A method for cross electrophilic coupling of aryl sulfone compounds with aryl halides

Abstract

The application relates to a cross electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide, and a series of (hetero) biaryl structure compounds are obtained. The reaction does not need waterless and oxygenless protection, is driven by electrochemistry at room temperature, takes a nickel (II) bromide diethylene glycol dimethyl ether complex as a catalyst, takes 2,2'-bipyridine or 2,2'-bipyridine-5,5'-dimethylate as a ligand, takes lithium bromide as an electrolyte, takes a stainless steel sheet or a zinc sheet as an anode, takes foamed nickel as a cathode, places the aryl sulfone compound and the aryl halide in N,N-dimethylformamide, connects the anode and the cathode to electricity for 10 hours, and then the biaryl compound can be obtained by using an automatic column machine for column chromatography purification. By adopting the method, a series of important drug molecules can be synthesized, and an electrochemical polymerization reaction can be carried out.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of C(sp 2 )-C(sp 2 ) construction, and particularly relates to a cross electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide. BACKGROUND

[0002] Biaryl compounds are widely present in drugs, natural products, chemical drugs, ligands and functional molecules / polymeric materials, and developing a synthetic method for constructing C(sp 2 )-C(sp 2 ) bonds to prepare biaryl compounds is also an important goal of modern synthetic chemistry. As a main method for constructing C(sp 2 )-C(sp 2 ) bonds, transition metal-catalyzed cross-coupling reaction is awarded the Nobel Prize in Chemistry in 2010 due to its advantages of high efficiency and wide application range. However, traditional cross-coupling needs to be carried out between one electrophilic reagent and one nucleophilic reagent, and the nucleophilic reagent is usually an organometallic compound, which is sensitive to water and air, and is mostly prepared from the corresponding aryl halide, which increases the synthetic steps, safety protection measures and functional group compatibility considerations.

[0003] In recent years, reductive cross-coupling of two electrophilic reagents in the presence of a metal reductant avoids these shortcomings, but it still faces the difficulties of poor selectivity and the need for high temperature in most reactions. Organic electro-synthesis uses renewable and readily available electricity to replace traditional redox reagents, thereby reducing the use of chemicals and waste generation, and the electric potential can be used to regulate selectivity. Electrochemical synthesis has the advantages of simple reaction device, low cost and accurate controllable reaction conditions, and can avoid the use of metal elements and high temperature in traditional reductive coupling, and is an important method for constructing C(sp 2 )-C(sp 2 ) bonds. SUMMARY

[0004] The application aims to overcome the deficiencies of the prior art and provide a cross electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide, which is a simple and highly selective electrochemical reductive coupling method.

[0005] The application solves the technical problems by adopting the following technical solutions:

[0006] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, comprising taking aryl sulfone compound and aryl halide as two electrophilic reagents respectively, adding ligand and electrolyte in turn under catalyst condition, adding solvent, and preparing biaromatic compound by coupling two electrophilic reagents driven by electrochemistry, and the reaction general formula is:

[0007]

[0008] Wherein, Ar 1 , Ar 2 represent the same or different aryl system;

[0009] X represents I, Br, Cl;

[0010] R represents alkyl, aryl.

[0011] Moreover, the catalyst is nickel (II) bromide diethylene glycol dimethyl ether complex, the electrolyte is lithium bromide, and the solvent is N, N-dimethylformamide.

[0012] Moreover, the ligand is 2, 2'-bipyridine or 2, 2'-bipyridine-5, 5'-dimethylate;

[0013] Wherein, the structural formula of 2, 2'-bipyridine is

[0014] The structural formula of 2, 2'-bipyridine-5, 5'-dimethylate is

[0015] Moreover, the aryl sulfone compound is any one of the following compounds:

[0016]

[0017] Wherein, R is independent C1-C 15 alkyl chain or aryl;

[0018] The alkyl chain includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl;

[0019] The aryl includes phenyl, naphthyl, and each substituted aryl;

[0020] R is also trifluoromethyl, difluoromethyl, vinyl, and each substituted aryl;

[0021] R 1 is independent C1-C 15 alkyl chain, halogen or aryl;

[0022] The alkyl chain includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl;

[0023] The halogen includes fluorine, chlorine, bromine;

[0024] The aryl includes phenyl, naphthyl, tolyl, and each substituted aromatic group;

[0025] R 1 or hydroxyl, carbonyl, cyano, amine, ester, aldehyde, borate, trifluoromethyl, alkoxy, ester.

[0026] Moreover, the aryl halide is any one of the following compounds:

[0027]

[0028] wherein X is a chlorine atom, a bromine atom or an iodine atom;

[0029] wherein R 2 is an independent C1-C 15 alkyl chain, alkoxy chain or aryl,

[0030] The alkyl chain includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl;

[0031] The alkoxy chain includes methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy;

[0032] The aryl includes phenyl, naphthyl, and each substituted aromatic group;

[0033] R 2 or hydroxyl, carbonyl, cyano, amine, ester, aldehyde, borate, trifluoromethyl, alkoxy, ester.

[0034] Moreover, the method specifically includes the following steps:

[0035] S1, the reactant aryl sulfone compound and aryl halide, catalyst nickel (II) bromide diethylene glycol dimethyl ether complex, ligand 2, 2'-bipyridine or 2, 2'-bipyridine-5, 5'-dimethyl acid dimethyl ester, electrolyte LiBr, are added into the electrolytic reaction bottle in turn, then the solvent N, N-dimethylformamide is added, and stirred at room temperature for 10-20 minutes;

[0036] S2, open the electrochemical reaction workstation, with stainless steel sheet or zinc sheet as anode, and foam nickel as cathode, electrolysis for 8-12 hours under constant current of 10-20 mA;

[0037] S3, the reaction solution is passed through a short diatomite column, washed with dichloromethane, and the organic solvent is removed under reduced pressure rotary evaporation, and the residue is purified by silica gel column chromatography to obtain the target product.

[0038] Moreover, the molar ratio of the aryl sulfone compound, the aryl halide, the catalyst, the ligand and N,N-dimethylformamide is 10:10:1:1:100.

[0039] Moreover, the eluent of the silica gel column chromatography is petroleum ether and dichloromethane, and the ratio of the petroleum ether and dichloromethane is 10:1.

[0040] Moreover, the aryl sulfone compound and the aryl halide are cross electrophilic coupling to construct C(sp 2 )-C(sp 2 ).

[0041] The application of a cross electrophilic coupling reaction of an aryl sulfone compound and an aryl halide in the preparation of an organic polymer.

[0042] The advantages and positive effects of the application are:

[0043] 1. The preparation method avoids the use of metal reducing agents, reduces the use of chemicals and waste generation, avoids the requirement of traditional heating, and can be carried out at room temperature, which is more green and environmentally friendly; and no inert gas protection is required, and the operation is more simple and convenient. The reaction has high selectivity, has a wide substrate range, can be applied to a reaction system of more than two grams, and can also obtain a high yield; and can be used to synthesize various drugs and modifications, and the reaction conditions are suitable for polymerization reaction to synthesize polymers with high molecular weight and narrow distribution.

[0044] 2. The application breaks through the limitation of traditional cross coupling reaction which requires one electrophilic reagent and one nucleophilic reagent, and the nucleophilic reagent is mostly an organic metal compound sensitive to water and air, reduces the synthesis steps, and reduces the requirement for safety protection measures and functional group compatibility.

[0045] 3. The application uses electrochemical synthesis to replace traditional redox reagents with renewable electricity, reduces the use of chemicals and waste generation, and meets the green chemistry concept. At the same time, the selectivity can be controlled by potential, which can avoid the disadvantages brought by the use of metal elements and high temperature in traditional reduction coupling, the reaction device is simple, the cost is low, the reaction conditions are accurately controllable, and the operation is convenient and suitable for large-scale application.

[0046] 4、The whole reaction process of the present application is clear in steps, from the mixing and stirring of reactants, electrolysis reaction to post-treatment (diatomite column filtration, washing, reduced pressure rotary evaporation and silica gel column chromatography purification), the operation conditions of each step are relatively mild, easy to implement in laboratory and industrial production. The cross-coupling of aryl sulfone compound and aryl halide can be realized more accurately, which is conducive to obtaining the target biaromatic compound, reducing the occurrence of side reactions, and improving the purity and yield of the product.

[0047] 5、The structure types of aryl sulfone compound and aryl halide of the present application are rich and various, including various alkyl chains, aryl groups and different functional group substituted types, which can adapt to the synthesis of biaromatic compounds with various structure requirements, and provide strong method support for the preparation of compounds containing biaromatic structure in the fields of drugs, natural products, chemical drugs, ligands and functional molecules / polymeric materials. BRIEF DESCRIPTION OF DRAWINGS

[0048] Figure 1 It is the ultraviolet-visible absorption spectrum and photoluminescence spectrum diagram of the polymer P(2,6-Q) in chloroform solution.

[0049] Figure 2 It is the thermogravimetric analysis diagram of the polymer P(2,6-Q).

[0050] Figure 3 It is the cyclic voltammogram of the polymer P(2,6-Q) in chloroform / n-Bu4NPF6 solution with ferrocene as an internal standard. DETAILED DESCRIPTION

[0051] The present application will be further described below through specific embodiments, the following examples are only descriptive, not limiting, and the protection scope of the present application cannot be limited by this.

[0052] Example 1

[0053]

[0054] A cross electrophilic coupling reaction method of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0055] To an electrolysis reaction flask, 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in turn, and after adding solvent DMF (concentration 0.1 M), stirring was carried out at room temperature for 15 minutes. Subsequently, the electrochemical reaction station was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (72% yield).

[0056] 1 H NMR (500 MHz, CDC13) δ 8.06 (d, J = 8.2 Hz, 1H), 7.99 (d, J = 7.9 Hz, 2H), 7.89 (d, J = 8.0 Hz, 1H), 7.48 (ddd, J = 8.3, 7.1, 1.2 Hz, 1H), 7.37 (td, J = 7.6, 7.1, 1.0 Hz, 1H), 7.30 (d, J = 7.8 Hz, 2H), 2.43 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 168.36, 154.27, 141.53, 135.05, 131.07, 129.82, 127.58, 126.33, 125.10, 123.14, 121.67, 21.61.

[0057] Example 2

[0058]

[0059] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0060] To an electrolysis reaction flask, 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in turn, and after adding solvent DMF (concentration 0.1 M), stirring was carried out at room temperature for 15 minutes. Subsequently, the electrochemical reaction station was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (72% yield).

[0061] 1H NMR (500 MHz, CDCI3) δ 8.06 (d, J = 8.2 Hz, 1 H), 7.99 (d, J = 7.9 Hz, 2 H), 7.89 (d, J = 8.0 Hz, 1 H), 7.48 (ddd, J = 8.3, 7.1, 1.2 Hz, 1 H), 7.37 (td, J = 7.6, 7.1, 1.0 Hz, 1 H), 7.30 (d, J = 7.8 Hz, 2 H), 2.43 (s, 3 H). 13 C NMR (126 MHz, CDCI3) δ 168.36, 154.27, 141.53, 135.05, 131.07, 129.82, 127.58, 126.33, 125.10, 123.14, 121.67, 21.61.

[0062] Example 3

[0063]

[0064] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0065] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2.diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (54% yield).

[0066] 1 H NMR (500 MHz, CDCI3) δ 8.06 (d, J = 8.2 Hz, 1 H), 7.99 (d, J = 7.9 Hz, 2 H), 7.89 (d, J = 8.0 Hz, 1 H), 7.48 (ddd, J = 8.3, 7.1, 1.2 Hz, 1 H), 7.37 (td, J = 7.6, 7.1, 1.0 Hz, 1 H), 7.30 (d, J = 7.8 Hz, 2 H), 2.43 (s, 3 H). 13 C NMR (126 MHz, CDCI3) δ 168.36, 154.27, 141.53, 135.05, 131.07, 129.82, 127.58, 126.33, 125.10, 123.14, 121.67, 21.61.

[0067] Example 4

[0068]

[0069] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0070] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode and foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (58% yield).

[0071] 1 H NMR (500 MHz, CDCl3) δ 8.06 (d, J = 8.2 Hz, 1H), 7.99 (d, J = 7.9 Hz, 2H), 7.89 (d, J = 8.0 Hz, 1H), 7.48 (ddd, J = 8.3, 7.1, 1.2 Hz, 1H), 7.37 (td, J = 7.6, 7.1, 1.0 Hz, 1H), 7.30 (d, J = 7.8 Hz, 2H), 2.43 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 168.36, 154.27, 141.53, 135.05, 131.07, 129.82, 127.58, 126.33, 125.10, 123.14, 121.67, 21.61.

[0072] Example 5

[0073]

[0074] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0075] To an electrolysis reaction flask, 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in turn, and after adding solvent DMF (concentration 0.1 M), stirring was carried out at room temperature for 15 minutes. Subsequently, the electrochemical reaction station was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (51% yield).

[0076] 1 H NMR (500 MHz, CDC13) δ 8.06 (d, J = 8.2 Hz, 1H), 7.99 (d, J = 7.9 Hz, 2H), 7.89 (d, J = 8.0 Hz, 1H), 7.48 (ddd, J = 8.3, 7.1, 1.2 Hz, 1H), 7.37 (td, J = 7.6, 7.1, 1.0 Hz, 1H), 7.30 (d, J = 7.8 Hz, 2H), 2.43 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 168.36, 154.27, 141.53, 135.05, 131.07, 129.82, 127.58, 126.33, 125.10, 123.14, 121.67, 21.61.

[0077] Example 6

[0078]

[0079] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0080] To an electrolysis reaction flask, 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in turn, and after adding solvent DMF (concentration 0.1 M), stirring was carried out at room temperature for 15 minutes. Subsequently, the electrochemical reaction station was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (51% yield).

[0081] 1H NMR (500 MHz, CDCI3) δ 8.06 (d, J = 8.2 Hz, 1 H), 7.99 (d, J = 7.9 Hz, 2 H), 7.89 (d, J = 8.0 Hz, 1 H), 7.48 (ddd, J = 8.3, 7.1, 1.2 Hz, 1 H), 7.37 (td, J = 7.6, 7.1, 1.0 Hz, 1 H), 7.30 (d, J = 7.8 Hz, 2 H), 2.43 (s, 3 H). 13 C NMR (126 MHz, CDCI3) δ 168.36, 154.27, 141.53, 135.05, 131.07, 129.82, 127.58, 126.33, 125.10, 123.14, 121.67, 21.61.

[0082] Example 7

[0083]

[0084] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0085] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2.diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (71 % yield).

[0086] 1 H NMR (500 MHz, CDCI3) δ 8.06 (d, J = 8.2 Hz, 1 H), 7.99 (d, J = 7.9 Hz, 2 H), 7.89 (d, J = 8.0 Hz, 1 H), 7.48 (ddd, J = 8.3, 7.1, 1.2 Hz, 1 H), 7.37 (td, J = 7.6, 7.1, 1.0 Hz, 1 H), 7.30 (d, J = 7.8 Hz, 2 H), 2.43 (s, 3 H). 13 C NMR (126 MHz, CDCI3) δ 168.36, 154.27, 141.53, 135.05, 131.07, 129.82, 127.58, 126.33, 125.10, 123.14, 121.67, 21.61.

[0087] Example 8

[0088]

[0089] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0090] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle. After adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (54% yield).

[0091] 1 H NMR (500 MHz, CDCl3) δ 8.06 (d, J = 8.2 Hz, 1H), 7.99 (d, J = 7.9 Hz, 2H), 7.89 (d, J = 8.0 Hz, 1H), 7.48 (ddd, J = 8.3, 7.1, 1.2 Hz, 1H), 7.37 (td, J = 7.6, 7.1, 1.0 Hz, 1H), 7.30 (d, J = 7.8 Hz, 2H), 2.43 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 168.36, 154.27, 141.53, 135.05, 131.07, 129.82, 127.58, 126.33, 125.10, 123.14, 121.67, 21.61.

[0092] Example 9

[0093]

[0094] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0095] To an electrolysis reaction flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added successively. After adding solvent DMF (0.1 M concentration), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction station was opened, with stainless steel as anode, foamed nickel as cathode, constant current 15 milliampere electrolysis for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography to obtain white solid product (43% yield).

[0096] 1 H NMR (500 MHz, CDC13) δ 8.06 (d, J = 8.2 Hz, 1H), 7.99 (d, J = 7.9 Hz, 2H), 7.89 (d, J = 8.0 Hz, 1H), 7.48 (ddd, J = 8.3, 7.1, 1.2 Hz, 1H), 7.37 (td, J = 7.6, 7.1, 1.0 Hz, 1H), 7.30 (d, J = 7.8 Hz, 2H), 2.43 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 168.36, 154.27, 141.53, 135.05, 131.07, 129.82, 127.58, 126.33, 125.10, 123.14, 121.67, 21.61.

[0097] Example 10

[0098]

[0099] A method for cross-electrophilic coupling reaction of arylsulfone compound and aryl halide, specifically comprising the following steps:

[0100] To an electrolysis reaction flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added successively. After adding solvent DMF (0.1 M concentration), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction station was opened, with stainless steel as anode, foamed nickel as cathode, constant current 15 milliampere electrolysis for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography to obtain white solid product (43% yield).

[0101] 1H NMR (500 MHz, CDCI3) δ 8.06 (d, J = 8.2 Hz, 1 H), 7.99 (d, J = 7.9 Hz, 2 H), 7.89 (d, J = 8.0 Hz, 1 H), 7.48 (ddd, J = 8.3, 7.1, 1.2 Hz, 1 H), 7.37 (td, J = 7.6, 7.1, 1.0 Hz, 1 H), 7.30 (d, J = 7.8 Hz, 2 H), 2.43 (s, 3 H). 13 C NMR (126 MHz, CDCI3) δ 168.36, 154.27, 141.53, 135.05, 131.07, 129.82, 127.58, 126.33, 125.10, 123.14, 121.67, 21.61.

[0102] Example 11

[0103]

[0104] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0105] 1.0 equivalent of aryl sulfide compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2.diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, after adding solvent DMF (concentration 0.1 M) and stirring at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, constant current 15 milliampere for electrolysis for 10 hours. Finally, the reaction liquid was washed with dichloromethane through a short diatomite column, the organic solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography to obtain white solid product (25% yield).

[0106] 1 H NMR (500 MHz, CDCI3) δ 8.06 (d, J = 8.2 Hz, 1 H), 7.99 (d, J = 7.9 Hz, 2 H), 7.89 (d, J = 8.0 Hz, 1 H), 7.48 (ddd, J = 8.3, 7.1, 1.2 Hz, 1 H), 7.37 (td, J = 7.6, 7.1, 1.0 Hz, 1 H), 7.30 (d, J = 7.8 Hz, 2 H), 2.43 (s, 3 H). 13 C NMR (126 MHz, CDCI3) δ 168.36, 154.27, 141.53, 135.05, 131.07, 129.82, 127.58, 126.33, 125.10, 123.14, 121.67, 21.61.

[0107] Example 12

[0108]

[0109] A method for cross-electrophilic coupling reaction of aryl sulfone compound with aryl halide, specifically comprising the following steps:

[0110] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (53% yield).

[0111] 1 H NMR (500 MHz, CDC13) δ 7.99 (d, J = 8.2 Hz, 2H), 7.71 (dd, J = 6.3, 2.8 Hz, 1H), 7.28 (d, J = 8.0 Hz, 2H), 7.26-7.24 (m, 2H), 2.79 (s, 3H), 2.42 (s, 3H). 13 CNMR (126 MHz, CDC13) δ 166.82, 153.65, 141.18, 134.97, 133.26, 131.42, 129.73, 127.53, 126.79, 124.95, 119.01, 21.61, 18.50. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 15 H 14 NS+240.0841, found 240.0836.

[0112] Example 13

[0113]

[0114] A method for cross-electrophilic coupling reaction of aryl sulfone compound with aryl halide, specifically comprising the following steps:

[0115] To an electrolysis reaction flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added successively, and stirred at room temperature for 15 minutes after adding solvent DMF (concentration 0.1 M). Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a light yellow solid product (74% yield).

[0116] 1 H NMR (500 MHz, CDCl3) δ 8.01 (d, J = 8.2 Hz, 2H), 7.65 (d, J = 8.0 Hz, 1H), 7.32 (dt, J = 11.3, 6.1 Hz, 3H), 7.21 - 7.16 (m, 1H), 2.43 (s, 3H). 19 F NMR (471 MHz, CDCl3) δ -122.03. 13 CNMR (126 MHz, CDCl3) δ 168.89, 156.96, 154.92, 141.94, 137.69, 137.66, 130.61, 129.83, 127.80, 125.80, 125.75, 117.36, 117.33, 112.13, 111.98, 21.65. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 14 H 11 FNS+244.0591, found 244.0587.

[0117] Example 14

[0118]

[0119] A method for cross-electrophilic coupling reaction of arylsulfone compound and aryl halide, specifically comprising the following steps:

[0120] To an electrolysis flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added successively. After adding solvent DMF (0.1 M concentration), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction station was opened, with stainless steel as anode, foamed nickel as cathode, constant current 15 milliampere electrolysis for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a yellow solid product (80% yield).

[0121] 1 H NMR (500 MHz, CDC13) δ 7.95 (d, J = 8.1 Hz, 2H), 7.85 (s, 1H), 7.73 (d, J = 8.1 Hz, 1H), 7.27 (d, J = 7.9 Hz, 2H), 7.18 (d, J = 8.1 Hz, 1H), 2.49 (s, 3H), 2.40 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 168.43, 154.66, 141.36, 136.38, 132.00, 131.20, 129.78, 127.51, 126.72, 123.19, 121.14, 21.62. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 15 H 14 NS+240.0841, found 240.0840.

[0122] Example 15

[0123]

[0124] A method for cross-electrophilic coupling reaction of arylsulfone compound and aryl halide, specifically comprising the following steps:

[0125] To an electrolysis flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added successively. After adding solvent DMF (0.1 M concentration), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction station was opened, with stainless steel as anode, foamed nickel as cathode, constant current 15 milliampere electrolysis for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a yellow solid product (80% yield).

[0126] 1 H NMR (500 MHz, CDCI3) δ 7.95 (d, J = 8.0 Hz, 2H), 7.79 (dd, J = 8.8, 5.1 Hz, 1H), 7.72 (dd, J = 9.6, 2.5 Hz, 1H), 7.29 (d, J = 8.5 Hz, 2H), 7.13 (td, J = 8.8, 2.5 Hz, 1H), 2.42 (s, 3H). 19 F NMR (471 MHz, CDCI3) δ -115.82. 13 C NMR (126 MHz, CDCI3) δ 170.81, 162.99, 161.06, 155.23, 155.13, 141.90, 130.80, 129.87, 127.56, 122.32, 122.24, 113.81, 113.61, 109.37, 109.18, 21.64. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 14 H 11 FNS+244.0591, found 244.0589.

[0127] Example 16

[0128]

[0129] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0130] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a light yellow solid product (41% yield).

[0131] 1 H NMR (500 MHz, CDCI3) δ 8.02 (d, J = 2.0 Hz, 1H), 7.95 (d, J = 7.9 Hz, 2H), 7.77 (d, J = 8.5 Hz, 1H), 7.33 (dd, J = 8.5, 2.0 Hz, 1H), 7.29 (d, J = 7.9 Hz, 2H), 2.42 (s, 3H).13 C NMR (126 MHz, CDC13) δ 170.19, 155.12, 142.00, 133.29, 132.31, 130.69, 129.89, 127.63, 125.53, 122.94, 122.34, 21.65.

[0132] Example 17

[0133]

[0134] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0135] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode and foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (43% yield).

[0136] 1 H NMR (500 MHz, CDC13) δ 8.18 (d, J = 1.9 Hz, 1H), 7.95 (d, J = 8.1 Hz, 2H), 7.73 (d, J = 8.4 Hz, 1H), 7.46 (dd, J = 8.5, 1.9 Hz, 1H), 7.29 (d, J = 7.9 Hz, 2H), 2.42 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 169.98, 155.45, 142.03, 133.84, 130.64, 129.90, 128.15, 127.65, 125.99, 122.69, 119.89. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 14 H 11 BrNS+303.9790, found 303.9787.

[0137] Example 18

[0138]

[0139] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0140] To an electrolysis reaction flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added successively, and stirred at room temperature for 15 minutes after adding solvent DMF (concentration 0.1 M). Subsequently, the electrochemical reaction workstation was opened, with stainless steel as anode, foamed nickel as cathode, constant current 15 milliampere, electrolysis for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a light yellow solid product (73% yield).

[0141] 1 H NMR (500 MHz, CDCl3) δ 8.31 (s, 1H), 7.99 (d, J = 6.2 Hz, 3H), 7.60 (d, J = 8.4 Hz, 1H), 7.32 (d, J = 7.8 Hz, 2H), 2.44 (s, 3H). 19 F NMR (471 MHz, CDCl3) δ -61.66. 13 C NMR (126 MHz, CDCl3) δ 170.37, 153.87, 142.28, 138.46, 130.48, 129.96, 128.88, 127.73, 123.25, 122.25, 121.42, 121.39, 120.29, 120.26, 21.66. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 15 H 11 F3NS+ 294.0559, found 294.0553.

[0142] Example 19

[0143]

[0144] A method for cross-electrophilic coupling reaction of arylsulfone compound and aryl halide, specifically comprising the following steps:

[0145] To an electrolysis reaction flask, 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in sequence. After adding solvent DMF (0.1 M concentration) and stirring for 15 minutes at room temperature, the electrochemical reaction workstation was opened, with stainless steel as the anode and foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (70% yield).

[0146] 1 H NMR (500 MHz, CDC13) δ 7.94 (dd, J = 9.9, 8.0 Hz, 3H), 7.64 (s, 1H), 7.27 (dd, J = 9.3, 3.8 Hz, 3H), 2.47 (s, 3H), 2.40 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 167.28, 152.39, 141.24, 135.21, 131.19, 129.77, 127.92, 127.44, 122.63, 121.44, 21.64, 21.61.

[0147] Example 20

[0148]

[0149] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0150] To an electrolysis reaction flask, 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in sequence. After adding solvent DMF (0.1 M concentration) and stirring for 15 minutes at room temperature, the electrochemical reaction workstation was opened, with stainless steel as the anode and foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (70% yield).

[0151] 1H NMR (500 MHz, CDCI3) δ 7.92 (dd, J = 8.5, 3.5 Hz, 3H), 7.34 - 7.29 (m, 1 H), 7.26 (d, J = 7.8 Hz, 2H), 7.07 (dd, J = 8.9, 2.6 Hz, 1 H), 3.86 (t, J = 2.5 Hz, 3H), 2.40 (s, 3H). 13 C NMR (126 MHz, CDCI3) δ 165.84, 157.74, 148.84, 141.00, 136.40, 131.21, 129.76, 127.26, 123.62, 115.56, 104.29, 55.87, 21.56.

[0152] Example 21

[0153]

[0154] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0155] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain light yellow solid product (81% yield).

[0156] 1 H NMR (500 MHz, CDCI3) δ 7.98 (dd, J = 8.9, 4.8 Hz, 1 H), 7.93 (d, J = 8.0 Hz, 2H), 7.56 (dd, J = 8.1, 2.6 Hz, 1 H), 7.29 (d, J = 7.9 Hz, 2H), 7.21 (td, J = 9.8, 9.4, 2.9 Hz, 1 H), 2.42 (s, 3H). 19 F NMR (471 MHz, CDCI3) δ -116.07. 13C NMR (126 MHz, CDCI3) δ 168.07, 168.05, 161.45, 159.50, 150.89, 141.63, 136.05, 135.96, 130.79, 129.87, 127.45, 124.03, 123.96, 115.02, 114.82, 108.00, 107.79, 21.61.

[0157] Example 22

[0158]

[0159] A method for cross electrophilic coupling reaction of aryl sulfone compound with aryl halide, specifically comprising the following steps:

[0160] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (44% yield).

[0161] 1 H NMR (500 MHz, CDCI3) δ 7.94 (dd, J = 8.5, 2.8 Hz, 3H), 7.85 (d, J = 2.1 Hz, 1H), 7.42 (dd, J = 8.7, 2.1 Hz, 1H), 7.29 (d, J = 7.9 Hz, 2H), 2.42 (s, 3H). 13 C NMR (126 MHz, CDCI3) δ 168.83, 152.79, 141.91, 136.19, 130.94, 130.64, 129.90, 127.57, 127.15, 123.82, 121.28, 21.65.

[0162] Example 23

[0163]

[0164] A method for cross electrophilic coupling reaction of aryl sulfone compound with aryl halide, specifically comprising the following steps:

[0165] To an electrolysis reaction flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added successively, and stirred at room temperature for 15 min after adding solvent DMF (0.1 M concentration). Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 h. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a light yellow solid product (59% yield).

[0166] 1 H NMR (500 MHz, CDCl3) δ 8.18 (s, 1H), 8.12 (d, J = 8.5 Hz, 1H), 7.99 (d, J = 8.1 Hz, 2H), 7.71 (d, J = 8.6 Hz, 1H), 7.32 (d, J = 7.9 Hz, 2H), 2.43 (s, 3H). 19 F NMR (471 MHz, CDCl3) δ -61.10. 13 C NMR (126 MHz, CDCl3) δ 171.41, 156.22, 142.43, 135.09, 130.48, 129.98, 127.80, 125.40, 124.79, 123.37, 119.34, 21.69. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 15 H 11 F3NS+ 294.0559, found 294.0554.

[0167] Example 24

[0168]

[0169] A method for cross-electrophilic coupling reaction of arylsulfone compound and aryl halide, specifically comprising the following steps:

[0170] To an electrolysis reaction flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added successively, and stirred at room temperature for 15 minutes after adding solvent DMF (concentration 0.1 M). Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a yellow solid product (25% yield).

[0171] 1 H NMR (500 MHz, CDCl3) δ 8.61 (s, 1H), 8.14 (d, J = 10.2 Hz, 1H), 8.05 (d, J = 8.5 Hz, 1H), 7.99 (d, J = 8.1 Hz, 2H), 7.31 (d, J = 7.9 Hz, 2H), 3.96 (s, 3H), 2.43 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 171.82, 166.80, 157.21, 142.34, 134.96, 130.66, 129.95, 127.80, 127.62, 126.79, 123.90, 122.77, 52.45, 21.69. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 16 H 14 NO2S+284.0740, found 284.0738.

[0172] Example 25

[0173]

[0174] A method for cross-electrophilic coupling reaction of arylsulfone compound and aryl halide, specifically comprising the following steps:

[0175] To an electrolysis reaction flask, 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in sequence, after adding solvent DMF (concentration 0.1 M) and stirring for 15 minutes at room temperature. Subsequently, the electrochemical reaction station was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (65% yield).

[0176] 1 H NMR (500 MHz, CDCl3) δ 8.91 (d, J = 9.5 Hz, 1H), 8.08 (d, J = 8.2 Hz, 2H), 7.94 (d, J = 8.1 Hz, 1H), 7.90 (d, J = 8.7 Hz, 1H), 7.79 (d, J = 8.7 Hz, 1H), 7.68 (t, J = 8.2 Hz, 1H), 7.58 (t, J = 7.5 Hz, 1H), 7.31 (d, J = 7.7 Hz, 2H), 2.43 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 167.37, 150.53, 141.07, 132.15, 131.56, 131.46, 129.82, 128.83, 128.15, 127.35, 126.96, 126.15, 125.77, 124.15, 119.08, 21.63.

[0177] Example 26

[0178]

[0179] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0180] To an electrolysis reaction flask, 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in sequence, after adding solvent DMF (concentration 0.1 M) and stirring for 15 minutes at room temperature. Subsequently, the electrochemical reaction station was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (65% yield).

[0181] 1 H NMR (500 MHz, CDCI3) δ 8.55 (dd, J = 4.7, 1.5 Hz, 1 H), 8.26 (dd, J = 8.2, 1.6 Hz, 1 H), 7.99 (d, J = 8.2 Hz, 2 H), 7.43 (dd, J = 8.2, 4.7 Hz, 1 H), 7.32 (d, J = 7.6 Hz, 2 H), 2.44 (s, 3 H). 13 C NMR (126 MHz, CDCI3) δ 168.94, 158.51, 147.42, 146.87, 142.31, 130.89, 129.94, 129.88, 127.65, 121.50, 21.66.

[0182] Example 27

[0183]

[0184] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0185] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (40% yield).

[0186] 1 H NMR (500 MHz, CDCI3) δ 8.55 (dd, J = 4.7, 1.5 Hz, 1 H), 8.26 (dd, J = 8.2, 1.6 Hz, 1 H), 7.99 (d, J = 8.2 Hz, 2 H), 7.43 (dd, J = 8.2, 4.7 Hz, 1 H), 7.32 (d, J = 7.6 Hz, 2 H), 2.44 (s, 3 H). 13 C NMR (126 MHz, CDCI3) δ 168.94, 158.51, 147.42, 146.87, 142.31, 130.89, 129.94, 129.88, 127.65, 121.50, 21.66.

[0187] Example 28

[0188]

[0189] A method for cross electrophilic coupling reaction of aryl sulfone compound with aryl halide, specifically comprising the following steps:

[0190] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and stirred at room temperature for 15 minutes after adding solvent DMF (concentration 0.1 M). Subsequently, the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (27% yield).

[0191] 1 H NMR (500 MHz, CDCl3) δ 7.88-7.81 (m, 3H), 7.30-7.22 (m, 3H), 2.39 (s, 3H). 13 CNMR (126 MHz, CDCl3) δ 168.72, 143.61, 140.33, 131.07, 129.74, 126.60, 118.43, 21.50.

[0192] Example 29

[0193]

[0194] A method for cross electrophilic coupling reaction of aryl sulfone compound with aryl halide, specifically comprising the following steps:

[0195] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and stirred at room temperature for 15 minutes after adding solvent DMF (concentration 0.1 M). Subsequently, the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (27% yield).

[0196] 1H NMR (500 MHz, CDC13) δ 8.40 (s, 1H), 7.87 (d, J = 8.2 Hz, 2H), 7.27 (d, J = 8.2 Hz, 2H), 3.92 (s, 3H), 2.41 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 173.82, 162.01, 149.39, 141.88, 130.42, 129.92, 128.13, 126.95, 52.51, 21.59. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 12 H 12 NO2S+234.0583, found 234.0579.

[0197] Example 30

[0198]

[0199] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0200] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode and foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a yellow solid product (48% yield).

[0201] 1 H NMR (500 MHz, CDC13) δ 8.40 (s, 1H), 7.87 (d, J = 8.2 Hz, 2H), 7.27 (d, J = 8.2 Hz, 2H), 3.92 (s, 3H), 2.41 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 167.50, 140.40, 139.10, 138.84, 131.59, 131.12, 129.75, 129.18, 128.29, 126.71, 126.36, 21.52.

[0202] Example 31

[0203]

[0204] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0205] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle. After adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with zinc sheet as anode, foamed nickel as cathode, constant current 15 milliampere for electrolysis for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation, and the residue was purified by silica gel column chromatography to obtain yellow solid product (63% yield).

[0206] 1 H NMR (500 MHz, CDCl3) δ 7.99 (d, J = 7.0 Hz, 2H), 7.93 (d, J = 8.2 Hz, 2H), 7.48-7.40 (m, 3H), 7.34 (t, J = 7.4 Hz, 1H), 7.25 (d, J = 8.4 Hz, 2H), 2.40 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 168.07, 156.14, 140.30, 134.63, 131.17, 129.62, 128.75, 128.13, 126.55, 126.47, 112.20, 21.48. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 16 H 14 NS+252.0841, found 252.0835.

[0207] Example 32

[0208]

[0209] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0210] To an electrolysis cell, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2- diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were added sequentially. After the addition of solvent DMF (0.1 M concentration), the mixture was stirred for 15 min at room temperature. Subsequently, the electrochemical reaction station was turned on with zinc sheet as anode and foamed nickel as cathode. The electrolysis was carried out at a constant current of 15 mA for 10 h. Finally, the reaction solution was passed through a short celite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography to give the product as a white solid (62% yield).

[0211] 1 H NMR (500 MHz, CDC13) δ 8.00 (d, J = 7.9 Hz, 2H), 7.72 (d, J = 7.0 Hz, 2H), 7.44 (t, J = 7.7 Hz, 3H), 7.33 (t, J = 7.4 Hz, 1H), 7.29 (d, J = 7.8 Hz, 2H), 2.41 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 161.52, 151.06, 140.75, 129.64, 129.02, 128.42, 128.22, 126.34, 124.87, 124.24, 123.42, 21.65.

[0212] Example 33

[0213]

[0214] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0215] To an electrolysis cell, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2- diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were added sequentially. After the addition of solvent DMF (0.1 M concentration), the mixture was stirred for 15 min at room temperature. Subsequently, the electrochemical reaction station was turned on with zinc sheet as anode and foamed nickel as cathode. The electrolysis was carried out at a constant current of 15 mA for 10 h. Finally, the reaction solution was passed through a short celite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography to give the product as a white solid (62% yield).

[0216] 1H NMR (500 MHz, DMSO-d6) δ 12.81 (s, 1H), 8.03 (d, J = 7.9 Hz, 2H), 7.60 (s, 1H), 7.47 (s, 1H), 7.32 (d, J = 7.9 Hz, 2H), 7.15 (s, 2H), 2.34 (s, 3H). 13 C NMR (126 MHz, DMSO-d6) δ 151.91, 144.31, 140.13, 135.46, 130.07, 127.95, 126.92, 122.88, 122.13, 119.22, 111.74, 21.51.

[0217] Example 34

[0218]

[0219] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0220] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle. After adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with zinc sheet as anode and foamed nickel as cathode, constant current 15 milliampere for electrolysis for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (68% yield).

[0221] 1 H NMR (500 MHz, CDCl3) δ 9.45 (s, 1H), 8.51 (d, J = 8.2 Hz, 2H), 8.11-8.03 (d, J = 8.2 Hz, 1H), 7.94-7.86 (m, 2H), 7.59 (ddd, J = 8.1, 6.9, 1.1 Hz, 1H), 7.34 (d, J = 7.9 Hz, 2H), 2.45 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 161.26, 160.54, 150.91, 140.97, 135.42, 134.14, 129.52, 128.66, 128.62, 127.22, 127.14, 123.62, 21.61.

[0222] Example 35

[0223]

[0224] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0225] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle. After adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with zinc sheet as anode, foamed nickel as cathode, constant current 15 milliampere for electrolysis for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (80% yield).

[0226] 1 H NMR (500 MHz, CDCl3) δ 8.32 (d, J = 8.0 Hz, 2H), 7.27 (d, J = 7.9 Hz, 2H), 6.89 (s, 1H), 2.53 (s, 6H), 2.41 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 166.73, 164.33, 140.48, 135.50, 129.28, 128.24, 117.75, 24.26, 21.53.

[0227] Example 36

[0228]

[0229] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0230] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle. After adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with zinc sheet as anode, foamed nickel as cathode, constant current 15 milliampere for electrolysis for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (80% yield).

[0231] 1H NMR (500 MHz, CDCI3) δ 8.17 (dd, J = 17.9, 8.6 Hz, 2H), 8.07 (d, J = 8.2 Hz, 2H), 7.86 (d, J = 8.6 Hz, 1 H), 7.81 (d, J = 8.1 Hz, 1 H), 7.71 (t, J = 7.7 Hz, 1 H), 7.55 - 7.47 (m, 1 H), 7.33 (d, J = 7.9 Hz, 2H), 2.43 (s, 3H). 13 C NMR (126 MHz, CDCI3) δ 157.43, 148.40, 139.50, 136.98, 136.76, 129.77, 129.68, 127.53, 127.20, 126.18, 118.96, 21.44.

[0232] Example 37

[0233]

[0234] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0235] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with zinc sheet as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (46% yield).

[0236] 1 H NMR (500 MHz, CDCI3) δ 9.32 (s, 1 H), 8.13 (dd, J = 17.8, 8.2 Hz, 4H), 7.76 (ddd, J = 15.1, 13.5, 6.8 Hz, 2H), 7.38 (d, J = 7.9 Hz, 2H), 2.46 (s, 3H). 13 C NMR (126 MHz, CDCI3) δ 151.96, 143.43, 142.44, 141.55, 140.62, 134.09, 130.31, 130.01, 129.64, 129.41, 129.20, 127.54, 21.53.

[0237] Example 38

[0238]

[0239] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0240] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle. After adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with zinc sheet as anode, foamed nickel as cathode, constant current 15 milliampere for electrolysis for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (52% yield).

[0241] 1 H NMR (500 MHz, CDCl3) δ 8.60 (d, J = 5.7 Hz, 1H), 8.14 (d, J = 8.6 Hz, 1H), 7.88 (d, J = 8.2 Hz, 1H), 7.69 (t, J = 7.6 Hz, 1H), 7.62 (dd, J = 14.5, 6.9 Hz, 3H), 7.54 (t, J = 7.7 Hz, 1H), 7.35 (d, J = 7.8 Hz, 2H), 2.47 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 160.86, 142.22, 138.61, 136.99, 136.69, 130.09, 129.97, 129.15, 127.82, 127.19, 127.07, 126.83, 119.83, 21.47.

[0242] Example 39

[0243]

[0244] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0245] To an electrolysis reaction flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were added in turn, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with zinc sheet as anode, foamed nickel as cathode, constant current 15 milliampere electrolysis for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (43% yield).

[0246] 1 H NMR (500 MHz, CDCl3) δ 8.70 (d, J = 8.3 Hz, 1H), 8.61 (d, J = 8.2 Hz, 1H), 8.23 (d, J = 8.2 Hz, 1H), 8.13 (d, J = 8.2 Hz, 1H), 7.88-7.83 (m, 1H), 7.75 (t, J = 6.9 Hz, 1H), 7.68 (t, J = 7.6 Hz, 1H), 7.65-7.59 (m, 3H), 7.36 (d, J = 7.8 Hz, 2H), 2.47 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 161.42, 144.13, 139.33, 137.06, 133.58, 130.64, 130.38, 129.81, 129.21, 129.20, 128.94, 127.19, 126.95, 125.40, 123.79, 122.29, 122.03, 21.51.

[0247] Example 40

[0248]

[0249] A method for cross electrophilic coupling reaction of arylsulfone compound and aryl halide, specifically comprising the following steps:

[0250] To an electrolysis cell, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2- diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were added successively. After the addition of solvent DMF (0.1 M concentration), the mixture was stirred for 15 min at room temperature. Subsequently, the electrochemical workstation was turned on, with zinc sheet as anode and foamed nickel as cathode, and electrolysis was carried out at a constant current of 15 mA for 10 h. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation. The residue was purified by silica gel column chromatography to obtain the product as a colorless liquid (41% yield).

[0251] 1 H NMR (500 MHz, CDC13) δ 8.59 (d, J = 5.3 Hz, 1H), 7.82 (d, J = 8.0 Hz, 2H), 7.67 - 7.59 (m, 2H), 7.20 (d, J = 7.9 Hz, 2H), 7.13 - 7.09 (m, 1H), 2.32 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 157.49, 149.62, 138.97, 136.71, 136.64, 129.51, 126.79, 121.82, 120.27, 21.30.

[0252] Example 41

[0253]

[0254] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0255] To an electrolysis cell, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2- diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were added successively. After the addition of solvent DMF (0.1 M concentration), the mixture was stirred for 15 min at room temperature. Subsequently, the electrochemical workstation was turned on, with zinc sheet as anode and foamed nickel as cathode, and electrolysis was carried out at a constant current of 15 mA for 10 h. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation. The residue was purified by silica gel column chromatography to obtain the product as a colorless liquid (41% yield).

[0256] 1H NMR (500 MHz, CDCI3) δ 9.26 (d, J = 2.3 Hz, 1 H), 8.35 - 8.29 (m, 1 H), 7.96 (d, J = 7.9 Hz, 2 H), 7.79 (d, J = 8.3 Hz, 1 H), 7.31 (d, J = 8.2 Hz, 2 H), 3.97 (s, 3 H), 2.42 (s, 3 H). 13 CNMR (126 MHz, CDCI3) δ 165.96, 160.92, 150.92, 140.24, 137.81, 135.47, 129.65, 127.24, 123.86, 119.48, 52.31, 21.35.

[0257] Example 42

[0258]

[0259] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0260] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with zinc sheet as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure and rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (82% yield).

[0261] 1 H NMR (500 MHz, CDCI3) δ 8.92 (s, 1 H), 7.98 - 7.91 (m, 3 H), 7.82 (d, J = 8.3 Hz, 1 H), 7.31 (d, J = 8.1 Hz, 2 H). 19 F NMR (471 MHz, CDCI3) δ -62.08. 13 C NMR (126 MHz, CDCI3) δ 160.76, 146.65, 140.42, 135.26, 133.95, 129.80, 127.24, 124.70, 122.83, 119.70, 21.44.

[0262] Example 43

[0263]

[0264] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0265] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle. After adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with zinc sheet as anode, foamed nickel as cathode, constant current 15 milliampere for electrolysis for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (71% yield).

[0266] 1 H NMR (500 MHz, CDCl3) δ 8.84 (d, J = 5.0 Hz, 1H), 7.95-7.88 (m, 3H), 7.41 (d, J = 3.5 Hz, 1H), 7.31 (d, J = 8.0 Hz, 2H), 2.43 (s, 3H). 19 F NMR (471 MHz, CDCl3) δ -64.72. 13 C NMR (126 MHz, CDCl3) δ 158.88, 150.64, 140.16, 139.28, 135.35, 129.80, 126.99, 124.17, 117.30, 115.78, 21.41.

[0267] Example 44

[0268]

[0269] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0270] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle. After adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode, foamed nickel as cathode, constant current 15 milliampere for electrolysis for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (89% yield).

[0271] 1 H NMR (500 MHz, CDC13) δ 8.13 - 8.06 (m, 3H), 7.91 (d, J = 8.0 Hz, 1H), 7.53 - 7.47 (m, 4H), 7.42 - 7.36 (m, 1H). 13 C NMR (126 MHz, CDC13) δ 168.18, 154.26, 135.17, 133.73, 131.07, 129.13, 127.67, 126.42, 125.29, 123.35, 121.73.

[0272] Example 45

[0273]

[0274] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0275] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode and foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (86% yield).

[0276] 1 H NMR (500 MHz, CDC13) δ 8.13 - 8.06 (m, 3H), 7.91 (d, J = 8.0 Hz, 1H), 7.53 - 7.47 (m, 4H), 7.42 - 7.36 (m, 1H). 13 C NMR (126 MHz, CDC13) δ 168.18, 154.26, 135.17, 133.73, 131.07, 129.13, 127.67, 126.42, 125.29, 123.35, 121.73.

[0277] Example 46

[0278]

[0279] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0280] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle. After adding solvent DMF (concentration 0.1 M) and stirring at room temperature for 15 minutes, the electrochemical reaction workstation was opened. The stainless steel was used as the anode, the foamed nickel was used as the cathode, and the electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography to obtain a white solid product (88% yield).

[0281] 1 H NMR (500 MHz, CDCl3) δ 8.05-7.99 (m, 3H), 7.86 (d, J = 8.0 Hz, 1H), 7.46 (ddd, J = 8.3, 7.1, 1.3 Hz, 1H), 7.37-7.31 (m, 1H), 7.02-6.96 (m, 2H), 3.86 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 167.96, 162.02, 154.33, 134.96, 129.21, 126.53, 126.30, 124.89, 122.92, 121.61, 114.46, 55.55.

[0282] Example 47

[0283]

[0284] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0285] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle. After adding solvent DMF (concentration 0.1 M) and stirring at room temperature for 15 minutes, the electrochemical reaction workstation was opened. The stainless steel was used as the anode, the foamed nickel was used as the cathode, and the electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography to obtain a white solid product (88% yield).

[0286] 1H NMR (500 MHz, CDCI3) δ 8.15 - 8.10 (m, 2H), 8.08 (d, J = 8.2 Hz, 1H), 7.93 - 7.88 (d, J = 8.0 Hz, 1H), 7.51 (ddd, J = 8.3, 7.2, 1.3 Hz, 1H), 7.43 - 7.38 (m, 1H), 7.37 - 7.30 (m, 2H). 19 FNMR (471 MHz, CDCI3) δ -57.57. 13 C NMR (126 MHz, CDCI3) δ 166.31, 154.20, 151.14, 135.24, 132.30, 129.18, 126.61, 125.57, 123.49, 121.77, 121.31.

[0287] Example 48

[0288]

[0289] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0290] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a light yellow solid product (72% yield).

[0291] 1 H NMR (500 MHz, CDCI3) δ 7.89 (dd, J = 11.9, 8.8 Hz, 3H), 7.75 (d, J = 9.1 Hz, 1H), 7.39 - 7.33 (m, 1H), 7.25 - 7.19 (m, 1H), 6.66 (d, J = 8.8 Hz, 2H), 2.96 (d, J = 0.9 Hz, 3H). 13 C NMR (126 MHz, CDCI3) δ 168.91, 154.53, 152.27, 134.66, 127.06, 126.08, 124.28, 122.38, 121.48, 121.45, 111.78, 40.27.

[0292] Example 49

[0293]

[0294] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0295] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode and foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (67% yield).

[0296] 1 H NMR (500 MHz, CDCI3) δ 8.09 (dd, J = 8.5, 2.5 Hz, 3H), 7.92 (t, J = 8.3 Hz, 3H), 7.50 (t, J = 7.7 Hz, 1H), 7.39 (t, J = 7.6 Hz, 1H), 1.37 (s, 12H). 13 C NMR (126 MHz, CDCI3) δ 168.09, 154.23, 135.92, 135.47, 135.22, 126.77, 126.48, 125.42, 123.43, 121.74, 84.21, 24.98.

[0297] Example 50

[0298]

[0299] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0300] A mixture of 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr was added into the electrolysis reaction bottle in turn, and stirred at room temperature for 15 minutes after adding solvent DMF (concentration 0.1 M). Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (50% yield).

[0301] 1 H NMR (500 MHz, DMSO-d6) δ 10.22 (s, 1H), 8.07 (d, J = 7.9 Hz, 1H), 7.95 (dd, J = 21.6, 8.2 Hz, 3H), 7.50 (t, J = 7.7 Hz, 1H), 7.40 (t, J = 7.6 Hz, 1H), 6.94 (d, J = 8.4 Hz, 2H). 13 CNMR (126 MHz, DMSO-d6) δ 168.00, 161.07, 154.27, 134.64, 129.58, 126.96, 125.44, 124.58, 122.84, 122.65, 116.62.

[0302] Example 51

[0303]

[0304] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0305] A mixture of 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr was added into the electrolysis reaction bottle in turn, and stirred at room temperature for 15 minutes after adding solvent DMF (concentration 0.1 M). Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (50% yield).

[0306] 1H NMR (500 MHz, CDCI3) δ 8.20 - 8.16 (m, 2H), 8.10 (d, J = 8.2 Hz, 1H), 8.08 - 8.03 (m, 2H), 7.92 (d, J = 8.0 Hz, 1H), 7.54 - 7.49 (m, 1H), 7.41 (ddd, J = 8.3, 7.1, 1.2 Hz, 1H), 2.65 (s, 3H). 13 C NMR (126 MHz, CDCI3) δ 197.41, 166.54, 154.24, 138.67, 137.61, 135.40, 129.08, 127.76, 126.73, 125.85, 123.73, 121.84, 26.85.

[0307] Example 52

[0308]

[0309] A method for cross-electrophilic coupling reaction of aryl sulfone compound with aryl halide, specifically comprising the following steps:

[0310] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain light yellow solid product (57% yield).

[0311] 1 H NMR (500 MHz, CDCI3) δ 8.18 (d, J = 8.1 Hz, 2H), 8.10 (d, J = 8.2 Hz, 1H), 7.91 (d, J = 8.0 Hz, 1H), 7.73 (d, J = 8.1 Hz, 2H), 7.52 (ddd, J = 8.3, 7.1, 1.3 Hz, 1H), 7.41 (td, J = 7.6, 7.1, 1.2 Hz, 1H). 13 C NMR (126 MHz, CDCI3) δ 166.12, 154.14, 136.86, 135.31, 132.41, 127.86, 126.75, 126.11, 126.08, 125.88, 123.73, 121.83.

[0312] Example 53

[0313]

[0314] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0315] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode and foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (40% yield).

[0316] 1 H NMR (500 MHz, CDCl3) δ 8.17 (d, J = 1.4 Hz, 4H), 8.11 (d, J = 8.2 Hz, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.53 (t, J = 7.7 Hz, 1H), 7.43 (t, J = 7.4 Hz, 1H), 4.42 (q, J = 7.1 Hz, 2H), 1.43 (t, J = 7.1 Hz, 3H). 13 C NMR (126 MHz, CDCl3) δ 166.77, 166.05, 154.22, 137.46, 135.37, 132.50, 130.32, 127.49, 126.69, 125.79, 123.68, 121.83, 61.41, 14.42.

[0317] Example 54

[0318]

[0319] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0320] To an electrolysis reaction flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in sequence. After adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction station was opened, with stainless steel as anode, foamed nickel as cathode, constant current 15 milliampere, electrolysis for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (49% yield).

[0321] 1 H NMR (500 MHz, CDC13) δ 8.19 (d, J = 8.1 Hz, 2H), 8.10 (d, J = 8.2 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.77 (d, J = 8.0 Hz, 2H), 7.53 (t, J = 7.7 Hz, 1H), 7.44 (t, J = 7.6 Hz, 1H). 13 CNMR (126 MHz, CDC13) δ 165.44, 154.13, 137.60, 135.41, 132.88, 128.03, 126.93, 126.18, 123.92, 121.91, 118.38, 114.23.

[0322] Example 55

[0323]

[0324] A method for cross-electrophilic coupling reaction of arylsulfone compound and aryl halide, specifically comprising the following steps:

[0325] To an electrolysis reaction flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in sequence. After adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction station was opened, with stainless steel as anode, foamed nickel as cathode, constant current 15 milliampere, electrolysis for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (49% yield).

[0326] 1H NMR (500 MHz, CDCI3) δ 8.06 (d, J = 8.2 Hz, 1 H), 7.98 - 7.92 (m, 2 H), 7.89 (d, J = 8.0 Hz, 1 H), 7.62 (d, J = 8.6 Hz, 2 H), 7.49 (ddd, J = 8.4, 7.2, 1.3 Hz, 1 H), 7.42 - 7.37 (m, 1 H). 13 C NMR (126 MHz, CDCI3) δ 166.80, 154.18, 138.29, 135.15, 132.66, 132.33, 129.00, 126.60, 125.55, 123.42, 121.77.

[0327] Example 56

[0328]

[0329] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0330] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2.diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain yellow solid product (71 % yield).

[0331] 1 H NMR (500 MHz, CDCI3) δ 8.06 (d, J = 8.2 Hz, 1 H), 7.98 - 7.92 (m, 2 H), 7.89 (d, J = 8.0 Hz, 1 H), 7.62 (d, J = 8.6 Hz, 2 H), 7.49 (ddd, J = 8.4, 7.2, 1.3 Hz, 1 H), 7.42 - 7.37 (m, 1 H). 13 C NMR (126 MHz, CDCI3) δ 166.80, 154.18, 138.29, 135.15, 132.66, 132.33, 129.00, 126.60, 125.55, 123.42, 121.77.

[0332] Example 57

[0333]

[0334] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0335] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle. After adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain yellow solid product (63% yield).

[0336] 1 H NMR (500 MHz, CDCl3) δ 8.07 (d, J = 8.1 Hz, 1H), 7.94 (s, 1H), 7.90 (d, J = 7.9 Hz, 1H), 7.87 (d, J = 7.7 Hz, 1H), 7.51-7.46 (m, 1H), 7.41-7.36 (m, 2H), 7.31 (d, J = 7.6 Hz, 1H), 2.45 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 168.46, 154.22, 138.99, 135.13, 133.61, 131.93, 129.03, 128.09, 126.40, 125.23, 124.97, 123.27, 121.71, 21.46.

[0337] Example 58

[0338]

[0339] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0340] To an electrolysis reaction flask, 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in turn, and after adding solvent DMF (concentration 0.1 M), stirring was carried out at room temperature for 15 minutes. Subsequently, the electrochemical reaction station was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliamperes for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a brown solid product (56% yield).

[0341] 1 H NMR (500 MHz, DMSO-d6) δ 9.87 (t, J = 2.1 Hz, 1H), 8.14 (d, J = 8.0 Hz, 1H), 8.06 (d, J = 8.1 Hz, 1H), 7.60-7.50 (m, 3H), 7.47 (t, J = 7.5 Hz, 1H), 7.38 (t, J = 7.8 Hz, 1H), 6.99 (d, J = 8.0 Hz, 1H). 13 C NMR (126 MHz, DMSO-d6) δ 167.90, 158.54, 154.07, 134.92, 134.59, 131.08, 127.15, 126.04, 123.40, 122.84, 119.09, 118.64, 113.99.

[0342] Example 59

[0343]

[0344] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0345] To an electrolysis reaction flask, 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in turn, and after adding solvent DMF (concentration 0.1 M), stirring was carried out at room temperature for 15 minutes. Subsequently, the electrochemical reaction station was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliamperes for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (75% yield).

[0346] 1H NMR (500 MHz, CDCI3) δ 8.07 (d, J = 8.2 Hz, 1 H), 7.90 (dd, J = 8.0, 1.2 Hz, 1 H), 7.71 (s, 2 H), 7.48 (ddd, J = 8.3, 7.2, 1.3 Hz, 1 H), 7.38 (ddd, J = 8.2, 7.2, 1.2 Hz, 1 H), 7.13 (s, 1 H), 2.41 (s, 6 H). 13 C NMR (126 MHz, CDCI3) δ 168.68, 154.20, 138.84, 135.09, 133.53, 132.88, 126.35, 125.44, 125.15, 123.20, 121.69, 21.33.

[0347] Example 60

[0348]

[0349] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0350] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain yellow brown solid product (49% yield).

[0351] 1 H NMR (500 MHz, CDCI3) δ 8.07 (d, J = 8.2 Hz, 1 H), 7.90 (dd, J = 8.0, 1.2 Hz, 1 H), 7.71 (s, 2 H), 7.48 (ddd, J = 8.3, 7.2, 1.3 Hz, 1 H), 7.38 (ddd, J = 8.2, 7.2, 1.2 Hz, 1 H), 7.13 (s, 1 H), 2.41 (s, 6 H). 19 F NMR (471 MHz, CDCI3) δ -62.86. 13 C NMR (126 MHz, CDCI3) δ 164.17, 153.96, 135.72, 135.25, 132.83, 132.56, 127.42, 127.07, 126.35, 124.12, 123.96, 121.95.

[0352] Example 61

[0353]

[0354] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0355] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle. After adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode, foamed nickel as cathode, constant current 15 milliampere for electrolysis for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation, and the residue was purified by silica gel column chromatography to obtain yellow solid product (91% yield).

[0356] 1 H NMR (500 MHz, CDCl3) δ 8.02 (d, J = 8.5 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.72 (s, 2H), 7.45 (t, J = 7.7 Hz, 1H), 7.33 (t, J = 7.6 Hz, 1H), 5.61 (s, 1H), 2.31 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ 168.63, 155.34, 154.21, 134.86, 128.17, 126.28, 125.71, 124.78, 124.10, 122.73, 121.59, 16.08. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 15 H 14 ONS+256.0791, found 256.0784.

[0357] Example 62

[0358]

[0359] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0360] To an electrolysis reaction flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in turn, and after adding solvent DMF (concentration 0.1 M), stirring was carried out at room temperature for 15 minutes. Subsequently, the electrochemical reaction station was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (87% yield).

[0361] 1 H NMR (500 MHz, CDC13) δ 8.06 (d, J = 8.0 Hz, 1H), 7.90 (d, J = 7.9 Hz, 1H), 7.50 (t, J = 7.7 Hz, 1H), 7.41 - 7.37 (m, 1H), 7.34 (s, 2H), 3.99 (s, 6H), 3.93 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 167.92, 154.15, 153.69, 140.74, 135.12, 129.16, 126.46, 125.24, 123.17, 121.66, 104.86, 61.12, 56.47.

[0362] Example 63

[0363]

[0364] A method for cross-electrophilic coupling reaction of arylsulfone compound and aryl halide, specifically comprising the following steps:

[0365] To an electrolysis reaction flask, 1.0 equivalent of arylsulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in turn, and after adding solvent DMF (concentration 0.1 M), stirring was carried out at room temperature for 15 minutes. Subsequently, the electrochemical reaction station was opened, with stainless steel as the anode, foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a yellow solid product (72% yield).

[0366] 1H NMR (500 MHz, CDC13) δ 8.94 (td, J = 7.9, 3.4 Hz, 1H), 8.20 (dt, J = 8.0, 3.4 Hz, 1H), 8.02 - 7.90 (m, 4H), 7.62 (ddd, J = 8.6, 6.8, 2.1 Hz, 1H), 7.56 (ddt, J = 10.4, 7.3, 3.3 Hz, 3H), 7.44 (t, J = 7.7 Hz, 1H). 13 C NMR (126 MHz, CDC13) δ 167.73, 154.29, 135.59, 134.14, 131.20, 130.97, 130.78, 129.52, 128.53, 127.76, 126.64, 126.40, 126.01, 125.42, 125.12, 123.69, 121.52.

[0367] Example 64

[0368]

[0369] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0370] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode and foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain white solid product (46% yield).

[0371] 1 H NMR (500 MHz, CDC13) δ 8.94 (td, J = 7.9, 3.4 Hz, 1H), 8.20 (dt, J = 8.0, 3.4 Hz, 1H), 8.02 - 7.90 (m, 4H), 7.62 (ddd, J = 8.6, 6.8, 2.1 Hz, 1H), 7.56 (ddt, J = 10.4, 7.3, 3.3 Hz, 3H), 7.44 (t, J = 7.7 Hz, 1H). 13C NMR (126 MHz, CDCI3) δ 169.48, 154.40, 151.54, 149.76, 137.10, 136.25, 126.37, 125.74, 125.36, 123.69, 122.11, 120.87.

[0372] Example 65

[0373]

[0374] A method for cross electrophilic coupling reaction of aryl sulfone compound with aryl halide, specifically comprising the following steps:

[0375] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2.diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain brown solid product (89% yield).

[0376] 1 H NMR (500 MHz, CDCI3) δ 9.29 (s, 1H), 8.74-8.67 (m, 1H), 8.36 (dt, J = 7.9, 2.0 Hz, 1H), 8.10 (d, J = 8.2 Hz, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.52 (t, J = 7.7 Hz, 1H), 7.46-7.38 (m, 2H). 13 C NMR (126 MHz, CDCI3) δ 164.66, 154.06, 151.71, 148.71, 135.07, 134.62, 129.79, 126.72, 125.80, 123.87, 123.59, 121.83.

[0377] Example 66

[0378]

[0379] A method for cross electrophilic coupling reaction of aryl sulfone compound with aryl halide, specifically comprising the following steps:

[0380] A mixture of 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr was added into the electrolysis reaction bottle in turn, and stirred at room temperature for 15 minutes after adding solvent DMF (concentration 0.1 M). Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a yellow solid product (55% yield).

[0381] 1 H NMR (500 MHz, CDC13) δ 8.77 (d, J = 5.1 Hz, 2H), 8.12 (d, J = 8.2 Hz, 1H), 8.01 - 7.86 (m, 3H), 7.54 (t, J = 7.7 Hz, 1H), 7.46 (q, J = 7.6, 6.3 Hz, 1H). 13 CNMR (126 MHz, CDC13) δ 165.17, 154.06, 150.84, 140.55, 135.30, 126.90, 126.29, 124.01, 121.95, 121.28.

[0382] Example 67

[0383]

[0384] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0385] A mixture of 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr was added into the electrolysis reaction bottle in turn, and stirred at room temperature for 15 minutes after adding solvent DMF (concentration 0.1 M). Then the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a yellow solid product (55% yield).

[0386] 1H NMR (500 MHz, CDC13) δ 9.05 (d, J = 4.5 Hz, 1H), 9.00 (dd, J = 8.6, 1.4 Hz, 1H), 8.23 (dd, J = 10.9, 8.2 Hz, 2H), 8.01 (d, J = 7.9 Hz, 1H), 7.84 - 7.77 (m, 2H), 7.69 (ddd, J = 8.3, 6.8, 1.3 Hz, 1H), 7.64 - 7.57 (m, 1H), 7.56 - 7.48 (m, 1H). 13 C NMR (126 MHz, CDC13) δ 164.89, 154.26, 149.89, 149.28, 138.41, 135.45, 130.11, 130.08, 128.26, 126.84, 126.25, 126.15, 125.06, 124.19, 122.28, 121.72.

[0387] Example 68

[0388]

[0389] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0390] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode and foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliampere for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a yellow solid product (61% yield).

[0391] 1 H NMR (500 MHz, CDC13) δ 8.98 (dd, J = 4.3, 1.7 Hz, 1H), 8.56 (d, J = 2.0 Hz, 1H), 8.44 (dd, J = 8.8, 2.0 Hz, 1H), 8.28 (dd, J = 8.3, 1.7 Hz, 1H), 8.22 (d, J = 8.8 Hz, 1H), 8.13 (d, J = 8.2 Hz, 1H), 7.95 (d, J = 7.8 Hz, 1H), 7.53 (ddd, J = 8.3, 7.2, 1.2 Hz, 1H), 7.48 (dd, J = 8.3, 4.1 Hz, 1H), 7.45 - 7.40 (m, 1H).13 C NMR (126 MHz, CDC13) δ 167.11, 154.30, 151.77, 149.41, 136.89, 135.35, 131.77, 130.53, 128.31, 128.29, 127.24, 126.67, 125.63, 123.52, 122.14, 121.82. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 16 H 11 N2S +263.0637, found 263.0630.

[0392] Example 69

[0393]

[0394] A method for cross-electrophilic coupling reaction of aryl sulfone compound with aryl halide, specifically comprising the following steps:

[0395] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were sequentially added into the electrolysis reaction bottle, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as the anode and foamed nickel as the cathode, and electrolysis was carried out at a constant current of 15 milliampere for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (53% yield).

[0396] 1 H NMR (500 MHz, CDC13) δ 8.08 (d, J = 8.2 Hz, 1H), 7.91-7.81 (m, 4H), 7.51-7.47 (m, 1H), 7.40 (td, J = 7.6, 6.7, 3.8 Hz, 3H). 13 C NMR (126 MHz, CDC13) δ 161.57, 153.79, 140.92, 139.64, 137.26, 135.09, 126.67, 126.26, 125.73, 125.40, 125.10, 124.68, 123.44, 122.72, 121.63.

[0397] Example 70

[0398]

[0399] A method for cross electrophilic coupling reaction of aryl sulfone compound with aryl halide, specifically comprising the following steps:

[0400] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added into the electrolysis reaction bottle in turn, and after adding solvent DMF (concentration 0.1 M), it was stirred at room temperature for 15 minutes. Subsequently, the electrochemical reaction workstation was opened, with stainless steel as anode and foamed nickel as cathode, and electrolysis was carried out at constant current of 15 milliampere for 10 hours. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain yellow solid product (43% yield).

[0401] 1 H NMR (500 MHz, CDCl3) δ 8.04 (d, J = 6.0 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.61 (s, 1H), 7.57-7.44 (m, 3H), 7.42-7.28 (m, 3H), 4.07 (s, 2H). 13 C NMR (126 MHz, CDCl3) δ 163.50, 153.40, 143.14, 143.07, 140.11, 134.31, 134.22, 126.38, 126.16, 125.69, 124.68, 123.54, 122.39, 121.78, 120.89, 38.89. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 16 H 12 NS+250.0685, found 250.0682.

[0402] Example 71

[0403]

[0404] A method for cross electrophilic coupling reaction of aryl sulfone compound with aryl halide, specifically comprising the following steps:

[0405] To an electrolysis reaction flask, 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in turn, and after adding solvent DMF (concentration 0.1 M), stirring was carried out at room temperature for 15 minutes. Subsequently, the electrochemical reaction station was opened, and electrolysis was carried out for 10 hours at a constant current of 15 milliampere with stainless steel as the anode and foamed nickel as the cathode. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a yellow solid product (68% yield).

[0406] 1 H NMR (500 MHz, CDC13) δ 7.97 (d, J = 8.2 Hz, 1H), 7.82 (d, J = 7.9 Hz, 1H), 7.42 (t, J = 7.1 Hz, 1H), 7.33 (t, J = 7.6 Hz, 1H), 6.81 (t, J = 4.1 Hz, 1H), 2.71 - 2.64 (m, 2H), 2.35 - 2.27 (m, 2H), 1.81 (p, J = 6.0 Hz, 2H), 1.72 (p, J = 6.0 Hz, 2H). 13 C NMR (126 MHz, CDC13) δ 170.69, 153.84, 134.21, 134.18, 133.49, 125.98, 124.93, 122.92, 121.42, 26.53, 26.16, 22.41, 22.05.

[0407] Example 72

[0408]

[0409] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, specifically comprising the following steps:

[0410] To an electrolysis reaction flask, 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, 1.0 equivalent of electrolyte LiBr were added in turn, and after adding solvent DMF (concentration 0.1 M), stirring was carried out at room temperature for 15 minutes. Subsequently, the electrochemical reaction station was opened, and electrolysis was carried out for 10 hours at a constant current of 15 milliampere with stainless steel as the anode and foamed nickel as the cathode. Finally, the reaction solution was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a yellow solid product (68% yield).

[0411] 1H NMR (500 MHz, CDC13) δ 7.99 (d, J = 8.1 Hz, 1H), 7.93 - 7.88 (m, 2H), 7.85 (d, J = 7.8 Hz, 1H), 7.45 (ddd, J = 8.3, 7.2, 1.2 Hz, 1H), 7.32 (ddd, J = 8.2, 7.2, 1.1 Hz, 1H), 6.77 - 6.72 (m, 2H), 4.00 (s, 2H). 13 C NMR (126 MHz, CDC13) δ 168.97, 153.92, 142.17, 137.22, 134.60, 126.39, 125.64, 123.47, 121.76, -1.47. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 12 H 16 NSSi+234.0767, found 234.0762.

[0412] Example 73

[0413]

[0414] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, the embodiment provides a new method for synthesizing a drug CJM, and specifically comprises the following steps:

[0415] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, and 1.0 equivalent of electrolyte LiBr are sequentially added into an electrolysis reaction bottle, and after adding a solvent DMF (concentration 0.1 M), stirring is carried out at room temperature for 15 minutes. Subsequently, an electrochemical reaction workstation is opened, stainless steel is used as an anode, foamed nickel is used as a cathode, and electrolysis is carried out at a constant current of 15 milliamperes for 10 hours. Finally, the reaction solution is washed with dichloromethane through a short diatomite column, the organic solvent is removed under the condition of reduced pressure and rotary evaporation, and the residue is purified through a silica gel column chromatography to obtain a yellow solid product (78% yield).

[0416] 1 H NMR (500 MHz, CDC13) δ 7.99 (d, J = 8.1 Hz, 1H), 7.93 - 7.88 (m, 2H), 7.85 (d, J = 7.8 Hz, 1H), 7.45 (ddd, J = 8.3, 7.2, 1.2 Hz, 1H), 7.32 (ddd, J = 8.2, 7.2, 1.1 Hz, 1H), 6.77 - 6.72 (m, 2H), 4.00 (s, 2H). 13C NMR (126 MHz, CDC13) δ 168.59, 154.36, 149.31, 134.69, 129.25, 126.16, 124.55, 124.08, 122.60, 121.51, 114.88.

[0417] Example 74

[0418]

[0419] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, the embodiment provides a new method for synthesizing drug 5F203, and specifically comprises the following steps:

[0420] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, and 1.0 equivalent of electrolyte LiBr are sequentially added into an electrolysis reaction bottle, and after adding a solvent DMF (concentration 0.1 M), stirring is performed at room temperature for 15 minutes. Subsequently, an electrochemical reaction workstation is opened, stainless steel is used as an anode, foamed nickel is used as a cathode, and electrolysis is performed at a constant current of 15 milliampere for 10 hours. Finally, the reaction solution is passed through a short diatomite column, washed with dichloromethane, and the organic solvent is removed under reduced pressure and rotary evaporation, and the residue is purified by silica gel column chromatography to obtain a yellow solid product (81% yield).

[0421] 1 H NMR (500 MHz, DMSO-d6) δ 8.00 (dd, J = 8.8, 5.4 Hz, 1H), 7.67 (dd, J = 10.0, 2.5 Hz, 1H), 7.64 (d, J = 2.6 Hz, 1H), 7.60 (dd, J = 8.3, 2.3 Hz, 1H), 7.19 (td, J = 9.0, 2.6 Hz, 1H), 6.67 (d, J = 8.3 Hz, 1H), 5.69 (s, 2H), 2.10 (s, 3H). 19 F NMR (471 MHz, DMSO-d6) δ -116.33. 13 C NMR (126 MHz, DMSO-d6) δ 171.59, 162.82 (d, J = 240.6 Hz), 155.47 (d, J = 12.2 Hz), 151.21, 130.01, 129.78, 127.16, 123.62 (d, J = 10.7 Hz), 121.54, 120.56, 114.10, 112.79 (d, J = 25.1 Hz), 108.20 (d, J = 23.4 Hz), 17.88.

[0422] Example 75

[0423]

[0424] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, the embodiment provides a new method for synthesizing a drug PMX610, and specifically comprises the following steps:

[0425] 1.0 equivalent of aryl sulfone compound, 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, and 1.0 equivalent of electrolyte LiBr are sequentially added into an electrolysis reaction bottle, and after adding a solvent DMF (concentration 0.1 M), stirring is performed at room temperature for 15 minutes. Subsequently, an electrochemical reaction workstation is opened, a stainless steel is used as an anode, a foamed nickel is used as a cathode, and electrolysis is performed at a constant current of 15 milliampere for 10 hours. Finally, the reaction solution is passed through a short diatomite column, washed with dichloromethane, and the organic solvent is removed under the condition of reduced pressure rotary evaporation, and the residue is purified by silica gel column chromatography to obtain a white solid product (73% yield).

[0426] 1 H NMR (500 MHz, DMSO-d6) δ 8.14 (dd, J = 5.4, 8.8 Hz, 1H), 7.85 (dd, J = 2.6, 9.8 Hz, 1H), 7.63 (m, 2H), 7.39 - 7.28 (dt, J = 2.5, 9.6 Hz, 1H), 7.19 - 7.08 (d, J = 9.0 Hz, 1H), 3.90 (s, 3H), 3.87 (s, 3H). 19 F NMR (471 MHz, DMSO-d6) δ -115.71. 13 C NMR (126 MHz, DMSO-d6) δ 170.58, 162.90, 160.98, 155.09, 155.00, 152.39, 149.67, 130.63, 125.88, 124.04, 123.96, 121.57, 114.08, 113.89, 112.49, 109.93, 109.13, 108.94, 56.28, 56.17.

[0427] Example 76

[0428]

[0429] A method for cross electrophilic coupling reaction of aryl sulfone compound and aryl halide, the embodiment provides a new method for synthesizing a drug Camalexin, and specifically comprises the following steps:

[0430] 1.0 equivalent of an aryl sulfone compound, 1.0 equivalent of an aryl halide, 10 mol% of the catalyst NiBr2·diglyme, 10 mol% of the ligand Me2bpydc, and 1.0 equivalent of the electrolyte LiBr were sequentially added to an electrolysis flask. DMF (0.1 M) solvent was added, and the mixture was stirred at room temperature for 15 minutes. Then, an electrochemical workstation was turned on, and electrolysis was performed for 10 hours at a constant current of 15 mA using stainless steel as the anode and nickel foam as the cathode. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed by rotary evaporation under reduced pressure. The residue was purified by silica gel column chromatography to obtain a white solid product (42% yield).

[0431] 1 H NMR (500MHz, CDCl3) δ8.95 (s, 1H), 8.25 (d, J = 8.8Hz, 1H), 7.84 (dd, J = 7.7, 3.0 Hz,2H),7.40(dd,J=6.3,2.9Hz,1H),7.32–7.27(m,2H),7.25(d,J=3.2Hz,1H). 13 C NMR (126MHz, CDCl3) δ163.46,142.52,136.51,124.73,124.69,123.25,121.53,120.59,116.11,112.42,111.77.

[0432] Example 77

[0433]

[0434] A method for the cross-electrophilic coupling reaction of an aryl sulfone compound and an aryl halide, specifically including the following steps: This embodiment provides a method for the first synthesis of the drug Octaverine.

[0435] 1.0 equivalent of an aryl sulfone compound, 1.0 equivalent of an aryl halide, 10 mol% of the catalyst NiBr2·diglyme, 10 mol% of the ligand bipy, and 1.0 equivalent of the electrolyte LiBr were sequentially added to an electrolysis flask. DMF (0.1 M) solvent was added, and the mixture was stirred at room temperature for 15 minutes. Then, an electrochemical workstation was turned on, and electrolysis was performed for 10 hours at a constant current of 15 mA using a zinc sheet as the anode and nickel foam as the cathode. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed by rotary evaporation under reduced pressure. The residue was purified by silica gel column chromatography to obtain a white solid product (49% yield).

[0436] 1H NMR (500 MHz, CDC13) δ 8.45 (d, J = 5.6 Hz, 1H), 7.49 (d, J = 4.9 Hz, 1H), 7.43 (s, 1H), 7.12 (s, 1H), 6.90 (s, 2H), 4.19 - 4.09 (m, 6H), 4.05 (s, 3H), 3.88 (s, 3H), 1.42 (dt, J = 18.7, 7.0 Hz, 9H). 13 C NMR (126 MHz, CDC13) δ 158.36, 153.02, 152.76, 150.03, 141.25, 138.21, 135.16, 133.88, 122.57, 118.77, 108.39, 105.79, 105.07, 68.99, 64.77, 56.19, 56.04, 15.72, 15.11. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 13 H 28 NO5+398.1962, found 398.1949.

[0437] Example 78

[0438]

[0439] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, the embodiment provides a new method for synthesizing a drug Thioflavine T, and specifically comprises the following steps:

[0440] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand Me2bpydc, and 1.0 equivalent of electrolyte LiBr are sequentially added into an electrolysis reaction bottle, and after adding a solvent DMF (concentration 0.1 M), stirring is carried out at room temperature for 15 minutes. Subsequently, an electrochemical reaction workstation is opened, stainless steel is used as an anode, foamed nickel is used as a cathode, and electrolysis is carried out at a constant current of 15 milliamperes for 10 hours. Finally, the reaction solution is passed through a short diatomite column, washed with dichloromethane, and the organic solvent is removed under the condition of reduced pressure rotary evaporation, and the residue is purified by silica gel column chromatography to obtain a light yellow solid product (78% yield).

[0441] 1 H NMR (500 MHz, CDC13) δ 8.45 (d, J = 5.6 Hz, 1H), 7.49 (d, J = 4.9 Hz, 1H), 7.43 (s, 1H), 7.12 (s, 1H), 6.90 (s, 2H), 4.19 - 4.09 (m, 6H), 4.05 (s, 3H), 3.88 (s, 3H), 1.42 (dt, J = 18.7, 7.0 Hz, 9H). 13C NMR (126 MHz, CDCI3) δ 167.90, 152.58, 152.14, 134.78, 134.32, 128.80, 127.59, 121.88, 121.65, 121.30, 111.80, 40.29, 21.58.

[0442] The solid was then stirred with iodomethane at 95 °C for 4 hours, then cooled to room temperature. It was dispersed in Amberlite IRA-400 with methanol and heated to boiling for 30 minutes, then filtered, extracted with chloroform, and the organic solvent was removed by rotary evaporation under reduced pressure to obtain the yellow solid product Thioflavine T (76% yield).

[0443] 1 H NMR (500 MHz, DMSO-d6) δ 8.17 (s, 1H), 8.11 (d, J = 8.6 Hz, 1H), 7.79 (d, J = 9.0 Hz, 2H), 7.66 (d, J = 8.7 Hz, 1H), 6.93 (d, J = 9.1 Hz, 2H), 4.19 (s, 3H), 3.08 (s, 6H), 2.46 (s, 3H). 13 C NMR (126 MHz, DMSO-d6) δ 173.16, 154.17, 141.51, 138.56, 132.79, 131.07, 128.71, 123.94, 117.11, 112.53, 111.50, 79.82, 38.74, 21.54.

[0444] Example 79

[0445]

[0446] A method for cross-electrophilic coupling reaction of aryl sulfone compound and aryl halide, the embodiment provides a new method for synthesizing a drug Cinchophen, and specifically comprises the following steps:

[0447] 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, and 1.0 equivalent of electrolyte LiBr were sequentially added into an electrolysis reaction bottle, and after adding a solvent DMF (concentration 0.1 M), stirring was performed at room temperature for 15 minutes. Then, an electrochemical reaction workstation was opened, a zinc sheet was used as an anode, a foamed nickel was used as a cathode, and electrolysis was performed at a constant current of 15 milliamperes for 10 hours. Finally, the reaction liquid was passed through a short diatomite column, washed with dichloromethane, and the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (76% yield).

[0448] 1 H NMR (500 MHz, CDC13) δ 8.75 (d, J = 8.6 Hz, 1H), 8.42 (s, 1H), 8.26 - 8.19 (m, 3H), 7.78 (t, J = 7.0 Hz, 1H), 7.64 (ddd, J = 8.3, 6.8, 1.3 Hz, 1H), 7.55 (t, J = 7.5 Hz, 2H), 7.50 (d, J = 7.4 Hz, 1H), 4.08 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 166.97, 156.83, 149.37, 138.89, 135.71, 130.43, 130.03, 129.84, 129.05, 127.92, 127.57, 125.52, 124.09, 120.46, 52.86.

[0449] The solid was dissolved in a mixture of methanol and water at room temperature, 5 equivalents of potassium hydroxide was added, followed by heating to 60°C until the raw material was completely reacted. After acidification by dilute hydrochloric acid, the organic solvent was removed under reduced pressure by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (93% yield).

[0450] 1 H NMR (500 MHz, DMSO-d6) δ 8.65 (d, J = 8.5 Hz, 1H), 8.45 (s, 1H), 8.30 (d, J = 7.7 Hz, 2H), 8.17 (d, J = 8.5 Hz, 1H), 7.85 (t, J = 7.7 Hz, 1H), 7.70 (t, J = 7.7 Hz, 1H), 7.57 (dt, J = 15.3, 7.2 Hz, 3H). 13 C NMR (126 MHz, DMSO-d6) δ 168.29, 156.35, 148.93, 138.68, 138.48, 130.74, 130.52, 130.29, 129.54, 128.24, 127.75, 126.02, 124.03, 119.54.

[0451] Example 80

[0452]

[0453] A method for cross-electrophilic coupling reaction of an aryl sulfone compound and an aryl halide, the embodiment provides a new route for synthesizing a drug Perafensine, which specifically comprises the following steps:

[0454] The initial material, 1,3-dibromoisoquinoline, was dissolved in 20 mL of DMF, followed by the addition of sodium thiomethoxide at room temperature, stirred for 1 hour, diluted with water and extracted with ethyl acetate, washed with water and saturated brine in turn, removed the organic solvent under reduced pressure, and the residue was purified by silica gel column chromatography to obtain a white solid product (97% yield).

[0455] 1 H NMR (500 MHz, CDC13) δ 8.12 (d, J = 8.3 Hz, 1H), 7.65 (t, J = 3.3 Hz, 2H), 7.53 (d, J = 6.8 Hz, 2H), 2.70 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 161.65, 137.18, 134.79, 131.14, 127.30, 126.34, 125.85, 124.71, 119.59, 13.34. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 10 H9BrNS+253.9634, found 253.9626.

[0456] One equivalent of the resulting white solid was added to 4 equivalents of N-tert-butoxycarbonylpiperazine, 5 mol% of Pd2(dba)3, 10 mol% of RuPhos, and 1.5 equivalents of sodium tert-butoxide in 1,4-dioxane, heated to 100°C and stirred open for 15 minutes. After cooling to room temperature, washed with ethyl acetate through a short diatomite column, removed the organic solvent under reduced pressure, and the residue was purified by silica gel column chromatography to obtain a yellow oily product (99% yield).

[0457] 1 H NMR (500 MHz, CDC13) δ 7.99 (d, J = 8.5 Hz, 1H), 7.53 (d, J = 8.3 Hz, 1H), 7.51-7.45 (m, 1H), 7.26-7.22 (m, 1H), 6.47 (s, 1H), 3.65-3.54 (m, 8H), 2.66 (s, 3H), 1.50 (s, 9H). 13 C NMR (126 MHz, CDC13) δ 159.07, 155.12, 154.93, 138.53, 130.38, 125.96, 124.55, 123.29, 122.21, 95.52, 80.01, 46.05, 28.54, 13.11. HRMS (ESI+) m / z: [M+H]+ Calcd. for C 19 H 26 N3O2S+360.1740, found 360.1722.

[0458] Dissolve 1 equivalent of yellow oil in ethanol, add 0.2 equivalent of sodium tungstate at 0 °C and stir for 5 minutes, then add 4 equivalents of hydrogen peroxide, slowly raise to room temperature and stir for 10 hours. Quench with aqueous sodium thiosulfate, extract with dichloromethane, remove the organic solvent under reduced pressure, and purify the residue by silica gel column chromatography to obtain the yellow solid sulfone product (80% yield).

[0459] 1 H NMR (500 MHz, CDC13) δ 8.70 (d, J = 8.7 Hz, 1H), 7.64 (d, J = 8.4 Hz, 1H), 7.59 - 7.54 (m, 1H), 7.38 (ddd, J = 8.7, 6.8, 1.2 Hz, 1H), 6.96 (s, 1H), 3.61 (t, J = 5.8 Hz, 4H), 3.56 (d, J = 7.2 Hz, 4H), 3.45 (s, 3H), 1.49 (s, 9H). 13 C NMR (126 MHz, CDC13) δ 155.01, 154.78, 153.42, 141.05, 131.35, 126.23, 125.54, 124.88, 117.77, 103.98, 80.30, 45.79, 40.56, 28.51. HRMS (ESI+) m / z: [M + Na]+ Calcd. for C 19 H 25 N3O4SNa + 414.1458, found 414.1440.

[0460] Dissolve 1.0 equivalent of aryl sulfone compound and 1.0 equivalent of aryl halide, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr in an electrolysis reaction bottle, add solvent DMF (0.1 M concentration) and stir for 15 minutes at room temperature. Then open the electrochemical reaction station, use zinc sheet as anode and foamed nickel as cathode, electrolyze for 10 hours under constant current of 15 milliampere. Finally, pass the reaction solution through a short diatomite column, wash with dichloromethane, remove the organic solvent under reduced pressure, and purify the residue by silica gel column chromatography to obtain the yellow solid product (57% yield).

[0461] 1H NMR (500 MHz, CDC13) δ 7.93 (d, J = 8.5 Hz, 1 H), 7.75 - 7.69 (m, 2 H), 7.65 (d, J = 8.3 Hz, 1 H), 7.56 - 7.43 (m, 4 H), 7.21 (t, J = 7.0 Hz, 1 H), 6.79 (s, 1 H), 3.62 (s, 8 H), 1.49 (s, 9 H). 13 C NMR (126 MHz, CDC13) δ 159.41, 155.48, 154.97, 140.06, 139.87, 130.16, 129.99, 128.58, 128.24, 127.68, 125.96, 123.51, 121.75, 98.87, 79.95, 46.11, 28.54. HRMS (ESI+) m / z: [M + Na]+ Calcd. for C 24 H 27 N3O2Na+ 412.1995, found 412.1974.

[0462] The resulting yellow solid was dissolved in dichloromethane and 40 equivalents of trifluoroacetic acid were added, followed by stirring at room temperature for 3 hours. After the addition water was extracted with dichloromethane, washed with saturated aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate, the organic solvent was removed under reduced pressure and oil pump dried to obtain the final yellow product perafensine (99% yield).

[0463] 1 H NMR (500 MHz, CDC13) δ 7.92 (d, J = 8.5 Hz, 1 H), 7.74 - 7.70 (m, 2 H), 7.64 (d, J = 8.3 Hz, 1 H), 7.49 (dt, J = 13.0, 6.8 Hz, 4 H), 7.19 (t, J = 7.0 Hz, 1 H), 6.78 (s, 1 H), 3.63 - 3.58 (m, 4 H), 3.09 - 3.03 (m, 4 H), 1.68 (s, 1 H). 13 C NMR (126 MHz, CDC13) δ 159.25, 156.08, 140.12, 140.04, 130.20, 129.85, 128.49, 128.21, 127.68, 125.94, 123.23, 121.60, 98.45, 47.35, 46.09. HRMS (ESI+) m / z: [M + Na]+ Calcd. for C 19 H20N3+ 290.1652, found 290.1637.

[0464] Applications

[0465]

[0466] A method for cross electrophilic coupling reaction of aryl sulfone compound with aryl halide, the embodiment provides a preparation method of an organic polymer polymer P(2, 6-Q) prepared by electrochemical polymerization, and specifically comprises the following steps:

[0467] 1.0 equivalent of bromo aryl sulfone compound, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr are sequentially added into an electrolysis reaction bottle, and after the addition of solvent DMF (concentration 0.1 M), stirring is carried out at room temperature for 15 minutes. Then, the electrochemical reaction workstation is opened, zinc sheet is used as an anode, foamed nickel is used as a cathode, and electrolysis is carried out at a constant current of 15 milliampere for 10 hours. Finally, the reaction solution is poured into methanol, the obtained polymer solid is filtered and washed with ammonia water, then the solid is sequentially subjected to soxhlet extraction with acetone, n-hexane and chloroform, the obtained chloroform solution is subjected to rotary evaporation under reduced pressure to remove the organic solvent, the obtained solid is dissolved in concentrated hydrochloric acid, and then the polymer solid is reprecipitated by using concentrated ammonia water, filtered, washed with water and dried to obtain a dark red solid polymer product (83% yield).

[0468] GPC (CHCl3, 25℃): M n = 13.9 kDa, M w = 23.5 kDa, 1 H NMR (500 MHz, CDCl3)

[0469] δ 8.74 (br, 1H), 8.41-7.90 (br, 2H), 7.80-7.50 (br, 1H), 3.31 (br, 2H), 1.97 (br, 2H), 1.62 (br, 2H), 1.08 (br, 3H). Analysis (calcd., found for (C 13 H 13 N) n ): C (85.21, 84.76), H (7.15, 6.88), N (7.64, 7.05).

[0470] Table 1 Optical, electrical and thermal properties of polymer P(2, 6-Q)

[0471]

[0472] Although the embodiments of the present application are disclosed for illustrative purposes, those skilled in the art can understand that various substitutions, changes and modifications are possible without departing from the spirit and scope of the present application and the appended claims, and therefore, the scope of the present application is not limited to the disclosed content of the embodiments.

Claims

1. A method for cross electrophilic coupling of an arylsulfone compound with an aryl halide, characterized in that: The preparation method of the biaromatic compound comprises the following steps: wherein Ar 1 , Ar 2 denote identical or different aryl systems; X represents I, Br, Cl; R represents alkyl, aryl; The catalyst is nickel(II) bromide diethylene glycol dimethyl ether complex, the ligand is 2,2'-bipyridine or 2,2'-bipyridine-5,5'-dimethyl acid dimethyl ester, the electrolyte is LiBr, and the solvent is N,N-dimethylformamide; the stainless steel sheet or zinc sheet is used as the anode, and the nickel foam is used as the cathode.

2. The cross electrophilic coupling reaction method of an aryl sulfone compound with an aryl halide according to claim 1, characterized by: The aryl halide is any one of the following compounds: wherein R is an independent C1-C 15 alkyl chain or aryl group; The alkyl chain includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl; The aryl includes phenyl, naphthyl and substituted aryl; R is also trifluoromethyl, difluoromethyl, ethenyl and substituted aryl; R 1 is independently C1-C 15 alkyl chain, halogen or aryl; The alkyl chain includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl; The halogen includes fluorine, chlorine and bromine; The aryl includes phenyl, naphthyl and substituted aryl; R 1 is hydroxyl, carbonyl, cyano, amine, ester, aldehyde, boronate ester, trifluoromethyl, alkoxy, ester.

3. The process according to claim 2, characterized in that it is a cross electrophilic coupling reaction of aryl sulfone compounds with aryl halides. The aryl halide is any one of the following compounds: X is a chlorine atom, a bromine atom or an iodine atom; wherein R 2 is an independent C1-C 15 alkyl chain, alkoxy chain or aryl group, The alkyl chain includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl; The alkoxy chain includes methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy and pentadecyloxy; The aryl includes phenyl, naphthyl and substituted aryl; R 2 is each independently hydrogen, halogen, hydroxy, carbonyl, cyano, amine, ester, aldehyde, boronate ester, trifluoromethyl, difluoromethyl, vinyl, or aryl each substituted with one or more of halogen, hydroxy, carbonyl, cyano, amine, ester, aldehyde, boronate ester, trifluoromethyl, difluoromethyl, vinyl, or aryl.

4. The process according to claim 3, characterized in that it is a cross electrophilic coupling reaction of aryl sulfone compounds with aryl halides. The method specifically comprises the following steps: S1, the reactants aryl sulfone compound and aryl halide, catalyst nickel(II) bromide diethylene glycol dimethyl ether complex, ligand 2,2'-bipyridine or 2,2'-bipyridine-5,5'-dimethyl acid dimethyl ester, electrolyte LiBr are sequentially added into an electrolysis reaction bottle, then the solvent N,N-dimethylformamide is added, and stirring is carried out at room temperature for 10-20 minutes; S2, the electrochemical reaction workstation is opened, the stainless steel sheet or zinc sheet is used as the anode, the nickel foam is used as the cathode, and electrolysis is carried out under a constant current of 10-20 mA for 8-12 hours; S3, the reaction solution is passed through a diatomite column, washed with dichloromethane, the organic solvent is removed under the condition of reduced pressure rotary evaporation, and the residual product is purified by silica gel column chromatography to obtain the target product.

5. The process according to claim 4, characterized in that it is a cross electrophilic coupling reaction of aryl sulfone compounds with aryl halides. The molar ratio of the aryl sulfone compound, the aryl halide, the catalyst, the ligand and N,N-dimethylformamide is 10:10:1:1:

100.

6. The process according to claim 5, characterized in that it is a cross electrophilic coupling reaction of an arylsulfone compound with an arylhalide. The eluent of the silica gel column chromatography is petroleum ether and dichloromethane, and the ratio of the petroleum ether and dichloromethane is 10:

1.

7. The method for the cross-electrophilic coupling reaction of aryl sulfone compounds and aryl halides according to claim 6, characterized in that: The aryl sulfone compounds and aryl halides, under electrolysis at room temperature, achieve cross electrophilic coupling to construct C(sp 2 )-C(sp 2 ).

8. Use of the cross electrophilic coupling reaction of the arylsulphone compound of any one of claims 1 to 7 with an aryl halide in the preparation of organic macromolecular polymers.

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