CN115160292A - Synthesis method of 3-perfluoroalkyl thioflavone - Google Patents
Synthesis method of 3-perfluoroalkyl thioflavone Download PDFInfo
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- CN115160292A CN115160292A CN202210633564.3A CN202210633564A CN115160292A CN 115160292 A CN115160292 A CN 115160292A CN 202210633564 A CN202210633564 A CN 202210633564A CN 115160292 A CN115160292 A CN 115160292A
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- reaction
- perfluoroalkyl
- thioflavone
- methylthio
- phenyl
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- 238000001308 synthesis method Methods 0.000 title abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000006243 chemical reaction Methods 0.000 claims abstract description 100
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 93
- -1 2-methylthio phenylpropargyl Chemical group 0.000 claims abstract description 82
- 239000012074 organic phase Substances 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 229910020366 ClO 4 Inorganic materials 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012046 mixed solvent Substances 0.000 claims abstract description 34
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 31
- 238000004440 column chromatography Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 29
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- GIQPSSZMIZARDW-UHFFFAOYSA-N 2-phenylthiochromen-4-one Chemical compound S1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 GIQPSSZMIZARDW-UHFFFAOYSA-N 0.000 claims abstract description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 12
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 8
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims abstract description 7
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims description 29
- 239000003960 organic solvent Substances 0.000 claims description 18
- KAVUKAXLXGRUCD-UHFFFAOYSA-M sodium trifluoromethanesulfinate Chemical compound [Na+].[O-]S(=O)C(F)(F)F KAVUKAXLXGRUCD-UHFFFAOYSA-M 0.000 claims description 16
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 6
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 5
- 238000009987 spinning Methods 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- FNPNRZLYTIVLNO-UHFFFAOYSA-N Cl(=O)(=O)(=O)O.C1(=C(C(=CC(=C1)C)C)C1C2=CC=CC=C2N(C=2C=CC=CC12)C)C Chemical compound Cl(=O)(=O)(=O)O.C1(=C(C(=CC(=C1)C)C)C1C2=CC=CC=C2N(C=2C=CC=CC12)C)C FNPNRZLYTIVLNO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- AWYYABCIESYFJD-UHFFFAOYSA-N CSC1=C(C=CC=C1)C(C#C)C(=O)C(C#C)C1=C(C=CC=C1)SC Chemical compound CSC1=C(C=CC=C1)C(C#C)C(=O)C(C#C)C1=C(C=CC=C1)SC AWYYABCIESYFJD-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 230000000259 anti-tumor effect Effects 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- GHASVSINZRGABV-UHFFFAOYSA-N Fluorouracil Chemical compound FC1=CNC(=O)NC1=O GHASVSINZRGABV-UHFFFAOYSA-N 0.000 abstract 1
- 229960002949 fluorouracil Drugs 0.000 abstract 1
- 238000010025 steaming Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 48
- 238000010183 spectrum analysis Methods 0.000 description 24
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- DFCYBFLXCKGZML-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfinic acid Chemical compound OS(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFCYBFLXCKGZML-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- MOFLIWVSDXPEDX-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfinic acid Chemical compound OS(=O)C(F)(F)C(F)(F)F MOFLIWVSDXPEDX-UHFFFAOYSA-N 0.000 description 2
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 2
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000012054 celltiter-glo Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229930003935 flavonoid Natural products 0.000 description 2
- 150000002215 flavonoids Chemical class 0.000 description 2
- 235000017173 flavonoids Nutrition 0.000 description 2
- 230000005918 in vitro anti-tumor Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- KSGPZCLVYJGMFY-UHFFFAOYSA-M sodium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfinate Chemical compound [Na+].[O-]S(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KSGPZCLVYJGMFY-UHFFFAOYSA-M 0.000 description 2
- OACUJLWTMMENAD-UHFFFAOYSA-M sodium;1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfinate Chemical compound [Na+].[O-]S(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F OACUJLWTMMENAD-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical compound C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000006037 cell lysis Effects 0.000 description 1
- 238000001516 cell proliferation assay Methods 0.000 description 1
- 239000006285 cell suspension Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- SFEBPWPPVGRFOA-UHFFFAOYSA-N trifluoromethanesulfinic acid Chemical compound OS(=O)C(F)(F)F SFEBPWPPVGRFOA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthesis method of 3-perfluoroalkyl thioflavone, which is characterized in that 2-methylthio phenylpropargyl ketone, perfluoroalkyl sodium sulfinate and catalyst Acr are added 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 a reaction solution by using ethyl acetate after the reaction is finished, combining organic phases, drying by using anhydrous sodium sulfate, decompressing, steaming to remove the solvent, and carrying out column chromatography on residues to obtain the target product 3-perfluoroalkyl-type thioflavone. The synthesis method does not need to use a strong oxidant and a transition metal catalyst, and the synthesis raw materials related to the synthesis method are simple and easy to obtain, and the reaction conditions are easy to control. The light source used in the method is green and pollution-free visible light. And was testedIt was found that a portion of the synthesized target compounds exhibited antitumor activity superior to that of the control drug 5-fluorouracil.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a synthesis method of 3-perfluoroalkyl thioflavone.
Background
Thioflavone is a predominant framework that is widely found in natural products, bioactive molecules and functional materials. Perfluoroalkyl groups, particularly trifluoromethyl groups, are present in over 70 drugs on the market and are critical to the activity of the drug (j.med. Chem.,2020,63, 13076). Therefore, the preparation of the thioflavone containing perfluoroalkyl has important significance. However, no synthesis method of perfluoroalkyl thioflavone has been reported at present.
The preparation of substituted thioflavones from 2-methylthiophenylpropargone as a starting material by addition cyclisation is a common strategy (j. Org. Chem.,2006,71,1626 org. Lett.,2019,21,1112-1115 org. Chem. Front., 2020,7, 3935-3940. Most of the preparation methods need high-temperature heating, transition metal catalysts or additional oxidants and other conditions, so that the problems of consumption of non-renewable resources, environmental pollution, cost increase and the like are caused.
Disclosure of Invention
The invention provides a synthesis method of 3-perfluoroalkyl thioflavone, which takes acetonitrile and water as mixed solvent to synthesize the 3-perfluoroalkyl thioflavone under the induction of visible light, can effectively solve the problem that no synthesis method of the 3-perfluoroalkyl thioflavone exists at present, and can reduce the consumption of non-renewable resources, environmental pollution and the like. Tests show that part of the synthesized compounds show better anti-tumor activity, and provide novel-structure miao-cephalin compounds for the development of new drugs.
The invention adopts the following technical scheme for solving the technical problems: a method for synthesizing 3-perfluoroalkyl thioflavone is characterized by comprising the following steps: adding 2-methylthio phenylpropargyl ketone, perfluoroalkyl sodium sulfinate and catalyst 9-mesityl-10-methylacridine perchlorate (Acr) into a reaction bottle + -Mes·ClO 4 – ) Then adding mixed solvent of acetonitrile and water and trifluoroacetic acid, stirring and reacting at room temperature under the irradiation of a blue light-emitting diode, and extracting by ethyl acetate after the reaction is finishedCombining organic phases of reaction liquid, drying by using anhydrous sodium sulfate, filtering, decompressing, removing an organic solvent, and performing column chromatography to obtain a target product, namely 3-perfluoroalkyl-type thioflavone, wherein the structural formula of 2-methylthio phenylproparganone is shown as a formula A, the structural formula of perfluoroalkyl-type sodium sulfinate is shown as a formula B, and the structural formula of 3-perfluoroalkyl-type thioflavone is shown as a formula C:
wherein R is 1 Is H, C 1-6 Alkyl radical, C 1-6 Alkoxy, trifluoromethyl, cyano, fluoro, chloro, bromo, or the like; r is f Is (CF) 2 ) n CF 3 And n is an integer from 0 to 7.
Further limited, the specific structural formula of the 3-perfluoroalkyl thioflavone is as follows:
further limited, the 2-methylthio phenylpropargyl ketone, the perfluoroalkyl sodium sulfinate and the catalyst Acr + -Mes·ClO 4 – And the feeding molar ratio of trifluoroacetic acid is 1-3.
Further defined, the reaction equation in the synthesis process of the 3-perfluoroalkyl thioflavone is as follows:
the catalyst Acr + -Mes·ClO 4 – The structural formula of (A) is:
a synthetic method of 3-perfluoroalkyl thioflavone is characterized by comprising the specific stepsThe method comprises the following steps: adding 1- (2- (methylthio) phenyl) -3- (3-pyridyl) -2-alkynyl-1-ketone, sodium trifluoromethanesulfonate and 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 a reaction solution by using ethyl acetate after the reaction is finished, combining organic phases, drying by using anhydrous sodium sulfate, filtering, decompressing, removing the organic solvent by rotation, and carrying out column chromatography to obtain a target product 3-perfluoroalkyl thioxanthone, wherein the structural formula of the target product 3-perfluoroalkyl thioxanthone is as follows:
further defined, the 1- (2- (methylthio) phenyl) -3- (3-pyridyl) -2-alkynyl-1-one, sodium trifluoromethylsulfinate, catalyst Acr + -Mes·ClO 4 – And the feeding molar ratio of trifluoroacetic acid is 1-3.
A method for synthesizing 3-perfluoroalkyl thioflavone is characterized by comprising the following steps: adding 1- (2- (methylthio) phenyl) -3- (2-naphthyl) -2-alkynyl-1-ketone, sodium trifluoromethanesulfonate and 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 a reaction solution by using ethyl acetate after the reaction is finished, combining organic phases, drying by using anhydrous sodium sulfate, filtering, decompressing, spinning off the organic solvent, and performing column chromatography to obtain a target product 3-perfluoroalkyl-type flavonoid, wherein the structural formula of the target product 3-perfluoroalkyl-type flavonoid is as follows:
further defined, the 1- (2- (methylthio) phenyl) -3- (2-naphthyl) -2-alkynyl-1-one, sodium triflate, catalyst Acr + -Mes·ClO 4 – And the feeding molar ratio of trifluoroacetic acid is 1-3.
Further defined, the reaction conditions of the reaction process are that a blue LED lamp is used as a visible light source, the wavelength of the blue LED lamp is 455-465nm, and the power of the blue LED lamp is 6-12W.
Further defined, the volume ratio of the acetonitrile to the water in the mixed solvent of the acetonitrile and the water is 10.
Compared with the prior art, the invention has the following advantages and beneficial effects: the invention provides a synthetic method of 3-perfluoroalkyl thioflavone, which solves the problem that no synthetic method of 3-perfluoroalkyl thioflavone exists at present. The synthesis method has the advantages of simple and easily obtained synthesis raw materials, easily controlled reaction conditions, and no need of adding a transition metal catalyst and an external oxidant to induce the reaction process by using visible light. And the antitumor activity evaluation of the target compound is preliminarily completed, and the antitumor compound with the activity superior to that of the contrast medicament 5-Fu and a brand-new structure is obtained by screening.
Detailed Description
The technical solution of the present invention is specifically described below by way of examples. It is to be noted that the following examples are only for further illustration of the present invention and should not be construed as limiting the scope of the present invention. Many non-essential modifications and adaptations of the present invention will occur to those skilled in the art in view of the foregoing description, and are intended to be within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
A clean and dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3-phenyl-2-alkynyl-1-one (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering, removing the organic solvent in a rotating way, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 75% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3-phenyl-2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 )δ177.7,158.4(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).HRMS Calcd for C 16 H 10 F 3 OS[M+H] + :m/z 307.0399,Found:307.0390。
example 2
A clean, dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- ((4-methyl) phenyl) -2-alkynyl-1-one (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), then adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction liquid by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing the organic solvent in a rotary manner, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 55% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3- ((4-methyl) phenyl) -2-alkyn-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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＝8.4Hz,1H), 7.34(d,J＝7.8Hz,2H),7.28(d,J＝7.8Hz,2H),2.43(s,3H). 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
A clean, dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- ((4-ethyl) phenyl) -2-alkynyl-1-one (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), then adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing the organic solvent, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 78% based on 100% molar 1- (2- (methylthio) phenyl) -3- ((4-ethyl) phenyl) -2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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＝7.2Hz, 3H). 13 C NMR(150MHz,CDCl 3 )δ 13 C NMR(150MHz,CDCl 3 )δ177.8,158.7(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).HRMS Calcd for C 18 H 14 F 3 OS[M+H] + :m/z 335.0712Found:335.0696。
example 4
A clean, dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- ((4-tert-butyl) phenyl) -2-alkynyl-1-one (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing an organic phase solvent in a rotary manner, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 75% based on 100% molar 1- (2- (methylthio) phenyl) -3- ((4-tert-butyl) phenyl) -2-alkyn-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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
A clean, dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- ((4-methoxy) phenyl) -2-alkynyl-1-one (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01mmol), adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing the organic phase solvent in a rotary manner, and carrying out column chromatography on the residue to obtain the target product which is a yellow solid. The yield of the desired product was 69% based on 100% molar 1- (2- (methylthio) phenyl) -3- ((4-methoxy) phenyl) -2-alkyn-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 )δ178.0, 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
A clean, dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- ((3-methyl) phenyl) -2-alkynyl-1-one (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), then adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction liquid by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing the organic solvent in a rotary manner, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the target product was found to be 100% based on the molar amount of 1- (2- (methylthio) phenyl) -3- ((3-methyl) phenyl) -2-alkynyl-1-one70 percent. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 )δ177.7,158.7(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 F NMR(376MHz,CDCl 3 )δ-55.8(s,3F).HRMS Calcd for C 17 H 12 F 3 OS[M+H] + :m/z 321.0555Found:321.0519。
example 7
A clean and dry reaction flask containing magnetons is charged with 1- (2- (methylthio) phenyl) -3- (4-fluorophenyl) -2-alkynyl-1-one (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing an organic phase solvent in a rotary manner, and carrying out column chromatography on the residue to obtain a target product which is a yellow solid. The yield of the desired product was 81% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3- (4-fluorophenyl) -2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 F NMR(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/z 325.0305Found:325.0277。
example 8
Adding 1- (2- (methylthio) phenyl) -3- (4-chlorophenyl) -2-alkynyl-1-ketone (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and a catalyst Acr into a clean and dry reaction bottle filled with magnetons + -Mes·ClO 4 – (0.01 mmol), then adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing the organic solvent, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 60% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3- (4-fluorophenyl) -2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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
A clean dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- (4-bromophenyl) -2-alkynyl-1-one (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), then adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing the organic solvent, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 86% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3- (4-bromophenyl) -2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 )δ177.5,156.9(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
A clean and dry reaction flask containing magnetons is charged with 1- (2- (methylthio) phenyl) -3- (3-fluorophenyl) -2-alkynyl-1-one (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), 3mL of a mixed solvent of acetonitrile/water (v/v = 10/1) was added thereto, the mixture was reacted at room temperature for 5 hours under irradiation of a blue light-emitting diode, the reaction mixture was extracted with ethyl acetate after the completion of the reaction, the organic phases were combined, dried over anhydrous sodium sulfate, and the mixture was filteredFiltering and removing the organic phase solvent by spinning, and carrying out column chromatography on the residue to obtain a target product, wherein the target product is a yellow solid. The yield of the desired product was 47% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3- (3-fluorophenyl) -2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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
A clean dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- (2-bromophenyl) -2-alkynyl-1-one (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing an organic phase solvent in a rotary manner, and carrying out column chromatography on the residue to obtain a target product which is a yellow solid. The yield of the desired product was 75% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3- (2-bromophenyl) -2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 )δ177.1,156.3(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 384.9504Found:384.9495。
example 12
A clean, dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- (4- (trifluoromethyl) phenyl) -2-alkynyl-1-one (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing an organic phase solvent in a rotary manner, and carrying out column chromatography on the residue to obtain a target product which is a yellow solid. The yield of the desired product was 88% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3- (4- (trifluoromethyl) phenyl) -2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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
A clean and dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- (4- (cyano) phenyl) -2-alkynyl-1-one (0.2 mmol), sodium trifluoromethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), then adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing the organic solvent, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 46% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3- (4- (cyano) phenyl) -2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were as follows: 1 H NMR(600MHz,CDCl 3 )δ8.54 (dd,J＝7.8,1.2Hz,1H),7.79(d,J＝8.4Hz,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 )δ177.1,155.6(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
1- (2- (methylthio) phenyl) -3- (3-pyridyl) -2-alkynyl-1-one (0.2 mmol) and trifluoromethanesulphinic acid were added to a clean, dry reaction flask containing magnetonsSodium (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing an organic phase solvent in a rotary manner, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 51% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3- (3-pyridyl) -2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were as follows: 1 H NMR(600MHz,CDCl 3 )δ8.76 (dd,J＝4.8,1.2Hz,1H),8.70(d,J＝1.8Hz,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 F NMR(565MHz,CDCl 3 )δ-55.4(s,3F).HRMS Calcd for C 15 H 9 F 3 NOS[M+H] + :m/z 308.0351Found:308.0348。
example 15
A clean and dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- (2-naphthyl) -2-alkynyl-1-one (0.2 mmol), sodium triflate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 5 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing an organic phase solvent in a rotary manner, and carrying out column chromatography on the residue to obtain a target product which is a yellow solid. With 1- (2- (methylthio) phenyl) -3- (2-naphthalene)The molar amount of the base) -2-alkynyl-1-one is 100%, and 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 were 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 )δ177.7,158.4(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
A clean and dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3-phenyl-2-alkynyl-1-one (0.2 mmol), sodium perfluoroethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 12 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing an organic phase solvent in a rotary manner, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 73% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3-phenyl-2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 F NMR(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/z 357.0367Found:357.0389。
example 17
Adding 1- (2- (methylthio) phenyl) -3-phenyl-2-alkynyl-1-ketone (0.2 mmol), sodium perfluorobutylsulfinate (0.6 mmol) and a catalyst Acr into a clean and dry reaction bottle with magnetons + -Mes·ClO 4 – (0.01 mmol), adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 12 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing an organic phase solvent in a rotary manner, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 40% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3-phenyl-2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 9 OS[M+H] + :m/z 457.0303Found: 457.0308。
example 18
Adding 1- (2- (methylthio) phenyl) -3-phenyl-2-alkynyl-1-ketone (0.2 mmol), sodium perfluorohexylsulfinate (0.6 mmol) and catalyst Acr into a clean and dry reaction bottle with magnetons + -Mes·ClO 4 – (0.01 mmol), adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 12 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing an organic phase solvent in a rotary manner, and carrying out column chromatography on the residue to obtain a target product which is a yellow solid. The yield of the desired product was 42% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3-phenyl-2-yn-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 for C 21 H 10 F 13 OS[M+H] + :m/z 557.0239Found:557.0253。
example 19
A clean and dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3-phenyl-2-alkynyl-1-one (0.2 mmol), sodium perfluorooctylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), 3mL of a mixed solvent of acetonitrile/water (v/v = 10/1) was added thereto, the mixture was reacted at room temperature for 12 hours under irradiation of a blue light emitting diode, the reaction mixture was extracted with ethyl acetate after the reaction was completed, the organic phases were combined, and the mixture was subjected to a reaction with ethyl acetateDrying with anhydrous sodium sulfate, filtering and removing the organic phase solvent, and performing column chromatography on the residue to obtain a target product, wherein the target product is a yellow solid. The yield of the desired product was 43% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3-phenyl-2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 )δ177.7,160.9(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). HRMS Calcd for C 23 H 10 F 17 OS[M+H] + :m/z 657.0175Found:657.0171。
example 20
A clean, dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- ((4-methyl) phenyl) -2-alkynyl-1-one (0.2 mmol), sodium perfluoroethylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), then adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 12 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing the organic solvent, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 84% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3- ((4-methyl) phenyl) -2-alkyn-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 )δ177.7,161.0(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
A clean, dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- ((4-methyl) phenyl) -2-alkynyl-1-one (0.2 mmol), sodium perfluorobutylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), then adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 12 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction liquid by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing the organic solvent in a rotary manner, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 73% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3- ((4-methyl) phenyl) -2-alkyn-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 )δ177.8,161.2,140.1,136.2,132.6,132.3, 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＝11.3Hz,3F),-99.3(t,J＝17.0Hz,2F),-117.5(m,2F),-126.2(m,2F).HRMS Calcd for C 20 H 12 F 9 OS[M+H] + :m/z 471.0460Found:471.0448。
example 22
A clean, dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- ((4-ethyl) phenyl) -2-alkynyl-1-one (0.2 mmol), sodium perfluorohexylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), then adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 12 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction liquid by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing the organic solvent in a rotary manner, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 55% based on 100% molar 1- (2- (methylthio) phenyl) -3- ((4-ethyl) phenyl) -2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 )δ177.8,161.3(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 585.0552 Found:585.0528。
example 23
Adding 1- (2- (methylthio) 1 into a clean and dry reaction bottle with magnetons) Phenyl) -3- ((4-methoxy) phenyl) -2-alkynyl-1-one (0.2 mmol), sodium perfluorooctylsulphinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), then adding 3mL of acetonitrile/water mixed solvent (v/v = 10/1), reacting for 12 hours at room temperature under the irradiation of a blue light-emitting diode, extracting the reaction solution by ethyl acetate after the reaction is finished, combining organic phases, drying by anhydrous sodium sulfate, filtering and removing the organic solvent, and carrying out column chromatography on the residue to obtain the target product which is yellow solid. The yield of the desired product was 54% based on 100% molar amount of 1- (2- (methylthio) phenyl) -3- ((4-methoxy) phenyl) -2-alkynyl-1-one. The structural formula of the target product is as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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
A clean, dry reaction flask containing magnetons was charged with 1- (2- (methylthio) phenyl) -3- ((4-fluorophenyl) -2-alkynyl-1-one (0.2 mmol), sodium perfluorooctylsulfinate (0.6 mmol) and catalyst Acr + -Mes·ClO 4 – (0.01 mmol), then, 3mL of acetonitrile/water mixed solvent (v/v = 10/1) was added thereto, the mixture was reacted at room temperature for 12 hours under irradiation of a blue light emitting diode, after the reaction was completed, the reaction solution was extracted with ethyl acetate,and combining organic phases, drying the combined organic phases by using anhydrous sodium sulfate, filtering and removing the organic solvent in a rotary manner, and carrying out column chromatography on the residue to obtain the target product, wherein the target product is a yellow solid. The yield of the target product was 41% based on the molar amount of 1- (2- (methylthio) phenyl) -3- ((4-fluorophenyl) -2-alkynyl-1-one of 100%. The structural formula of the target product was as follows:
nuclear magnetic spectrum analysis was performed on the above yellow solid, and the data were 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 F NMR(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
The method comprises the following steps:
in vitro anti-Ramos cell proliferation assay was performed using the CellTiter-Glo (Promega, USA) assay. After the Ramos cell suspension was diluted to an appropriate concentration using the medium, 95 μ L was added to a 96-well plate. After adding 5. Mu.L of the test compound at different concentrations thereto, the plates were allowed to complete a CO-reduction at 37 ℃ in a volume fraction of 5% 2 And (3) incubating for 72 hours. The plate was removed and allowed to stand at room temperature for testing. Cell lysis was induced by adding 20. Mu.L of CellTiter-Glo reagent to each well and mixing for 2 minutes on a shaker. The fluorescence signal was stabilized by incubation for 10 min at room temperature. The fluorescence intensity was recorded using a multifunctional microplate reader. Calculating the cell according to the formula and the fluorescence intensity of the blank control groupActivity, and thus calculating the IC of the target Compound 50 。
In vitro antitumor Activity of representative Compounds of Table 1
While there have been shown and described what are at present considered to be the principles of the invention, its essential features and advantages, it will be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for synthesizing 3-perfluoroalkyl thioflavone is characterized by comprising the following steps: adding 2-methylthio phenylpropargyl ketone, perfluoroalkyl sodium sulfinate and catalyst 9-mesityl-10-methylacridine perchlorate 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 a reaction solution by using ethyl acetate after the reaction is finished, combining organic phases, drying by using anhydrous sodium sulfate, filtering, decompressing, and spinning off the organic solvent, and obtaining a target product, namely 3-perfluoroalkyl-group-containing thioflavone, wherein the structural formula of 2-methylthio-phenylpropargyl ketone is shown as a formula A, the structural formula of perfluoroalkyl-group sodium sulfinate is shown as a formula B, and the structural formula of 3-perfluoroalkyl-group-containing thioflavone is shown as a formula C:
wherein R is 1 Is H, C 1-6 Alkyl radical, C 1-6 Alkoxy, trifluoromethyl, cyano, fluoro, chloro or bromo; r is f Is (CF) 2 ) n CF 3 And n is an integer from 0 to 7.
2. The method for synthesizing 3-perfluoroalkyl thioflavone according to claim 1, wherein the specific structural formula of the 3-perfluoroalkyl thioflavone is as follows:
3. the method of synthesizing 3-perfluoroalkylated thioflavone of claim 1, wherein: the 2-methylthio phenylproparganone, the perfluoroalkyl sodium sulfinate and the catalyst Acr + -Mes·ClO 4 – And the feeding molar ratio of trifluoroacetic acid is 1-3.
4. The method for synthesizing 3-perfluoroalkylated thioflavone as claimed in claim 1, wherein the reaction equation in the process of synthesizing 3-perfluoroalkylated thioflavone is as follows:
the catalyst Acr + -Mes·ClO 4 – The structural formula of (A) is:
5. a method for synthesizing 3-perfluoroalkyl thioflavone is characterized by comprising the following steps: adding 1- (2- (methylthio) phenyl) -3- (3-pyridyl) -2-alkynyl-1-ketone, sodium trifluoromethylsulfinate and catalyst Acr into a reaction bottle + -Mes·ClO 4 – Then, the mixed solvent of acetonitrile and water and trifluoroacetic acid are added to the mixture in blueStirring and reacting at room temperature under the irradiation of a light-emitting diode, extracting reaction liquid by using ethyl acetate after the reaction is finished, combining organic phases, drying by using anhydrous sodium sulfate, filtering, decompressing, removing an organic solvent by rotation, and performing column chromatography to obtain a target product 3-perfluoroalkyl thioflavone, wherein the structural formula of the target product 3-perfluoroalkyl thioflavone is as follows:
6. the method of synthesizing 3-perfluoroalkylated thioflavone of claim 5, wherein: the 1- (2- (methylthio) phenyl) -3- (3-pyridyl) -2-alkynyl-1-ketone, sodium trifluoromethylsulfinate and a catalyst Acr + -Mes·ClO 4 – And the feeding molar ratio of trifluoroacetic acid is 1-3.
7. A method for synthesizing 3-perfluoroalkyl thioflavone is characterized by comprising the following steps: adding 1- (2- (methylthio) phenyl) -3- (2-naphthyl) -2-alkynyl-1-ketone, sodium trifluoromethanesulfonate and 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 a reaction solution by using ethyl acetate after the reaction is finished, combining organic phases, drying by using anhydrous sodium sulfate, filtering, decompressing, removing the organic solvent by rotation, and carrying out column chromatography to obtain a target product 3-perfluoroalkyl thioxanthone, wherein the structural formula of the target product 3-perfluoroalkyl thioxanthone is as follows:
8. the method of synthesizing 3-perfluoroalkylated thioflavone of claim 7, wherein said steps comprise: the 1- (2- (methylthio) phenyl) -3- (2-naphthyl) -2-alkynyl-1-ketone, sodium trifluoromethanesulfonate and catalyst Acr + -Mes·ClO 4 – And trifluoroThe feeding molar ratio of the acetic acid is 1-3.
9. The method of synthesizing 3-perfluoroalkylated thioflavone of claim 1, 5 or 7, wherein said steps of: the reaction conditions of the reaction process are that a blue LED lamp is used as a visible light source, the wavelength of the blue LED lamp is 455-465nm, and the power of the blue LED lamp is 6-12W.
10. The method of synthesizing 3-perfluoroalkylated thioflavone of claims 1, 5 or 7, wherein: the volume ratio of acetonitrile to water in the mixed solvent of acetonitrile and water is 10.
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