or 1.1:1:1.2:0.2. Batch addition of EDCI•HCl is conducive to uniform stirring.

[0042] In some alternative embodiments, in step S3, the molar ratio of intermediate product 2 obtained in step S2 to NaHCO3 and Na2S2O4 is 1:(2-4):(1.5-2.5), the reaction temperature is 56-65℃, and the reaction time is 2-6 h.

[0043] In these embodiments, the molar ratio of intermediate product 2 obtained in step S2 to NaHCO3 and Na2S2O4 is 1:(2-4):(1.5-2.5), which ensures that the reaction proceeds fully and ultimately significantly improves the yield of the target product. Preferably, the molar ratio of intermediate product 2 to NaHCO3 and Na2S2O4 can be 1:2:1.5, 1:3:1.5, 1:2:1.6, 1:2:2, 1:2:2.5, 1:3:2 or 1:3:2.5.

[0044] In these embodiments, in step S3, the reaction temperature is controlled at 56-65℃, which can accelerate the reaction rate, improve production efficiency and ensure that the reaction proceeds smoothly compared to room temperature. Preferably, the reaction temperature is controlled at 56℃, 57℃, 58℃, 59℃, 60℃, 61℃, 62℃, 63℃, 64℃ or 65℃.

[0045] In some alternative embodiments, in step S4, the hydrogen peroxide oxidation process is: dropwise addition of H2O2 under ice water bath, after the reaction exothermic ends, heating reaction, after the reaction ends, the reaction liquid is cooled to room temperature, batch slow addition of NaHSO3 under ice water bath, after the reaction liquid is non-oxidizing, the oil liquid anion is obtained after post-treatment.

[0046] In the embodiments, the reaction is initially started by adding H2O2 dropwise in an ice water bath to utilize the reaction heat to initiate the oxidation, and then the deep reaction is completed by heating to make the oxidation process smooth and complete, and reduce the residual of unreacted intermediate products.

[0047] It should be noted that the reaction solution is tested by starch KI test paper to determine whether the reaction solution is oxidizable; the post-treatment process is: NaHCO3 is added to the reaction solution to adjust the pH to 6-7, the solid is removed by filtration, and the filtrate is separated by standing, and the organic phase is dried to obtain colorless transparent oil anion.

[0048] In the embodiments, in step S4, the intermediate product 3 obtained in step S3 is reacted with H2O2 at a molar ratio of 1:(0.5-1.5), the heating reaction temperature is 45-55°C, and the heating reaction time is 2-4 h.

[0049] Preferably, the molar ratio of the intermediate product 3 to H2O2 can be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:15; the heating reaction temperature can be 45°C, 46°C, 47°C, 48°C, 49°C, 50°C, 51°C, 52°C, 53°C, 54°C or 55°C; and the heating reaction time can be 2 h, 3 h or 4 h.

[0050] In some alternative embodiments, in step S5, the molar ratio of the triphenylsulfonium chloride sulfonium salt to the oil liquid anion obtained in step S4 is (0.8-1):1.

[0051] In the embodiments, the molar ratio of the triphenylsulfonium chloride sulfonium salt to the oil liquid anion obtained in step S4 is controlled to be (0.8-1):1, which is conducive to controlling the cost while ensuring that the reaction proceeds sufficiently and reducing impurities and by-products.

[0052] In some alternative embodiments, in step S5, the crude product purification step is: adding a beating solvent to the crude product for beating, and filtering to obtain white solid product 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt; and the beating solvent is one of n-hexane, methyl tert-butyl ether, diethyl ether, and isopropyl ether.

[0053] In the embodiments, n-hexane, methyl tert-butyl ether, diethyl ether, or isopropyl ether is selected as the beating solvent, which can selectively dissolve the unreacted raw materials and small molecule by-products in the crude product by low polarity characteristics, so that the target product 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt remains solid and insoluble, and high-purity product can be obtained by simple filtration.

[0054] In some optional embodiments, in step S3, the organic solvent is acetonitrile, and the volume ratio of acetonitrile to pure water is 1: (1-3).

[0055] Alternatively, the volume ratio of acetonitrile to pure water can be 1:1, 1:2 or 1:3.

[0056] In some optional embodiments, in step S4, the organic solvent is acetonitrile, and the volume ratio of acetonitrile to pure water is 1: (1-3).

[0057] Alternatively, the volume ratio of acetonitrile to pure water can be 1:1, 1:2 or 1:3.

[0058] In some optional embodiments, in step S5, the organic solvent is DCM, and the volume ratio of DCM to pure water is 1: (1-2).

[0059] Alternatively, the volume ratio of DCM to pure water can be 1:1 or 1:2.

[0060] The application will be further described below in conjunction with specific examples. The experimental methods in the following examples, if no specific conditions are noted, are generally determined according to national standards / industry standards; if there is no corresponding national standard / industry standard, they are determined according to the general international standards, conventional conditions or the conditions recommended by the manufacturers.

[0061] Example 1 A method for preparing 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1- sulfonic acid salt triphenylsulfonium salt, comprising the following steps: S1, 20.0 g of trifluoropropylene oxide was slowly added dropwise to 36.1 g of HBr (48%) at 0°C, and after the addition was completed, the reaction was carried out at 0°C for 2 h, TLC showed that the raw material was completely reacted. The reaction solution was diluted with ice water, and saturated NaHCO3 The pH was adjusted to 7-8, extracted twice with DCM, the organic phases were combined, and the solvent was rotary evaporated to obtain 21.5 g of colorless transparent oil crude product, which was directly used in the next step reaction without purification.

[0062] S2, the colorless transparent oil crude product obtained in step S1 was dissolved in 100 mL of DCM, 19.9 g of 1-adamantane carboxylic acid and 2.7 g of DMAP were added, 19.4 g of EDCI•HCl was added portionwise under stirring, and the reaction was carried out at room temperature overnight. After the reaction was completed, the reaction solution was quenched with pure water, and the liquid was separated by standing, the water phase was extracted once with DCM, the organic phases were combined, washed with 5% dilute hydrochloric acid 3 times, washed with pure water once, and the solvent was rotary evaporated to obtain 35.5 g of colorless transparent oil crude product, which was directly used in the next step reaction without purification.

[0063] S3, dissolve the colorless transparent oil-like crude product obtained in step S2 in 140 mL acetonitrile and 210 mL pure water, slowly add 25.2 g NaHCO3 and 34.8 g Na2S2O4 in batches, heat to 60 ℃ and react for 4 h, GC shows that the raw material is completely reacted. Stand and separate, the organic phase is rotary dried to obtain 32.0 g of colorless transparent oil-like crude product.

[0064] S4, dissolve the colorless transparent oil-like crude product obtained in step S3 in 80 mL acetonitrile and 80 mL pure water, slowly add 24 g of 30% H2O2 under ice water bath, after the addition is completed, heat to 50 ℃ and react for 2 h, cool to room temperature, slowly add 20 g of NaHSO3 in batches under ice water bath, after the reaction solution is tested by starch KI test paper and no oxidizing property is found, add NaHCO3 to adjust the pH to 6-7, filter to remove the solid, and the filtrate is separated, the organic phase is rotary dried to obtain 33.0 g of colorless transparent oil-like anion crude product.

[0065] S5, dissolve the colorless oil-like anion crude product obtained in step S4 in 300 mL DCM and 300 mL pure water, add 26.1 g of triphenylsulfonium chloride salt cation under stirring, and stir at room temperature overnight. Stand and separate, the organic phase is rotary dried to obtain a white solid-liquid mixed crude product, add n-hexane to pulp, filter to obtain white solid product (2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt) 16.3 g, purity 98%.

[0066] Example 2 A method for preparing 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt, comprising the following steps: S1, slowly drop 100 g of trifluoroepoxypropane into 180.5 g of HBr (48%) at 0 ℃, after the drop is completed, react at 0 ℃ for 2 h, TLC shows that the raw material is completely reacted. Dilute the reaction solution with ice water, add saturated NaHCO3 to adjust the pH to 7-8, extract twice with DCM, combine the organic phases, and rotary dry the solvent to obtain 103 g of colorless transparent oil-like crude product, which is directly used in the next step reaction without purification.

[0067] S2, dissolve the colorless transparent oil obtained in step S1 in 500 mL DCM, add 95.3 g 1-adamantane carboxylic acid and 12.9 g DMAP, and add 92.9 g EDCI•HCl portionwise under stirring, and react overnight at room temperature. After the reaction is completed, quench the reaction liquid by adding pure water, separate the liquid, add DCM to the aqueous phase to extract once, combine the organic phases, wash with 5% dilute hydrochloric acid for 3 times, wash with pure water once, and spin dry to obtain 205 g of colorless transparent oil, which is directly used in the next step without purification.

[0068] S3, dissolve the colorless transparent oil obtained in step S2 in 800 mL acetonitrile and 1200 mL pure water, slowly add 145.5 g NaHCO3 and 201 g Na2S2O4 portionwise, heat to 60 ℃ and react for 4 h, and GC shows that the raw material is completely reacted. Separate the liquid after standing, spin dry the organic phase to obtain 180 g of colorless transparent oil.

[0069] S4, dissolve the colorless transparent oil obtained in step S3 in 450 mL acetonitrile and 450 mL pure water, slowly drop 136 g 30% H2O2 under ice water bath, after the dropwise addition is completed, heat to 50 ℃ and react for 2 h after the heat is finished, cool to room temperature, slowly add 114 g NaHSO3 portionwise under ice water bath, after the reaction liquid is tested by starch KI test paper and no oxidizing property is found, adjust the pH to 6-7 by adding NaHCO3, filter to remove the solid, and spin dry the organic phase after the liquid is separated to obtain 150 g of colorless transparent oil anion crude product.

[0070] S5, dissolve the colorless oil anion crude product obtained in step S4 in 750 mL DCM and 750 mL pure water, add 118.5 g triphenylsulfonium chloride under stirring, and stir overnight at room temperature. Separate the liquid after standing, spin dry the organic phase to obtain a white solid-liquid mixed crude product, add n-hexane to make a slurry, and filter to obtain 80 g of white solid product (2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt) with a purity of 99%.

[0071] Example 3 A preparation method of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenyl sulfonium salt, comprising the following steps: S1. At 0 °C, 200 g of trifluoropropylene oxide was slowly added dropwise to 361 g of HBr (48%). After the addition was complete, the reaction was carried out at 0 °C for 2 h. TLC showed that the starting material reacted completely. The reaction solution was diluted with ice water, and the pH was adjusted to 7-8 with saturated NaHCO3. The mixture was extracted twice with DCM, and the organic phases were combined. The solvent was evaporated to obtain 210 g of colorless, transparent, oily crude product, which could be used directly in the next reaction without purification.

[0072] S2. Dissolve the colorless, transparent, oily crude product obtained in step S1 in 1 L of DCM, add 191 g of 1-adamantanecarboxylic acid and 26 g of DMAP, and add 186 g of EDCI•HCl in portions while stirring. React overnight at room temperature. After the reaction is complete, quench the reaction solution with pure water, allow it to stand and separate the layers. Extract the aqueous phase once with DCM, combine the organic phases, wash three times with 5% dilute hydrochloric acid and once with pure water, and evaporate the solvent to obtain 416 g of colorless, transparent, oily crude product, which can be used directly in the next reaction without purification.

[0073] S3. Dissolve the colorless, transparent, oily crude product obtained in step S2 in 1 L of acetonitrile and 2 L of pure water. Slowly add 292 g of NaHCO3 and 405 g of Na2S2O4 in portions. Heat to 60 °C and react for 4 h. GC shows that the reaction of the starting material is complete. Allow to stand and separate the liquids. Rotate the organic phase to dryness to obtain 364 g of colorless, transparent, oily crude product.

[0074] S4. Dissolve the colorless, transparent, oily crude product obtained in step S3 in 900 mL of acetonitrile and 900 mL of pure water. Slowly add 272 g of 30% H2O2 dropwise under an ice-water bath. After the addition is complete and the exothermic reaction is finished, heat to 50 ℃ and react for 2 h. Cool to room temperature and slowly add 230 g of NaHSO3 in batches under an ice-water bath. After the reaction solution is tested with starch-KI test paper and found to have no oxidizing properties, add NaHCO3 to adjust the pH to 6-7. Filter to remove the solid, let the filtrate stand and separate the liquids. Rotate the organic phase to dryness to obtain 310 g of colorless, transparent, oily, anionic crude product.

[0075] S5. Dissolve the colorless, oily crude anionic product obtained in step S4 in 1.5 L of DCM and 1.5 L of pure water. Add 244.9 g of triphenylsulfonium chloride cation while stirring, and stir overnight at room temperature. Allow to stand and separate the liquids. Rotate the organic phase to dryness to obtain a white solid-liquid mixture of crude product. Add n-hexane and slurry. Filter to obtain 172 g of white solid product (2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt), with a purity of 98%.

[0076] Example 4 A method for preparing 2-((adamantan-1-ylcarbonyl)oxy)-3,3,3-trifluoropropane-1- sulfonate triphenylsulfonium salt, comprising the following steps: S1, 500 g of trifluoropropene oxide was slowly added dropwise to 902.5 g of HBr (48%) at 0°C, and after the addition was completed, the reaction was carried out at 0°C for 4 h. TLC showed that the raw material was completely reacted. Ice water was added to dilute the reaction solution, saturated NaHCO3 was added to adjust the pH to 7-8, and DCM was used for extraction twice. The organic phase was combined and the solvent was rotary evaporated to obtain 530 g of colorless transparent oil. The crude product was directly used in the next step without purification.

[0077] S2, the colorless transparent oil obtained in step S1 was dissolved in 5 L of DCM, 478 g of 1-adamantane carboxylic acid and 65 g of DMAP were added, and 465 g of EDCI•HCl was added portionwise with stirring. The reaction was carried out at room temperature overnight. After the reaction was completed, pure water was added to quench the reaction, and the solution was allowed to stand and separate. The aqueous phase was extracted once with DCM, and the organic phase was combined and washed with 5% dilute hydrochloric acid three times and pure water once. The solvent was rotary evaporated to obtain 1040 g of colorless transparent oil. The crude product was directly used in the next step without purification.

[0078] S3, the colorless transparent oil obtained in step S2 was dissolved in 2.5 L of acetonitrile and 5 L of pure water, 730 g of NaHCO3 and 1013 g of Na2S2O4 were slowly added portionwise, and the reaction was carried out at 60°C for 4 h. GC showed that the raw material was completely reacted. The solution was allowed to stand and separate, and the organic phase was rotary evaporated to obtain 915 g of colorless transparent oil.

[0079] S4, the colorless transparent oil obtained in step S3 was dissolved in 2.2 L of acetonitrile and 2.2 L of pure water, 680 g of 30% H2O2 was slowly added dropwise under ice water bath, and after the addition was completed, the solution was heated to 50°C and reacted for 2 h. After cooling to room temperature, 580 g of NaHSO3 was slowly added portionwise under ice water bath. After the reaction solution was tested with starch KI paper and no oxidizing property was found, NaHCO3 was added to adjust the pH to 6-7. The solid was removed by filtration, and the filtrate was allowed to stand and separate. The organic phase was rotary evaporated to obtain 776 g of colorless transparent oil anion crude product.

[0080] S5, the colorless oil anion crude product obtained in step S4 was dissolved in 3.5 L of DCM and 3.5 L of pure water, and 613 g of triphenylsulfonium chloride salt cation was added with stirring. The solution was stirred at room temperature overnight. The solution was allowed to stand and separate, and the organic phase was rotary evaporated to obtain a white solid-liquid mixed crude product. Hexane was added to make a slurry, and the white solid product (2-((adamantan-1-ylcarbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt) was obtained by filtration. The purity was 98%.

[0081] Example 5 A method for preparing 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1- sulfonate triphenylsulfonium salt, comprising the following steps: S1, 1000 g of trifluoropropene oxide was slowly added dropwise to 1805 g of HBr (48%) at 0°C, and after the addition was completed, the reaction was carried out at 0°C for 4 h. TLC showed that the raw material was completely reacted. The reaction solution was diluted with ice water, and saturated NaHCO3 was added to adjust the pH to 7-8. DCM was used for extraction twice, and the organic phase was combined and the solvent was rotary evaporated to obtain 1075 g of colorless transparent oil. The crude product was directly used in the next step without purification.

[0082] S2, the colorless transparent oil obtained in step S1 was dissolved in 10 L of DCM, 956 g of 1-adamantane carboxylic acid and 130 g of DMAP were added, and 930 g of EDCI•HCl was added portionwise under stirring. The reaction was carried out at room temperature overnight. After the reaction was completed, the reaction solution was quenched with pure water, and the liquid was separated at rest. The aqueous phase was extracted once with DCM, and the organic phase was combined and washed with 5% dilute hydrochloric acid 3 times and pure water 1 time. The solvent was rotary evaporated to obtain 2103 g of colorless transparent oil. The crude product was directly used in the next step without purification.

[0083] S3, the colorless transparent oil obtained in step S2 was dissolved in 5 L of acetonitrile and 10 L of pure water, and 1470 g of NaHCO3 and 2030 g of Na2S2O4 were slowly added portionwise. The reaction was carried out at 60°C for 4 h. GC showed that the raw material was completely reacted. The liquid was separated at rest, and the organic phase was rotary evaporated to obtain 1850 g of colorless transparent oil.

[0084] S4, the colorless transparent oil obtained in step S3 was dissolved in 4.6 L of acetonitrile and 4.6 L of pure water, and 1360 g of 30% H2O2 was slowly added dropwise under ice water bath. After the addition was completed, the heat was allowed to end, and the reaction was carried out at 50°C for 2 h. The reaction solution was cooled to room temperature, and 1200 g of NaHSO3 was slowly added portionwise under ice water bath. After the reaction solution was tested with starch KI test paper and no oxidizing property was found, NaHCO3 was added to adjust the pH to 6-7. The solid was removed by filtration, and the filtrate was separated at rest. The organic phase was rotary evaporated to obtain 1560 g of anhydrous transparent oil anion crude product.

[0085] S5, the colorless oil anion crude product obtained in step S4 was dissolved in 7.8 L of DCM and 7.8 L of pure water, and 1232.4 g of triphenylsulfonium chloride salt cation was added under stirring. The reaction was carried out at room temperature overnight. The liquid was separated at rest, and the organic phase was rotary evaporated to obtain a white solid-liquid mixed crude product. N-hexane was added to pulp, and the white solid product (2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt) was obtained by filtration. The purity was 98%.

[0086] Comparative Example 1 Comparative Example 1 is different from Example 1 as follows, and the rest are the same: In step S1, the molar ratio of the feeding amount of trifluoropropene oxide and hydrobromic acid is 1:3.

[0087] Comparative Example 2 Comparative Example 2 is different from Example 1 as follows, and the rest are the same: In step S3, the reaction temperature is controlled at 50°C.

[0088] Comparative Example 3 Comparative Example 3 is different from Example 1 as follows, and the rest are the same: In step S5, the feeding amount of triphenylsulfonium chloride salt cation is 24 g.

[0089] Related experiments and effect data: 1. The adamantane sulfonium salt photoacid generator obtained in Example 1 has the following nuclear magnetic resonance spectrum data: 1 H NMR (DMSO, 400 MHz) δ 7.77-7.89 (m, 15H), 5.68-7.76 (m, 1H), 3.89-3.93 (dd, J = 11.2 and 3.6 Hz, 1H), 3.71-3.76 (dd, J = 11.6 and 8.4 Hz, 1H), 1.98-2.01 (m, 3H), 1.87-1.88 (d, J = 2.8 Hz, 6H), 1.68-1.69 (d, J = 3.2 Hz, 6H).2. The yield and purity of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropyl-1-sulfonate triphenylsulfonium salt obtained in each example and comparative example are counted respectively, and the results are shown in Table 1.

[0090]

[0091] As can be seen from Table 1, the preparation method of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropyl-1-sulfonate triphenylsulfonium salt provided in the examples has a purity of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropyl-1-sulfonate triphenylsulfonium salt of more than 98.0%; compared with Example 1, the feeding amount of hydrobromic acid (48%) in Comparative Example 1 is more, but the yield is not significantly improved, and from the cost point of view, the feeding amount of hydrobromic acid (48%) in Example 1 is selected; Compared with Example 1, the reaction temperature in Step S3 of Comparative Example 2 is 50°C, which is lower than that of Example 1, the yield of Comparative Example 2 is obviously lower than that of Example 1, and the purity is also lower than that of Example 1; compared with Example 1, the amount of triphenylsulfonium chloride cation added in Comparative Example 3 is less, the reaction is insufficient, and the yield of Comparative Example 3 is lower than that of Example 1.

[0092] In summary, the preparation method of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt provided by the embodiments of the present application has a simple flow, high yield, mild reaction conditions, simple post-treatment and purification, good reproducibility, easy-to-obtain and inexpensive raw materials, and good industrial production potential.

[0093] The above description is merely a specific implementation of the present application, which enables those skilled in the art to understand or implement the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined in the present application can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown in the present application, but will conform to the widest scope consistent with the principles and novel features of the present application.

Claims

1. A method for preparing a triphenylsulfonium salt of 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate, characterized in that, The preparation method includes the following steps: S1. Trifluoropropylene oxide was slowly added dropwise to hydrobromic acid to carry out the reaction. The reaction solution was post-treated to obtain intermediate product 1. S2. The intermediate product 1 obtained in step S1 is subjected to esterification reaction with 1-adamantanecarboxylic acid under the catalysis of DMAP and EDCI•HCl. The reaction solution is post-treated to obtain intermediate product 2. S3. Dissolve the intermediate product 2 obtained in step S2 in a mixture of organic solvent and pure water, add sodium dithionite and sodium bicarbonate, and heat the reaction. The reaction solution is then post-treated to obtain intermediate product 3. S4. Dissolve the intermediate product 3 obtained in step S3 in a mixture of organic solvent and pure water, and oxidize it with hydrogen peroxide to obtain an oily liquid anion. S5. The oily liquid anion obtained in step S4 is stirred with triphenylsulfonium chloride in an organic solvent and pure water to obtain a crude product. The crude product is purified to obtain a pure product, namely 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt.

2. The method for preparing a 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt according to claim 1, characterized in that, In step S1, the temperature at which the trifluoropropylene oxide is added is -5 to 5°C; and / or the molar ratio of the trifluoropropylene oxide to hydrobromic acid is 1:(1 to 2), and the reaction time is 2 to 4 h.

3. The method for preparing a 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt according to claim 1, characterized in that, In step S2, the molar ratio of intermediate product 1 obtained in step S1 to 1-adamantanecarboxylic acid, DMAP and EDCI•HCl is (1~1.1):1:(1~1.2):0.

2.

4. The method for preparing a 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt according to claim 1, characterized in that, In step S3, the molar ratio of intermediate product 2 obtained in step S2 to NaHCO3 and Na2S2O4 is 1:(2-4):(1.5-2.5), the heating reaction temperature is 56-65℃, and the heating reaction time is 2-6 h.

5. The method for preparing a 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt according to claim 1, characterized in that, In step S4, the hydrogen peroxide oxidation process is as follows: H2O2 is added dropwise under an ice-water bath. After the reaction is exothermic, the reaction is heated. After the reaction is completed, the reaction solution is cooled to room temperature. NaHSO3 is slowly added in batches under an ice-water bath. After the reaction solution is no longer oxidizing, it is post-treated to obtain an oily liquid anion.

6. The method for preparing a 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt according to claim 5, characterized in that, In step S4, the molar ratio of intermediate product 3 obtained in step S3 to H2O2 is 1:(0.5~1.5), the heating reaction temperature is 45~55℃, and the heating reaction time is 2~4 h.

7. The method for preparing a 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt according to claim 1, characterized in that, In step S5, the molar ratio of the triphenylsulfonium chloride salt to the oily liquid anion obtained in step S4 is (0.8-1):

1.

8. The method for preparing a 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt according to claim 1, characterized in that, In step S5, the crude product purification step is as follows: a pulping solvent is added to the crude product for pulping, and the mixture is filtered to obtain a white solid product 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt; the pulping solvent is one of n-hexane, methyl tert-butyl ether, diethyl ether, and isopropyl ether.

9. The method for preparing a 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt according to claim 1, characterized in that, In step S1, the post-treatment process is as follows: diluting the reaction solution, adjusting the pH, extracting with an organic solution, and evaporating the solvent to obtain an oily liquid intermediate product 1; and / or in step S2, the post-treatment process is as follows: adding pure water to quench the reaction solution, allowing it to stand and separate, extracting the aqueous phase once with DCM, combining the organic phases, washing three times with 5% dilute hydrochloric acid, washing once with pure water, and evaporating the solvent to obtain an oily liquid intermediate product 2; and / or in step S3, the post-treatment process is as follows: allowing the reaction solution to stand and separate, and evaporating the organic phase to obtain an oily liquid intermediate product 3.

10. The method for preparing a 2-((adamantane-1-carbonyl)oxy)-3,3,3-trifluoropropane-1-sulfonate triphenylsulfonium salt according to claim 1, characterized in that, In step S3, the organic solvent is acetonitrile, and the volume ratio of acetonitrile to pure water is 1:(1-3); and / or in step S4, the organic solvent is acetonitrile, and the volume ratio of acetonitrile to pure water is 1:(1-3); and / or in step S5, the organic solvent is DCM, and the volume ratio of DCM to pure water is 1:(1-2).

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