A method for synthesis of diaryl ethers promoted by visible light with copper catalyst

Abstract

The application discloses a kind of by visible light promotes copper catalysis phenol derivative and the cross-coupling reaction of aryl triazene. With tetrafluoroboric acid tetra (acetonitrile) copper as catalyst, pyridine is ligand, aryl triazene is synthesized as aryl source and base a series of structural variable diaryl ether compounds. Compared with the preparation method of reported diaryl ether compounds, the advantages of the present application include: visible light promotion, raw material is cheap and easy to obtain, wide substrate range, can be prepared in large quantities, no additional base, mild reaction conditions.

Description

Technical Field

[0001] This invention discloses a visible light-promoted copper-catalyzed cross-coupling reaction of phenol derivatives and aryltriazenes. A series of structurally diverse diaryl ether compounds were synthesized using tetra(acetonitrile)copper tetrafluoroborate as a catalyst, pyridine as a ligand, aryltriazene as the aryl source, and a base. Compared with previously reported methods for preparing diaryl ether compounds, the advantages of this invention include: visible light promotion, inexpensive and readily available raw materials, broad substrate range, large-scale preparation capability, no need for external base addition, and mild reaction conditions. Background Technology

[0002] Diaryl ethers are a common structural skeleton, widely found in natural products and drug molecules. For example, magnolol is a typical natural phenol containing a diaryl ether skeleton and possesses various activities, including antitumor, anti-inflammatory, and anti-anxiety activities; Thyroxine is an antithyroid drug (levothyroxine); fenprofen is a drug used to treat rheumatoid arthritis; Rodgersinol is an anti-aging agent; Antitumor riccardin is a riccardin C-targeted anticancer drug; vitamin E is one of the most important antioxidants; and bensulfuron-methyl is an important herbicide in agriculture. Simultaneously, diaryl ethers are also important intermediates in organic synthesis. By breaking the aryl CO bond, different functional groups can be introduced, thereby enabling the synthesis of organic compounds with different functions. Tanaka K, Gotoh H. Development of the radical C–O coupling reaction ofphenols toward the synthesis of natural products comprising a diaryl etherskeleton[J].Tetrahedron.2019,75(29):3875-3885.Fu Z,Wang X,Ren X,Guo Z,Wang C,Zhou CY.Rhodium-Catalyzed C(sp2)–O Cross Couplings of Diazo Quinones withPhenols to Construct Diaryl Ethers[J].Organic Letters.2024,26(1):292-297.TangHao LJX P.Advances on the Synthesis of Aryl Ethers via DehydrogenativeCoupling[J].Chinese Journal of Organic Chemistry.2019,39(10):2735-2743.

[0003] Visible light-induced reactions have attracted widespread attention in the synthetic community because they can be catalytically synthesized under relatively mild conditions. In recent years, research on visible light-mediated photoredox synthesis of diaryl ethers has yielded a series of excellent results.

[0004] Terrett J A,Cuthbertson J D,Shurtleff V W,MacMillan D W C.Switchingon elusive organometallic mechanisms with photoredox catalysis[J].Nature.2015,524(7565):330-334.Monnier F,Taillefer M.Catalytic C-C,C-N,and C-O Ullmann-Type Coupling Reactions[J].Angewandte Chemie InternationalEdition.2009,48(38):6954-6971.

[0005] Fan M,Zhou W,Jiang Y,Ma D.CuI / Oxalamide Catalyzed Couplings of(Hetero)aryl Chlorides and Phenols for Diaryl Ether Formation[J].AngewandteChemie International Edition.2016,55(21):6211-6215.Delaney C P,Lin E,Huang Q,Yu I F,Rao G,Tao L,Jed A,Fantasia S M,Püntener K A,Britt R D,Hartwig JF.Cross-coupling by a noncanonical mechanisminvolving the addition of arylhalide to Cu(II)[J].Science.2023,381(6662):1079-1085.Heravi M M,Zadsirjan V,Malmir M,Mohammadi L.Buchwald–Hartwig reaction:an update[J].Monatshefte fürChemie-Chemical Monthly.2021,152(10):1127-1171.Salvi L,Davis N R,Ali S Z,Buchwald S L.A New Biarylphosphine Ligand for the Pd-Catalyzed Synthesis ofDiaryl Ethers under Mild Conditions[J].Organic Letters.2012,14(1):170-173.MaoR,Balon J,Hu X.Decarboxylative C(sp 3)-O Cross-Coupling[J].Angewandte ChemieInternational Edition.2018,57(41):13624-13628.Yang QQ,Liu N,Yan JY,Ren ZL,Wang L.Visible Light-and Heat-Promoted CO Coupling Reaction of Phenols andAryl Halides[J].Asian Journal of Organic Chemistry.2020,9(1):116-120.Zhu DL,Jiang S,Wu Q,Wang H,Li HY,Li HX.Nickel-Catalyzed Etherification of Phenolsand Aryl Halides through Visible-Light-Induced Energy Transfer[J].OrganicLetters.2021,23(21):8327-8332. In the past few decades, chemists have successfully designed a variety of synthetic transformation strategies for constructing diaryl ether molecules. The traditional synthesis of aromatic ether compounds is carried out through the Ullmann cross-coupling reaction, but this reaction requires stoichiometric copper reagents and high reaction temperatures. In contrast, the Buchwald-Hartwig cross-coupling reaction provides a more efficient strategy for the construction of CO bonds. It achieves the preparation of aromatic ether compounds through palladium-catalyzed coupling of aryl halides with phenols or alcohols. Recently, Mac-Millan et al. developed a bimetallic catalytic strategy of nickel and iridium using photocatalytic redox methods to achieve the coupling reaction of aryl halides with alcohols. In arylation reactions, aryltriazene is often used as a substitute for aryl diazonium salts and is widely used to construct C-C bonds and carbon-heteroatom bonds. Recently, photo-promoted direct C-H functionalization of aryltriazenes with organic compounds under mild conditions has paved the way for the cross-coupling reactions of aryltriazenes. Therefore, aryltriazenes, as stable and readily available precursors of aryl diazo ions, possess the fundamental conditions to serve as aryl sources. Based on this, in this invention, we report a photo-promoted copper-catalyzed process where aryltriazenes act as a base to remove hydrogen from phenol, while phenol acts as an acid to activate the triazene, completing the construction of diaryl ether molecules under mild, base-free conditions without the formation of additional byproducts such as halide salts. Summary of the Invention

[0006] This invention discloses a visible light-promoted copper-catalyzed cross-coupling reaction of phenol derivatives and aryltriazenes. A series of structurally diverse diaryl ether compounds were synthesized using tetra(acetonitrile)copper tetrafluoroborate as a catalyst, pyridine as a ligand, aryltriazene as the aryl source, and a base. Compared with previously reported methods for preparing diaryl ether compounds, the advantages of this invention include: visible light promotion, inexpensive and readily available raw materials, broad substrate range, large-scale preparation capability, no need for external base addition, and mild reaction conditions. To achieve the above objectives, the technical solution of this invention is as follows:

[0007] Under light irradiation, substituted phenol (2) and aryltriazene (3) undergo a cross-coupling reaction at room temperature (reaction formula 1). After the reaction, the products are separated and characterized by conventional separation and purification methods to obtain the corresponding diaryl ether compound (1).

[0008] The diaryl ether compound has the following structural formula (1):

[0009]

[0010] Substituent R 1 It is one or more of the following: nitro, trifluoromethyl, cyano, or methyl carbonyl, ethyl carbonyl, ester, halogen, aldehyde, biphenyl, p-cyanobiphenyl, and quinoline ring or carbonyl group having 1-4 carbon atoms; the halogen is one or more of F or Cl;

[0011] 2) Substituent R 2 It is one or more of H, methylthioSCH3, methoxyOCH3, halogen, or alkyl with 1-4 carbon atoms, or heterocyclic and benzo[d]thiazole substituted triazine; the halogen is one or more of F, Cl or Br.

[0012] Its features are:

[0013] Using substituted phenol (2) as a raw material, it was reacted with aryltriazene (3) under visible light in the presence of a catalyst and ligand; after the reaction was completed, the products were separated to obtain diaryl ether compound (1).

[0014]

[0015] Wherein the substituent R 1 and substituent R 2 Same as above;

[0016] The reaction solvent is one of dimethyl sulfoxide, N,N-dimethylaniline, 2,2,2-trifluoroethanol, hexafluoroisopropanol, ethanol, methanol, H2O, tetrahydrofuran, ethyl acetate, dichloroethane, dichloromethane, and ultra-dry acetonitrile; the molar ratio of aryltriazene (3) is 1:1-1:2.5; the reaction time is 1-24 hours; the reaction system is irradiated with light; the reaction is carried out in the presence of a catalyst and ligands; after the reaction is completed, the product is separated to obtain diaryl ether compound (1).

[0017] When substituted phenol (2) reacts with aryltriazene (3), it is best to carry out the reaction under violet light (390-395nm) or blue-violet light (410-415nm), with blue-violet light (410-415nm) being the best. The power of the irradiation light source is one or two of 3W, 5W, 7W, 10W, 12W, and 15W, with 12W blue-violet light (410-415nm) being the best.

[0018] When substituted phenol (2) reacts with aryltriazene (3), the catalyst is one or more of the following: [Cu(MeCN)4]BF4, CuCl, CuBr, CuI, [Cu(MeCN)4]PF6, CuBr2, Cu(CF3SO3)2, and Cu(NO3)2; [Cu(MeCN)4]BF4 is the most effective. The molar concentration of the catalyst in the reaction solvent is 10-20 mol%, with 20 mol% being optimal.

[0019] When substituted phenol (2) reacts with aryltriazine (3), a ligand is added to the reaction. The ligand is one or more of the following: pyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, 2,2'-bipyridine, and 4,4'-bipyridine, with pyridine being the best. The concentration of the ligand in the reaction solvent is 10-40 mol%, with 20 mol% being the best.

[0020] The solvent added to the reaction is one of dimethyl sulfoxide, N,N-dimethylaniline, 2,2,2-trifluoroethanol, hexafluoroisopropanol, ethanol, methanol, H2O, tetrahydrofuran, ethyl acetate, dichloroethane, dichloromethane, and ultra-dry acetonitrile, with ultra-dry acetonitrile being the best solvent; 1.0-5 mL of solvent is added for every 0.1 mmol of substituted phenol (2).

[0021] When substituted phenol (2) reacts with aryltriazine (3), the molar ratio of substituted phenol (2) to aryltriazine (3) is in the range of 1:1.0-1:2.5, and the preferred molar ratio is 1:2.0.

[0022] When substituted phenol (2) reacts with aryltriazine (3), the preferred reaction time is 1-24 hours, with the optimal reaction time being 24 hours.

[0023] The synthesis reaction of the aryltriazine compound of the present invention includes the following steps:

[0024] Synthesis of p-methyltriazine 3c:

[0025]

[0026] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-methylaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the p-methylaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added all at once to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0027] Synthesis of aryltriazine 3p:

[0028]

[0029] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) Aniline (10 mmol) was added to a 100 mL round-bottom flask and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the aniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for about 15 minutes. Then, the diazonium salt solution was added all at once to a mixture containing 10 mL K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for about 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0030] Synthesis of o-methyltriazine 3q:

[0031]

[0032] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, 10 mmol of o-methylaniline was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the hydrochloric acid solution of o-methylaniline. The resulting diazonium salt solution was stirred in an ice bath for about 15 minutes. Then, the diazonium salt solution was added all at once to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for about 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0033] Synthesis of m-methyltriazine 3r

[0034]

[0035] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, m-methylaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the m-methylaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added in one go to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0036] Synthesis of p-methylthiotriazine 3s

[0037]

[0038] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-methylthioaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the hydrochloric acid solution of p-methylthioaniline. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added all at once to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0039] Synthesis of p-methoxytriazine 3t

[0040]

[0041] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-methoxyaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the p-methoxyaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added all at once to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0042] Synthesis of isopropyltriazine 3u

[0043]

[0044] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-isopropylaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the hydrochloric acid solution of p-isopropylaniline. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added in one go to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0045] Synthesis of p-tert-butyltriazine 3v

[0046]

[0047] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-tert-butylaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the p-tert-butylaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added in a single batch to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0048] Synthesis of p-fluorotriazine 3w

[0049]

[0050] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-fluoroaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the p-fluoroaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added in one go to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0051] Synthesis of p-chlorotriazine 3x

[0052]

[0053] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-chloroaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the p-chloroaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added in one go to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0054] Synthesis of p-bromotriazine 3y

[0055]

[0056] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-bromoaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the p-bromoaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added in one go to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0057] Synthesis of benzo[d]thiazol-5-triazine 3z

[0058]

[0059] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) Benzo[d]thiazol-5-aniline (10 mmol) was added to a 100 mL round-bottom flask and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. An aqueous solution of NaNO2 (11 mmol) (5 mL) was prepared and slowly added dropwise to the hydrochloric acid solution of benzo[d]thiazol-5-aniline. The resulting diazonium salt solution was stirred in an ice bath for about 15 minutes. Then, the diazonium salt solution was added in one go to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for about 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy. Attached image description:

[0060] Figure 1 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 1.

[0061] Figure 2 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 6.

[0062] Figure 3 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 7.

[0063] Figure 4 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 8.

[0064] Figure 5 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 9.

[0065] Figure 6 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 10.

[0066] Figure 7 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 11.

[0067] Figure 8 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 12.

[0068] Figure 9 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 13.

[0069] Figure 10 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 14.

[0070] Figure 11 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 15.

[0071] Figure 12 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 16.

[0072] Figure 13 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 17.

[0073] Figure 14 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 18.

[0074] Figure 15 The NMR spectra of the NMR spectra of Example 19 are the hydrogen NMR spectrum and carbon NMR spectrum.

[0075] Figure 16 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 20.

[0076] Figure 17 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 21.

[0077] Figure 18 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 22.

[0078] Figure 19 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 23.

[0079] Figure 20 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 24.

[0080] Figure 21 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 25.

[0081] Figure 22 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 26.

[0082] Figure 23 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 27.

[0083] Figure 24 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 28.

[0084] Figure 25 The NMR spectra of the NMR spectra of Example 29 are the hydrogen NMR spectrum and carbon NMR spectrum.

[0085] Figure 26 The images show the hydrogen and carbon NMR spectra of the NMR spectra used in Example 30. Detailed Implementation

[0086] The present invention will be further described in detail below with reference to specific embodiments. However, the scope of protection of the present invention is not limited to these embodiments. All variations and advantages that can be conceived by those skilled in the art without departing from the spirit and scope of the inventive concept are included in the present invention and are protected by the appended claims. The processes, conditions, reagents, experimental methods, etc., used to implement the present invention, except as specifically mentioned below, are all common knowledge and general knowledge in the art, and the present invention does not have any particular limitations. The data given in the following embodiments include specific operations, reaction conditions, and products. Product purity was determined by NMR.

[0087] The experimental raw materials in this invention were prepared under the following conditions with different substituents:

[0088] Synthesis of p-methyltriazine 3c:

[0089]

[0090] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-methylaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the p-methylaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added all at once to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0091] Synthesis of triazine 3p:

[0092]

[0093] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) Aniline (10 mmol) was added to a 100 mL round-bottom flask and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the aniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for about 15 minutes. Then, the diazonium salt solution was added all at once to a mixture containing 10 mL K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for about 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0094] Synthesis of o-methyltriazine 3q:

[0095]

[0096] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, 10 mmol of o-methylaniline was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the hydrochloric acid solution of o-methylaniline. The resulting diazonium salt solution was stirred in an ice bath for about 15 minutes. Then, the diazonium salt solution was added all at once to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for about 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0097] Synthesis of m-methyltriazine 3r

[0098]

[0099] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, m-methylaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the m-methylaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added in one go to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0100] Synthesis of p-methylthiotriazine 3s

[0101]

[0102] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-methylthioaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the hydrochloric acid solution of p-methylthioaniline. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added all at once to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0103] Synthesis of p-methoxytriazine 3t

[0104]

[0105] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-methoxyaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the p-methoxyaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added all at once to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0106] Synthesis of isopropyltriazine 3u

[0107]

[0108] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-isopropylaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the hydrochloric acid solution of p-isopropylaniline. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added in one go to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0109] Synthesis of p-tert-butyltriazine 3v

[0110]

[0111] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-tert-butylaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the p-tert-butylaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added in a single batch to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0112] Synthesis of p-fluorotriazine 3w

[0113]

[0114] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-fluoroaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the p-fluoroaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added in one go to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0115] Synthesis of p-chlorotriazine 3x

[0116]

[0117] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-chloroaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the p-chloroaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added in one go to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0118] Synthesis of p-bromotriazine 3y

[0119]

[0120] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) In a 100 mL round-bottom flask, p-bromoaniline (10 mmol) was added and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. A NaNO2 (11 mmol) aqueous solution (5 mL) was prepared and slowly added dropwise to the p-bromoaniline hydrochloric acid solution. The resulting diazonium salt solution was stirred in an ice bath for approximately 15 minutes. Then, the diazonium salt solution was added in one go to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for approximately 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0121] Synthesis of benzo[d]thiazol-5-triazine 3z

[0122]

[0123] According to previous literature reports (Sutar SM, Kalkhambkar R G. Ultrasonic Assisted Facilitation Synthesis of N-Arylamides using Nitriles and 1-Aryltriazenes Precursors Promoted by...), Acidic Ionic Liquid under metal-free conditions [J]. Chemistry Select, 2021, 6, 6548-6556.) Benzo[d]thiazol-5-aniline (10 mmol) was added to a 100 mL round-bottom flask and cooled in an ice bath (0-5 °C). Then, concentrated HCl (2 mL) was slowly added at 0 °C. An aqueous solution of NaNO2 (11 mmol) (5 mL) was prepared and slowly added dropwise to the hydrochloric acid solution of benzo[d]thiazol-5-aniline. The resulting diazonium salt solution was stirred in an ice bath for about 15 minutes. Then, the diazonium salt solution was added in one go to a mixture containing 10 mL of K2CO3 (1.2 mol / L) and thiomorpholine (10 mmol) in an ice bath. The reaction mixture was stirred at room temperature for about 30 minutes. After the reaction was detected by thin-layer chromatography, the crude product was filtered and recrystallized from ethanol or purified by column chromatography to obtain the pure product, which was confirmed by nuclear magnetic resonance spectroscopy.

[0124] Example 1:

[0125]

[0126] Under a nitrogen atmosphere, 4-nitrophenol (13.9 mg, 0.1 mmol), p-methyltriazine 3c (44.2 mg, 0.2 mmol), and [Cu(MeCN)4]BF4 (20 mol%) were added to 10 mL quartz reaction tubes, respectively. Pyridine (20 mol%) and ultra-dry acetonitrile (1.0 mL) were added to the reaction tubes using a syringe. The mixture was stirred for 24 hours under 12 W blue-violet light (410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was complete, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain a yellow oily target product 1a (13.79 mg, 60% yield). The target product was confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. The product parameters were 1-Methyl-4-(4-nitrophenoxy)benzene (1a). Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as yellow oil (13.79 mg, 60%). 1 H NMR (600MHz, CDCl3) δ8.18 (dt, J = 9.24Hz, J = 3.36Hz, 2H), 7.23 (d, J = 8.04Hz, 2H), 7.00-6.97 (m, 4H), 2.38 (s, 3H). 13 C NMR (150MHz, CDCl3) δ163.93,152.45,142.57,135.36,130.94,126.05,120.61,116.88,20.98.

[0127] Example 2

[0128] The reaction steps and operating conditions were the same as in Example 1, except that the reaction was carried out under light-free conditions. The reaction was stopped, and the target product 1a was not obtained after the same post-treatment as described above. This indicates that the reaction cannot proceed without light.

[0129] Example 3

[0130] The reaction steps and operating conditions were the same as in Example 1, except that the reaction was carried out under red light. The reaction was stopped, and the target product 1a was not obtained after the same post-treatment as described above. This indicates that the reaction cannot proceed without light.

[0131] Example 4

[0132] The reaction steps and operating conditions were the same as in Example 1, except that the reaction was carried out without the catalyst [Cu(MeCN)4]BF4. The reaction was stopped, and the target product 1a was not obtained after the same post-treatment as described above. This indicates that the reaction cannot proceed smoothly without [Cu(MeCN)4]BF4.

[0133] Example 5

[0134] The reaction procedure and operating conditions were the same as in Example 1, except that the reaction was carried out in the absence of the ligand pyridine. The reaction was stopped, and the target product 1a (9.2 mg, 40% yield) was obtained after the same post-treatment as described above. This indicates that the ligand pyridine has a significant impact on the system.

[0135] Example 6

[0136]

[0137] The reaction steps and operating conditions were the same as in Example 1, except that para-trifluoromethyl-substituted phenol was used as the starting material, and the reaction system was different in that 2b (16.2 mg, 0.1 mmol) was added instead of the substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (elution: petroleum ether / dichloromethane = 15:1, v / v) to obtain a white solid target product 1b (19.12 mg, yield 76%). The product was identified as the target product by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were: 1-Methyl-4-(4-(trifluoromethyl)phenoxy)benzene (1b) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a white solid (19.12 mg, 76%), mp: 63.7–64.7 °C. 1 H NMR (600MHz, CDCl3) δ7.56 (d, J = 8.58 Hz, 2H), 7.20 (d, J = 8.16 Hz, 2H), 7.02 (d, J = 8.52 Hz, 2H), 6.96 (dt, J = 8.46 Hz, J = 2.76 Hz, 2H), 2.37 (s, 3H).13 C NMR (150MHz, CDCl3) δ161.15, 153.38, 134.41, 130.71, 127.18 (q, J = 3.83Hz), 124.63 (q, J = 32.51Hz), 124.41 (q, J = 269.75Hz), 120.17, 117.52, 20.92.

[0138] 19 F NMR (565MHz, CDCl3) δ -61.69.

[0139] Example 7

[0140]

[0141] The reaction steps and operating conditions were the same as in Example 1, except that para-trifluoromethyl-substituted phenol was used as the starting material, and the reaction system was different in that 2c (11.9 mg, 0.1 mmol) was added instead of the substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain the yellow oily target product 1c (18.17 mg, yield 87%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were 4-(p-tolyloxy)benzonitrile (1c). Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a yellow oil (18.17 mg, 87%). 1 H NMR (600MHz, CDCl3) δ7.57 (dt, J = 8.94Hz, J = 2.58Hz, 2H), 7.21 (d, J = 8.16Hz, 2H), 6.99-6.97 (m, 2H), 6.96-6.94 (m, 2H), 2.37 (s, 3H). 13 C NMR (150MHz, CDCl3) δ162.15,152.45,135.01,134.15,130.80,120.46,119.00,117.63,105.53,20.90.

[0142] Example 8

[0143]

[0144] The reaction steps and operating conditions were the same as in Example 1, except that the raw material used was para-ketone carbonyl-substituted phenol, and the reaction system was different in that 2d (13.6 mg, 0.1 mmol) was added instead of the substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (elution: petroleum ether / dichloromethane = 15:1, v / v) to obtain the orange-yellow solid target product 1d (15.85 mg, yield 70%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were 1-(4-(p-tolyloxy)phenyl)ethan-1-one(1d) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as an orange solid (15.85 mg, 70%), mp: 42.2-42.8℃. 1 H NMR (600MHz, CDCl3) δ7.92 (d, J = 8.70Hz, 2H), 7.19 (d, J = 8.22Hz, 2H), 6.97 (dd, J = 5.4, 3.42Hz, 4H), 2.56 (s, 3H), 2.37 (s, 3H). 13 C NMR (150MHz, CDCl3) δ196.85,162.57,153.13,134.48,131.72,130.67,120.33,116.97,26.5,20.92.

[0145] Example 9

[0146]

[0147] The reaction steps and operating conditions were the same as in Example 1, except that para-carbonyl-substituted phenol was used as the starting material, and the reaction system was different in that 2e (15.21 mg, 0.1 mmol) was added instead of the substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain the brown oily target product 1e (23.54 mg, yield 91%). The target product was confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. The product parameters were: Methyl 4-(p-tolyloxy)benzoate (1e) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a brown oil (23.54 mg, 91%). 1 HNMR (600MHz, CDCl3) δ7.99(d,J=8.76Hz,2H),7.19(d,J=8.28Hz,2H),6.96(dd,J=5.40,3.00Hz,4H),3.89(s,3H),2.36(s,3H). 13 C NMR (150MHz, CDCl3) δ166.74,162.40,153.25,134.34,131.73,130.63,124.23,120.27,116.94,52.06,20.90.

[0148] Example 10

[0149]

[0150] The reaction steps and operating conditions were the same as in Example 1, except that para-carbonyl-substituted phenol was used as the starting material, and the reaction system was different in that 2f (16.6 mg, 0.1 mmol) was added instead of the substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (elution: petroleum ether / dichloromethane = 15:1, v / v) to obtain the yellow oily target product 1f (24.34 mg, yield 94%). The target product was confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. The product parameters obtained were: Ethyl 4-(p-tolyloxy)benzoate (1f) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a yellow oil (24.34 mg, 94%). 1 HNMR(600MHz, CDCl3)δ7.99(d,J=8.76Hz,2H),7.19(d,J=8.22Hz,2H),6.96(d ,J=8.04Hz,4H),4.36(q,J=7.14Hz,2H),2.36(s,3H),1.38(t,J=7.14Hz,3H). 13 C NMR (150MHz, CDCl3) δ166.30,162.29,153.35,134.30,131.70,130.63,124.64,120.23,116.99,60.91,20.92,14.50.

[0151] Example 11

[0152]

[0153] The reaction steps and operating conditions were the same as in Example 1, except that para-fluorinated phenol was used as the starting material, and the reaction system was different in that 2 g (11.2 mg, 0.1 mmol) of the starting material was added to the reaction system instead of the substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (elution: petroleum ether / dichloromethane = 15:1, v / v) to obtain 1 g (12.1 mg, yield 60%) of the yellow oily target product. The target product was confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. The product parameters were 1-Fluoro-4-(p-tolyloxy)benzene (1g) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a yellow oil (12.10mg, 60%). 1 HNMR (600MHz, CDCl3) δ7.13(d,J=8.28Hz,2H),7.02-7.00(m,2H),6.97-6.94(m,2H),6.88(d,J=8.46Hz,2H),2.34(s,3H). 13 C NMR(150MHz,CDCl3)δ158.72(d J=240.00Hz),155.36,153.63(d,J=3.00Hz),132.95,130.41,120.10(d,J=7.50Hz),118.65,116.31(d,J=22.50Hz),20.80. 19 F NMR(565MHz, CDCl3)δ-120.77(s).

[0154] Example 12

[0155]

[0156] The reaction steps and operating conditions were the same as in Example 1, except that para-chlorosubstituted phenol was used as the starting material, and the reaction system was different in that 2h (12.9 mg, 0.1 mmol) was added instead of the substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain a white solid target product 1h (10.71 mg, yield 49%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were: 1-Chloro-4-(p-tolyloxy)benzene (1h) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a white solid (10.71 mg, 49%), mp: 50.4-51.7℃. 1 H NMR (600MHz, CDCl3) δ7.25 (dt, J = 8.76Hz, J = 3.54Hz, 2H), 7.14 (d, J = 8.28Hz, 2H), 6.91-6.89 (m, 4H), 2.33 (s, 3H). 13 C NMR (150MHz, CDCl3) δ156.68,154.50,133.5130.50,129.74,127.88,119.63,119.29,20.86.

[0157] Example 13

[0158]

[0159] The reaction steps and operating conditions were the same as in Example 1, except that the raw material used was para-cyano-meta-trifluoromethyl substituted phenol, and the reaction system was different in that the reactant added to the reaction system was 2i (18.7 mg, 0.1 mmol) instead of the reaction substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (elution: petroleum ether / dichloromethane = 15:1, v / v) to obtain the orange oily target product 1i (22.1 mg, yield 80%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were 4-(p-tolyloxy)-2-(trifluoromethyl)benzonitrile (1i). Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as orange oil (22.10 mg, 80%). 1 H NMR (600MHz, CDCl3) δ7.73(d,J=8.64Hz,1H),7.32(d,J=2.40Hz,1H),7.25(d,J= 8.22Hz, 2H), 7.11 (dd, J=8.64, 2.40Hz, 1H), 6.97 (d, J=8.46Hz, 2H), 2.39 (s, 3H). 13 C NMR(150MHz, CDCl3)δ162.19,151.68,136.76,135.95,135.04(q,J=33.00Hz),131.16,1 22.16(q,J=273Hz),120.55,119.56,115.67(q,J=4.50Hz),102.79(d,J=1.5Hz),20.98. 19 F NMR (565MHz, CDCl3) δ -62.26.

[0160] Example 14

[0161]

[0162] The reaction steps and operating conditions were the same as in Example 1, except that the raw material used was a meta-aldehyde substituted ortho-methoxy phenol, and the reaction system was different in that the raw material added to the reaction system was 2j (15.2 mg, 0.1 mmol) instead of the reaction substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (elution: petroleum ether / dichloromethane = 15:1, v / v) to obtain a yellow solid target product 1j (18.21 mg, yield 75%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were 4-Methoxy-3-(p-tolyloxy)benzaldehyde (1j). Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a yellow solid (18.21 mg, 75%), mp: 108.4-109.9℃. 1 H NMR(600MHz, CDCl3) δ9.80(s,1H),7.62(dd,J=8.34,1.92Hz,1H),7.37(d,J=1.92Hz,1H),7.14(d,J =8.28Hz, 2H), 7.09 (d, J = 8.34Hz, 1H), 6.90 (dt, J = 8.46Hz, J = 2.7Hz, 2H), 3.96 (s, 3H), 2.34 (s, 3H). 13 C NMR (150MHz, CDCl3) δ190.55,156.10,154.28,147.32,133.48,130.50,130.28,127.68,118.65,118.56,111.99,56.41,20.85.

[0163] Example 15

[0164]

[0165] The reaction steps and operating conditions were the same as in Example 1, except that the raw material used was para-carbonyl-ortho-methoxy-substituted phenol, and the reaction system was different in that 2k (18.2 mg, 0.1 mmol) was added instead of the substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (elution: petroleum ether / dichloromethane = 15:1, v / v) to obtain a white solid target product 1k (25.32 mg, yield 93%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were: Methyl 3-methoxy-4-(p-tolyloxy)benzoate (1k) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a white solid (25.32 mg, 93%), mp: 78.3-80.1℃. 1 H NMR(600MHz, CDCl3) δ7.66(d,J=1.92Hz,1H),7.57(dd,J=8.40,1.92Hz,1H),7.14(d,J=8.28Hz,2H) ,6.92(dt,J=8.46Hz,J=2.76Hz,2H),6.81(d,J=8.40Hz,1H),3.94(s,3H),3.90(s,3H),2.33(s,3H). 13 C NMR (150MHz, CDCl3) δ166.71,153.92,151.03,150.13,133.65,130.41,125.21,123.19,119.18,117.53,113.41,56.20,52.18,20.81.

[0166] Example 16

[0167]

[0168] The reaction steps and operating conditions were the same as in Example 1, except that the raw material used was meta-carbonyl-ortho-methoxy substituted phenol, and the reaction system was different in that 2l (18.2 mg, 0.1 mmol) of the raw material was added to the reaction system instead of the reaction substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain 1l (21.91 mg, yield 80%) of orange oily target product. The target product was confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. The product parameters were: Methyl 4-methoxy-3-(p-tolyloxy)benzoate (1L) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as an orange oil (21.91 mg, 80%). 1 H NMR (600MHz, CDCl3) δ7.75 (dd, J=8.52, 1.86Hz, 1H), 7.51 (d, J=1.92Hz, 1H), 7.03 (d, J=8.34H z,2H),6.92(d,J=8.52Hz,1H),6.79(d,J=8.40Hz,2H),3.83(s,3H),3.76(s,3H),2.24(s,3H). 13 C NMR (150MHz, CDCl3) δ166.48,155.11,155.00145.67,132.72,130.30,126.55,123.10,121.12,117.84,111.76,56.20,52.07,20.77.

[0169] Example 17

[0170]

[0171] The reaction steps and operating conditions were the same as in Example 1, except that 3-hydroxyquinoline was selected as the starting material, and the reaction system was different in that 2m (14.5 mg, 0.1 mmol) was added instead of the substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (elution: petroleum ether / dichloromethane = 15:1, v / v) to obtain the black oily target product 1m (8.98 mg, yield 38%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were 3-(p-tolyloxy)quinoline (1m). Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a black oil (8.98 mg, 38%). 1 H NMR (600MHz, CDCl3) δ8.81(d,J=2.34Hz,1H),8.09(d,J=8.40Hz,1H),7.66(d,J=8.10Hz,1H),7.63-7.60(m,1H),7 .52-7.49(m,1H),7.47(d,J=2.7Hz,1H),7.22(d,J=8.28Hz,2H),7.01(dt,J=8.46Hz,J=2.70Hz,2H),2.38(s,3H). 13 C NMR (150MHz, CDCl3) δ153.88,145.24,144.70,134.25,130.77,129.41,127.79,127.33,127.12,119.57,119.43,20.94.

[0172] Example 18

[0173]

[0174] The reaction steps and operating conditions were the same as in Example 1, except that para-phenyl-substituted phenol was used as the starting material, and the reaction system was different in that 2n (17.0 mg, 0.1 mmol) was added instead of the substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain a yellow solid target product 1n (12.58 mg, yield 46%). The product was identified as the target product by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were 4-(p-tolyloxy)-1,1'-biphenyl(1n). Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a yellow solid (12.58 mg, 46%), mp: 92.5-94.3℃. 1 H NMR (600MHz, CDCl3) δ7.59-7.57(m,2H),7.55(dt,J=8.64Hz,J=2.88Hz,2H),7.44(t,J=7.5Hz,2H),7.34(t,J =7.4Hz, 1H), 7.18 (d, J = 8.28Hz, 2H), 7.07 (dt, J = 8.64Hz, J = 2.70Hz, 2H), 6.99 (d, J = 8.46Hz, 2H), 2.37 (s, 3H). 13 CNMR (150MHz, CDCl3) δ157.57,154.75,140.75,136.00,133.22,130.44,128.90,128.48,127.09,127.02,119.39,118.63,20.87.

[0175] Example 19

[0176]

[0177] The reaction steps and operating conditions were the same as in Example 1, except that cyanobiphenol was selected as the raw material, and the reaction system was different in that 2o (19.5 mg, 0.1 mmol) was added instead of the substrate (2a). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (elution: petroleum ether / dichloromethane = 15:1, v / v) to obtain a yellow solid target product 1o (20.03 mg, yield 68%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were: 4'-(p-tolyloxy)-[1,1'-biphenyl]-4-carbonitrile (1o) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v). The desired product was a yellow solid (20.03 mg, 68%), mp: 94.3-96.8℃. 1 H NMR (600MHz, CDCl3) δ7.71-7.70(m,2H),7.66-7.64(m,2H),7.54(dt,J=8.76Hz,J=2.88Hz,2H),7.19( d,J=8.22Hz,2H),7.07(dt,J=8.76Hz,J=2.88Hz,2H),6.98(dt,J=8.46Hz,J=2.64Hz,2H),2.37(s,3H). 13 C NMR (150MHz, CDCl3) δ158.90,154.10,145.11,133.74,133.53,132.71,130.53,128.64,127.42,119.70,119.10,118.54,110.59,20.87.

[0178] Example 20

[0179]

[0180] The reaction steps and operating conditions were the same as in Example 1, except that unsubstituted aryltriazene was selected as the starting material, and the reaction system was different in that 3p (41.4 mg, 0.2 mmol) was added instead of the substrate (3c). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (elution: petroleum ether / dichloromethane = 15:1, v / v) to obtain the brown oily target product 1p (17.44 mg, yield 89%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were 4-Phenoxybenzonitrile (1p) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) which afforded the desired product as a brown oil (17.44 mg, 89%). 1 H NMR (600MHz, CDCl3) δ7.60 (dt, J=8.88Hz, J=2.58Hz, 2H), 7.43-7.40 (m, 2H), 7 .23(t,J=7.44Hz,1H),7.08-7.06(m,2H),7.01(dt,J=8.88Hz,J=2.46Hz,2H), 13 C NMR (150MHz, CDCl3) δ161.80,154.95,134.27,130.37,125.28,120.55,118.99,118.05,105.96.

[0181] Example 21

[0182]

[0183] The reaction steps and operating conditions were the same as in Example 1, except that the starting material used was ortho-methyl-substituted aryltriazene, and the reaction system was different in that the starting material added to the reaction system was 3q (44.2 mg, 0.2 mmol) instead of the reaction substrate (3c). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain the orange oily target product 1q (13.78 mg, yield 66%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were 4-(o-tolyloxy)benzonitrile (1q). Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as an orange oil (13.78 mg, 66%). 1 H NMR (600MHz, CDCl3) δ7.58 (dt, J=8.94Hz, J=2.64Hz, 2H), 7.29 (d, J=7.50Hz, 1H), 7.24 (td, J=7.50, 1.26Hz, 1H) ,7.17(td,J=7.5,1.14Hz,1H),6.98(dd,J=7.08,0.84Hz,1H),6.91(dt,J=8.94Hz,J=2.58Hz,2H),2.17(s,3H). 13 C NMR (150MHz, CDCl3) δ161.89,152.53,134.30,132.05,130.69,127.78,125.83,121.22,119.08,116.90,105.38,16.14.

[0184] Example 22

[0185]

[0186] The reaction steps and operating conditions were the same as in Example 1, except that the raw material used in the preparation of Example 1 was a meta-methyl-substituted aryltriazene, and the reaction system was different in that the raw material added to the reaction system was 3r (44.2 mg, 0.2 mmol) instead of the reaction substrate (3c). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain the orange oily target product 1r (16.74 mg, yield 80%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were 4-(m-tolyloxy)benzonitrile (1r). Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as an orange oil (16.74 mg, 80%). 1 H NMR (600MHz, CDCl3) δ7.59(dt,J=8.94Hz,J=2.58Hz,2H),7.29(t,J=7.8Hz,1H),7.04( d,J=7.56Hz,1H),7.00(dt,J=8.88Hz,J=2.52Hz,2H),6.88-6.85(m,2H),2.37(s,3H). 13 C NMR (150MHz, CDCl3) δ161.93,154.88,140.70,134.23,130.04,126.07,121.16,119.04,118.00,117.50,105.78,21.49.

[0187] Example 23

[0188]

[0189] The reaction steps and operating conditions were the same as in Example 1, except that the starting material used was para-methylthiolated aryltriazene, and the reaction system was different in that 3S (50.6 mg, 0.2 mmol) was added instead of the substrate (3C). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain the orange oily target product 1S (15.25 mg, yield 63%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were 4-(4-(Methylthio)phenoxy)benzonitrile (1s) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) and the desired product was aorange oil (15.25 mg, 63%). 1 H NMR (600MHz, CDCl3) δ7.59 (dt, J = 8.88Hz, J = 2.64, 2H), 7.30 (dt, J = 8.70Hz, J = 3Hz, 2H), 7.01-6.98 (m, 4H), 2.50 (s, 3H). 13 C NMR (150MHz, CDCl3) δ161.80,152.60,135.14,134.27,128.92,121.18,118.92,117.87,106.00,16.68.

[0190] Example 24

[0191]

[0192] The reaction steps and operating conditions were the same as in Example 1, except that the starting material used was para-methoxy-substituted aryltriazene, and the reaction system was different in that 3t (47.4 mg, 0.2 mmol) was added instead of the substrate (3c). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (elution: petroleum ether / dichloromethane = 15:1, v / v) to obtain 1t (14.90 mg, yield 66%) of the target product as a brown solid. The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were: 4-(4-Methoxyphenoxy)benzonitrile (1t) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a brown solid (14.90 mg, 66%), mp: 103.1–105.3 °C. 1 H NMR (600MHz, CDCl3) δ7.57 (d, J = 8.76Hz, 2H), 7.00 (d, J = 8.94Hz, 2H), 6.96-6.92 (m, 4H), 3.83 (s, 3H). 13 C NMR (150MHz, CDCl3) δ162.63,157.14,147.99,134.20,121.94,119.08,117.26,115.36,105.39,55.80.

[0193] Example 25

[0194]

[0195] The reaction steps and operating conditions were the same as in Example 1, except that the starting material used was para-isopropyl-substituted aryltriazene, and the reaction system was different in that 3u (49.8 mg, 0.2 mmol) was added instead of the substrate (3c). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain a brown oily target product 1u (18.12 mg, yield 76%). The target product was confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. The product parameters were 4-(4-Isopropylphenoxy)benzonitrile (1u). Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a brown oil (18.12 mg, 76%). 1 H NMR (600MHz, CDCl3) δ7.58 (dt, J=8.94Hz, J=2.64Hz, 2H), 7.26 (dt, J=8.40Hz, J=2 .822H),7.00-6.97(m,4H),2.94(Sept,J=6.96Hz,1H),1.28(s,3H),1.27(s,3H). 13 C NMR (150MHz, CDCl3) δ162.15,152.64,146.02,134.17,128.19,120.43,119.05,117.75,105.57,33.70,24.19.

[0196] Example 26

[0197]

[0198] The reaction steps and operating conditions were the same as in Example 1, except that the starting material used was para-tert-butyl-substituted aryltriazene, and the reaction system was different in that 3v (52.6 mg, 0.2 mmol) was added instead of the substrate (3c). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain the orange solid target product 1v (22.17 mg, yield 88%). The product was identified as the target product by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were: 4-(4-(tert-butyl)phenoxy)benzonitrile (1v) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as an orange solid (22.17 mg, 88%), mp: 82.3-85.6℃. 1 H NMR (600MHz, CDCl3) δ7.58 (dt, J = 8.94Hz J = 2.58Hz, 2H), 7.42 (dt, J = 8.70Hz J = 3.06Hz, 2H), 7.01-6.97 (m, 4H), 1.34 (s, 9H). 13 CNMR (150MHz, CDCl3) δ162.11,152.40,148.31,134.19,127.18,120.04,119.07,117.82,105.62,34.62,31.57.

[0199] Example 27

[0200]

[0201] The reaction steps and operating conditions were the same as in Example 1, except that para-fluorinated aryltriazene was selected as the starting material, and the reaction system was different in that 3w (45.0 mg, 0.2 mmol) was added instead of the substrate (3c). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain 1w (13.0 mg, yield 61%) of brown oily target product. The target product was confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. The product parameters were 4-(4-Fluorophenoxy)benzonitrile (1w) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a brown oil (13.0 mg, 61%). 1 H NMR (600MHz, CDCl3) δ7.60 (dt, J = 8.94Hz, J = 2.58Hz, 2H), 7.12-7.08 (m, 2H), 7.06-7.02 (m, 2H), 6.97 (dt, J = 8.88Hz, J = 2.58Hz, 2H). 13 C NMR (150MHz, CDCl3) δ161.91, 159.93 (d, J = 243.12Hz), 150.65 (d, J = 3.02Hz), 1 34.31, 122.16 (d, J = 8.45Hz), 118.87, 117.66, 117.03 (d, J = 23.07Hz), 106.07. 19 F NMR (565MHz, CDCl3) δ-117.24.

[0202] Example 28

[0203]

[0204] The reaction steps and operating conditions were the same as in Example 1, except that para-chloro-substituted aryltriazene was used as the starting material, and the reaction system was different in that 3x (48.2 mg, 0.2 mmol) was added instead of the substrate (3c). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain a yellow solid target product 1x (16.77 mg, yield 73%). The product was identified as the target product by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were: 4-(4-Chlorophenoxy)benzonitrile (1x) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a yellow solid (16.77 mg, 73%), mp: 74.3-76.1℃. 1 H NMR (600MHz, CDCl3) δ7.61 (dt, J = 8.82Hz, J = 2.52Hz, 2H), 7.37 (dt, J = 8.82Hz, J = 3.3Hz, 2H), 7.02-7.00 (m, 4H). 13 C NMR (150MHz, CDCl3) δ161.34,153.58,134.36,130.50,130.42,121.79,118.78,118.13,106.48.

[0205] Example 29

[0206]

[0207] The reaction steps and operating conditions were the same as in Example 1, except that the starting material used in the preparation of Example 1 was para-bromine-substituted aryltriazene, and the reaction system was different in that the starting material added to the reaction system was 3y (57.2 mg, 0.2 mmol) instead of the reaction substrate (3c). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (elution: petroleum ether / dichloromethane = 15:1, v / v) to obtain the brown solid target product 1y (18.2 mg, yield 66%). The product was identified as the target product by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were: 4-(4-Bromophenoxy)benzonitrile (1y) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane = 15:1, v / v) afforded the desired product as a brown solid (18.20 mg, 66%), mp: 72.5-74.2℃. 1 H NMR (600MHz, CDCl3) δ7.61 (dt, J=8.88Hz, J=2.58Hz, 2H), 7.52 (dt, J=6.72Hz, J=2. 10Hz, 2H), 7.01 (dt, J=8.88Hz, J=2.58Hz, 2H), 6.95 (dt, J=8.88Hz, J=3.24Hz, 2H). 13 C NMR (150MHz, CDCl3) δ161.19,154.17,134.36,133.39,122.16,118.76,118.20,118.01,106.54.

[0208] Example 30

[0209]

[0210] The reaction steps and operating conditions were the same as in Example 1, except that benzo[d]thiazole-5-triazine was selected as the starting material, and the reaction system was different in that 3z (52.8 mg, 0.2 mmol) was added instead of the substrate (3c). The mixture was stirred for 24 hours under 12W blue-violet light (wavelength 410 nm). The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 15:1, v / v) to obtain a white solid target product 1z (13.19 mg, yield 52%). The target product was confirmed by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMS). The product parameters were: 4-(Benzo[d]thiazol-5-yloxy)benzonitrile(1z) Column chromatography (SiO2, eluent: petroleum ether / dichloromethane=15:1, v / v) afforded the desired product as a white solid (13.19 mg, 52%), mp: 77.3-80.7℃. 1 H NMR (600MHz, CDCl3) δ9.07 (s, 1H), 7.98 (d, J = 8.64Hz, 1H), 7.82 (d, J = 2.28Hz, 1H), 7.62 (dt, J=8.88Hz, J=2.52Hz, 2H), 7.22(dd, J=8.64, 2.22Hz, 1H), 7.06 (dt, J=8.82Hz, J=2.46Hz, 2H). 13 C NMR (150MHz, CDCl3) δ161.54,156.15,154.63,153.82,134.26,123.15,119.11,118.73,118.10,114.85,106.31.

[0211] Application examples

[0212]

[0213] Furthermore, a scale-up experiment was conducted on the target product 1c obtained in Example 5 to further demonstrate the synthetic application of this scheme. 4-hydroxybenzonitrile 2c and p-methyltriazine 3c were selected as substrates, and the reaction was scaled up to 5 mmol. The reaction was carried out for 27 hours at a 50 W light source with a wavelength of 410-415 nm, yielding the expected product 1c, 4-(4-methylphenoxy)benzonitrile, in 81% yield. The target product was confirmed by NMR spectroscopy, demonstrating the value of this reaction in the practical application of diaryl ether compounds.

[0214] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention's specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A method for preparing copper-catalyzed diaryl ethers using visible light promotion, characterized in that, The synthetic route is shown in the following reaction formula. Using substituted phenol (2) as a raw material, it is coupled with aryltriazene (3) under visible light conditions in the presence of a catalyst and ligand to generate diaryl ether compound (1). ； Substituent R 1 It is one or more of the following groups: nitro, trifluoromethyl, cyano, halogen, aldehyde, and / or carbonyl with 1-4 carbon atoms; the halogen is one or two of F or Cl; Substituent R 2 The halogen is one or more of H, methylthioSCH3, methoxyOCH3, halogen, or alkyl groups having 1-4 carbon atoms; the halogen is one or more of F, Cl, or Br; the visible light for the reaction is violet light 390-395 nm, blue light 460-465 nm, or blue-violet light 410-415 nm; the reaction is carried out in the presence of a catalyst, which is one or more of [Cu(MeCN)4]BF4, CuCl, CuBr, CuI, [Cu(MeCN)4]PF6, CuBr2, Cu(CF3SO3)2, and Cu(NO3)2; a ligand is added to the reaction, which is one or more of pyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, 2,2'-bipyridine, and 4,4'-bipyridine.

2. The preparation method according to claim 1, characterized in that: The power of the illumination light source is one of 3 W, 5 W, 7 W, 10 W, 12 W, or 15 W.

3. The preparation method according to claim 1, characterized in that: The reaction is carried out with a solvent, which is dimethyl sulfoxide, N,N-dimethylaniline, 2,2,2-trifluoroethanol, hexafluoroisopropanol, ethanol, methanol, H2O, tetrahydrofuran, ethyl acetate, dichloroethane, dichloromethane and acetonitrile; the solvent is 1.0-5 mL of solvent added for every 0.1 mmol of substituted phenol (2).

4. The preparation method according to claim 1, characterized in that: The molar ratio of substituted phenol (2) to aryltriazene (3) in the reaction ranges from 1:1.0 to 1:2.

5.

5. The preparation method according to claim 1, characterized in that: The reaction time is 1-24 hours.

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