阅读说明：本技术 一种通过镍/酮双催化卤代芳烃与芳基酚反应合成二芳基醚的方法 (Method for synthesizing diaryl ether by nickel/ketone double-catalysis reaction of halogenated aromatic hydrocarbon and aryl phenol ) 是由 李红喜 朱大亮 李海燕 于 2021-09-26 设计创作，主要内容包括：本发明公开了一种通过镍/酮双催化卤代芳烃与芳基酚反应合成二芳基醚的方法,在惰性气体保护下,将上述卤代芳烃、苯酚、TXO、Ni(bpy)Br-(2)、t-BuNH(i-Pr)加入到配备搅拌装置的反应容器中,再加入溶剂,于光照射下,室温搅拌反应,得到二芳基醚类化合物。本发明整个过程绿色、高效且易于操作,是一种合成二芳基醚类化合物的好方法。(The invention discloses a method for synthesizing diaryl ether by nickel/ketone double-catalysis reaction of halogenated aromatic hydrocarbon and aryl phenol, under the protection of inert gas, the halogenated aromatic hydrocarbon, phenol, TXO and Ni (bpy) Br are reacted 2 、 t ‑BuNH( i -Pr) is added into a reaction vessel provided with a stirring device, then a solvent is added, and the mixture is stirred and reacted at room temperature under the irradiation of light, so as to obtain the diaryl ether compound. The whole process is green, efficient and easy to operate, and the method is a good method for synthesizing diaryl ether compounds.)

1. The application of nickel/ketone double catalyst in synthesizing diaryl ether by the reaction of halogenated aromatic hydrocarbon and aryl phenol.

2. Use according to claim 1, characterized in that: the ketone is a photocatalyst, and the nickel is Ni (bpy) Br₂(ii) a The structural formula of the halogenated aromatic hydrocarbon is as follows:

ar is phenyl or substituted phenyl; x is halogen;

the structural formula of the aryl phenol is as follows:

ar' is phenyl or substituted phenyl.

3. Use according to claim 1, characterized in that: the reaction is carried out in a solvent in the presence of a base under the protection of inert gas.

4. Use according to claim 1, characterized in that: the using amount of the ketone is 15-25% of the molar weight of the halogenated aromatic hydrocarbon; the using amount of the nickel is 8-11% of the molar weight of the halogenated aromatic hydrocarbon.

5. A method for synthesizing diaryl ether by nickel/ketone double catalysis reaction of halogenated aromatic hydrocarbon and aryl phenol is characterized by comprising the following steps of reacting halogenated aromatic hydrocarbon and aryl phenol in the presence of a nickel catalyst, a ketone catalyst and alkali to prepare diphenyl ether.

6. The method according to claim 5, wherein the reaction is carried out under protection of inert gas, at room temperature and under irradiation of light; the reaction time is 20-120 hours.

7. The method of claim 5, wherein: the base is selected from cesium carbonate, 1, 8-diazabicycloundecen-7-ene, triethylamine, diethylamine, N-diisopropylamine or N-tert-butylisopropanolamine.

8. The method of claim 5, wherein: the molar ratio of the halogenated aromatic hydrocarbon to the aryl phenol to the ketone catalyst to the nickel catalyst to the alkali is 1:3: 0.15-0.25: 0.08-0.11: 1.8-2.2.

9. The method of claim 5, wherein: the ketone catalyst is a photocatalyst, and the nickel catalyst is Ni (bpy) Br₂(ii) a The structural formula of the halogenated aromatic hydrocarbon is as follows:

ar is phenyl or substituted phenyl; x is halogen;

the structural formula of the aryl phenol is as follows:

ar' is phenyl or substituted phenyl.

10. A diaryl ether prepared according to the process of claim 5.

Technical Field

The invention belongs to the technical field of catalytic chemistry, and particularly relates to a method for synthesizing diphenyl ether by using nickel/ketone double catalysis to realize reaction of halogenated aromatic hydrocarbon and aryl phenol.

Background

The cross coupling of the metal-catalyzed halogenated aromatic hydrocarbon and the nucleophilic reagent is to construct carbon (sp)²) -carbon bond and carbon (sp)²) Heteroatom bonding is the most widespread method [ p. Ruiz-Castillo, s.l. Buchwald, chem. rev. 2016,116, 12564-12649]. Especially the synthesis of diaryl ethers by cross-coupling reactions of phenolic compounds with halogenated aromatics is of most interest [ i.p. Beletskaya, a.v. Cheprakov,Coord. Chem. Rev.2004, 248, 2337-2364]mainly because the compounds are important structural units of natural products, biological molecules and medical compounds [ D.A. Evans, J.L. Katz, T.R. West,Tetrahedron Lett.1998, 39, 2937-2940]. In the last decades, researchers have mainly used copper and palladium to catalyze the cross-coupling reaction of phenol and halogenated aromatic hydrocarbons to synthesize diaryl ether compounds [ a.s. Dudnik, g.c. Fu,J. Am. Chem. Soc.2012, 134, 10693-10697; R. Frlan, D. Kikelj, Synthesis2006, 14, 2271-2285]. However, strongly basic conditions, well-designed ancillary ligands and high temperatures are the necessary conditions for the construction of such compounds.

Disclosure of Invention

In order to overcome the technical problems, the invention provides a brand-new synergetic catalysis system utilizing a photocatalyst and a metal catalyst to realize the synthesis of diaryl ether compounds. In a specific example, 9-thioxanthone (A), (B), (C) and (D) are usedTXO as photosensitizer, Ni (bpy) Br₂As a catalyst, tot-BuNH(i-Pr) as alkali, under the irradiation of 45W CFL, a series of etherification reactions of halogenated aromatic hydrocarbon and phenol are realized. In addition, the diaryl ether compound is obtained with higher yield. The whole catalytic process is green, efficient and easy to operate, and the method is a good method for synthesizing diaryl ether compounds.

Specifically, the invention adopts the following technical scheme:

a method for synthesizing diaryl ether by nickel/ketone double catalysis halogenated aromatic hydrocarbon and aryl phenol reaction comprises the following steps, in the presence of nickel catalyst, ketone catalyst and alkali, halogenated aromatic hydrocarbon and aryl phenol react to prepare diaryl ether; preferably, under the protection of inert gas, the halogenated aromatic hydrocarbon, the aryl phenol, the ketone catalyst, the nickel catalyst and the alkali are added into a reaction vessel provided with a stirring device according to the molar ratio of 1:3: 0.15-0.25: 0.08-0.11: 1.8-2.2, then the solvent is added, and the diaryl ether compound is obtained after the mixture is irradiated for 20-120 hours at room temperature.

The invention also discloses the application of the nickel/ketone double catalyst in the synthesis of diaryl ether by the reaction of halogenated aromatic hydrocarbon and aryl phenol.

In the present invention, the inert gas is selected from any one of nitrogen, helium, neon and argon, and preferably nitrogen.

Preferably, the nickel catalyst is Ni (bpy) Br₂(ii) a The ketone catalyst is a photocatalyst, specifically 9-Thioxanthone (TXO), and has a structural formula shown in a formula (A):

in the invention, the structural formula of the halogenated aromatic hydrocarbon is as follows:

ar is phenyl or substituted phenyl; x is halogen, and specifically, the halogenated aromatic hydrocarbon is in a structure shown in any one of a formula (B) to a formula (I):

the structural formula of the aryl phenol is as follows:

specifically, the aryl phenol has a structure shown in any one of a formula (J) to a formula (M):

ar' is phenyl or substituted phenyl;

the structural formula of the product diaryl ether is as follows:

in the above structural formula, R¹Can be selected from carbonyl, ester, cyano, trifluoromethyl, phenyl; r²Can be selected from hydrogen, methyl, tert-butyl, isopropyl, n-propyl, carbonyl, ester group; r³May be selected from methoxy and ester groups.

In the present invention, the base is selected from cesium carbonate (Cs)₂CO₃) 1, 8-diazabicycloundecen-7-ene (DBU), triethylamine (Et)₃N), diethylamine (Et)₂NH), N-diisopropylamine (, (i-Pr)₂NH), N-tert-butylisopropanolamine (N-tert-butylisopropanolamine)t-BuNH(i-Pr)); the solvent is selected from any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile (MeCN) and ethanol (EtOH).

Preferably, in the method for synthesizing the diaryl ether compound, the molar ratio of the halogenated aromatic hydrocarbon to the aryl phenol to the ketone catalyst to the nickel catalyst to the base is 1:3:0.2:0.1: 2.0.

In the present invention, the illumination is 45W CFL (45W compact fluorescent lamp) illumination.

Preferably, in the method for synthesizing the diaryl ether compound, the reaction time is 72 hours or 120 hours.

For example, the method for synthesizing diphenyl ether by using nickel/ketone double-catalysis halogenated aromatic hydrocarbon to react with aryl phenol is schematically shown as follows:

compared with the prior art, the invention adopting the technical scheme has the following advantages: the invention takes 9-Thioxanthone (TXO) as photosensitizer for the first time and Ni (bpy) Br₂N-tert-butyl isopropanolamine is used as a catalyst, and a series of diaryl ether compounds are synthesized under the irradiation of 45W CFL. In addition, the diaryl ether compound can be obtained with higher yield. The whole process is green, efficient and easy to operate, and is a good method for synthesizing diaryl ether compounds.

Detailed Description

The invention will be further described with reference to specific embodiments. Unless otherwise indicated, reagents, materials, instruments and the like used in the following examples are commercially available; the specific operation method and the test method of the invention are conventional methods in the field; the reactions of the examples were all carried out at room temperature, and the yields of the examples refer to isolated yields unless otherwise indicated.

Example 1: TXO is used as a photosensitizer, and nickel catalyzes the reaction of p-bromoacetophenone and phenol.

P-bromoacetophenone (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（0.02mmol，10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction is finished, 5 mL of water is added, then ethyl acetate of 3X 5 mL is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography is carried out to obtain the target product (yield is 88%) and HPLC yield is 91%.

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.94 (d, J = 8.6 Hz, 2H), 7.40 (t, J = 7.8 Hz, 2H), 7.20 (t, J = 7.3 Hz, 1H), 7.07 (d, J = 7.9 Hz, 2H), 7.00 (d, J = 8.6 Hz, 2H), 2.57 (s, 3H)。¹³C-NMR (101 MHz, CDCl₃, ppm): 197.0, 162.2, 155.7, 132.1, 130.8, 130.3, 124.8, 120.4, 117.5, 26.7。

Development of the embodiment

Basic experiment: p-bromoacetophenone (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 24 hours under 45W CFL irradiation with 3 replacements. After the reaction is finished, 5 mL of water is added, then 3X 5 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography separation is carried out, so that the target product is obtained, and the HPLC yield is 74%.

P-bromoacetophenone (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and DMSO (3 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N₂The reaction was stirred for 24 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3X 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then chromatographed on silica gelAnd (4) performing chromatographic column separation to obtain a target product, wherein the HPLC yield is 40%.

P-bromoacetophenone (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and DMF (3 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N₂The reaction was stirred for 24 hours under 45W CFL irradiation with 3 replacements. After the reaction is finished, 5 mL of water is added, then 3X 5 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography separation is carried out, so that the target product is obtained, and the HPLC yield is 68%.

P-bromoacetophenone (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），(i-Pr)₂NH (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 24 hours under 45W CFL irradiation with 3 replacements. After the reaction is finished, 5 mL of water is added, then 3X 5 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography separation is carried out, so that the target product is obtained, and the HPLC yield is 48%.

In basic experiments, if TXO and Ni (bpy) Br are omitted₂Ort-BuNH(i-Pr), product yield 0; if the reaction is carried out at 50 ℃ in the dark, the product yield is 0; replacing 45W CFL irradiation with solar illumination, and obtaining a product with the yield of 60%; if TXO is replaced by Eosin Y, the product yield is < 1%. The yield in this stage is referred to as HPLC yield.

Example 2: TXO is used as a photosensitizer, and nickel catalyzes the reaction of methyl p-bromobenzoate and phenol.

Methyl p-bromobenzoate (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 87%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 8.00 (d, J = 8.6 Hz, 2H), 7.39 (t, J = 7.7 Hz, 2H), 7.19 (t, J = 7.3 Hz, 1H), 7.07 (d, J = 7.9 Hz, 2H), 6.98 (d, J = 8.6 Hz, 2H), 3.90 (s, 3H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 166.8, 162.0, 155.8, 131.9, 130.2, 124.7, 124.7, 120.3, 117.5, 52.2。

Example 3: TXO is used as a photosensitizer, and nickel catalyzes the reaction of ethyl p-bromobenzoate and phenol.

Ethyl p-bromobenzoate (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water is added, and then the mixture is extracted by 3X 5 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and the filtrate is subjected to rotary evaporation and concentration and then is separated by silica gel chromatography to obtain the target product (yield is 90%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 8.01 (d, J = 8.6 Hz, 2H), 7.39 (t, J = 7.7 Hz, 2H), 7.19 (t, J = 7.3 Hz, 1H), 7.06 (d, J = 7.9 Hz, 2H), 6.99 (d, J = 8.6 Hz, 2H), 4.36 (q, J = 7.1 Hz, 2H), 1.38 (t, J = 7.1 Hz, 3H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 166.4, 161.9, 155.9, 131.8, 130.2, 125.1, 124.7, 120.3, 117.5, 61.1, 14.6。

Example 4: TXO is used as a photosensitizer, and nickel catalyzes the reaction of p-bromobenzonitrile and phenol.

Para-bromobenzonitrile (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 86%).

¹H-NMR (400 MHz, CDCl₃, ppm): 7.60 (d, J = 8.6 Hz, 2H), 7.42 (t, J = 7.7 Hz, 2H), 7.22 (d, J = 7.3 Hz, 1H), 7.07 (d, J = 7.9 Hz, 2H), 7.00 (d, J = 8.6 Hz, 2H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 161.9, 155.0, 134.3, 130.4, 125.3, 120.6, 119.0, 118.1, 106.0。

Example 5: TXO is used as a photosensitizer, and nickel catalyzes 4- (3-trifluoromethyl) bromobenzene to react with phenol.

4- (3-trifluoromethyl) bromobenzene (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 91%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.59 (d, J = 8.1 Hz, 2H), 7.41 (t, J = 7.4 Hz, 2H), 7.21 (t, J = 7.2 Hz, 1H), 7.07 (t, J = 7.4 Hz, 4H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 160.8, 156.0, 130.3, 127.3 (q, ³ J _C-F = 3.8 Hz), 125.1 (q, ² J _C-F = 32.7 Hz), 124.7, 124.5 (q, ¹ J _C-F = 271.3 Hz), 120.2, 118.1。

Example 6: TXO is used as a photosensitizer, and nickel catalyzes p-bromobiphenyl and phenol to react.

P-bromobiphenyl (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 60%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.56 (s, 4H), 7.43 (t, J = 6.9 Hz, 2H), 7.36 (t, J = 6.8 Hz, 3H), 7.17–7.01 (m, 5H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 157.4, 157.1, 140.8, 136.5, 130.0, 129.0, 128.6, 127.3, 127.1, 123.6, 119.3。

Example 7: TXO is used as a photosensitizer, and nickel catalyzes the reaction of methyl 3-bromobenzoate and phenol.

3-Bromobenzoic acid methyl ester (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 73%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.78 (d, J = 7.5 Hz, 1H), 7.66 (s, 1H), 7.45–7.31 (m, 3H), 7.21 (d, J = 7.9 Hz, 1H), 7.14 (t, J = 7.1 Hz, 1H), 7.02 (d, J = 7.6 Hz, 2H), 3.89 (s, 3H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 166.7, 157.7, 156.9, 132.1, 130.1, 129.9, 124.5, 123.9, 123.5, 119.8, 119.3, 52.4。

Example 8: TXO is used as a photosensitizer, and nickel catalyzes the reaction of 2-bromonaphthalene and phenol.

2-bromonaphthalene (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3X 5 mL of ethyl acetate, and the organic phases were combined and the organic phase was washed with waterDrying with anhydrous sodium sulfate, filtering, concentrating the filtrate by rotary evaporation, and separating by silica gel chromatography to obtain the target product (yield 51%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.85 (dd, J = 7.7, 4.8 Hz, 2H), 7.72 (d, J = 8.0 Hz, 1H), 7.43 (ddd, J = 20.5, 15.0, 7.3 Hz, 4H), 7.33 (s, 1H), 7.31–7.27 (m, 1H), 7.16 (t, J = 7.3 Hz, 1H), 7.10 (d, J = 7.9 Hz, 2H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 157.4, 155.3, 134.6, 130.4, 130.1, 130.0, 128.0, 127.3, 126.7, 124.9, 123.7, 120.2, 119.3, 114.3。

Example 9: TXO is used as a photosensitizer, and nickel catalyzes the reaction of 2-bromo-5-fluorobenzaldehyde and phenol.

2-bromo-5-fluorobenzaldehyde (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 61%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 10.42 (s, 1H), 7.60 (d, J = 7.9 Hz, 1H), 7.39 (t, J = 7.1 Hz, 2H), 7.21 (dt, J = 14.2, 8.1 Hz, 2H), 7.03 (d, J = 7.6 Hz, 2H), 6.93 (d, J = 8.6 Hz, 1H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 188.5 (d, ⁴ J _C-F = 1.6 Hz), 158.8 (d, ¹ J _C-F = 245.0 Hz), 157.1, 156.0 (d, ⁴ J _C-F = 2.2 Hz), 130.4, 128.3 (d, ³ J _C-F = 6.4 Hz), 124.5, 123.0 (d, ² J _C-F = 24.1 Hz), 121.1 (d, ³ J _C-F = 7.4 Hz), 119.0, 114.2 (d, ² J _C-F = 23.8 Hz)。

Example 10: TXO is used as a photosensitizer, and nickel catalyzes the reaction of 3-methyl-4- (trifluoromethyl) bromobenzene and phenol.

3-methyl-4- (trifluoromethyl) bromobenzene (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 69%).

¹H-NMR (400 MHz, CDCl₃, ppm): 7.55 (d, J = 8.5 Hz, 1H), 7.39 (t, J = 7.4 Hz, 2H), 7.19 (t, J = 7.1 Hz, 1H), 7.05 (d, J = 7.7 Hz, 2H), 6.88 (s, 1H), 6.82 (d, J = 8.4 Hz, 1H), 2.44 (s, 3H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 160.4, 156.0, 139.3 (q, ⁴ J _C-F = 1.6 Hz), 130.2, 127.9 (q, ³ J _C-F = 5.6 Hz), 124.8 (q, ¹ J _C-F = 272.6 Hz), 124.6, 123.6 (q, ² J _C-F = 30.2 Hz), 121.2, 120.1, 114.8, 19.6 (q, ⁴ J _C-F = 1.8 Hz)。

Example 11: TXO is used as a photosensitizer, and nickel catalyzes the reaction of 3-bromoquinoline and phenol.

3-bromoquinoline (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 53%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 8.77 (s, 1H), 8.06 (d, J = 8.3 Hz, 1H), 7.67–7.55 (m, 2H), 7.47 (d, J = 8.8 Hz, 2H), 7.37 (t, J = 7.5 Hz, 2H), 7.17 (t, J = 7.2 Hz, 1H), 7.06 (d, J = 7.8 Hz, 2H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 156.5, 151.4, 145.4, 144.9, 130.4, 129.5, 128.8, 128.1, 127.5, 127.3, 124.6, 120.4, 119.5。

Example 12: TXO is used as a photosensitizer, and nickel catalyzes the reaction of 2-bromo-6-phenylpyridine and phenol.

2-bromo-6-phenylpyridine (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 92%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.92 (d, J = 7.2 Hz, 2H), 7.70 (t, J = 7.7 Hz, 1H), 7.45 (d, J = 7.5 Hz, 1H), 7.38 (dd, J = 13.9, 6.4 Hz, 5H), 7.21 (d, J = 8.5 Hz, 3H), 6.76 (d, J = 8.1 Hz, 1H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 163.5, 155.8, 154.5, 140.3, 138.5, 129.7, 129.3, 128.8, 126.9, 124.6, 121.4, 114.8, 109.6。

Example 13: TXO is used as a photosensitizer, and nickel catalyzes the reaction of 4-iodopyridine and phenol.

4-iodopyridine (0.2 mmol), phenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water is added, and then the mixture is extracted by 3X 5 mL of ethyl acetate, organic phases are combined, the organic phases are dried by using anhydrous sodium sulfate, the mixture is filtered, filtrate is concentrated by rotary evaporation, and the product is separated by silica gel chromatography to obtain the target product (yield is 40%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 8.46 (d, J = 5.2 Hz, 2H), 7.43 (t, J = 7.7 Hz, 2H), 7.25 (d, J = 9.9 Hz, 2H), 7.10 (d, J = 7.9 Hz, 2H), 6.84 (d, J = 5.4 Hz, 2H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 165.0, 154.2, 151.6, 130.4, 125.6, 121.0, 112.4。

Example 14: TXO is used as a photosensitizer, and nickel catalyzes the reaction of p-bromoacetophenone and 4-methylphenol.

Will be to bromineAcetophenone (0.2 mmol), 4-methylphenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mo l%），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 89%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.92 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 7.6 Hz, 2H), 6.97 (d, J = 7.8 Hz, 4H), 2.56 (s, 3H), 2.37 (s, 3H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 196.9, 162.7, 153.2, 134.6, 131.8, 130.8, 120.4, 117.1, 26.6, 21.0。

Example 15: TXO is used as a photosensitizer, and nickel catalyzes the reaction of p-bromoacetophenone and 4-tert-butylphenol.

P-bromoacetophenone 0.2 mmol, 4-tert-butylphenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 89%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.93 (d, J = 8.0 Hz, 2H), 7.40 (d, J = 7.8 Hz, 2H), 6.99 (d, J = 8.0 Hz, 4H), 2.57 (s, 3H), 1.34 (s, 9H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 196.9, 162.5, 153.1, 147.8, 131.8, 130.7, 127.1, 119.9, 117.2, 34.6, 31.7, 26.6。

Example 16: TXO is used as a photosensitizer, and nickel catalyzes the reaction of p-bromoacetophenone and 4-isopropylphenol.

P-bromoacetophenone (0.2 mmol), 4-isopropylphenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 91%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.92 (d, J = 7.7 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.4 Hz, 4H), 2.93 (dt, J = 13.1, 6.4 Hz, 1H), 2.56 (s, 3H), 1.27 (d, J = 6.6 Hz, 6H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 196.9, 162.6, 153.4, 145.5, 131.8, 130.7, 128.1, 120.3, 117.2, 33.8, 26.6, 24.3。

Example 17: TXO is used as a photosensitizer, and nickel catalyzes the reaction of p-bromoacetophenone and 4-n-propylphenol.

P-bromoacetophenone (0.2 mmol), 4-n-propylphenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to the dry with magnetic stirrerIn a dry reaction tube, followed by N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water is added, and then the mixture is extracted by 3X 5 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and the filtrate is subjected to rotary evaporation and concentration and then is separated by silica gel chromatography to obtain the target product (yield is 90%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.92 (d, J = 8.4 Hz, 2H), 7.19 (d, J = 7.9 Hz, 2H), 6.98 (d, J = 8.2 Hz, 4H), 2.63–2.58 (m, 2H), 2.56 (s, 3H), 1.71–1.61 (m, 2H), 0.96 (t, J = 7.3 Hz, 3H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 196.9, 162.6, 153.4, 139.4, 131.8, 130.8, 130.1, 120.3, 117.1, 37.6, 26.6, 24.8, 14.0。

Example 18: TXO is used as a photosensitizer, and nickel catalyzes the reaction of p-bromoacetophenone and 4-acetyl phenol.

P-bromoacetophenone (0.2 mmol), 4-acetylphenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 120 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water is added, and then the mixture is extracted by 3X 5 mL of ethyl acetate, organic phases are combined, the organic phases are dried by using anhydrous sodium sulfate, the mixture is filtered, filtrate is concentrated by rotary evaporation, and the product is separated by silica gel chromatography to obtain the target product (yield is 50%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.99 (d, J = 7.8 Hz, 4H), 7.08 (d, J = 7.8 Hz, 4H), 2.60 (s, 6H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 196.9, 160.4, 133.3, 130.9, 119.0, 26.7。

Example 19: TXO is used as a photosensitizer, and nickel catalyzes the reaction of p-bromoacetophenone and methyl p-hydroxybenzoate.

P-bromoacetophenone (0.2 mmol), methylparaben (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 120 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 53%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 8.06 (d, J = 8.1 Hz, 2H), 7.98 (d, J = 8.1 Hz, 2H), 7.07 (d, J = 7.0 Hz, 4H), 3.91 (s, 3H), 2.59 (s, 3H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 196.9, 166.6, 160.5, 160.2, 133.2, 132.1, 130.9, 126.1, 118.9, 118.9, 52.4, 26.7。

Example 20: TXO is used as a photosensitizer, and nickel catalyzes the reaction of the p-bromoacetophenone and the 3-methoxyphenol.

P-bromoacetophenone (0.2 mmol), 3-methoxyphenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3X 5 mL of ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and filteredThe solution was concentrated by rotary evaporation and then separated by silica gel chromatography to give the desired product (yield 65%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.94 (d, J = 8.3 Hz, 2H), 7.32–7.26 (m, 1H), 7.02 (d, J = 8.3 Hz, 2H), 6.75 (d, J = 8.1, 1H), 6.64 (d, J = 12.0 Hz, 2H), 3.79 (s, 3H), 2.57 (s, 3H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 196.9, 161.9, 161.3, 156.8, 132.2, 130.8, 130.6, 117.6, 112.3, 110.5, 106.3, 55.6, 26.6。

Example 21: TXO is used as a photosensitizer, and nickel catalyzes the reaction of the p-bromoacetophenone and the methyl 3-hydroxybenzoate.

P-bromoacetophenone (0.2 mmol), methyl 3-hydroxybenzoate (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 120 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 51%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.95 (d, J = 8.2 Hz, 2H), 7.87 (d, J = 7.5 Hz, 1H), 7.71 (s, 1H), 7.48 (s, 1H), 7.27 (d, J = 6.4 Hz, 1H), 7.01 (d, J= 8.2 Hz, 2H), 3.90 (s, 3H), 2.58 (s, 3H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 196.9, 166.4, 161.5, 155.9, 132.6, 132.5, 130.9, 130.3, 125.8, 124.7, 121.1, 117.8, 52.5, 26.7。

Example 22: TXO is used as a photosensitizer, and nickel catalyzes the reaction of the p-bromoacetophenone and 3, 5-dimethylphenol.

P-bromoacetophenone (0.2 mmol), 3, 5-dimethylphenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 72 hours under 45W CFL irradiation with 3 replacements. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 62%).

¹H-NMR (400 MHz, CDCl₃, ppm): δ7.93 (d, J = 8.6 Hz, 2H), 6.98 (d, J = 8.6 Hz, 2H), 6.84 (s, 1H), 6.68 (s, 2H), 2.57 (s, 3H), 2.31 (s, 6H)。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 197.0, 162.5, 155.6, 140.2, 131.9, 130.8, 126.5, 118.0, 117.5, 26.6, 21.5。

Example 23: TXO is used as a photosensitizer, and nickel catalyzes the reaction of the p-bromoacetophenone and 2-methoxy-4-methylphenol.

P-bromoacetophenone (0.2 mmol), 2-methoxy-4-methylphenol (0.6 mmol), TXO (20 mol%), Ni (bpy) Br₂（10 mol %），t-BuNH(i-Pr) (0.4 mmol) and MeCN (3 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N₂The reaction was stirred for 120 hours under 45W CFL irradiation with 3 replacements. After the reaction is finished, 5 mL of water is added, then ethyl acetate of 3 multiplied by 5 mL is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is rotated, evaporated and concentrated, and silica gel chromatography is carried out to separate the filtrate to obtain the target product (the yield is 44 percent)）。

¹H-NMR (400 MHz, CDCl₃, ppm): δ 7.90 (d, J = 8.6 Hz, 2H), 6.93 (dd, J= 19.6, 8.3 Hz, 3H), 6.83 (s, 1H), 6.78 (d, J = 7.8 Hz, 1H), 3.77 (s, 3H), 2.55 (s, 3H), 2.39 (s, 3H).。¹³C-NMR (101 MHz, CDCl₃, ppm): δ 197.0, 162.9, 151.6, 141.0, 136.5, 131.5, 130.7, 122.4, 121.9, 115.8, 114.1, 56.1, 26.6, 21.6。