CN115160292B - Synthesis method of 3-perfluoroalkyl thioflavone - Google Patents

Abstract

The invention discloses a method for synthesizing 3-perfluoroalkyl thioflavone, which comprises the steps of adding 2-methylthio phenylpropionyl ketone, sodium perfluoroalkyl sulfinate and a catalyst Acr into a reaction bottle ⁺ ‑Mes·ClO ₄ ^– Then adding a mixed solvent of acetonitrile and water and trifluoroacetic acid, stirring at room temperature under the irradiation of a blue light-emitting diode for reaction, extracting reaction liquid by using ethyl acetate after the reaction is finished, combining organic phases, drying by using anhydrous sodium sulfate, decompressing and evaporating the solvent, and carrying out column chromatography on residues to obtain a target product, namely the 3-perfluoroalkyl thioflavone. The synthesis method does not need to use a strong oxidant and a transition metal catalyst, and the synthesis method has the advantages of simple and easily available synthesis raw materials and easily controlled reaction conditions. The light source used in the method is green and pollution-free. And the test shows that the synthesized part of target compounds show antitumor activity superior to that of the control drug 5-fluorouracil.

Description

A kind of synthesis method of 3-perfluoroalkylated thioflavones

Technical field

The invention belongs to the technical field of organic chemical synthesis, and specifically relates to a synthesis method of 3-perfluoroalkylated thioflavones.

Background technique

Thioflavones are a dominant framework widely found in natural products, bioactive molecules and functional materials. Perfluoroalkyl groups, especially trifluoromethyl, are present in more than 70 marketed drugs and are critical to the drug's activity (J. Med. Chem., 2020, 63, 13076). Therefore, the preparation of perfluoroalkyl-containing thioflavones is of great significance. However, no synthesis method of perfluoroalkylthioflavonoids has been reported so far.

It is a common strategy to prepare substituted thioflavones using 2-methylthiophenylpropynone as raw material through addition cyclization reaction (J.Org.Chem., 2006, 71, 1626; Org. Lett., 2019 , 21, 1112-1115; Org. Chem. Front., 2020, 7, 3935-3940). Most of these preparation methods require high-temperature heating, transition metal catalysts or external oxidants and other conditions, causing problems such as consumption of non-renewable resources, environmental pollution and increased costs.

Contents of the invention

The technical problem solved by the present invention is to provide a method for synthesizing 3-perfluoroalkylated thioflavones, which uses acetonitrile and water as mixed solvents to synthesize 3-perfluoroalkylated thioflavones under visible light induction. It can effectively solve the problem that there is currently no synthesis method for 3-perfluoroalkylated thioflavones, and reduce the consumption of non-renewable resources and environmental pollution. After testing, it was found that some of the synthesized compounds showed good anti-tumor activity, providing novel structural clues for the development of new drugs.

In order to solve the above technical problems, the present invention adopts the following technical solution: a synthesis method of 3-perfluoroalkylated thioflavones, which is characterized in that the specific steps are: adding 2-methylthiophenylpropynone in the reaction bottle, After sodium perfluoroalkyl sulfinate and the catalyst 9-mesitylyl-10-methylacridine perchlorate (Acr ⁺ -Mes·ClO ₄ ^– ), add a mixed solvent of acetonitrile and water and trifluoro Acetic acid, stir the reaction at room temperature under the illumination of a blue light-emitting diode. After the reaction, extract the reaction solution with ethyl acetate, combine the organic phases and dry over anhydrous sodium sulfate, filter and spin off the organic solvent under reduced pressure, and obtain through column chromatography The target product 3-perfluoroalkylated thioflavone, the structural formula of 2-methylthiophenylpropynone is shown in formula A, the structural formula of perfluoroalkylated sodium sulfinate is shown in formula B, 3-all The structural formula of fluoroalkylated thioflavonoids is shown in Formula C:

Wherein R ¹ is H, C _1-6 alkyl, C _1-6 alkoxy, trifluoromethyl, cyano, fluorine, chlorine or bromine, etc.; R _f is (CF ₂ ) _n CF ₃ , n is selected from An integer between 0-7.

To further limit, the specific structural formula of the 3-perfluoroalkylated thioflavonoids is:

It is further limited that the molar ratio of the 2-methylthiophenylpropynone, sodium perfluoroalkyl sulfinate, catalyst Acr ⁺ -Mes·ClO ₄ ^– and trifluoroacetic acid is 1:1-3:1% -10%:1-3.

To further limit, the reaction equation in the synthesis process of the 3-perfluoroalkylated thioflavones is:

The structural formula of the catalyst Acr ⁺ -Mes·ClO ₄ ^– is:

A method for synthesizing 3-perfluoroalkylated thioflavonoids, which is characterized in that the specific steps are: adding 1-(2-(methylthio)phenyl)-3-(3-pyridyl) into the reaction bottle )-2-ynyl-1-one, sodium trifluoromethanesulfinate and catalyst Acr ⁺ -Mes·ClO ₄ ^– , then add a mixed solvent of acetonitrile and water and trifluoroacetic acid, in the blue light-emitting diode The reaction was stirred at room temperature under irradiation. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phases were combined and dried over anhydrous sodium sulfate, filtered and the organic solvent was spun off under reduced pressure. The target product 3-perfluoroalkyl was obtained through column chromatography. thioflavones, the structural formula of the target product 3-perfluoroalkylated thioflavones is:

Further limited, the 1-(2-(methylthio)phenyl)-3-(3-pyridyl)-2-ynyl-1-one, sodium trifluoromethanesulfinate, catalyst Acr ⁺ The feeding molar ratio of -Mes·ClO ₄ ^- and trifluoroacetic acid is 1:1-3:1%-10%:1-3.

A method for synthesizing 3-perfluoroalkylated thioflavonoids, which is characterized in that the specific steps are: adding 1-(2-(methylthio)phenyl)-3-(2-naphthyl) into the reaction bottle )-2-ynyl-1-one, sodium trifluoromethanesulfinate and catalyst Acr ⁺ -Mes·ClO ₄ ^– , then add a mixed solvent of acetonitrile and water and trifluoroacetic acid, in the blue light-emitting diode The reaction was stirred at room temperature under irradiation. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phases were combined and dried over anhydrous sodium sulfate, filtered and the organic solvent was spun off under reduced pressure. The target product 3-perfluoroalkyl was obtained through column chromatography. Thioflavones, the structural formula of the target product 3-perfluoroalkylated thioflavones is:

Further limited, the 1-(2-(methylthio)phenyl)-3-(2-naphthyl)-2-ynyl-1-one, sodium trifluoromethanesulfinate, catalyst Acr ⁺ The feeding molar ratio of -Mes·ClO ₄ ^- and trifluoroacetic acid is 1:1-3:1%-10%:1-3.

It is further limited that the reaction conditions of the reaction process are to use a blue LED lamp as a visible light source, with a wavelength of 455-465nm and a power of 6-12W.

It is further limited that the volume ratio of acetonitrile to water in the mixed solvent of acetonitrile and water is 10:1.

Compared with the existing technology, the present invention has the following advantages and beneficial effects: The present invention provides a synthesis method of 3-perfluoroalkylated thioflavones, which solves the problem that there is currently no 3-perfluoroalkylated thioflavones. Problems with synthesis methods. The synthetic raw materials involved in this synthesis method are simple and easy to obtain, the reaction conditions are easy to control, visible light is used to induce the reaction process, and there is no need to add transition metal catalysts and external oxidants. Moreover, the anti-tumor activity evaluation of the target compound was initially completed, and anti-tumor compounds with better activity than the control drug 5-Fu and a completely new structure were screened.

Detailed ways

The technical solutions of the present invention are specifically described below through examples. It is necessary to point out here that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of the present invention. Some non-essential improvements and adjustments made by professionals in this field based on the above content of the present invention still belong to the protection scope of the present invention. In addition, unless otherwise stated, all raw materials used are commercially available.

Example 1

In a clean and dry reaction bottle equipped with a magnet, add 1-(2-(methylthio)phenyl)-3-phenyl-2-ynyl-1-one (0.2mmol), trifluoromethyl After sodium sulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), add 3mL of acetonitrile/water mixed solvent (v/v=10/1), and place under the irradiation of a blue light-emitting diode. React at room temperature for 5 hours. After the reaction, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic solvent. The residue is subjected to column chromatography to obtain the target product, which is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-phenyl-2-ynyl-1-one being 100%, the yield of the target product is 75%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.54 (dd, J = 7.8, 1.2Hz, 1H), 7.69-7.67 (m, 1H), 7.61 (t, J＝7.2Hz, 1H), 7.56 (d, J＝8.4Hz, 1H), 7.53-7.43 (m, 5H). ¹³ C NMR (150MHz, CDCl ₃ ) δ 177.7, 158.4 (q, J＝3.0Hz), 136.1,135.4,132.6,131.6(q,J＝1.5Hz),130.5,129.4,128.7,128.6,128.0(q,J＝1.3Hz),125.4,122.74(q,J＝276Hz),122.70(q,J =27Hz). ¹⁹ F NMR (565MHz, CDCl ₃ ) δ-55.7 (s, 3F). HRMSCalcd for C ₁₆ H ₁₀ F ₃ OS [M+H] ⁺ : m/z 307.0399, Found: 307.0390.

Example 2

Add 1-(2-(methylthio)phenyl)-3-((4-methyl)phenyl)-2-alkynyl-1-one ( 0.2mmol), sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL acetonitrile/water mixed solvent (v/v=10/1), React at room temperature for 5 hours under the illumination of a blue light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic solvent. The residue is subjected to column chromatography to obtain the target Product, the target product is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-((4-methyl)phenyl)-2-ynyl-1-one being 100%, the yield of the target product is 55%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.53 (dd, J = 8.4, 1.2Hz, 1H), 7.68-7.65 (m, 1H), 7.61-7.58 ( ¹³ C NMR (150MHz, CDCl ₃ ) δ177.8,158.7(q,J＝2.2Hz),140.9,136.2,132.54,132.50,131.6,129.4,129.3,128.6,127.9(q,J＝1.5Hz),125.4,122.8(q ,J＝275Hz),122.6(q,J＝26Hz),21.6. ¹⁹ F NMR(565MHz, CDCl ₃ )δ-55.7(s,3F).HRMS Calcd for C ₁₇ H ₁₂ F ₃ OS[M+H] ⁺ :m/z 321.0555, Found: 321.0542.

Example 3

Add 1-(2-(methylthio)phenyl)-3-((4-ethyl)phenyl)-2-ynyl-1-one ( 0.2mmol), sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL acetonitrile/water mixed solvent (v/v=10/1), React at room temperature for 5 hours under the illumination of a blue light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic solvent. The residue is subjected to column chromatography to obtain the target Product, the target product is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-((4-ethyl)phenyl)-2-ynyl-1-one being 100%, the yield of the target product is 78%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.53 (dd, J = 8.4, 1.2Hz, 1H), 7.68-7.65 (m, 1H), 7.61-7.58 ( m,1H),7.55(d,J＝7.8Hz,1H), 7.36(d,J＝8.4Hz,2H),7.30(d,J＝7.8Hz,2H),2.73(q,J＝7.2Hz, 2H), 1.29 (t, J = 7.2 Hz, 3H). ¹³ CNMR (150MHz, CDCl ₃ ) δ ¹³ C NMR (150MHz, CDCl ₃ ) δ 177.8, 158.7 (q, J = 2.2 Hz), 147.0, 136.2, 132.7 ,132.5,131.6,129.4,128.6,128.1,128.0(q,J＝1.5Hz),125.4,122.8(q,J＝276Hz),122.5(q,J＝27Hz),28.9,15.3. ¹⁹ F NMR (565MHz ,CDCl ₃ )δ-55.7 (s,3F).HRMSCalcd for C ₁₈ H ₁₄ F ₃ OS[M+H] ⁺ :m/z 335.0712Found:335.0696.

Example 4

Add 1-(2-(methylthio)phenyl)-3-((4-tert-butyl)phenyl)-2-ynyl-1-one to a clean and dry reaction bottle equipped with a magnet. (0.2mmol), sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01 mmol), then add 3mL of acetonitrile/water mixed solvent (v/v=10/1) , react at room temperature for 5 hours under the irradiation of a blue light-emitting diode. After the reaction, the reaction solution is extracted with ethyl acetate, the organic phases are combined and dried over anhydrous sodium sulfate, filtered and the organic phase solvent is spun off, and the residue is subjected to column chromatography. The target product was obtained as a yellow solid. Based on the molar weight of 1-(2-(methylthio)phenyl)-3-((4-tert-butyl)phenyl)-2-ynyl-1-one as 100%, the yield of the target product is 75%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.53 (d, J＝8.4Hz, 1H), 7.68-7.66 (m, 1H), 7.60 (t, J＝ 7.2Hz,1H),7.55(d,J＝7.8Hz,1H),7.48(d,J＝7.8Hz,2H),7.38(d,J＝7.8Hz,2H),1.37(s,9H). ¹³ C NMR (150MHz, CDCl ₃ ) δ177.9, 158.8 (q, J = 1.5Hz), 154.0, 136.3, 132.48, 132.47, 131.6, 129.4, 128.6, 127.8, 125.6, 125.4, 122.8 (q, J = 274Hz) ,122.5(q,J＝27Hz),35.1,31.3. ¹⁹ F NMR(376MHz,CDCl ₃ )δ-55.7 (s,3F).HRMS Calcd for C ₂₀ H ₁₈ F ₃ OS[M+H] ⁺ :m /z 363.1025Found:363.1016.

Example 5

Add 1-(2-(methylthio)phenyl)-3-((4-methoxy)phenyl)-2-ynyl-1-one into a clean and dry reaction bottle equipped with a magnet. (0.2mmol), sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01 mmol), then add 3mL of acetonitrile/water mixed solvent (v/v=10/1) , react at room temperature for 5 hours under the irradiation of a blue light-emitting diode. After the reaction, the reaction solution is extracted with ethyl acetate, the organic phases are combined and dried over anhydrous sodium sulfate, filtered and the organic phase solvent is spun off, and the residue is subjected to column chromatography. The target product was obtained as a yellow solid. Based on the molar weight of 1-(2-(methylthio)phenyl)-3-((4-methoxy)phenyl)-2-ynyl-1-one as 100%, the yield of the target product is 69%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.52 (d, J＝7.8Hz, 1H), 7.68-7.65 (m, 1H), 7.59 (t, J＝ 7.8Hz,1H),7.55(d,J＝7.8Hz,1H),7.40(d,J＝8.4Hz,2H),6.99(d,J＝8.4Hz,2H),3.88(s,3H). ¹³ C NMR (150MHz, CDCl ₃ ) δ 178.0, 161.5, 158.4 (q, J = 3.0Hz), 136.2, 132.5, 131.7, 129.7 (q, J = 1.5Hz), 129.4, 128.6, 127.6, 125.4, 122.9 ( q, J＝276Hz), 122.5 (q, J＝27Hz), 114.1, 55.6. ¹⁹ F NMR (565MHz, CDCl ₃ ) δ -55.6 (s, 3F). HRMS Calcd for C ₁₇ H ₁₂ F ₃ O ₂ S [M+H] ⁺ :m/z 337.0505Found:337.0494.

Example 6

Add 1-(2-(methylthio)phenyl)-3-((3-methyl)phenyl)-2-ynyl-1-one ( 0.2mmol), sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL acetonitrile/water mixed solvent (v/v=10/1), React at room temperature for 5 hours under the illumination of a blue light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic solvent. The residue is subjected to column chromatography to obtain the target Product, the target product is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-((3-methyl)phenyl)-2-ynyl-1-one being 100%, the yield of the target product 70%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.54 (dd, J = 8.4, 1.2Hz, 1H), 7.69-7.66 (m, 1H), 7.61-7.59 ( m,1H),7.55(d,J＝7.8Hz,1H), 7.36(t,J＝7.8Hz,1H),7.32(d,J＝7.8Hz,1H),7.25-7.23(m,2H), 2.43 (s, 3H). ¹³ C NMR (150MHz, CDCl ₃ ) δ 177.7, 158.7 (q, J = 3.0Hz), 138.5, 136.1, 135.3, 132.5, 131.6, 131.2, 129.4, 128.7, 128.49, 128.47, 125.4, 125.2, 122.8 (q, J = 275Hz), 122.6 (q, J = 27Hz), 21.5. ¹⁹ FNMR (376MHz, CDCl ₃ ) δ-55.8 (s, 3F). HRMS Calcd for C ₁₇ H ₁₂ F ₃ OS [ M+H] ⁺ :m/z321.0555Found:321.0519.

Example 7

Add 1-(2-(methylthio)phenyl)-3-(4-fluorophenyl)-2-ynyl-1-one (0.2mmol) into a clean and dry reaction bottle equipped with a magnet. , after sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL acetonitrile/water mixed solvent (v/v=10/1), in blue React at room temperature for 5 hours under light-emitting diode irradiation. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic phase solvent. The residue is subjected to column chromatography to obtain the target product. The target product is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-(4-fluorophenyl)-2-ynyl-1-one being 100%, the yield of the target product was 81%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.53 (dd, J = 7.8, 0.6Hz, 1H), 7.70-7.67 (m, 1H), 7.62-7.60 ( m,1H),7.56(d,J=8.4Hz,1H), 7.45-7.43(m,2H),7.19-7.16(m,2H). ¹³ C NMR (150MHz, CDCl ₃ ) δ177.6,164.0(d, J＝249Hz),157.2(q,J＝3.0Hz),135.8,132.7,131.6,131.3(d,J＝3.0Hz),130.1(dd,J＝9.0,1.5Hz),129.4,128.8,125.4,123.0 (q, J=27Hz), 122.7 (q, J=274.5Hz), 116.0 (d, J=22.5 Hz). ¹⁹ FNMR (565MHz, CDCl ₃ ) δ-55.6 (s, 3F), -109.5 (s, 1F).HRMS Calcd for C ₁₆ H ₉ F ₄ OS[M+H] ⁺ :m/z325.0305Found:325.0277.

Example 8

Add 1-(2-(methylthio)phenyl)-3-(4-chlorophenyl)-2-ynyl-1-one (0.2mmol) into a clean and dry reaction bottle equipped with a magnet. , after sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL acetonitrile/water mixed solvent (v/v=10/1), in blue React at room temperature for 5 hours under the illumination of a light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic solvent. The residue is subjected to column chromatography to obtain the target product. The target product is The product is a yellow solid. Based on the molar weight of 1-(2-(methylthio)phenyl)-3-(4-fluorophenyl)-2-ynyl-1-one as 100%, the yield of the target product is 60%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ8.53 (d, J＝8.0Hz, 1H), 7.71-7.67 (m, 1H), 7.61 (t, J＝ 7.6Hz, 1H), 7.56 (d, J = 8.0Hz, 1H), 7.46 (d, J = 8.4Hz, 2H), 7.38 (d, J = 8.4Hz, 2H). ¹³ C NMR (150MHz, CDCl ₃ )δ177.5,156.9(q,J＝3.0Hz),136.9,135.8,133.7,132.7,131.5,129.43,129.36(q,J＝1.5Hz),129.0,128.9,125.5,122.9(q,J＝27Hz), 122.6 (q, J=276Hz). ¹⁹ F NMR (565MHz, CDCl ₃ ) δ-55.6 (s, 3F). HRMS Calcd for C ₁₆ H ₉ ClF ₃ OS [M+H] ⁺ :m/z 341.0009Found: 340.9990.

Example 9

Add 1-(2-(methylthio)phenyl)-3-(4-bromophenyl)-2-ynyl-1-one (0.2mmol) into a clean and dry reaction bottle equipped with a magnet. , after sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL acetonitrile/water mixed solvent (v/v=10/1), in blue React at room temperature for 5 hours under the illumination of a light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic solvent. The residue is subjected to column chromatography to obtain the target product. The target product is The product is a yellow solid. Based on the molar weight of 1-(2-(methylthio)phenyl)-3-(4-bromophenyl)-2-ynyl-1-one as 100%, the yield of the target product is 86%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ8.53 (d, J=8.0Hz, 1H), 7.71-7.67 (m, 1H), 7.63-7.60 (m, 3H), 7.56 (d, J = 8.0Hz, 1H), 7.32 (d, J = 8.0Hz, 2H). ¹³ C NMR (150MHz, CDCl ₃ ) δ 177.5, 156.9 (q, J = 1.5Hz), 135.7, 134.2, 132.7, 132.0, 131.5, 129.55 (q, J = 1.5Hz), 129.46, 128.9, 125.5, 125.1, 122.9 (q, J = 27Hz), 122.6 (q, J = 276Hz). ¹⁹ F NMR (565MHz, CDCl ₃ )δ-55.6(s,3F).HRMS Calcd for C ₁₆ H ₉ BrF ₃ OS[M+H] ⁺ :m/z 384.9504Found:384.9496.

Example 10

Add 1-(2-(methylthio)phenyl)-3-(3-fluorophenyl)-2-ynyl-1-one (0.2mmol) into a clean and dry reaction bottle equipped with a magnet. , after sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL acetonitrile/water mixed solvent (v/v=10/1), in blue React at room temperature for 5 hours under the illumination of a light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic phase solvent. The residue is subjected to column chromatography to obtain the target product. The target product is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-(3-fluorophenyl)-2-ynyl-1-one being 100%, the yield of the target product is 47%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (600MHz, CDCl3) δ8.54 (dd, J = 8.4, 1.2Hz, 1H), 7.71-7.68 (m, 1H), 7.63-7.60 (m ,1H),7.56(d,J＝7.8Hz,1H),7.48-7.44(m,1H),7.23-7.20(m,2H),7.18-7.16(m,1H). ¹³ C NMR (150MHz, CDCl ₃ ) δ177.4,162.3(d,J＝247.5Hz), 156.6(q,J＝3.0Hz), 137.0(d,J＝7.5Hz), 135.7,132.7, 131.5,130.5(d,J＝9.0Hz), 129.4,128.9,125.5,123.9(q,J＝1.5Hz),123.0(q,J＝27Hz),122.6(q,J＝274.5Hz),117.5(d,J＝21Hz),115.4(dq,J＝ 22.5,1.5Hz). ¹⁹ F NMR(565 MHz, CDCl ₃ )δ-55.8(s,3F),-111.5(s,1F).HRMS Calcd for C ₁₆ H ₉ F ₄ OS[M+H] ⁺ : m/z 325.0305Found:325.0298.

Example 11

Add 1-(2-(methylthio)phenyl)-3-(2-bromophenyl)-2-ynyl-1-one (0.2mmol) into a clean and dry reaction bottle equipped with a magnet. , after sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL acetonitrile/water mixed solvent (v/v=10/1), in blue React at room temperature for 5 hours under the illumination of a light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic phase solvent. The residue is subjected to column chromatography to obtain the target product. The target product is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-(2-bromophenyl)-2-ynyl-1-one being 100%, the yield of the target product is 75%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.58 (d, J＝7.8Hz, 1H), 7.71-7.68 (m, 2H), 7.62 (t, J＝ 7.8Hz, 1H), 7.57 (d, J = 7.8Hz, 1H), 7.45-7.42 (m, 1H), 7.37-7.34 (m, 2H). ¹³ C NMR (150MHz, CDCl ₃ ) δ 177.1, 156.3 (q ,J＝3.0 Hz),136.1,135.9,133.2,132.7,131.43,131.38,129.5,129.4,128.9,127.5,125.6,124.0(q,J＝27Hz),122.5(q,J＝276Hz),121.8(q , J=3.0Hz). ¹⁹ F NMR (376MHz, CDCl ₃ ) δ-58.4 (s, 3F). HRMS Calcd for C ₁₆ H ₉ BrF ₃ OS [M+H] ⁺ :m/z 384.9504 Found: 384.9495.

Example 12

In a clean and dry reaction bottle equipped with a magnet, add 1-(2-(methylthio)phenyl)-3-(4-(trifluoromethyl)phenyl)-2-ynyl-1- After ketone (0.2mmol), sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01 mmol), then add 3mL of acetonitrile/water mixed solvent (v/v=10/1 ), react at room temperature for 5 hours under the irradiation of a blue light-emitting diode. After the reaction, extract the reaction solution with ethyl acetate, combine the organic phases and dry them with anhydrous sodium sulfate, filter and spin off the organic phase solvent, and pass the residue through a column layer The target product was obtained by analysis, and the target product was a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-(4-(trifluoromethyl)phenyl)-2-ynyl-1-one being 100%, the yield of the target product The rate is 88%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ8.55 (d, J＝8.0Hz, 1H), 7.78-7.69 (m, 3H), 7.63 (t, J＝ 7.6Hz, 1H), 7.58-7.56 (m, 3H). ¹³ C NMR (150MHz, CDCl ₃ ) δ177.2, 156.4 (q, J = 3.0Hz), 138.8, 135.5, 132.8, 132.5 (q, J = 33Hz) ,131.4(q,J＝0.9Hz),129.5,129.1,128.5(q,J＝1.5Hz),125.7(q,J＝3.0Hz),125.5,123.7(q,J＝270Hz),123.1(q, J=27Hz), 122.5 (q, J=276Hz). ¹⁹ F NMR (565MHz, CDCl ₃ ) δ -55.7 (s, 3F), -62.9 (s, 3F). HRMS Calcd for C ₁₇ H ₉ F ₆ OS [M+H] ⁺ :m/z 375.0273Found: 375.0259.

Example 13

Add 1-(2-(methylthio)phenyl)-3-(4-(cyano)phenyl)-2-alkynyl-1-one ( 0.2mmol), sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL acetonitrile/water mixed solvent (v/v=10/1), React at room temperature for 5 hours under the illumination of a blue light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic solvent. The residue is subjected to column chromatography to obtain the target Product, the target product is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-(4-(cyano)phenyl)-2-ynyl-1-one being 100%, the yield of the target product is 46%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.54 (dd, J = 7.8, 1.2 Hz, 1H), 7.79 (d, J = 8.4 Hz, 2H), 7.73 -7.70 (m, 1H), 7.66-7.63 (m, 1H), 7.58-7.56 (m, 3H). ¹³ C NMR (150MHz, CDCl ₃ ) δ 177.1, 155.6 (q, J = 3.0Hz), 139.6, 135.3 , 133.0,132.5,131.4,129.5,129.2,128.8(q,J＝1.5Hz),125.6,123.2(q,J＝27Hz),122.5(q,J＝276Hz),117.9,114.5. ¹⁹ F NMR (565MHz ,CDCl ₃ )δ-55.6(s,3F).HRMS Calcd for C ₁₇ H ₉ F ₃ NOS[M+H] ⁺ :m/z 332.0351Found:332.0345.

Example 14

Add 1-(2-(methylthio)phenyl)-3-(3-pyridyl)-2-ynyl-1-one (0.2mmol) into a clean and dry reaction bottle equipped with a magnet. After sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL of acetonitrile/water mixed solvent (v/v=10/1), and the light will glow in blue. React at room temperature for 5 hours under diode irradiation. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic phase solvent. The residue is subjected to column chromatography to obtain the target product. The target product is The product is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-(3-pyridyl)-2-ynyl-1-one being 100%, the yield of the target product is 51%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.76 (dd, J = 4.8, 1.2 Hz, 1H), 8.70 (d, J = 1.8 Hz, 1H), 8.54 (dd,J＝8.4,1.2Hz,1H),7.78-7.76 (m,1H),7.72-7.69(m,1H),7.65-7.62(m,1H),7.58(dd,J＝7.8,0.6Hz ,1H),7.45-7.43(m,1H). ¹³ C NMR(150MHz,CDCl ₃ )δ177.2,154.3,151.5,147.9,135.5,135.4(q,J=3.0Hz), 132.8,131.6,131.4,129.5, 129.1, 125.5, 123.6 (q, J = 27Hz), 123.3, 122.6 (q, J = 274.5Hz). ¹⁹ FNMR (565MHz, CDCl ₃ ) δ-55.4 (s, 3F). HRMS Calcd for C ₁₅ H ₉ F ₃ NOS[M+H] ⁺ :m/z308.0351Found:308.0348.

Example 15

Add 1-(2-(methylthio)phenyl)-3-(2-naphthyl)-2-ynyl-1-one (0.2mmol) into a clean and dry reaction bottle equipped with a magnet. After sodium trifluoromethanesulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL of acetonitrile/water mixed solvent (v/v=10/1), and the light will glow in blue. React at room temperature for 5 hours under diode irradiation. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic phase solvent. The residue is subjected to column chromatography to obtain the target product. The target product is The product is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-(2-naphthyl)-2-ynyl-1-one being 100%, the yield of the target product is 33%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ8.57 (dd, J = 8.0, 1.2Hz, 1H), 7.96-7.91 (m, 4H), 7.72-7.68 ( m, 1H), 7.65-7.57 (m, 4H), 7.52 (dd, J＝8.4, 2.0Hz, 1H). ¹³ C NMR (150MHz, CDCl ₃ ) δ 177.7, 158.4 (q, J＝1.5Hz), 136.2 , 133.9,132.8,132.6,132.1,131.6,129.5,128.8,128.7,128.5,128.1,127.8,127.7,127.3,125.5,125.3,122.9(q,J＝27Hz),122.8(q,J＝276Hz). ¹⁹ F NMR (565MHz, CDCl ₃ ) δ -55.7 (s, 3F).HRMS Calcd for C ₂₀ H ₁₂ F ₃ OS[M+H] ⁺ :m/z 357.0555Found: 357.0545.

Example 16

In a clean and dry reaction bottle equipped with a magnet, add 1-(2-(methylthio)phenyl)-3-phenyl-2-ynyl-1-one (0.2mmol), perfluoroethyl After sodium sulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), add 3mL of acetonitrile/water mixed solvent (v/v=10/1), and place under the irradiation of a blue light-emitting diode. React at room temperature for 12 hours. After the reaction, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic phase solvent. The residue is subjected to column chromatography to obtain the target product, which is a yellow solid. . Based on the molar amount of 1-(2-(methylthio)phenyl)-3-phenyl-2-ynyl-1-one being 100%, the yield of the target product is 73%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ8.54 (dd, J = 8.0, 1.2Hz, 1H), 7.70-7.66 (m, 1H), 7.63-7.58 ( m,1H),7.53(d,J＝8.0Hz,1H), 7.48-7.42(m,3H),7.37(d,J＝6.8Hz,2H). ¹³ C NMR (150MHz, CDCl ₃ ) δ177.6,160.7 (t,J =3.0Hz),136.0,135.3,132.6,131.4,129.9,129.4,128.8,128.1,127.8,125.2,122.2-112.2(m). ¹⁹ FNMR(376MHz, CDCl ₃ )δ-80.1(s, 3F),-102.6(s,2F).HRMS Calcd for C ₁₇ H ₁₀ F ₅ OS[M+H] ⁺ :m/z357.0367Found:357.0389.

Example 17

In a clean and dry reaction bottle equipped with a magnet, add 1-(2-(methylthio)phenyl)-3-phenyl-2-ynyl-1-one (0.2mmol), perfluorobutyl After sodium sulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL of acetonitrile/water mixed solvent (v/v=10/1), and place under the irradiation of a blue light-emitting diode. React at room temperature for 12 hours. After the reaction, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic phase solvent. The residue is subjected to column chromatography to obtain the target product, which is a yellow solid. . Based on the molar amount of 1-(2-(methylthio)phenyl)-3-phenyl-2-ynyl-1-one being 100%, the yield of the target product is 40%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.54 (d, J=8.4Hz, 1H), 7.68 (t, J=7.8Hz, 1H), 7.61 (t ,J＝7.8Hz,1H),7.53(d,J＝7.8Hz,1H),7.49-7.42(m,3H),7.37(d,J＝7.2Hz,2H). ¹³ C NMR (150MHz, CDCl ₃ )δ177.7,160.9(t,J =3.0Hz),136.0,135.1,132.7,131.5,129.9,129.5,128.9,128.1,127.9,125.1,122.3-110.6(m). ¹⁹ F NMR (565MHz, CDCl ₃ )δ -80.7(t,J＝11.3Hz,3F),-99.3(t,J＝17.0Hz,2F), -117.6(m,2F),-126.2(m,2F).HRMS Calcd for C ₁₉ H ₁₀ F _9OS [M+H] ⁺ :m/z 457.0303Found:457.0308.

Example 18

In a clean and dry reaction bottle equipped with a magnet, add 1-(2-(methylthio)phenyl)-3-phenyl-2-ynyl-1-one (0.2mmol), perfluorohexylene After sodium sulfonate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), add 3mL of acetonitrile/water mixed solvent (v/v=10/1), and incubate at room temperature under the irradiation of a blue light-emitting diode. The reaction was carried out for 12 hours. After the reaction, the reaction solution was extracted with ethyl acetate. The organic phases were combined and dried over anhydrous sodium sulfate. The organic phase solvent was filtered and evaporated. The residue was subjected to column chromatography to obtain the target product, which was a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-phenyl-2-ynyl-1-one being 100%, the yield of the target product is 42%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ8.54 (dd, J = 8.0, 1.2Hz, 1H), 7.70-7.66 (m, 1H), 7.63-7.59 ( m, 1H), 7.53 (dd, J＝8.0, 0.8Hz, 1H), 7.48-7.42 (m, 3H), 7.37 (d, J＝7.2Hz, 2H). ¹³ C NMR (150MHz, CDCl ₃ ) δ177 .7,160.9 (t,J＝3.0Hz),136.0,135.1,132.7,131.5,129.9,129.5,128.9,128.1,127.9,125.1,122.4(t,J＝18Hz),119.2-109.1(m). ¹⁹ F NMR (376MHz, CDCl ₃ )δ-80.8(t,J＝11.3Hz,3F),-99.2 (m,2F),-116.8(m,2F),-122.0(m,2F),-122.5(m,2F ),-126.1(m,2F).HRMS Calcd forC ₂₁ H ₁₀ F ₁₃ OS[M+H] ⁺ :m/z 557.0239Found:557.0253.

Example 19

In a clean and dry reaction bottle equipped with a magnet, add 1-(2-(methylthio)phenyl)-3-phenyl-2-ynyl-1-one (0.2mmol), perfluorooctyl After sodium sulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), add 3mL of acetonitrile/water mixed solvent (v/v=10/1), and place under the irradiation of a blue light-emitting diode. React at room temperature for 12 hours. After the reaction, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic phase solvent. The residue is subjected to column chromatography to obtain the target product, which is a yellow solid. . Based on the molar amount of 1-(2-(methylthio)phenyl)-3-phenyl-2-ynyl-1-one being 100%, the yield of the target product is 43%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.54 (d, J=8.4Hz, 1H), 7.69-7.66 (m, 1H), 7.62-7.59 (m, 1H), 7.53 (d, J=7.8Hz, 1H), 7.49-7.42 (m, 3H), 7.37 (d, J=7.8Hz, 2H). ¹³ C NMR (150MHz, CDCl ₃ ) δ 177.7, 160.9 (t , J＝3.0Hz), 136.0,135.2,132.6,131.5,129.9,129.5,128.9,128.1,127.9,125.1,122.4(t,J＝19.5Hz), 119.2-107.9(m). ¹⁹ F NMR (376MHz, CDCl ₃ )δ-80.8(t,J＝11.3Hz,3F),-99.2(m,2F), -116.7(m,2F),-121.5(m,2F),-121.8(m,2F),- 121.9(m,2F),-122.7(m,2F),-126.1(m,2F).HRMSCalcd for C ₂₃ H ₁₀ F ₁₇ OS[M+H] ⁺ :m/z 657.0175Found:657.0171.

Example 20

Add 1-(2-(methylthio)phenyl)-3-((4-methyl)phenyl)-2-alkynyl-1-one ( 0.2mmol), sodium perfluoroethyl sulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL of acetonitrile/water mixed solvent (v/v=10/1), React at room temperature for 12 hours under the irradiation of a blue light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic solvent. The residue is subjected to column chromatography to obtain the target Product, the target product is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-((4-methyl)phenyl)-2-ynyl-1-one being 100%, the yield of the target product is 84%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ8.54 (dd, J = 8.0, 1.2Hz, 1H), 7.70-7.65 (m, 1H), 7.62-7.58 ( m, 1H), 7.53 (dd, J = 8.0, 0.8Hz, 1H), 7.28-7.24 (m, 4H), 2.43 (s, 3H). ¹³ C NMR (150MHz, CDCl ₃ ) δ 177.7, 161.0 (t, J=3.0 Hz), 140.1, 136.1, 132.6, 132.4, 131.5, 129.4, 128.8, 128.7, 127.7, 125.1, 122.2-112.3 (m), 21.5. ¹⁹ F NMR (376MHz, CDCl ₃ ) δ-80.0 (s, 3F),-102.6(s,2F).HRMS Calcd for C ₁₈ H ₁₂ F ₅ OS[M+H] ⁺ :m/z 371.0524Found:371.0530.

Example 21

Add 1-(2-(methylthio)phenyl)-3-((4-methyl)phenyl)-2-alkynyl-1-one ( 0.2mmol), sodium perfluorobutylsulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL of acetonitrile/water mixed solvent (v/v=10/1), React at room temperature for 12 hours under the irradiation of a blue light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic solvent. The residue is subjected to column chromatography to obtain the target Product, the target product is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-((4-methyl)phenyl)-2-ynyl-1-one being 100%, the yield of the target product is 73%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.53 (d, J=8.4Hz, 1H), 7.68-7.66 (m, 1H), 7.61-7.58 (m, 1H), 7.52 (d, J = 7.8Hz, 1H), 7.25-7.23 (m, 4H), 2.43 (s, 3H). ¹³ C NMR (150MHz, CDCl ₃ ) δ 177.8, 161.2, 140.1, 136.2, 132.6, 132.3, 131.5, 129.4, 128.8, 127.8, 125.1, 122.4-111.5 (m), 21.5. ¹⁹ F NMR (565MHz, CDCl ₃ ) δ -80.7 (t, J = 11.3 Hz, 3F), -99.3 (t, J =17.0Hz,2F),-117.5(m,2F),-126.2(m,2F).HRMS Calcdfor C ₂₀ H ₁₂ F ₉ OS[M+H] ⁺ :m/z 471.0460Found:471.0448.

Example 22

Add 1-(2-(methylthio)phenyl)-3-((4-ethyl)phenyl)-2-ynyl-1-one ( 0.2mmol), sodium perfluorohexylsulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL acetonitrile/water mixed solvent (v/v=10/1), React at room temperature for 12 hours under the irradiation of a blue light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic solvent. The residue is subjected to column chromatography to obtain the target product. , the target product is a yellow solid. Based on the molar amount of 1-(2-(methylthio)phenyl)-3-((4-ethyl)phenyl)-2-ynyl-1-one being 100%, the yield of the target product is 55%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.53 (d, J＝7.8Hz, 1H), 7.68-7.65 (m, 1H), 7.59 (t, J＝ 7.8Hz,1H),7.51(d,J＝7.8Hz,1H), 7.28-7.25(m,4H),2.72(q,J＝7.8Hz,2H),1.29(t,J＝7.8Hz,3H) . ¹³ C NMR (150MHz, CDCl ₃ ) δ 177.8, 161.3 (t, J = 3.0Hz), 146.3, 136.2, 132.6, 132.5, 131.6, 129.4, 128.8, 127.9, 127.5, 125.1, 122.4 (t, J = 19.5Hz ),119.2-106.8(m),28.8,15.3. ¹⁹ F NMR (565MHz, CDCl ₃ )δ-80.8(t,J＝11.3Hz,3F),-99.1(t,J＝17.0Hz,2F),- 116.7(t,J＝17.0Hz,2F),-121.9(m,2F),-122.5(m,2F),-126.1(m,2F).HRMS Calcd for C ₂₃ H ₁₄ F ₁₃ OS[M+H ] ⁺ :m/z 585.0552Found:585.0528.

Example 23

Add 1-(2-(methylthio)phenyl)-3-((4-methoxy)phenyl)-2-ynyl-1-one into a clean and dry reaction bottle equipped with a magnet. (0.2mmol), sodium perfluorooctyl sulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01 mmol), then add 3mL of acetonitrile/water mixed solvent (v/v=10/1) , react at room temperature for 12 hours under the irradiation of a blue light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate, the organic phases are combined, dried over anhydrous sodium sulfate, filtered and the organic solvent is spun off, and the residue is obtained by column chromatography. The target product is a yellow solid. Based on the molar weight of 1-(2-(methylthio)phenyl)-3-((4-methoxy)phenyl)-2-ynyl-1-one as 100%, the yield of the target product is 54%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.53 (d, J=8.4Hz, 1H), 7.66 (t, J=7.2Hz, 1H), 7.59 (t ,J＝7.8Hz,1H),7.52(d,J＝8.4Hz,1H), 7.30(d,J＝8.4Hz,2H),6.95(d,J＝7.8Hz,2H),3.87(s,3H ). ¹³ C NMR (150MHz, CDCl ₃ ) δ177.9,161.0(t,J＝3.0Hz),160.9,136.2,132.6,131.6,129.43,129.40,128.8,127.3,125.1,122.6(t,J＝19.5Hz) ,119.5-115.8(m),113.6,113.3-108.4(m),55.5. ¹⁹ F NMR (376MHz, CDCl ₃ )δ-80.8(t,J＝9.8Hz,3F),-99.1(m,2F), -116.6(m,2F),-121.5(m,2F),-121.7(m,2F),-121.8(m,2F),-122.7(m,2F),-126.1(m,2F).HRMS Calcd for C ₂₄ H ₁₂ F ₁₇ O ₂ S[M+H] ⁺ : m/z 687.0281Found:687.0268.

Example 24

In a clean and dry reaction bottle equipped with a magnet, add 1-(2-(methylthio)phenyl)-3-((4-fluorophenyl)-2-ynyl-1-one (0.2mmol ), sodium perfluorooctyl sulfinate (0.6mmol) and catalyst Acr ⁺ -Mes·ClO ₄ ^– (0.01mmol), then add 3mL acetonitrile/water mixed solvent (v/v=10/1), in blue React at room temperature for 12 hours under the irradiation of a color light-emitting diode. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic solvent. The residue is subjected to column chromatography to obtain the target product. The target product is a yellow solid. Based on the molar weight of 1-(2-(methylthio)phenyl)-3-((4-fluorophenyl)-2-ynyl-1-one) being 100%, the target product The yield is 41%. The structural formula of the target product is as follows:

Nuclear magnetic spectrum analysis was performed on the above yellow solid. The data are as follows: ¹ H NMR (600MHz, CDCl ₃ ) δ8.53 (d, J=8.4Hz, 1H), 7.69 (t, J=7.8Hz, 1H), 7.61 (t , J=7.8Hz, 1H), 7.53 (d, J=7.8Hz, 1H), 7.37-7.35 (m, 2H), 7.15-7.12 (m, 2H). ¹³ C NMR (150MHz, CDCl ₃ ) δ177. 6,163.6(d,J＝249Hz),159.8(t,J＝3.0Hz),135.8,132.7,131.5,131.0,130.0(d,J＝7.5Hz),129.5,129.0,125.1,122.8(t,J＝18Hz ),120.2-115.7(m),115.4(d,J＝22.5Hz),113.3-108.7(m). ¹⁹ FNMR(565MHz,CDCl ₃ )δ-80.8(t,J＝9.6Hz,3F),-99.2 (t,J＝13.6Hz,2F),-110.5(s,1F), -116.8(m,2F),-121.5(s,2F),-121.7(s,2F),-121.9(s,2F) ,-122.7(s,2F),-126.1(m,2F).HRMS Calcd for C ₂₃ H ₉ F ₁₈ OS[M+H] ⁺ :m/z 675.0081Found:675.0094.

Example 25

In vitro antitumor activity test

method:

The in vitro anti-Ramos cell proliferation test used the CellTiter-Glo (Promega, USA) test method. After diluting the Ramos cell suspension to an appropriate concentration with culture medium, add 95 μL to a 96-well plate. After adding 5 μL of the compound to be tested at different concentrations, the culture plate was incubated at 37°C and 5% _CO2 for 72 hours. Take out the culture plate and bring it to room temperature to start testing. Add 20 μL CellTiter-Glo reagent to each well and mix on a shaker for 2 minutes to induce cell lysis. Incubate at room temperature for 10 minutes to stabilize the fluorescent signal. Record the fluorescence intensity using a multifunctional microplate reader. Calculate the cell viability based on the formula and the fluorescence intensity of the blank control group, and then calculate the IC ₅₀ of the target compound.

Table 1 In vitro antitumor activity of representative compounds

The basic principles, main features and advantages of the present invention have been shown and described above. Without departing from the spirit and scope of the present invention, there are various changes and improvements in the present invention. These changes and improvements all fall within the scope of the claimed invention. range.

Claims (10)

1. A synthesis method of 3-perfluoroalkylated thioflavones, characterized in that the specific steps are: adding 2-methylthiophenylpropynone, sodium perfluoroalkylsulfinate and a catalyst in the reaction bottle After adding 9-mesitylyl-10-methylacridine perchlorate Acr ⁺ -Mes·ClO ₄ ^– , a mixed solvent of acetonitrile and water and trifluoroacetic acid were added, and the mixture was heated at room temperature under the illumination of a blue light-emitting diode. Stir the reaction. After the reaction is completed, the reaction solution is extracted with ethyl acetate. The organic phases are combined and dried over anhydrous sodium sulfate. Filter and spin off the organic solvent under reduced pressure. The target product 3-perfluoroalkylated thioflavonoids is obtained through column chromatography. , the structural formula of 2-methylthiophenylpropynone is shown in formula A, the structural formula of sodium perfluoroalkyl sulfinate is shown in formula B, and the structural formula of 3-perfluoroalkylated thioflavonoids is shown in formula C. Show: Wherein R ¹ is H, C _1-6 alkyl, C _1-6 alkoxy, trifluoromethyl, cyano, fluorine, chlorine or bromine; R _f is (CF ₂ ) _n CF ₃ , n is selected from 0 An integer between -7. 2. The synthetic method of 3-perfluoroalkylated thioflavones according to claim 1, characterized in that the specific structural formula of the 3-perfluoroalkylated thioflavones is: 3. The synthetic method of 3-perfluoroalkylated thioflavones according to claim 1, characterized in that: the 2-methylthiophenylpropynone, sodium perfluoroalkylsulfinate, catalyst Acr The feeding molar ratio of ⁺ -Mes·ClO ₄ ^- and trifluoroacetic acid is 1:1-3:1%-10%:1-3. 4. The synthesis method of 3-perfluoroalkylated thioflavones according to claim 1, characterized in that the structural formula of the catalyst Acr ⁺ -Mes·ClO ₄ ^- is: 5. A method for synthesizing 3-perfluoroalkylated thioflavonoids, which is characterized in that the specific steps are: adding 1-(2-(methylthio)phenyl)-3-(3- After adding pyridyl)-2-ynyl-1-one, sodium trifluoromethylsulfinate and catalyst Acr ⁺ -Mes·ClO ₄ ^- , add a mixed solvent of acetonitrile and water and trifluoroacetic acid, and it will glow in blue. The reaction was stirred at room temperature under the irradiation of a diode. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phases were combined and dried over anhydrous sodium sulfate, filtered, and the organic solvent was spun off under reduced pressure. The target product 3-perfluorocarbon was obtained through column chromatography. Alkylated thioflavones, the structural formula of the target product 3-perfluoroalkylated thioflavones is: 6. The synthetic method of 3-perfluoroalkylated thioflavones according to claim 5, characterized in that: the 1-(2-(methylthio)phenyl)-3-(3-pyridine The molar ratio of the base)-2-alkynyl-1-one, sodium trifluoromethanesulfinate, catalyst Acr ⁺ -Mes·ClO ₄ ^- and trifluoroacetic acid is 1:1-3:1%-10% :1-3. 7. A method for synthesizing 3-perfluoroalkylated thioflavonoids, which is characterized in that the specific steps are: adding 1-(2-(methylthio)phenyl)-3-(2- After adding naphthyl)-2-ynyl-1-one, sodium trifluoromethanesulfinate and catalyst Acr ⁺ -Mes·ClO ₄ ^– , add a mixed solvent of acetonitrile and water and trifluoroacetic acid, and it will glow in blue. The reaction was stirred at room temperature under the irradiation of a diode. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phases were combined and dried over anhydrous sodium sulfate, filtered, and the organic solvent was spun off under reduced pressure. The target product 3-perfluorocarbon was obtained through column chromatography. Alkylated thioflavones, the structural formula of the target product 3-perfluoroalkylated thioflavones is: 8. The synthetic method of 3-perfluoroalkylated thioflavones according to claim 7, characterized in that: the 1-(2-(methylthio)phenyl)-3-(2-naphthalene The molar ratio of the base)-2-alkynyl-1-one, sodium trifluoromethanesulfinate, catalyst Acr ⁺ -Mes·ClO ₄ ^- and trifluoroacetic acid is 1:1-3:1%-10% :1-3. 9. The synthesis method of 3-perfluoroalkylated thioflavones according to claim 1, 5 or 7, characterized in that: the reaction conditions of the reaction process are to use blue LED lamps as visible light sources, and their wavelengths are 455-465nm, power 6-12W. 10. The synthesis method of 3-perfluoroalkylated thioflavones according to claim 1, 5 or 7, characterized in that: the volume ratio of acetonitrile and water in the mixed solvent of acetonitrile and water is 10:1. .