A perfluorohydrocarbon thio-based silver reagent and its preparation and application methods

Abstract

The present invention discloses a perfluoroalkylthio silver reagent and its preparation and application methods, belonging to the field of organic chemistry. In this method, an intermediate thio-perfluoroacetate is prepared through the reaction of (trifluoromethyl)trimethylsilane, cesium fluoride and carbon disulfide, and then a desulfurization fluorination reaction is carried out with silver fluoride to successfully obtain the perfluoroethylthio silver reagent. The perfluoroethylthio silver reagent obtained in the present invention can be regarded as a reactant, which reacts with N-halo-phthalimide compounds to obtain an electrophilic N-perfluoroethylthio phthalimide reagent, enriching the types of pentafluoroethylthiolating reagents; at the same time, this perfluoroethylthio silver reagent has potential application values in the fields of drug research and development, organic synthesis and antibacterial coatings, etc.

Description

Technical Field

[0001] The present invention specifically relates to a perfluoroalkylthio silver reagent and its preparation and application methods, belonging to the field of organic chemistry. Background Art

[0002] Introducing a fluorinated alkylthio group into an organic molecule can improve the lipophilicity of the parent molecule, enhance its absorption rate and metabolic stability in organisms, and has high value in the research and application of medicinal chemistry. Driven by market demand, the number of drugs containing fluorinated alkylthio fragments on the market is also increasing rapidly. Therefore, reactions related to fluorinated alkylthiolation have also attracted the attention of researchers, and how to efficiently introduce a fluorinated alkylthio functional group onto the parent structure has become the research focus of organofluorine chemistry. In recent years, various fluorinated alkylthio reagents have been successively developed by researchers and applied to the research of fluorinated alkylthiolation reactions of organic molecules. However, these reagents are often limited to SCF3 and SCF2H groups, and the preparation and reaction research of perfluoroethylthio reagents are rarely reported. Designing efficient, convenient and economical fluorinated alkylthio reagents is crucial, especially the currently scarce pentafluoroethylthio reagents urgently need to be studied and developed. Therefore, designing and synthesizing novel pentafluoroethylthio reagents and expanding the corresponding pentafluoroethylthiolation reaction strategies have important research value and significance. Summary of the Invention

[0003] The present invention develops the preparation and application of a novel perfluoroalkylthio silver reagent, that is, the preparation of a perfluoroethylthio silver reagent and its application in the synthesis of electrophilic N-perfluoroethylthiolated reagents and antibacterial coatings. In the preparation method of perfluoroethylthio silver, the present invention reacts (trifluoromethyl)trimethylsilane, cesium fluoride with carbon disulfide to obtain a cesium salt intermediate of thio-perfluoroacetic acid; the cesium salt of thio-perfluoroacetic acid reacts with silver fluoride to prepare a perfluoroethylthio silver compound; in the synthesis method of electrophilic N-perfluoroethylthiolated reagents, the present invention synthesizes N-perfluoroethylphthalimide by reacting N-halo-phthalimide with perfluoroethylthio silver. In addition, the inhibitory effects of perfluoroethylthio silver on Staphylococcus aureus, Escherichia coli and Klebsiella pneumoniae were also investigated.

[0004] The object of the present invention is to provide a perfluoroethylthio silver with the structural formula AgSC2F5.

[0005] The present invention also provides a preparation method for the above-mentioned perfluoroethylthio silver, including the following steps:

[0006]

[0007] (1) In an organic solvent, (trifluoromethyl)trimethylsilane shown by formula (1), cesium fluoride shown by formula (2), and carbon disulfide shown by formula (3) are used as reactants for a reaction. After the reaction ends, cesium perfluorothioacetate (CF3CS2Cs) shown by formula (4) is obtained;

[0008] (2) The obtained cesium perfluorothioacetate shown by formula (4) and silver fluoride are used as reactants for a reaction. After the reaction ends, silver perfluoroethylthiol shown by formula (5) is obtained.

[0009] In one embodiment of the present invention, the reaction in step (1) is carried out in an organic solvent environment. The organic solvent includes any one or more of ethylene glycol dimethyl ether (DME), diethyl ether (Et2O), and ethylene glycol diethyl ether, and DME is preferred.

[0010] In one embodiment of the present invention, the dosage of cesium fluoride relative to the organic solvent in step (1) is 0.1 - 1.0 mmol / mL. Specifically, 0.4 mmol / mL can be selected.

[0011] In one embodiment of the present invention, in step (1), the molar ratio of cesium fluoride to carbon disulfide is 1:(1.0 - 2.0). Specifically, 1:1.8 is preferred.

[0012] In one embodiment of the present invention, in step (1), the molar ratio of cesium fluoride to (trifluoromethyl)trimethylsilane is 1:(1.0 - 2.0). Specifically, 1:1.5 is preferred.

[0013] In one embodiment of the present invention, the temperature of the reaction in step (1) is -10°C - 10°C. 0°C is preferred.

[0014] In one embodiment of the present invention, the reaction time in step (1) is 3 - 8 h. 6 h is preferred.

[0015] In one embodiment of the present invention, the reaction in step (1) is carried out in an inert atmosphere. Such as nitrogen.

[0016] In one embodiment of the present invention, in step (2), the molar ratio of cesium perfluorothioacetate to silver fluoride is 1:(3.0 - 6.0). Specifically, 1:3.3 is preferred.

[0017] In one embodiment of the present invention, the reaction in step (2) is carried out in a solvent. The solvent is any one or more of tetrahydrofuran (THF) and acetonitrile (MeCN). THF is preferred.

[0018] In one embodiment of the present invention, the amount of cesium perfluorothioacetate relative to the solvent in step (2) is 0.2 - 0.5 mmol / mL. Specifically, 0.36 mmol / mL can be selected.

[0019] In one embodiment of the present invention, the temperature of the reaction in step (2) is 70°C - 90°C. Preferably 70°C.

[0020] In one embodiment of the present invention, the reaction time in step (2) is 6 - 24 h. Specifically, 14 h can be selected.

[0021] In one embodiment of the present invention, the reaction in step (2) is carried out in an inert atmosphere. Such as nitrogen.

[0022] The present invention also provides the use of the above-mentioned silver perfluoroethylthiolate in the preparation of N-perfluoroethylthio phthalimide reagent.

[0023] In one embodiment of the present invention, a method for preparing N-perfluoroethylthio phthalimide reagent includes the following process:

[0024] In a solvent, N-halo phthalimide shown in formula (6) and silver perfluoroethylthiolate shown in formula (5) are used as reactants for reaction, and after the reaction is completed, the N-perfluoroethylthio phthalimide reagent shown in formula (7) is obtained;

[0025]

[0026] Among them, X is selected from Cl, Br; formula (7) is N-perfluoroethylthio phthalimide or N-perfluoroethylthio hexahydrophthalimide.

[0027] In one embodiment of the present invention, when synthesizing the N-perfluoroethylthio phthalimide reagent shown in formula (7), the reaction is carried out in a solvent, and the solvent includes one or more of acetonitrile (MeCN), tetrahydrofuran (THF), preferably MeCN.

[0028] In one embodiment of the present invention, the molar ratio of the N-halo phthalimide to silver perfluoroethylthiolate is 1:(1.0 - 2.0). Preferably 1:1.1.

[0029] In one embodiment of the present invention, the amount of the N-halo phthalimide relative to the solvent is 0.1 - 1.0 mmol / mL. Specifically, 0.4 mmol / mL can be selected.

[0030] In one embodiment of the present invention, when synthesizing the N-perfluoroethylthio phthalimide reagent shown in formula (7), the reaction temperature is 20°C - 50°C. Preferably room temperature (20 - 30°C).

[0031] In one embodiment of the present invention, when synthesizing the N-perfluoroethylthio phthalimide reagent shown in formula (7), the reaction time is 2 - 8 h. Preferably 4 h.

[0032] In one embodiment of the present invention, a preparation method of a novel green economy silver perfluoroethylthiolate is as follows:

[0033] Using (trifluoromethyl)trimethylsilane, cesium fluoride and carbon disulfide as raw materials, after stirring and reacting for a period of time in a nitrogen (N2) atmosphere at -10°C - 10°C, a crude product of cesium perfluorothioacetate is obtained, and then cesium perfluorothioacetate is obtained through filtration, washing and vacuum distillation; then, using cesium perfluorothioacetate and silver fluoride as raw materials, after stirring and reacting for a period of time in a nitrogen (N2) atmosphere at 70°C - 90°C, a crude product of silver perfluoroethylthiolate is obtained, and then silver perfluoroethylthiolate is obtained through filtration, washing and vacuum distillation.

[0034] In one embodiment of the present invention, the method is preferably carried out as follows: Under the condition of maintaining a nitrogen atmosphere, (trifluoromethyl)trimethylsilane, cesium fluoride and carbon disulfide are added to a reaction vessel containing ethylene glycol dimethyl ether solvent according to a molar ratio of 1.5:1:1.8, and stirred at -10°C - 10°C for 3 - 8 hours, and then the intermediate cesium perfluorothioacetate is obtained by separation and purification. Cesium perfluorothioacetate and silver fluoride are added to a reaction vessel containing tetrahydrofuran solvent according to a molar ratio of 1:3.3, and stirred at 70°C - 90°C for 12 - 24 hours, and the silver perfluoroethylthiolate reagent is obtained by separation and purification.

[0035] In one embodiment of the present invention, a synthesis method of N-perfluoroethylthio phthalimide is as follows:

[0036] Using N-halo phthalimide and silver perfluoroethylthiolate as raw materials, after stirring and reacting for a period of time in a nitrogen (N2) atmosphere at 20°C - 50°C, a crude product of N-perfluoroethylthio phthalimide reagent is obtained, and then a pure product is obtained through filtration, washing, extraction and vacuum distillation.

[0037] In one embodiment of the present invention, the method is preferably carried out as follows: Under the condition of maintaining a nitrogen atmosphere, N-halo phthalimide and silver perfluoroethylthiolate are added to a reaction vessel containing acetonitrile solvent according to a molar ratio of 1:1.1, and stirred at 20°C - 50°C for 2 - 8 hours, and then separated and purified to obtain a pure N-perfluoroethylthio phthalimide reagent.

[0038] In one embodiment of the present invention, the obtained N-perfluoroethylthio phthalimide can be used as a reagent for the perfluoroethylthiolation of various bioactive molecules. For example, as described in the existing literature (Electrophilic Reagents for the Direct Incorporation of Uncommon SCF2CF2H and SCF2CF3 Motifs. J. Org. Chem. 2022, 87, 10791-10806).

[0039] The present invention also provides the application of the above-mentioned silver perfluoroethylthiolate in the preparation of antibacterial agents.

[0040] The present invention also provides an antibacterial agent containing the above-mentioned silver perfluoroethylthiolate.

[0041] The present invention provides the application of the above-mentioned silver perfluoroethylthiolate in the antibacterial field of non-disease diagnosis and treatment.

[0042] Beneficial effects

[0043] In the method of the present invention, under a nitrogen atmosphere, (trifluoromethyl)trimethylsilane, cesium fluoride and carbon disulfide react to obtain a cesium perfluorothioacetate salt intermediate. The cesium perfluorothioacetate salt reacts with silver fluoride to prepare a silver perfluoroethylthiolate reagent, and the silver perfluoroethylthiolate reacts with N-halo phthalimide to generate an N-perfluoroethylthio phthalimide reagent, enriching the types of pentafluoroethylthiolation reagents.

[0044] The target compound of the method of the present invention has potential application values in the fields of drug research and development, organic synthesis, antibacterial coatings, etc. Description of the drawings

[0045] Figure 1 It is a synthetic route diagram of the silver perfluorohydrocarbonthiolate reagent of the present invention.

[0046] Figure 2 It is a synthetic route diagram of the N-perfluoroethylthio phthalimide reagent of the present invention. Specific embodiments

[0047] The following are the specific embodiments of silver perfluoroethylthiolate in the present invention.

[0048] The synthetic route diagram of the examples of the present invention is as Figure 1 shown:

[0049] Using (trifluoromethyl)trimethylsilane, cesium fluoride, and carbon disulfide as raw materials, they were added to a reaction flask containing ethylene glycol dimethyl ether under a nitrogen atmosphere. Then, the reaction flask was placed in an ice bath at -10°C to 10°C and reacted for 3 to 8 hours to obtain a crude product of cesium perfluorothioacetate. After separation and purification, using cesium perfluorothioacetate and silver fluoride as raw materials, they were added to a reaction flask containing acetonitrile under a nitrogen atmosphere. Then, the reaction flask was placed in an oil bath at 70°C to 90°C and reacted for 12 to 24 hours.

[0050] Example 1: Preparation of Silver Perfluoroethyl Thiolate

[0051] (1) Weigh 1.52 g (10.0 mmol, 1.0 equiv) of cesium fluoride and add it to a 50 mL Schlenk reaction flask. Under 0°C and nitrogen protection, add 25 mL of anhydrous ethylene glycol dimethyl ether (DME) and 1.37 g (18.0 mmol, 1.8 equiv) of carbon disulfide, stir for 5 minutes, and slowly add TMSCF3 (2.13 g, 15.0 mmol, 1.5 equiv) dropwise with a syringe. After the addition is complete, control the temperature at 0°C and continue the reaction for 3 h. As the reaction proceeds, the color of the solution gradually deepens (finally dark red). After the reaction is completed, dilute the reaction solution with ethyl acetate, filter to remove unreacted CsF, distill off the solvent under reduced pressure, add petroleum ether to precipitate a solid, collect the filter residue, dry it, and obtain an orange solid intermediate, cesium salt of CF3CS2Cs (2.23 g, yield 80%);

[0052] (2) Weigh 2.00 g (7.2 mmol, 1.0 equiv) of the obtained cesium salt of CF3CS2Cs and 3.0 g (23.7 mmol, 3.3 equiv) of silver fluoride respectively, add them to a 50 mL three-necked flask. Under nitrogen protection, add 20 mL of dry THF, reflux and react at 70°C for 14 h, and then end the reaction. Distill off the solvent under reduced pressure, add ethyl acetate (20 mL), filter with diatomaceous earth, collect the filtrate, distill off the solvent under reduced pressure, add a small amount of acetonitrile to dissolve the solid, and then add an appropriate amount of petroleum ether along the wall of the flask for recrystallization to obtain a large amount of solid. Filter, collect the filter residue, dry it, and obtain 1.64 g of yellow solid AgSC2F5 with a yield of 80%.

[0053] 19 19F NMR (376 MHz, DMSO-d6) δ -63.46 (q, J = 5.5 Hz, 2F), -82.51 (t, J = 5.5 Hz, 3F).

[0054] Example 2: Influence of Different Solvents on the Preparation of Cesium Perfluorothioacetate

[0055] Referring to Example 1, adjust the solvent in step (1) and keep other conditions unchanged to prepare the corresponding product. The results are shown in Table 1.

[0056] Table 1 Influence of Different Solvents on the Preparation of Cesium Thioheptafluorobutyrate

[0057] Solvent <![CDATA[Yield (%) a > DME 80 Ethylene glycol diethyl ether 74 Diethyl ether 43 <![CDATA[H2O]]> 0

[0058] a. The yield is the isolated yield

[0059] It was found that: When using diethyleneglycol dimethyl ether, diethyl ether, or water to replace the dimethoxyethane in Example 1 as the solvent, the yields of the obtained products were all worse than that in Example 1.

[0060] Example 3: Influence of Different Temperatures on the Preparation of Cesium Thioheptafluorobutyrate

[0061] Referring to Example 1, adjust the temperature in step (1) while keeping other conditions unchanged to prepare the corresponding product. The results are shown in Table 2.

[0062] Table 2 Influence of Different Temperatures on the Preparation of Cesium Thioheptafluorobutyrate

[0063] Temperature (°C) <![CDATA[Yield (%) a > -10 70 0 80 10 67

[0064] a. The yield is the isolated yield

[0065] It was found that: When using -10°C or 10°C to replace 0°C in Example 1, the yields of the obtained products were all worse than that in Example 1.

[0066] Example 4: Influence of Different Solvents on the Preparation of Silver Perfluoroethylthiolate

[0067] Referring to Example 1, adjust the solvent in step (2) while keeping other conditions unchanged to prepare the corresponding product. The results are shown in Table 3.

[0068] Table 3 Influence of Different Solvents on the Preparation of Silver Perfluoroethylthiolate

[0069] Solvent <![CDATA[Yield (%) a > THF 80 MeCN 64

[0070] a. The yield is the isolated yield

[0071] It was found that: When using acetonitrile to replace tetrahydrofuran in Example 1 as the solvent, the yield of the obtained product was worse than that in Example 1.

[0072] Example 5: Influence of Different Temperatures on the Preparation of Silver Perfluoroethylthiolate

[0073] Referring to Example 1, adjust the temperature in step (2) while keeping other conditions unchanged to prepare the corresponding product. The results are shown in Table 4.

[0074] Table 4 Influence of Different Temperatures on the Preparation of Cesium Thioheptafluorobutyrate

[0075] Temperature (°C) <![CDATA[Yield (%) a > 70 80 80 79 90 76

[0076] a. The yield is the separation yield.

[0077] It was found that when 80 °C and 90 °C were used to replace 70 °C in Example 1, the product yields obtained were all worse than that in Example 1.

[0078] Example 6: Antibacterial performance test of silver perfluoroethyl sulfide

[0079] Take 100 g of steel plate topcoat, add 0.5 g of AgSC2F5, and stir at high speed for one hour to prepare an antibacterial coating. Then, on the steel plate coated with primer, use an RDS#16 bar to apply the antibacterial coating, and bake it in a forced-air oven at 260 °C for 55 seconds to form a 15-μm steel plate topcoat coating, thus preparing a sample for evaluation. A total of 19 samples for evaluation were prepared and entrusted to a third-party testing agency to test the samples for evaluation according to JIS Z2801:2010 amendment1 - 2012 "Antibacterial processed products - Test for antibacterial activity and effectiveness". The test results showed that for Staphylococcus aureus, the antibacterial activity value was 5.7; for Escherichia coli, the antibacterial activity value was 6.5; for Klebsiella pneumoniae, the antibacterial activity value was 6.3. Convert the above activity values to antibacterial rates, and the antibacterial rates of AgSC2F5 against the above three bacteria, Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae, all reached over 99.9%.

[0080] Performance comparison of existing known similar structures: Refer to the above antibacterial test process to compare the antibacterial effects against Staphylococcus aureus and Escherichia coli. Replace AgSC2F5 with an equal mass of AgSCF3, and it was found that for Staphylococcus aureus, the antibacterial activity value of AgSCF3 was 0.7; for Escherichia coli, the antibacterial activity value was 1.2; convert them to antibacterial rates, and the antibacterial rates against Staphylococcus aureus and Escherichia coli were 80.00% and 93.32 respectively, which were significantly inferior to AgSC2F5.

[0081] Example 7: Synthesis of aryl perfluoroethyl sulfide using silver perfluoroethyl sulfide

[0082]

[0083] Under room temperature air conditions, 4-nitrobenzenediazonium tetrafluoroborate (118 mg, 0.5 mmol), AgSC2F5 (194 mg, 0.75 mmol), copper(I) iodide (95 mg, 0.5 mmol), potassium carbonate (138 mg, 1.0 mmol) and acetonitrile (5 mL) were added to a 50 ml reaction tube equipped with a magnetic stir bar and stirred vigorously at room temperature for 12 hours. After the reaction was completed, the reaction mixture was diluted with dichloromethane, filtered through diatomaceous earth, and washed with dichloromethane. The organic phases were combined, dried over anhydrous MgS2O4, filtered, a small amount of silica gel was added to the filtrate, concentrated under vacuum, and the target compound was purified by column chromatography using n-hexane / ethyl acetate as the eluent to obtain 95 mg of the product with a yield of 70%.

[0084] 1 H NMR (400 MHz, CDCl3) δ 8.28 (d, J = 8.9 Hz, 2H), 7.85 (d, J = 8.8 Hz, 2H). 19 F NMR (376 MHz, CDCl3) δ -82.53 (t, J = 3.4 Hz, 3F), -90.83 (q, J = 3.4 Hz, 2F). 13 C NMR (101 MHz, CDCl3) δ 149.6 (s), 137.6 (s), 131.0 (t, J = 2.6 Hz), 124.4 (s), 120.1 (tq, J = 291.0, 41.0 Hz), 118.6 (qt, J = 286.7, 36.2 Hz).

[0085] The reported method (Synthesis of aryl perfluoroalkyl sulfides from aromatic disulfides. Russ. Chem. Bull., Int. Ed., Vol. 53, No. 2, February, 2004) for constructing aryl ethyl sulfide is as follows:

[0086]

[0087] Specific preparation process: At -20 °C, XeF2 (1.4 g, 8.2 mmol), perfluoroacetic acid (1.5 mL), 1,2-bis(4-nitrophenyl) disulfide (832 mg, 2.7 mmol) and dichloromethane (30 mL) were added to a reaction tube, stirred and allowed to warm to 5 °C naturally. Neutralized with aqueous Na2CO3 solution, extracted with chloroform, dried the extract with Na2SO4, removed the solvent by distillation under reduced pressure, and purified the crude product by column chromatography using petroleum ether as the eluent to obtain the target compound with a yield of 30.3%.

[0088] Corresponding preparation results: The yield of the 4-nitrophenyl perfluoroethyl sulfide compound obtained by the above method is only 30.3%, which is significantly lower than the yield of the method of the present invention (70%).

[0089] The following are the specific embodiments for preparing the N-perfluoroethylthio phthalimide reagent in the present invention.

[0090] The preparation route diagram of the examples of the present invention is as Figure 1 shown

[0091] Using N-halo phthalimide and silver perfluoroethyl sulfide as raw materials, they are added to a reaction flask containing acetonitrile under a nitrogen atmosphere, and then the reaction flask is placed in an oil bath at 20°C - 50°C and reacted for 2 - 8 hours.

[0092] Example 8: Synthesis of N-perfluoroethylthio phthalimide

[0093] Weigh 1.81 g (10.0 mmol, 1.0 equiv) of N-chloro phthalimide and 2.85 g (10.0 mmol, 1.0 equiv) of silver perfluoroethyl sulfide, add them to a 50 mL Schlenk reaction flask, and add 25 mL of anhydrous acetonitrile under nitrogen protection. Stir at room temperature (25°C) for 4 hours, distill off acetonitrile under reduced pressure, add ethyl acetate (20 ml), filter with diatomaceous earth, collect the filtrate, distill off the solvent under reduced pressure, and further vacuum dry the remaining solid to obtain 2.1 g of a white solid with a yield of 70%.

[0094] 1 H NMR (400 MHz, CDCl3) δ 8.06–7.97 (m, 2H), 7.91–7.83 (m, 2H). 19 F NMR (376 MHz, CDCl3) δ -82.82 (t, J = 3.1 Hz, 3F), -98.58 (q, J = 2.8 Hz, 2F). 13 C NMR (101 MHz, CDCl3) δ 165.9 (s), 135.6 (s), 131.6 (s), 124.8 (s), 118.6 (tq, J = 293.1 Hz, 41.4 Hz), 118.2 (qt, J = 284.6 Hz, 36.0 Hz). HRMS (ESI) m / z calculated for C 10 H5F5NO2S [M + H] + : 297.9961, found 297.9956.

[0095] Example 9: Synthesis of N-perfluoroethylthio hexahydrophthalimide

[0096] Weigh 1.81 g (10.0 mmol, 1.0 equiv) of N-perfluoroethylthiohexahydrophthalimide and 2.85 g (10.0 mmol, 1.0 equiv) of silver perfluoroethylthiolate, add them into a 50 mL Schlenk reaction flask, and add 25 mL of anhydrous acetonitrile under nitrogen protection. Stir at room temperature for 4 hours, distill off acetonitrile under reduced pressure, add ethyl acetate (20 ml), filter through diatomaceous earth, collect the filtrate, distill off the solvent under reduced pressure, and further dry the remaining solid under vacuum to obtain 2.1 g of a white solid with a yield of 61%.

[0097] 1 H NMR (400 MHz, CDCl3) δ 3.07 (td, J = 4.4, 2.3 Hz, 1H), 2.91 (tt, J = 4.6, 2.1 Hz, 1H), 1.98–1.72 (m, 4H), 1.47 (tq, J = 9.1, 4.6, 4.0 Hz, 4H). 19 F NMR (376 MHz, CDCl3) δ -82.97 (t, J = 3.4 Hz), -98.05 (q, J = 3.3 Hz). 13 C NMR (101 MHz, CDCl3) δ 180.04–179.92, 177.07–176.88, 122.70–121.24 (m), 120.13–118.25 (m), 117.32–115.76 (m), 41.24–40.74 (d, J = 29.4 Hz), 24.37–23.70 (d, J = 42.6 Hz), 22.18–21.74 (d, J = 23.1 Hz). HRMS (ESI) m / z calculated for C 10 H 11 F5N1O2S [M+H] + : 304.0434, found: 304.0431。

[0098] Example 10: Influence of Different Solvents on the Synthesis of N-Perfluoroethylthiol Phthalimide

[0099] Referring to Example 8, adjust the type of solvent and keep others unchanged. The corresponding preparation results are shown in Table 5.

[0100] Table 5 Influence of Different Solvents on the Synthesis of Cesium Thio Perfluoroacetate

[0101] Solvent <![CDATA[Yield (%) a > Acetonitrile 70 THF 57

[0102] a. The yield is the isolated yield

[0103] It was found that: when tetrahydrofuran was used to replace acetonitrile in Example 8 as the solvent, the yields of the obtained products were all worse than those in Example 8.

[0104] Example 11: Influence of Different Temperatures on the Synthesis of N-Perfluoroethylthio Phthalimide

[0105] Referring to Example 8, adjust the temperature while keeping other conditions unchanged. The corresponding preparation results are shown in Table 6.

[0106] Table 6 Influence of Different Temperatures on the Synthesis of Cesium Thio Perfluoroacetate

[0107] Temperature (°C) <![CDATA[Yield (%) a > 0 34 25 70 50 51

[0108] a. The yield is the isolated yield

[0109] It was found that: When 0 °C and 50 °C were used to replace 25 °C in Example 8, the product yields obtained were worse than those in Example 8.

[0110] The examples provided above are not intended to limit the scope covered by the present invention, nor are the described steps intended to limit the order of their execution. Obvious improvements made by those skilled in the art in combination with the existing common general knowledge also fall within the protection scope defined by the claims of the present invention.

Claims

1. A method for preparing silver perfluoroethylthiolate, characterized in that, The structural formula of the silver perfluoroethylthiolate is AgSC2F5, and it includes the following steps: (1) In an organic solvent, (trifluoromethyl)trimethylsilane shown in formula (1), cesium fluoride shown in (2), and carbon disulfide shown in formula (3) are used as reactants for reaction. After the reaction is completed, cesium perfluorothioacetate (CF3CS2Cs) shown in (4) is obtained; (2) The obtained cesium perfluorothioacetate shown in formula (4) and silver fluoride are used as reactants for reaction. After the reaction is completed, silver perfluoroethylthiolate shown in (5) is obtained.

2. The method according to claim 1, wherein The reaction in step (1) is carried out in an organic solvent environment, and the organic solvent includes any one or more of ethylene glycol dimethyl ether, diethyl ether, and ethylene glycol diethyl ether.

3. The method according to claim 1, wherein In step (1), the amount of cesium fluoride relative to the organic solvent is 0.1 - 1.0 mmol / mL; the molar ratio of cesium fluoride to carbon disulfide is 1:(1.0 - 2.0); the molar ratio of cesium fluoride to (trifluoromethyl)trimethylsilane is 1:(1.0 - 2.0).

4. The method according to claim 1, characterized in that The reaction in step (2) is carried out in a solvent, and the solvent is any one or more of tetrahydrofuran and acetonitrile.

5. The method according to claim 4, characterized in that In step (2), the amount of cesium perfluorothioacetate relative to the solvent is 0.2 - 0.5 mmol / mL; the molar ratio of cesium perfluorothioacetate to silver fluoride is 1:(3.0 - 6.0).

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