A method for synthesizing a 2-perfluoroethylthio-1-arylethyl ketone compound

Abstract

This invention discloses a method for synthesizing 2-perfluoroethylthio-1-aryl ethyl ketone, belonging to the field of organic chemistry. This method, under an O2 atmosphere, uses inexpensive and readily available arylethylene as a substrate, perfluoroethylthiosilver as the perfluoroethylthio source, and potassium persulfate as the oxidant to synthesize the 2-perfluoroethylthio-1-aryl ethyl ketone compound. This invention features broad substrate applicability, convenient operation, and yields a good amount of the target compound within 3-24 hours. The target compound has wide applications in pharmaceuticals, pesticides, and petrochemicals.

Description

Technical Field

[0001] This invention relates to a method for synthesizing a 2-perfluoroethylthio-1-arylethyl ketone compound, belonging to the field of organic chemistry. Background Technology

[0002] Fluorine-containing organic compounds are widely used in daily life. It is reported that approximately 20% of pharmaceuticals and 35% of pesticides currently on the market contain fluorine atoms. In the pharmaceutical field, for example, the literature (Science Direct 1986; 22:1721–1729) reports that losartan analogs containing the SCF3 group are representative drugs of angiotensin II receptor antagonists (ARBs), which dilate peripheral blood vessels and reduce peripheral resistance by blocking the vasoconstrictive effect of angiotensin II, thereby steadily lowering blood pressure. In the pesticide field, for example, the literature (Pest Manag Sci 2024; 80: 3065–3087) reports that the calcium-activated channel (KCa2) modulator acaricide, acinonap, has a certain acaricidal effect and can be used as an acaricide. In the chemical field, for example, the literature (J. Med. Chem. 2025, 68, 2942)... 4-Trifluoromethylbenzoic acid (4-trifluoromethylbenzoic acid) was reported in 2962 as a precursor compound for the synthesis of novel 1,3,4-thiadiazole compounds, which are inhibitors of deformylases of drug-resistant Gram-positive and Gram-negative bacterial peptides. 4-Trifluoromethylbenzoic acid has numerous applications in pharmaceutical synthesis intermediates, pesticide intermediates, materials, and electronic chemicals.

[0003] Due to increasing market demand, the synthesis of α-fluorinated aryl ethyl ketones has attracted much attention. Researchers have found that the multifunctionalization strategy of important organic intermediates (enes and alkynes) has become an effective route for synthesizing α-fluorinated ethyl ketones. Currently, methods for obtaining α-fluorinated ethyl ketones from ethylene (alkynes) structures cover most fluorinated functional groups, such as -CF2H, -CF3, -C2F5, and -SCF3. However, a systematic synthetic method for α-perfluoroethyl thiolated aryl ethyl ketones has not yet been developed. Therefore, developing a simple and efficient synthetic method for α-perfluoroethyl thiolated aryl ethyl ketones has significant practical application value. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a method for synthesizing 2-perfluoroethylthio-1-arylethyl ketone compounds. Under an oxygen atmosphere, using arylethylene compounds as substrates and AgSC2F5 reagent as the perfluoroethylthiolation reagent, and with the aid of an oxidizing agent, this invention enables the one-step perfluoroethylthiolation and carbonylation of arylethylene compounds to obtain the target compound.

[0005] This invention is achieved through the following technical solution: The first objective of this invention is to provide a method for synthesizing a 2-perfluoroethylthio-1-aryl ethyl ketone compound, wherein the method involves reacting an aryl ethylene compound of formula (1) with a perfluoroethylthio-silver compound of formula (2) as reactants in an organic solvent under an oxygen atmosphere, and the reaction is carried out under the action of an oxidant, and the 2-perfluoroethylthio-1-aryl ethyl ketone compound of formula (3) is obtained after the reaction is completed.

[0006] Among them, R 1 Selected from H, C1-C8 alkyl, C1-C8 haloalkyl, aryl, halogen (F, Cl, Br), cyano, nitro, C1-C8 alkoxy, acyl; R 2 Selected from H and C1-C8 alkyl groups.

[0007] In one embodiment of the present invention, the acyl group is -C(O)R', where R' is selected from C1-C8 alkyl groups.

[0008] In one embodiment of the present invention, the aryl group includes a substituted or unsubstituted benzene ring or a naphthalene ring; wherein the substitution can be one to three substitutions; the substituted group is selected from halogens, C1-C8 alkyl groups, and C1-C8 alkoxy groups.

[0009] In one embodiment of the present invention, the solvent includes acetonitrile (MeCN). N , N -Dimethylformamide (DMF) N , N - One or more of dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO). DMSO is preferred.

[0010] In one embodiment of the present invention, the oxidant includes any one or more of potassium persulfate, sodium persulfate, ammonium persulfate, and tert-butyl hydroperoxide. Potassium persulfate is preferred.

[0011] In one embodiment of the invention, the reaction temperature is 25 °C-100 °C, preferably 30-50 °C.

[0012] In one embodiment of the invention, the reaction time is 3-24 h, preferably 4 h.

[0013] In one embodiment of the present invention, the molar ratio of aryl olefin to perfluoroethyl thiosilicon is 1:(1.0-3.0). More preferably, it is 1:1.5.

[0014] In one embodiment of the present invention, the molar ratio of aryl olefin to oxidant is 1:(1.0-4.0). Specifically, it is preferably 1:2.

[0015] In one embodiment of the present invention, the reaction concentration of the aryl olefin compound is 0.05-5 mmol / mL. Specifically, 0.1 mmol / mL is preferred.

[0016] In one embodiment of the invention, the reaction must be carried out in an oxygen (O2) atmosphere.

[0017] In one embodiment of the present invention, the synthesis method specifically includes the following steps: Using aryl olefins and perfluoroethylthiosilver as raw materials, a crude product of 2-perfluoroethylthio-1-aryl ethyl ketone was obtained by stirring and reacting in an oxygen (O2) atmosphere at 25 ℃-100 ℃ for a period of time. The purified 2-perfluoroethylthio-1-aryl ethyl ketone was then obtained by filtration, washing, vacuum distillation and column chromatography.

[0018] In one embodiment of the present invention, the separation method is to use rapid column chromatography to obtain the final product 2-perfluoroethylthio-1-arylethyl ketone.

[0019] In one embodiment of the present invention, the method is preferably carried out as follows: under an oxygen atmosphere, aryl olefin, perfluoroethyl thiosilver, and potassium persulfate are added to a reaction vessel containing dimethyl sulfoxide solvent in a molar ratio of 1:1.5:2, stirred at 30 ℃-50 ℃ for 3-24 hours, and then separated and purified to obtain the target product.

[0020] In one embodiment of the present invention, the reaction mechanism is as follows: In the presence of persulfate, Ag(Ⅰ)SC2F5 is oxidized to Ag(Ⅱ)SC2F5. Due to its instability, after losing one Ag(Ⅰ), a perfluoroethylthio radical (•SC2F5) is generated, which then directly attacks the double bond of the olefin to obtain a benzyl radical intermediate. Finally, with the participation of O2, it interacts with the benzyl radical and successfully yields the final product.

[0021] The beneficial effects of this invention are: The method of this invention, under an oxygen atmosphere, uses arylethylene compounds as substrates and AgSC2F5 reagent as perfluoroethyl thiolation reagent. Under the action of an oxidant, the perfluoroethyl thiolation and carbonylation of arylethylene can be achieved in one step to obtain the target compound.

[0022] The method of this invention has a wide substrate applicability, and the synthesis of the target product can be achieved with a good yield in just 3-24 hours, making it faster and more efficient.

[0023] The method of this invention converts readily available aryl ethylene into a 2-perfluoroethylthio-1-aryl ethyl ketone compound under relatively simple conditions, achieving perfluoroethylthiolation and carbonylation of aryl ethylene in one step. The pentafluoroethylthio group in the target compound has excellent lipophilicity, bioavailability, and metabolic stability, and has wide applications in the fields of medicine, pesticides, and chemicals. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 This is a synthesis route diagram for the method of the present invention. Detailed Implementation

[0026] The present invention will be further illustrated below with specific examples. These embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0027] Source of raw materials The following examples involve 4-methylstyrene (p-methylstyrene), CAS: 622-97-9; 4-nitrostyrene (p-nitrostyrene), CAS: 100-13-0; 4-bromostyrene (p-bromostyrene), CAS: 2039-82-9; 4-fluorostyrene (p-fluorostyrene), CAS: 405-99-2; 4-chlorostyrene (p-chlorostyrene), CAS: 1073-67-2; methyl 4-vinylbenzoate, CAS: 1076-96-6; and 4-tert-butylstyrene (p-tert-butylstyrene), CAS: 1746-23-2, which were synthesized using methods reported in existing literature.

[0028] Dimethyl sulfoxide, ethyl acetate, sodium chloride, sodium persulfate (Na2S2O4), potassium persulfate (K2S2O4), and anhydrous MgSO4 were all purchased from Adamas.

[0029] The chromatographic separation and purification methods involved in the following examples: Column type: G3, stationary phase: silica gel (particle size 200-300 mesh), mobile phase: V 石油醚 :V 乙酸乙酯 =50:1.

[0030] The synthesis route diagram of this invention embodiment is as follows: Figure 1 As shown: Arylethylene and AgSC2F5 were used as raw materials, and potassium persulfate was used as an oxidant. The raw materials were added to a reaction flask containing dimethyl sulfoxide under an O2 atmosphere. The reaction flask was then placed in an oil bath at 25℃-100℃ and allowed to react for 3-24 hours.

[0031] The technical solution of the present invention will be described in detail below with reference to specific embodiments. In the following embodiments, unless otherwise specified, the reagents, materials and equipment used can be purchased commercially, prepared by conventional methods, or commonly used in the industry.

[0032] Example 1: Synthesis of 2-perfluoroethylthio-1-p-methylacetophenone Accurately weigh p-methylstyrene (59.0 mg, 0.5 mmol, 1.0 equiv.), AgSC2F5 (193.9 mg, 0.75 mmol, 1.5 equiv.), and potassium persulfate (269.9 mg, 1.0 mmol, 2.0 equiv.) into a dry 25 mL Schlenk tube. Inject 5 mL of DMSO under an oxygen atmosphere. Place the reaction mixture in a 35 °C oil bath and stir thoroughly for 4 h. After the reaction is complete, allow the reaction system to cool to room temperature, filter through diatomaceous earth, and wash with dichloromethane. The resulting mixture is washed with distilled water and saturated sodium chloride solution, respectively. The solvent is removed by vacuum concentration, and the target analyte is purified by column chromatography to obtain 92.24 mg of the product, with a yield of 65% (68% yield according to fluorine chromatography).

[0033] 1 H NMR (400 MHz, CDCl3) d 7.85 (d, J = 8.3 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 4.51 (s, 2H), 2.44 (s, 3H). 19 F NMR (376 MHz, CDCl3) d -83.26 (t, J = 3.5Hz, 3F), -92.03 (q, J = 3.5 Hz, 2F). 13 C NMR (101 MHz, CDCl3) d 191.5 (s), 145.6 (s), 132.4 (s), 129.8 (s), 128.7 (s), 121.7 (tq,J = 286.2, 41.2 Hz), 119.0 (qt, J = 286.2, 36.6 Hz), 37.3 (t, J = 2.5 Hz), 21.9 (s). HRMS (APGC) m / zcalculated for C 11 H 10 F5OS (M+H) + : 285.0373, found: 285.0377. Example 2: Synthesis of 2-perfluoroethylthio-1-p-nitroacetophenone Accurately weigh p-nitrostyrene (74.0 mg, 0.5 mmol, 1.0 equiv.), AgSC2F5 (193.9 mg, 0.75 mmol, 1.5 equiv.), and potassium persulfate (269.9 mg, 1.0 mmol, 2.0 equiv.) into a dry 25 mL Schlenk tube. Inject 5 mL of DMSO under an oxygen atmosphere. Place the reaction mixture in an oil bath at 35 °C and stir thoroughly for 4 h. After the reaction is complete, allow the reaction system to cool to room temperature, filter through diatomaceous earth, and wash with dichloromethane. The resulting mixture is washed with distilled water and saturated sodium chloride solution, respectively. The solvent is removed by vacuum concentration, and the target analyte is purified by column chromatography to obtain 70.92 mg of product, with a yield of 45%.

[0034] 1 H NMR (400 MHz, CDCl3) d 8.37 (d, J = 8.8 Hz, 2H), 8.13 (d, J = 8.8 Hz, 2H), 4.53 (s, 2H). 19 F NMR (376 MHz, CDCl3) d -83.22 (t, J = 3.4 Hz, 3F), -91.90(q, J = 3.4 Hz, 2F). 13 C NMR (101 MHz, CDCl3) d 190.7 (s), 151.1 (s), 139.2 (s), 129.7 (s), 124.4 (s), 121.3 (tq, J = 287.2, 41.4 Hz), 118.6 (qt, J= 284.4 Hz, 36.5 Hz), 37.1 (t, J = 3.0 Hz). HRMS (APGC) m / z calculated for C 10 H7F5NO3S (M+H) + : 316.0067, found: 316.0073. Example 3: Synthesis of 2-perfluoroethylthio-1-p-bromoacetophenone Accurately weigh p-bromostyrene (91.0 mg, 0.5 mmol, 1.0 equiv.), AgSC2F5 (193.9 mg, 0.75 mmol, 1.5 equiv.), and potassium persulfate (269.9 mg, 1.0 mmol, 2.0 equiv.) into a dry 25 mL Schlenk tube. Inject 5 mL of DMSO under an oxygen atmosphere. Place the reaction mixture in a 35 °C oil bath and stir thoroughly for 4 h. After the reaction is complete, allow the reaction system to cool to room temperature, filter through diatomaceous earth, and wash with dichloromethane. Wash the resulting mixture with distilled water and saturated sodium chloride solution, respectively. Concentrate under vacuum to remove the solvent, and then purify the target analyte by column chromatography to obtain 79.75 mg of the product, with a yield of 59%.

[0035] 1 H NMR (400 MHz, CDCl3) d 7.88 – 7.78 (m, 2H), 7.69 – 7.61 (m, 2H), 4.48 (s, 2H). 19 F NMR (376 MHz, CDCl3) d -83.23 (t, J = 3.5 Hz, 3F), -91.98 (q, J =3.4 Hz, 2F). 13 C NMR (101 MHz, CDCl3) d 191.1 (s), 134.5 (s), 132.5 (s), 132.4 (d, J = 4.8 Hz), 130.0 (s), 121.5 (tq, J = 286.8, 40.9 Hz), 118.7 (tq, J =284.2, 36.3 Hz), 37.0 (t, J= 2.8 Hz). HRMS (APGC) m / z calculated forC 10 H7BrF5OS (M+H) + : 348.9321, found: 348.9318. Example 4: Synthesis of 2-perfluoroethylthio-1-p-fluoroacetophenone Accurately weigh p-fluorostyrene (61.0 mg, 0.5 mmol, 1.0 equiv.), AgSC2F5 (193.9 mg, 0.75 mmol, 1.5 equiv.), and potassium persulfate (269.9 mg, 1.0 mmol, 2.0 equiv.) into a dry 25 mL Schlenk tube. Inject 5 mL of DMSO under an oxygen atmosphere. Place the reaction mixture in a 35 °C oil bath and stir thoroughly for 4 h. After the reaction is complete, allow the reaction system to cool to room temperature, filter through diatomaceous earth, and wash with dichloromethane. Wash the resulting mixture with distilled water and saturated sodium chloride solution, respectively. Concentrate under vacuum to remove the solvent, and then purify the target analyte by column chromatography to obtain 72 mg of product, with a yield of 50%.

[0036] 1 H NMR (400 MHz, CDCl3) d 8.05 – 7.94 (m, 2H), 7.24 – 7.14 (m, 2H), 4.50 (s, 2H). 19 F NMR (376 MHz, CDCl3) d -83.25 (t, J = 3.5 Hz, 3F), -92.02 (q, J =3.5 Hz, 2F), -102.54 (s, 1F). 13 C NMR (101 MHz, CDCl3) d 190.4 (s), 166.5 (d, J =257.2 Hz), 131.32 (d, J = 9.6 Hz), 121.5 (tq, J = 286.6, 41.2 Hz), 118.7 (qt, J =284.3, 36.4 Hz), 116.4 (d, J = 22.2 Hz), 37.1 (t, J= 2.7 Hz). HRMS (APGC) m / zcalculated for C 10 H6F6OS [M] + : 288.0044, found: 288.0038. Example 5: Synthesis of 2-perfluoroethylthio-1-p-chloroacetophenone Accurately weigh p-chlorostyrene (69.0 mg, 0.5 mmol, 1.0 equiv.), AgSC2F5 (193.9 mg, 0.75 mmol, 1.5 equiv.), and potassium persulfate (269.9 mg, 1.0 mmol, 2.0 equiv.) into a dry 25 mL Schlenk tube. Inject 5 mL of DMSO under an oxygen atmosphere. Place the reaction mixture in a 35 °C oil bath and stir thoroughly for 4 h. After the reaction is complete, allow the reaction system to cool to room temperature, filter through diatomaceous earth, and wash with dichloromethane. Wash the resulting mixture with distilled water and saturated sodium chloride solution, respectively. Concentrate under vacuum to remove the solvent, and then purify the target analyte by column chromatography to obtain 70 mg of product, with a yield of 46%.

[0037] 1 H NMR (400 MHz, CDCl3) d 7.94 – 7.86 (m, 2H), 7.52 – 7.46 (m, 2H), 4.49 (s, 2H). 19 F NMR (376 MHz, CDCl3) d -83.24 (t, J = 3.5 Hz, 3F), -91.99 (q, J = 3.5 Hz, 2F). 13 C NMR (101 MHz, CDCl3) d 190.8 (s), 141.1 (s), 133.2 (s), 129.9 (s), 129.5 (s), 121.5 (tq, J = 286.8, 41.1 Hz), 118.7 (qt, J = 284.3, 36.5 Hz), 37.1 (t, J = 2.8 Hz). HRMS (APGC) m / z calculated for C 10 H7ClF5OS (M+H) + :304.9826, found: 304.9824. Example 6: Synthesis of methyl 2-perfluoroethylthio-1-p-formate acetophenone Methyl 4-vinylbenzoate (81.0 mg, 0.5 mmol, 1.0 equiv.), AgSC2F5 (193.9 mg, 0.75 mmol, 1.5 equiv.), and potassium persulfate (269.9 mg, 1.0 mmol, 2.0 equiv.) were accurately weighed into a dry 25 mL Schlenk tube. 5 mL of DMSO was injected under an oxygen atmosphere. The reaction mixture was placed in an oil bath at 35 °C and stirred thoroughly for 4 h. After the reaction was complete, the reaction system was cooled to room temperature, filtered through diatomaceous earth, and washed with dichloromethane. The resulting mixture was washed with distilled water and saturated sodium chloride solution, respectively. The solvent was removed by vacuum concentration, and the target analyte was purified by column chromatography to obtain 75 mg of the product, with a yield of 45%.

[0038] 1 H NMR (400 MHz, CDCl3) d 7.96 (d, J = 8.5 Hz, 2H), 7.22 (d, J = 8.4 Hz, 2H), 4.48 (s, 2H), 2.31 (s, 3H). 19 F NMR (376 MHz, CDCl3) d -83.24 (s, 3F), -91.81 – -92.28 (m, 2F). 13 C NMR (101 MHz, CDCl3) d 189.6 (s), 167.6 (s), 154.2 (s), 130.2 (s), 129.1 (s), 121.2 (s), 120.4 (tq, J = 287.3, 40.9 Hz), 117.5 (qt, J = 284.2, 36.4 Hz), 36.0 (t, J = 2.6 Hz), 20.1 (s). HRMS (APGC) m / zcalculated for C 12 H 10 F5O3S (M+H) + : 329.0271, found: 329.0272. Example 7: Synthesis of 2-perfluoroethylthio-1-p-tert-butylacetophenone Accurately weigh p-tert-butylstyrene (80.0 mg, 0.5 mmol, 1.0 equiv.), AgSC2F5 (193.9 mg, 0.75 mmol, 1.5 equiv.), and potassium persulfate (269.9 mg, 1.0 mmol, 2.0 equiv.) into a dry 25 mL Schlenk tube. Inject 5 mL of DMSO under an oxygen atmosphere. Place the reaction mixture in a 35 °C oil bath and stir thoroughly for 4 h. After the reaction is complete, allow the reaction system to cool to room temperature, filter through diatomaceous earth, and wash with dichloromethane. The resulting mixture is washed with distilled water and saturated sodium chloride solution, respectively. The solvent is removed by vacuum concentration, and the target analyte is purified by column chromatography to obtain 65 mg of product, with a yield of 40%.

[0039] 1 H NMR (400 MHz, CDCl3) d 7.90 (dq, J = 8.8, 2.2 Hz, 2H), 7.56 – 7.49(m, 2H), 4.52 (s, 2H), 1.35 (s, 9H). 19 F NMR (376 MHz, CDCl3) d -83.23 (t, J =3.5 Hz, 3F), -92.03 (q, J = 3.5 Hz, 2F). 13 C NMR (101 MHz, CDCl3) d 191.6 (s),158.5 (s), 132.3 (s), 128.5 (s), 126.1 (s), 118.8 (tq, J = 286.1, 40.7 Hz), 115.9 (qt, J = 284.1, 36.7 Hz), 37.2 (t, J = 2.6 Hz), 35.6 (s), 31.2 (s). HRMS(APGC) m / z calculated for C 14 H 16 F5OS (M+H) + : 327.0842, found: 327.0841. Example 8: Effect of different oxidants on the synthesis of 2-perfluoroethylthio-1-p-methylacetophenone Referring to Example 1, the oxidant was replaced by sodium persulfate and ammonium persulfate (equal molar amounts of persulfate ions), respectively, instead of potassium persulfate. Additionally, an experiment was conducted without any oxidant, with all other conditions remaining unchanged, to synthesize 2-perfluoroethylthio-1-p-methylacetophenone. Specific yield results are shown in Table 1.

[0040] Table 1. Effects of different oxidants on the synthesis of 2-perfluoroethylthio-1-p-methylacetophenone

[0041] a. Yield of fluorine spectrum yield The results showed that no product could be obtained without the addition of an oxidant, and the yield obtained by replacing potassium persulfate with sodium persulfate or ammonium persulfate as the oxidant was not as high as the yield of potassium persulfate in Example 1.

[0042] Example 9: Effect of different solvents on the synthesis of 2-perfluoroethylthio-1-p-methylacetophenone Referring to Example 1, the solvent was replaced by N,N-dimethylformamide, N,N-dimethylacetamide, water, and dimethylpyrrolidone, respectively, while keeping other conditions unchanged, to synthesize 2-perfluoroethylthio-1-p-methylacetophenone. Specific yield results are shown in Table 2.

[0043] Table 2. Effects of different solvents on the synthesis of 2-perfluoroethylthio-1-p-methylacetophenone

[0044] a. Yield of fluorine spectrum yield The results showed that using water as a solvent failed to yield the product, while using acetonitrile... N, N -Dimethylformamide, N, N Replacing dimethyl sulfoxide with dimethyl acetamide and NMP as solvents in Example 1 resulted in a lower product yield compared to Example 1.

[0045] Example 10: Effect of different reaction temperatures on the synthesis of 2-perfluoroethylthio-1-p-methylacetophenone Referring to Example 1, the reaction temperature was changed from 35 °C to 25 °C, 55 °C, and 75 °C respectively, while other conditions remained unchanged, to synthesize 2-perfluoroethylthio-1-p-methylacetophenone. The specific yield results are shown in Table 3.

[0046] Table 3 Effect of different reaction temperatures on the synthesis of 2-perfluoroethylthio-1-p-methylacetophenone

[0047] a. Yield of fluorine spectrum yield The results showed that replacing 35℃ in Example 1 with 25℃, 55℃, and 75℃ all resulted in lower product yields than in Example 1.

[0048] Example 11: Effect of different additives on the synthesis of 2-perfluoroethylthio-1-p-methylacetophenone Referring to Example 1, the additives were replaced with triphenylphosphine, potassium carbonate, potassium tert-butoxide, and tetrabutylammonium bromide, respectively, while keeping other conditions unchanged, to synthesize 2-perfluoroethylthio-1-p-methylacetophenone. Specific yield results are shown in Table 4.

[0049] Table 4. Effects of different additives on the synthesis of 2-perfluoroethylthio-1-p-methylacetophenone

[0050] a. Yield of fluorine spectrum yield The results showed that the yields obtained by adding triphenylphosphine, potassium carbonate, potassium tert-butoxide, and tetrabutylammonium bromide were all worse than those in Example 1.

[0051] The embodiments provided above are not intended to limit the scope of the invention, nor are the described steps intended to limit the order of execution. Any obvious modifications made to the invention by those skilled in the art based on existing common knowledge also fall within the scope of protection defined by the claims.

Claims

1. A method for synthesizing a 2-perfluoroethylthio-1-arylethyl ketone compound, characterized in that, The method involves reacting an aryl ethylene compound of formula (1) with a perfluoroethyl thiosilver compound of formula (2) in an organic solvent under an oxygen atmosphere, with an oxidant acting on the reaction, to obtain a 2-perfluoroethyl thio-1-aryl ethyl ketone compound of formula (3) after the reaction is completed. Among them, R 1 Selected from H, C1-C8 alkyl, C1-C8 haloalkyl, aryl, halogen, cyano, nitro, C1-C8 alkoxy, acyl; R 2 Selected from H and C1-C8 alkyl groups.

2. The synthesis method according to claim 1, characterized in that, The acyl group is -C(O)R', where R' is selected from C1-C8 alkyl groups.

3. The synthesis method according to claim 1, characterized in that, Aryl groups include substituted or unsubstituted benzene rings and naphthalene rings; wherein, the substitution can be one to three; the substituted group is selected from halogens, C1-C8 alkyl groups, and C1-C8 alkoxy groups.

4. The synthesis method according to any one of claims 1-3, characterized in that, The solvents include acetonitrile, N , N -Dimethylformamide, N , N -Dimethylacetamide, dimethyl sulfoxide, or any one or more of these.

5. The synthesis method according to any one of claims 1-3, characterized in that, The oxidizing agent includes any one or more of potassium persulfate, sodium persulfate, ammonium persulfate, and tert-butyl hydroperoxide.

6. The synthesis method according to any one of claims 1-3, characterized in that, The reaction temperature is 25 ℃-100 ℃.

7. The synthesis method according to any one of claims 1-3, characterized in that, The reaction time is 3-24 h.

8. The synthesis method according to any one of claims 1-3, characterized in that, The molar ratio of aryl hydrocarbons to perfluoroethyl thiosilicon is 1:(1.0-3.0).

9. The synthesis method according to any one of claims 1-3, characterized in that, The molar ratio of aryl olefin to oxidant is 1:(1.0-4.0).

10. The synthesis method according to any one of claims 1-3, characterized in that, The reaction concentration of aryl olefin compounds is 0.05-5 mmol / mL.

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