Cross electrophilic coupling reaction method of aryl sulfone compound and aryl halide

Abstract

The invention relates to a cross electrophilic coupling reaction method of aryl sulfone compounds and aryl halides. A series of (hetero) biaryl structure compounds are obtained. The reaction does not need anhydrous and anaerobic protection, is driven by electrochemistry at room temperature, takes a nickel bromide (II) diethylene glycol dimethyl ether compound as a catalyst, takes 2, 2 '-bipyridine or 2, 2'-bipyridine-5, 5 '-dimethyl phthalate 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, and takes nickel hydroxide as a cathode. The preparation method comprises the following steps: placing an aryl sulfone compound and aryl halide in N, N-dimethylformamide, respectively electrifying a positive electrode and a negative electrode for 10 hours, and carrying out column chromatography purification by using an automatic column chromatography machine to obtain the biaryl compound. By adopting the method, not only can a series of important drug molecules be synthesized, but also electrochemical polymerization reaction can be performed.

Description

Technical Field

[0001] The present invention belongs to C(sp 2 )-C(sp 2 ) construction technology field, especially a cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide. Background Art

[0002] Biaromatic compounds are widely found in drugs, natural products, chemicals, ligands and functional molecules / polymeric materials. 2 )-C(sp 2 ) bonds to prepare biaromatic compounds is also an important goal of modern synthetic chemistry. Transition metal-catalyzed cross-coupling reactions are used as a tool to construct C(sp 2 )-C(sp 2 ) bonds, and was awarded the 2010 Nobel Prize in Chemistry due to its high efficiency and wide range of applications. However, traditional cross-coupling reactions need to be carried out between an electrophile and a nucleophile, where the nucleophile is usually an organometallic compound that is sensitive to water and air, and most of them are prepared from the corresponding aryl halides, which increases the number of synthetic steps, safety protection measures, and functional group compatibility considerations.

[0003] In recent years, reductive cross-coupling, which directly couples two electrophilic reagents in the presence of a metal reducing agent, avoids these disadvantages, but faces the dilemma of poor selectivity and the need for high temperatures in most reactions. Organic electrosynthesis uses renewable and readily available electricity to replace traditional redox reagents, thereby reducing the use of chemicals and waste generation, and can use electric potential to control selectivity. Electrochemical synthesis has the advantages of simple reaction equipment, low cost, and precise and controllable reaction conditions. It can avoid the use of metal elements and high temperatures in traditional reductive coupling and is a good choice for constructing C(sp 2 )-C(sp 2 ) key. Summary of the invention

[0004] The purpose of the present invention is 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 reduction coupling synthesis method.

[0005] The present invention solves the technical problem by adopting the following technical solutions:

[0006] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises using an aryl sulfone compound and an aryl halide as two electrophilic reagents respectively, adding a ligand and an electrolyte in sequence under a catalyst condition, adding a solvent, and coupling the two electrophilic reagents by electrochemical driving to prepare a biaromatic compound, wherein the general reaction formula is:

[0007]

[0008] Among them, Ar 1 ,Ar 2 denote the same or different aromatic systems;

[0009] X represents I, Br, Cl;

[0010] R represents an alkyl group or an aryl group.

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

[0012] Furthermore, the ligand is 2,2'-bipyridine or 2,2'-bipyridine-5,5'-dicarboxylic acid dimethyl ester;

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

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

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

[0016]

[0017] Where R is an independent C1-C 15 An alkyl chain or an aryl group;

[0018] Alkyl chains include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl;

[0019] Aryl includes phenyl, naphthyl, and substituted aromatic groups thereof;

[0020] R is also an aromatic group substituted by trifluoromethyl, difluoromethyl, or vinyl;

[0021] R 1 For independent C1-C 15 alkyl chains, halogens or aryl groups;

[0022] Alkyl chains include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl;

[0023] Halogens include fluorine, chlorine, and bromine;

[0024] Aryl includes phenyl, naphthyl, tolyl, and substituted aromatic groups thereof;

[0025] R 1 It can also be a hydroxyl group, a carbonyl group, a cyano group, an amine group, an ester group, an aldehyde group, a borate group, a trifluoromethyl group, an alkoxy group, or an ester group.

[0026] Furthermore, 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] Among them, R 2 For independent C1-C 15 an alkyl chain, an alkoxy chain or an aryl group,

[0030] Alkyl chains include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl;

[0031] Alkoxy chains include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy;

[0032] Aryl includes phenyl, naphthyl, and substituted aromatic groups thereof;

[0033] R 2 It may also be an aromatic group substituted by a hydroxyl group, a carbonyl group, a cyano group, an amine group, an ester group, an aldehyde group, a borate group, a trifluoromethyl group, a difluoromethyl group, or a vinyl group.

[0034] Furthermore, the method specifically comprises the following steps:

[0035] S1. Add the reactant aryl sulfone compound and aryl halide, the catalyst nickel bromide (II) diethylene glycol dimethyl ether complex, the ligand 2,2'-bipyridine or 2,2'-bipyridine-5,5'-dimethyl dicarboxylate, and the electrolyte LiBr to an electrolysis reaction bottle in sequence, and then add the solvent N,N-dimethylformamide, and stir at room temperature for 10-20 minutes;

[0036] S2. Turn on the electrochemical reaction workstation, use a stainless steel sheet or zinc sheet as the anode and nickel foam as the cathode, and perform electrolysis at a constant current of 10-20 mA for 8-12 hours;

[0037] S3. The reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was 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 eluents of the silica gel column chromatography are petroleum ether and dichloromethane, and the ratio of the petroleum ether to dichloromethane is 10:1.

[0040] Moreover, the aryl sulfone compound and the aryl halide can realize cross-electrophilic coupling under room temperature electrolysis to construct C(sp 2 )-C(sp 2 ).

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

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

[0043] 1. The preparation method of the present invention avoids the use of metal reducing agents, reduces the use of chemicals and the generation of waste, avoids the requirement of traditional heating, can be carried out at room temperature, is more environmentally friendly, and does not require inert gas protection, and is simpler and more convenient to operate. The reaction of the present invention has high selectivity and a wide range of substrates, can be applied to reaction systems of more than two grams, and can also obtain high yields; and can be used to synthesize a variety of drugs and modifications, and the reaction conditions are suitable for polymerization reactions to synthesize high molecular weight narrow distribution polymers.

[0044] 2. The present invention adopts a method of direct coupling of two electrophilic reagents, breaking through the limitation that the traditional cross-coupling reaction requires one electrophilic reagent and one nucleophilic reagent, and the nucleophilic reagent is mostly an organic metal compound sensitive to water and air, thereby reducing the number of synthesis steps and lowering the requirements for safety protection measures and functional group compatibility.

[0045] 3. The present invention utilizes electrochemical synthesis to replace traditional redox reagents with renewable electricity, reducing the use of chemicals and waste generation, which is in line with the concept of green chemistry. At the same time, by regulating selectivity through potential, the disadvantages of using metal elements and high temperatures in traditional reduction coupling can be avoided. The reaction device is simple, low-cost, and the reaction conditions are precisely controllable, which is easy to operate and apply on a large scale.

[0046] 4. The whole reaction process of the present invention has clear steps, from mixing and stirring of reactants, electrolytic reaction to post-treatment (filtration of diatomaceous earth column, washing, vacuum rotary evaporation and purification by silica gel column chromatography), the operating conditions of each step are relatively mild, and it is easy to implement in laboratory and industrial production. The cross-coupling of aryl sulfone compound and aryl halide can be achieved 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 structural types of the aryl sulfone compounds and aryl halides of the present invention are rich and varied, including various types of alkyl chains, aryl groups and different functional group substitutions, which can adapt to the synthesis of biaromatic compounds with various structural requirements, and provide powerful method support for the preparation of compounds containing biaromatic structures in the fields of drugs, natural products, chemicals, ligands and functional molecules / polymeric materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 The UV-visible absorption spectrum and photoluminescence spectrum of the polymer P(2,6-Q) of the present invention in chloroform solution are shown.

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

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

[0051] The present invention is further described in detail below through specific examples. The following examples are only illustrative and not restrictive, and the protection scope of the present invention cannot be limited thereto.

[0052] Example 1

[0053]

[0054] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0055] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (82% yield).

[0056] 1 H NMR (500MHz, CDCl3) δ8.06(d,J=8.2Hz,1H),7.99(d,J=7.9Hz,2H),7.89(d,J=8.0Hz,1H),7.48(d dd,J=8.3,7.1,1.2Hz,1H),7.37(td,J=7.6,7.1,1.0Hz,1H),7.30(d,J=7.8Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ168.36,154.27,141.53,135.05,131.07,129.82,127.58,126.33,125.10,123.14,121.67,21.61.

[0057] Example 2

[0058]

[0059] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0060] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (72% yield).

[0061] 1H NMR (500MHz, CDCl3) δ8.06(d,J=8.2Hz,1H),7.99(d,J=7.9Hz,2H),7.89(d,J=8.0Hz,1H),7.48(d dd,J=8.3,7.1,1.2Hz,1H),7.37(td,J=7.6,7.1,1.0Hz,1H),7.30(d,J=7.8Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ168.36,154.27,141.53,135.05,131.07,129.82,127.58,126.33,125.10,123.14,121.67,21.61.

[0062] Example 3

[0063]

[0064] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (54% yield).

[0066] 1 H NMR (500MHz, CDCl3) δ8.06(d,J=8.2Hz,1H),7.99(d,J=7.9Hz,2H),7.89(d,J=8.0Hz,1H),7.48(d dd,J=8.3,7.1,1.2Hz,1H),7.37(td,J=7.6,7.1,1.0Hz,1H),7.30(d,J=7.8Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ168.36,154.27,141.53,135.05,131.07,129.82,127.58,126.33,125.10,123.14,121.67,21.61.

[0067] Example 4

[0068]

[0069] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (58% yield).

[0071] 1 H NMR (500MHz, CDCl3) δ8.06(d,J=8.2Hz,1H),7.99(d,J=7.9Hz,2H),7.89(d,J=8.0Hz,1H),7.48(d dd,J=8.3,7.1,1.2Hz,1H),7.37(td,J=7.6,7.1,1.0Hz,1H),7.30(d,J=7.8Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ168.36,154.27,141.53,135.05,131.07,129.82,127.58,126.33,125.10,123.14,121.67,21.61.

[0072] Example 5

[0073]

[0074] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0075] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (51% yield).

[0076] 1 H NMR (500MHz, CDCl3) δ8.06(d,J=8.2Hz,1H),7.99(d,J=7.9Hz,2H),7.89(d,J=8.0Hz,1H),7.48(d dd,J=8.3,7.1,1.2Hz,1H),7.37(td,J=7.6,7.1,1.0Hz,1H),7.30(d,J=7.8Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ168.36,154.27,141.53,135.05,131.07,129.82,127.58,126.33,125.10,123.14,121.67,21.61.

[0077] Example 6

[0078]

[0079] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0080] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (35% yield).

[0081] 1H NMR (500MHz, CDCl3) δ8.06(d,J=8.2Hz,1H),7.99(d,J=7.9Hz,2H),7.89(d,J=8.0Hz,1H),7.48(d dd,J=8.3,7.1,1.2Hz,1H),7.37(td,J=7.6,7.1,1.0Hz,1H),7.30(d,J=7.8Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ168.36,154.27,141.53,135.05,131.07,129.82,127.58,126.33,125.10,123.14,121.67,21.61.

[0082] Example 7

[0083]

[0084] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (71% yield).

[0086] 1 H NMR (500MHz, CDCl3) δ8.06(d,J=8.2Hz,1H),7.99(d,J=7.9Hz,2H),7.89(d,J=8.0Hz,1H),7.48(d dd,J=8.3,7.1,1.2Hz,1H),7.37(td,J=7.6,7.1,1.0Hz,1H),7.30(d,J=7.8Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ168.36,154.27,141.53,135.05,131.07,129.82,127.58,126.33,125.10,123.14,121.67,21.61.

[0087] Example 8

[0088]

[0089] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (54% yield).

[0091] 1 H NMR (500MHz, CDCl3) δ8.06(d,J=8.2Hz,1H),7.99(d,J=7.9Hz,2H),7.89(d,J=8.0Hz,1H),7.48(d dd,J=8.3,7.1,1.2Hz,1H),7.37(td,J=7.6,7.1,1.0Hz,1H),7.30(d,J=7.8Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ168.36,154.27,141.53,135.05,131.07,129.82,127.58,126.33,125.10,123.14,121.67,21.61.

[0092] Example 9

[0093]

[0094] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0095] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (43% yield).

[0096] 1 H NMR (500MHz, CDCl3) δ8.06(d,J=8.2Hz,1H),7.99(d,J=7.9Hz,2H),7.89(d,J=8.0Hz,1H),7.48(d dd,J=8.3,7.1,1.2Hz,1H),7.37(td,J=7.6,7.1,1.0Hz,1H),7.30(d,J=7.8Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ168.36,154.27,141.53,135.05,131.07,129.82,127.58,126.33,125.10,123.14,121.67,21.61.

[0097] Example 10

[0098]

[0099] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0100] 1.0 equivalent of aryl sulfoxide 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (59% yield).

[0101] 1H NMR (500MHz, CDCl3) δ8.06(d,J=8.2Hz,1H),7.99(d,J=7.9Hz,2H),7.89(d,J=8.0Hz,1H),7.48(d dd,J=8.3,7.1,1.2Hz,1H),7.37(td,J=7.6,7.1,1.0Hz,1H),7.30(d,J=7.8Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ168.36,154.27,141.53,135.05,131.07,129.82,127.58,126.33,125.10,123.14,121.67,21.61.

[0102] Embodiment 11

[0103]

[0104] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (25% yield).

[0106] 1 H NMR (500MHz, CDCl3) δ8.06(d,J=8.2Hz,1H),7.99(d,J=7.9Hz,2H),7.89(d,J=8.0Hz,1H),7.48(d dd,J=8.3,7.1,1.2Hz,1H),7.37(td,J=7.6,7.1,1.0Hz,1H),7.30(d,J=7.8Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ168.36,154.27,141.53,135.05,131.07,129.82,127.58,126.33,125.10,123.14,121.67,21.61.

[0107] Example 12

[0108]

[0109] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (53% yield).

[0111] 1 H NMR (500MHz, CDCl3) δ7.99(d,J=8.2Hz,2H),7.71(dd,J=6.3,2.8Hz,1H),7.28(d,J=8.0Hz,2H),7.26–7.24(m,2H),2.79(s,3H),2.42(s,3H). 13 CNMR (126MHz, CDCl3) δ166.82,153.65,141.18,134.97,133.26,131.42,129.73, 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 cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0115] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (74% yield).

[0116] 1 H NMR (500MHz, CDCl3) δ8.01(d,J=8.2Hz,2H),7.65(d,J=8.0Hz,1H),7.32(dt,J=11.3,6.1Hz,3H),7.21–7.16(m,1H),2.43(s,3H). 19 F NMR(471MHz, CDCl3)δ–122.03. 13 CNMR (126MHz, CDCl3) δ168.89,156.96,154.92,141.94,137.69,137.66,130.61,129.83,127. 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] Embodiment 14

[0118]

[0119] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0120] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (80% yield).

[0121] 1 H NMR (500MHz, CDCl3) δ7.95(d,J=8.1Hz,2H),7.85(s,1H),7.73(d,J=8.1Hz,1H),7.27(d,J=7.9Hz,2H),7.18(d,J=8.1Hz,1H),2.49(s,3H),2.40(s,3H). 13 C NMR(126MHz, CDCl3)δ168.43,154.66,141.36,136.38,132.00,131.20,129.78,127.51,126.72,123.19,121.14,21.62.HRMS(ESI+)m / z:[M+H]+Calcd.for C 15 H 14 NS+240.0841, found 240.0840.

[0122] Embodiment 15

[0123]

[0124] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0125] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (70% yield).

[0126] 1 H NMR (500MHz, CDCl3) δ7.95 (d, J=8.0Hz, 2H), 7.79 (dd, J=8.8, 5.1Hz, 1H), 7.72 (dd, J=9.6,2.5Hz,1H),7.29(d,J=8.5Hz,2H),7.13(td,J=8.8,2.5Hz,1H),2.42(s,3H). 19 F NMR(471MHz, CDCl3)δ–115.82. 13 C NMR (126MHz, CDCl3) δ170.81,162.99,161.06,155.23,155.13,141.90,130.80,129.87,127.5 6,122.32,122.24,113.81,113.61,109.37,109.18,21.64.HRMS(ESI+)m / z:[M+H]+Calcd.for C 14 H 11 FNS+244.0591, found 244.0589.

[0127] Example 16

[0128]

[0129] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (41% yield).

[0131] 1 H NMR (500MHz, CDCl3) δ8.02(d,J=2.0Hz,1H),7.95(d,J=7.9Hz,2H),7.77(d,J=8.5Hz,1H),7.33(dd,J=8.5,2.0Hz,1H),7.29(d,J=7.9Hz,2H),2.42(s,3H).13 C NMR (126MHz, CDCl3) δ170.19,155.12,142.00,133.29,132.31,130.69,129.89,127.63,125.53,122.94,122.34,21.65.

[0132] Embodiment 17

[0133]

[0134] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (43% yield).

[0136] 1 H NMR (500MHz, CDCl3) δ8.18(d,J=1.9Hz,1H),7.95(d,J=8.1Hz,2H),7.73(d,J=8.4Hz,1H),7.46(dd,J=8.5,1.9Hz,1H),7.29(d,J=7.9Hz,2H),2.42(s,3H). 13 C NMR(126MHz, CDCl3)δ169.98,155.45,142.03,133.84,130.64,129.90,128.15,127.65,125.99,122.69,119.89.HRMS(ESI+)m / z:[M+H]+Calcd.for C 14 H 11 BrNS+303.9790, found303.9787.

[0137] Embodiment 18

[0138]

[0139] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0140] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (73% yield).

[0141] 1 H NMR (500MHz, CDCl3) δ8.31 (s, 1H), 7.99 (d, J = 6.2Hz, 3H), 7.60 (d, J = 8.4Hz, 1H), 7.32 (d, J = 7.8Hz, 2H), 2.44 (s, 3H). 19 F NMR(471MHz, CDCl3)δ–61.66. 13 C NMR (126MHz, CDCl3) δ170.37,153.87,142.28,138.46,130.48,129.96,128.88,127.73,1 23.25,122.25,121.42,121.39,120.29,120.26,21.66.HRMS(ESI+)m / z:[M+H]+Calcd.for C 15 H 11 F3NS+294.0559, found 294.0553.

[0142] Embodiment 19

[0143]

[0144] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0145] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (70% yield).

[0146] 1 H NMR (500MHz, CDCl3) δ7.94(dd,J=9.9,8.0Hz,3H),7.64(s,1H),7.27(dd,J=9.3,3.8Hz,3H),2.47(s,3H),2.40(s,3H). 13 C NMR (126MHz, CDCl3) δ167.28,152.39,141.24,135.21,131.19,129.77,127.92,127.44,122.63,121.44,21.64,21.61.

[0147] Embodiment 20

[0148]

[0149] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0150] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (60% yield).

[0151] 1H NMR(500MHz, CDCl3)δ7.92(dd,J=8.5,3.5Hz,3H),7.34–7.29(m,1H),7.26(d, J=7.8Hz,2H),7.07(dd,J=8.9,2.6Hz,1H),3.86(t,J=2.5Hz,3H),2.40(s,3H). 13 C NMR (126MHz, CDCl3) δ165.84,157.74,148.84,141.00,136.40,131.21,129.76,127.26,123.62,115.56,104.29,55.87,21.56.

[0152] Embodiment 21

[0153]

[0154] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (81% yield).

[0156] 1 H NMR (500MHz, CDCl3) δ7.98 (dd, J=8.9, 4.8Hz, 1H), 7.93 (d, J=8.0Hz, 2H), 7.56 (dd, J= 8.1, 2.6Hz, 1H), 7.29 (d, J=7.9Hz, 2H), 7.21 (td, J=9.8, 9.4, 2.9Hz, 1H), 2.42 (s, 3H). 19 F NMR(471MHz, CDCl3)δ–116.07. 13C NMR (126MHz, CDCl3) δ168.07,168.05,161.45,159.50,150.89,141.63,136.05,135. 96,130.79,129.87,127.45,124.03,123.96,115.02,114.82,108.00,107.79,21.61.

[0157] Embodiment 22

[0158]

[0159] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (44% yield).

[0161] 1 H NMR (500MHz, CDCl3) δ7.94(dd,J=8.5,2.8Hz,3H),7.85(d,J=2.1Hz,1H),7.42(dd,J=8.7,2.1Hz,1H),7.29(d,J=7.9Hz,2H),2.42(s,3H). 13 C NMR (126MHz, CDCl3) δ168.83,152.79,141.91,136.19,130.94,130.64,129.90,127.57,127.15,123.82,121.28,21.65.

[0162] Embodiment 23

[0163]

[0164] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0165] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (59% yield).

[0166] 1 H NMR (500MHz, CDCl3) δ8.18(s,1H),8.12(d,J=8.5Hz,1H),7.99(d,J=8.1Hz,2H),7.71(d,J=8.6Hz,1H),7.32(d,J=7.9Hz,2H),2.43(s,3H). 19 FNMR (471MHz,CDCl3)δ–61.10. 13 C NMR(126MHz, CDCl3)δ171.41,156.22,142.43,135.09,130.48,129.98,127.80,125.40,124.79,123.37,119.34,21.69.HRMS(ESI+)m / z:[M+H]+Calcd.for C 15 H 11 F3NS+294.0559, found 294.0554.

[0167] Embodiment 24

[0168]

[0169] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0170] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (25% yield).

[0171] 1 H NMR (500MHz, CDCl3) δ8.61 (s, 1H), 8.14 (d, J = 10.2Hz, 1H), 8.05 (d, J = 8.5Hz, 1H),7.99(d,J=8.1Hz,2H),7.31(d,J=7.9Hz,2H),3.96(s,3H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ171.82,166.80,157.21,142.34,134.96,130.66,129.95,127.8 0,127.62,126.79,123.90,122.77,52.45,21.69.HRMS(ESI+)m / z:[M+H]+Calcd.forC 16 H 14 NO2S+284.0740, found 284.0738.

[0172] Embodiment 25

[0173]

[0174] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0175] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (78% yield).

[0176] 1 H NMR (500MHz, CDCl3) δ8.91(d,J=9.5Hz,1H),8.08(d,J=8.2Hz,2H),7.94(d,J=8.1Hz,1H),7.90(d,J=8.7Hz, 1H),7.79(d,J=8.7Hz,1H),7.68(t,J=8.2Hz,1H),7.58(t,J=7.5Hz,1H),7.31(d,J=7.7Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ167.37,150.53,141.07,132.15,131.56,131.46,129. 82,128.83,128.15,127.35,126.96,126.15,125.77,124.15,119.08,21.63.

[0177] Embodiment 26

[0178]

[0179] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0180] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (65% yield).

[0181] 1 H NMR (500MHz, CDCl3) δ8.55 (dd, J=4.7, 1.5Hz, 1H), 8.26 (dd, J=8.2, 1.6Hz, 1H), 7.9 9(d,J=8.2Hz,2H),7.43(dd,J=8.2,4.7Hz,1H),7.32(d,J=7.6Hz,2H),2.44(s,3H). 13 C NMR (126MHz, CDCl3) δ168.94,158.51,147.42,146.87,142.31,130.89,129.94,129.88,127.65,121.50,21.66.

[0182] Embodiment 27

[0183]

[0184] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (40% yield).

[0186] 1 H NMR (500MHz, CDCl3) δ8.03–7.98(m,2H),7.90(d,J=8.0Hz,2H),7.52–7.47(m,3H),7.29(d,J=7.8Hz,2H),2.42(s,3H). 13 C NMR (126MHz, CDCl3) δ168.27,167.74,141.60,131.01,130.29,129.87,129.16,127.91,127.86,127.48,21.53.

[0187] Embodiment 28

[0188]

[0189] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (27% yield).

[0191] 1 H NMR (500MHz, CDCl3) δ7.88–7.81(m,3H),7.30–7.22(m,3H),2.39(s,3H). 13 CNMR (126MHz, CDCl3) δ168.72,143.61,140.33,131.07,129.74,126.60,118.43,21.50.

[0192] Embodiment 29

[0193]

[0194] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (34% yield).

[0196] 1H NMR (500MHz, CDCl3) δ8.40(s,1H),7.87(d,J=8.2Hz,2H),7.27(d,J=8.2Hz,2H),3.92(s,3H),2.41(s,3H). 13 C NMR(126MHz, CDCl3)δ173.82,162.01,149.39,141.88,130.42,129.92,128.13,126.95,52.51,21.59.HRMS(ESI+)m / z:[M+H]+Calcd.forC 12 H 12 NO2S+234.0583, found 234.0579.

[0197] Embodiment 30

[0198]

[0199] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (48% yield).

[0201] 1 H NMR (500MHz, CDCl3) δ7.99 (s, 1H), 7.85 (s, 2H), 7.60 (dd, J = 8.3, 1.2Hz, 2H), 7.41 ( dd,J=8.3,6.9Hz,2H),7.36–7.31(m,1H),7.26(dd,J=7.3,1.5Hz,2H),2.40(s,3H). 13 C NMR (126MHz, CDCl3) δ167.50,140.40,139.10,138.84,131.59,131.12,129.75,129.18,128.29,126.71,126.36,21.52.

[0202] Embodiment 31

[0203]

[0204] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (63% yield).

[0206] 1 H NMR (500MHz, CDCl3) δ7.99(d,J=7.0Hz,2H),7.93(d,J=8.2Hz,2H),7.48–7.40(m,3H),7.34(t,J=7.4Hz,1H),7.25(d,J=8.4Hz,2H),2.40(s,3H). 13 C NMR(126MHz, CDCl3)δ168.07,156.14,140.30,134.63,131.17,129.62,128.75,128.13,126.55,126.47,112.20,21.48.HRMS(ESI+)m / z:[M+H]+Calcd.for C 16 H 14 NS+252.0841, found 252.0835.

[0207] Embodiment 32

[0208]

[0209] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0210] 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (62% yield).

[0211] 1 H NMR (500MHz, CDCl3) δ8.00(d,J=7.9Hz,2H),7.72(d,J=7.0Hz,2H),7.44(t,J=7.7Hz,3H),7.33(t,J=7.4Hz,1H),7.29(d,J=7.8Hz,2H),2.41(s,3H). 13 C NMR (126MHz, CDCl3) δ161.52,151.06,140.75,129.64,129.02,128.42,128.22,126.34,124.87,124.24,123.42,21.65.

[0212] Embodiment 33

[0213]

[0214] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0215] 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (74% yield).

[0216] 1H NMR (500MHz, DMSO-d6) δ12.81(s,1H),8.03(d,J=7.9Hz,2H),7.60(s,1H),7.47(s,1H),7.32(d,J=7.9Hz,2H),7.15(s,2H),2.34(s,3H). 13 C NMR (126MHz, DMSO-d6) δ151.91,144.31,140.13,135.46,130.07,127.95,126.92,122.88,122.13,119.22,111.74,21.51.

[0217] Embodiment 34

[0218]

[0219] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (68% yield).

[0221] 1 H NMR(500MHz, CDCl3)δ9.45(s,1H),8.51(d,J=8.2Hz,2H),8.11–8.03(d,J=8.2Hz,1H),7 .94–7.86(m,2H),7.59(ddd,J=8.1,6.9,1.1Hz,1H),7.34(d,J=7.9Hz,2H),2.45(s,3H). 13 C NMR (126MHz, CDCl3) δ161.26,160.54,150.91,140.97,135.42,134.14,129.52,128.66,128.62,127.22,127.14,123.62,21.61.

[0222] Embodiment 35

[0223]

[0224] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (80% yield).

[0226] 1 H NMR (500MHz, CDCl3) δ8.32(d,J=8.0Hz,2H),7.27(d,J=7.9Hz,2H),6.89(s,1H),2.53(s,6H),2.41(s,3H). 13 C NMR (126MHz, CDCl3) δ166.73,164.33,140.48,135.50,129.28,128.24,117.75,24.26,21.53.

[0227] Embodiment 36

[0228]

[0229] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (78% yield).

[0231] 1H NMR (500MHz, CDCl3) δ8.17(dd,J=17.9,8.6Hz,2H),8.07(d,J=8.2Hz,2H),7.86(d,J=8.6Hz,1H),7 .81(d,J=8.1Hz,1H),7.71(t,J=7.7Hz,1H),7.55–7.47(m,1H),7.33(d,J=7.9Hz,2H),2.43(s,3H). 13 C NMR (126MHz, CDCl3) δ157.43,148.40,139.50,136.98,136.76,129.77,129.68,127.53,127.20,126.18,118.96,21.44.

[0232] Embodiment 37

[0233]

[0234] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (46% yield).

[0236] 1 H NMR (500MHz, CDCl3) δ9.32(s,1H),8.13(dd,J=17.8,8.2Hz,4H),7.76(ddd,J=15.1,13.5,6.8Hz,2H),7.38(d,J=7.9Hz,2H),2.46(s,3H). 13 C NMR (126MHz, CDCl3) δ151.96,143.43,142.44,141.55,140.62,134.09,130.31,130.01,129.64,129.41,129.20,127.54,21.53.

[0237] Embodiment 38

[0238]

[0239] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (52% yield).

[0241] 1 H NMR (500MHz, CDCl3) δ8.60(d,J=5.7Hz,1H),8.14(d,J=8.6Hz,1H),7.88(d,J=8.2Hz,1H),7.69(t,J= 7.6Hz,1H),7.62(dd,J=14.5,6.9Hz,3H),7.54(t,J=7.7Hz,1H),7.35(d,J=7.8Hz,2H),2.47(s,3H). 13 C NMR (126MHz, CDCl3) δ160.86,142.22,138.61,136.99,136.69,130.09,129.97,129.15,127.82,127.19,127.07,126.83,119.83,21.47.

[0242] Embodiment 39

[0243]

[0244] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0245] 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (43% yield).

[0246] 1 H NMR (500MHz, CDCl3) δ8.70(d,J=8.3Hz,1H),8.61(d,J=8.2Hz,1H),8.23(d,J=8.2Hz,1H),8.13(d,J=8.2Hz,1H),7.8 8–7.83(m,1H),7.75(t,J=6.9Hz,1H),7.68(t,J=7.6Hz,1H),7.65–7.59(m,3H),7.36(d,J=7.8Hz,2H),2.47(s,3H). 13 C NMR (126MHz, CDCl3) δ161.42,144.13,139.33,137.06,133.58,130.64,130.38,129. 81,129.21,129.20,128.94,127.19,126.95,125.40,123.79,122.29,122.03,21.51.

[0247] Embodiment 40

[0248]

[0249] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0250] 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a colorless liquid product (41% yield).

[0251] 1 H NMR (500MHz, CDCl3) δ8.59(d,J=5.3Hz,1H),7.82(d,J=8.0Hz,2H),7.67–7.59(m,2H),7.20(d,J=7.9Hz,2H),7.13–7.09(m,1H),2.32(s,3H). 13 C NMR (126MHz, CDCl3) δ157.49,149.62,138.97,136.71,136.64,129.51,126.79,121.82,120.27,21.30.

[0252] Embodiment 41

[0253]

[0254] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0255] 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (68% yield).

[0256] 1H NMR(500MHz, CDCl3)δ9.26(d,J=2.3Hz,1H),8.35–8.29(m,1H),7.96(d,J=7.9H z,2H),7.79(d,J=8.3Hz,1H),7.31(d,J=8.2Hz,2H),3.97(s,3H),2.42(s,3H). 13 CNMR (126MHz, CDCl3) δ165.96,160.92,150.92,140.24,137.81,135.47,129.65,127.24,123.86,119.48,52.31,21.35.

[0257] Embodiment 42

[0258]

[0259] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (82% yield).

[0261] 1 H NMR (500MHz, CDCl3) δ8.92 (s, 1H), 7.98–7.91 (m, 3H), 7.82 (d, J = 8.3Hz, 1H), 7.31 (d, J = 8.1Hz, 2H). 19 F NMR(471MHz, CDCl3)δ–62.08. 13 C NMR (126MHz, CDCl3) δ160.76,146.65,140.42,135.26,133.95,129.80,127.24,124.70,122.83,119.70,21.44.

[0262] Embodiment 43

[0263]

[0264] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (71% yield).

[0266] 1 H NMR (500MHz, CDCl3) δ8.84(d,J=5.0Hz,1H),7.95–7.88(m,3H),7.41(d,J=3.5Hz,1H),7.31(d,J=8.0Hz,2H),2.43(s,3H). 19 F NMR(471MHz, CDCl3)δ–64.72. 13 C NMR (126MHz, CDCl3) δ158.88,150.64,140.16,139.28,135.35,129.80,126.99,124.17,117.30,115.78,21.41.

[0267] Embodiment 44

[0268]

[0269] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (89% yield).

[0271] 1 H NMR (500MHz, CDCl3) δ8.13–8.06(m,3H),7.91(d,J=8.0Hz,1H),7.53–7.47(m,4H),7.42–7.36(m,1H). 13 C NMR (126MHz, CDCl3) δ168.18,154.26,135.17,133.73,131.07,129.13,127.67,126.42,125.29,123.35,121.73.

[0272] Embodiment 45

[0273]

[0274] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (86% yield).

[0276] 1 H NMR(500MHz, CDCl3)δ8.07(d,J=8.2Hz,1H),8.04–8.00(m,2H),7.90(d,J=8 .0Hz,1H),7.54–7.46(m,3H),7.37(td,J=7.5,7.1,1.2Hz,1H),1.37(s,9H). 13 C NMR (126MHz, CDCl3) δ168.24,154.64,154.32,135.08,131.00,127.44,126.32,126.09,125.09,123.18,121.67,35.08,31.27.

[0277] Embodiment 46

[0278]

[0279] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (88% yield).

[0281] 1 H NMR (500MHz, CDCl3) δ8.05–7.99(m,3H),7.86(d,J=8.0Hz,1H),7.46(ddd,J=8.3,7.1,1.3Hz,1H),7.37–7.31(m,1H),7.02–6.96(m,2H),3.86(s,3H). 13 C NMR (126MHz, CDCl3) δ167.96,162.02,154.33,134.96,129.21,126.53,126.30,124.89,122.92,121.61,114.46,55.55.

[0282] Embodiment 47

[0283]

[0284] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (72% yield).

[0286] 1H NMR (500MHz, CDCl3) δ8.15–8.10(m,2H),8.08(d,J=8.2Hz,1H),7.93–7.88(d,J=8. 0Hz,1H),7.51(ddd,J=8.3,7.2,1.3Hz,1H),7.43–7.38(m,1H),7.37–7.30(m,2H). 19 FNMR (471MHz,CDCl3)δ–57.57. 13 C NMR (126MHz, CDCl3) δ166.31,154.20,151.14,135.24,132.30,129.18,126.61,125.57,123.49,121.77,121.31.

[0287] Embodiment 48

[0288]

[0289] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (72% yield).

[0291] 1 H NMR (500MHz, CDCl3) δ7.89 (dd, J=11.9, 8.8Hz, 3H), 7.75 (d, J=9.1Hz, 1H), 7.39 –7.33(m,1H),7.25–7.19(m,1H),6.66(d,J=8.8Hz,2H),2.96(d,J=0.9Hz,3H). 13 CNMR(126MHz, CDCl3)δ168.91,154.53,152.27,134.66,127.06,126.08,124.28,122.38,121.48,121.45,111.78,40.27.

[0292] Embodiment 49

[0293]

[0294] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (67% yield).

[0296] 1 H NMR (500MHz, CDCl3) δ8.09(dd,J=8.5,2.5Hz,3H),7.92(t,J=8.3Hz,3H),7.50(t,J=7.7Hz,1H),7.39(t,J=7.6Hz,1H),1.37(s,12H). 13 C NMR (126MHz, CDCl3) δ168.09,154.23,135.92,135.47,135.22,126.77,126.48,125.42,123.43,121.74,84.21,24.98.

[0297] Embodiment 50

[0298]

[0299] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0300] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (50% yield).

[0301] 1 H NMR(500MHz,DMSO-d6)δ10.22(s,1H),8.07(d,J=7.9Hz,1H),7.95(dd,J=21.6, 8.2Hz, 3H), 7.50 (t, J = 7.7Hz, 1H), 7.40 (t, J = 7.6Hz, 1H), 6.94 (d, J = 8.4Hz, 2H). 13 CNMR(126MHz,DMSO-d6)δ168.00,161.07,154.27,134.64,129.58,126.96,125.44,124.58,122.84,122.65,116.62.

[0302] Embodiment 51

[0303]

[0304] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0305] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (52% yield).

[0306] 1H NMR(500MHz, CDCl3)δ8.20–8.16(m,2H),8.10(d,J=8.2Hz,1H),8.08–8.03(m,2H),7.9 2(d,J=8.0Hz,1H),7.54–7.49(m,1H),7.41(ddd,J=8.3,7.1,1.2Hz,1H),2.65(s,3H). 13 C NMR (126MHz, CDCl3) δ197.41,166.54,154.24,138.67,137.61,135.40,129.08,127.76,126.73,125.85,123.73,121.84,26.85.

[0307] Embodiment 52

[0308]

[0309] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (57% yield).

[0311] 1 H NMR (500MHz, CDCl3) δ8.18(d,J=8.1Hz,2H),8.10(d,J=8.2Hz,1H),7.91(d,J=8.0Hz,1H), 7.73(d,J=8.1Hz,2H), 7.52(ddd,J=8.3,7.1,1.3Hz,1H), 7.41(td,J=7.6,7.1,1.2Hz,1H). 13 C NMR (126MHz, CDCl3) δ166.12,154.14,136.86,135.31,132.41,127.86,126.75,126.11,126.08,125.88,123.73,121.83.

[0312] Embodiment 53

[0313]

[0314] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (40% yield).

[0316] 1 H NMR (500MHz, CDCl3) δ8.17(d,J=1.4Hz,4H),8.11(d,J=8.2Hz,1H),7.94(d,J=8.0Hz,1H), 7.53(t,J=7.7Hz,1H), 7.43(t,J=7.4Hz,1H), 4.42(q,J=7.1Hz,2H), 1.43(t,J=7.1Hz,3H). 13 C NMR (126MHz, CDCl3) δ166.77,166.05,154.22,137.46,135.37,132.50,130.32,127.49,126.69,125.79,123.68,121.83,61.41,14.42.

[0317] Embodiment 54

[0318]

[0319] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0320] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (26% yield).

[0321] 1 H NMR (500MHz, CDCl3) δ8.19(d,J=8.1Hz,2H),8.10(d,J=8.2Hz,1H),7.93(d,J=8 .0Hz,1H),7.77(d,J=8.0Hz,2H),7.53(t,J=7.7Hz,1H),7.44(t,J=7.6Hz,1H). 13 CNMR (126MHz, CDCl3) δ165.44,154.13,137.60,135.41,132.88,128.03,126.93,126.18,123.92,121.91,118.38,114.23.

[0322] Embodiment 55

[0323]

[0324] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0325] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (49% yield).

[0326] 1H NMR(500MHz, CDCl3)δ8.06(d,J=8.2Hz,1H),7.98–7.92(m,2H),7.89(d,J=8.0Hz, 1H),7.62(d,J=8.6Hz,2H),7.49(ddd,J=8.4,7.2,1.3Hz,1H),7.42–7.37(m,1H). 13 C NMR (126MHz, CDCl3) δ166.80,154.18,138.29,135.15,132.66,132.33,129.00,126.60,125.55,123.42,121.77.

[0327] Embodiment 56

[0328]

[0329] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (71% yield).

[0331] 1 H NMR (500MHz, CDCl3) δ8.11(dd,J=8.2,1.5Hz,1H),7.93(d,J=8.0Hz,1H),7.76(dd,J=7.7,1.7Hz,1H),7.54–7.48(m,1H),7.43–7.28(m,4H),2.67(s,3H). 13 C NMR (126MHz, CDCl3) δ168.09,153.92,137.36,135.72,133.21,131.64,130.64,130.10,126.22,126.20,125.19,123.49,121.46,21.44.

[0332] Embodiment 57

[0333]

[0334] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (63% yield).

[0336] 1 H NMR (500MHz, CDCl3) δ8.07(d,J=8.1Hz,1H),7.94(s,1H),7.90(d,J=7.9Hz,1H),7.87(d, J=7.7Hz,1H),7.51–7.46(m,1H),7.41–7.36(m,2H),7.31(d,J=7.6Hz,1H),2.45(s,3H). 13 C NMR (126MHz, CDCl3) δ168.46,154.22,138.99,135.13,133.61,131.93,129.03,128.09,126.40,125.23,124.97,123.27,121.71,21.46.

[0337] Embodiment 58

[0338]

[0339] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0340] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a brown solid product (56% yield).

[0341] 1 H NMR (500MHz, DMSO-d6) δ9.87(t,J=2.1Hz,1H),8.14(d,J=8.0Hz,1H),8.06(d,J=8.1Hz,1H ),7.60–7.50(m,3H),7.47(t,J=7.5Hz,1H),7.38(t,J=7.8Hz,1H),6.99(d,J=8.0Hz,1H). 13 C NMR (126MHz, DMSO-d6) δ167.90,158.54,154.07,134.92,134.59,131.08,127.15,126.04,123.40,122.84,119.09,118.64,113.99.

[0342] Embodiment 59

[0343]

[0344] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0345] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (75% yield).

[0346] 1H NMR (500MHz, CDCl3) δ8.07 (d, J=8.2Hz, 1H), 7.90 (dd, J=8.0, 1.2Hz, 1H), 7.71 (s, 2H), 7.48 (ddd,J=8.3,7.2,1.3Hz,1H),7.38(ddd,J=8.2,7.2,1.2Hz,1H),7.13(s,1H),2.41(s,6H). 13 C NMR (126MHz, CDCl3) δ168.68,154.20,138.84,135.09,133.53,132.88,126.35,125.44,125.15,123.20,121.69,21.33.

[0347] Embodiment 60

[0348]

[0349] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow-brown solid product (49% yield).

[0351] 1 H NMR (500MHz, CDCl3) δ8.51 (s, 2H), 8.11 (d, J = 8.2Hz, 1H), 7.99–7.91 (m, 2H), 7.57–7.52 (m, 1H), 7.45 (t, J = 7.7Hz, 1H). 19 F NMR(471MHz, CDCl3)δ–62.86. 13 C NMR (126MHz, CDCl3) δ164.17,153.96,135.72,135.25,132.83,132.56,127.42,127.07,126.35,124.12,123.96,121.95.

[0352] Embodiment 61

[0353]

[0354] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (91% yield).

[0356] 1 H NMR (500MHz, CDCl3) δ8.02(d,J=8.5Hz,1H),7.86(d,J=8.0Hz,1H),7.72(s,2H),7.45(t,J=7.7Hz,1H),7.33(t,J=7.6Hz,1H),5.61(s,1H),2.31(s,6H). 13 C NMR(126MHz, CDCl3)δ168.63,155.34,154.21,134.86,128.17,126.28,125.71,124.78,124.10,122.73,121.59,16.08.HRMS(ESI+)m / z:[M+H]+Calcd.for C 15 H 14 ONS+256.0791, found 256.0784.

[0357] Embodiment 62

[0358]

[0359] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0360] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (87% yield).

[0361] 1 H NMR (500MHz, CDCl3) δ8.06(d,J=8.0Hz,1H),7.90(d,J=7.9Hz,1H),7.50(t,J=7.7Hz,1H),7.41–7.37(m,1H),7.34(s,2H),3.99(s,6H),3.93(s,3H). 13 C NMR (126MHz, CDCl3) δ167.92,154.15,153.69,140.74,135.12,129.16,126.46,125.24,123.17,121.66,104.86,61.12,56.47.

[0362] Embodiment 63

[0363]

[0364] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0365] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (72% yield).

[0366] 1H NMR(500MHz, CDCl3)δ8.94(td,J=7.9,3.4Hz,1H),8.20(dt,J=8.0,3.4Hz,1H),8.02–7.90(m,4ll H),7.62(ddd,J=8.6,6.8,2.1Hz,1H),7.56(ddt,J=10.4,7.3,3.3Hz,3H),7.44(t,J=7.7Hz,1H). 13 C NMR (126MHz, CDCl3) δ167.73,154.29,135.59,134.14,131.20,130.97,130.78,1 29.52,128.53,127.76,126.64,126.40,126.01,125.42,125.12,123.69,121.52.

[0367] Embodiment 64

[0368]

[0369] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (46% yield).

[0371] 1 H NMR (500MHz, CDCl3) δ8.70–8.65(m,1H),8.36(d,J=7.9Hz,1H),8.08(d,J=8.2Hz,1H),7 .95(d,J=7.9Hz,1H),7.83(td,J=7.7,1.7Hz,1H),7.51–7.47(m,1H),7.43–7.34(m,2H). 13C NMR (126MHz, CDCl3) δ169.48,154.40,151.54,149.76,137.10,136.25,126.37,125.74,125.36,123.69,122.11,120.87.

[0372] Embodiment 65

[0373]

[0374] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a brown solid product (89% yield).

[0376] 1 H NMR (500MHz, CDCl3) δ9.29 (s, 1H), 8.74–8.67 (m, 1H), 8.36 (dt, J = 7.9, 2.0Hz, 1H), 8. 10(d,J=8.2Hz,1H),7.92(d,J=8.0Hz,1H),7.52(t,J=7.7Hz,1H),7.46–7.38(m,2H). 13 C NMR (126MHz, CDCl3) δ164.66,154.06,151.71,148.71,135.07,134.62,129.79,126.72,125.80,123.87,123.59,121.83.

[0377] Embodiment 66

[0378]

[0379] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0380] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (55% yield).

[0381] 1 H NMR (500MHz, CDCl3) δ8.77(d,J=5.1Hz,2H),8.12(d,J=8.2Hz,1H),8.01–7.86(m,3H),7.54(t,J=7.7Hz,1H),7.46(q,J=7.6,6.3Hz,1H). 13 CNMR (126MHz, CDCl3) δ165.17,154.06,150.84,140.55,135.30,126.90,126.29,124.01,121.95,121.28.

[0382] Embodiment 67

[0383]

[0384] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0385] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a brown solid product (46% yield).

[0386] 1H NMR (500MHz, CDCl3) δ9.05(d,J=4.5Hz,1H),9.00(dd,J=8.6,1.4Hz,1H),8.23(dd,J=10.9,8.2Hz,2H),8.01( d,J=7.9Hz,1H),7.84–7.77(m,2H),7.69(ddd,J=8.3,6.8,1.3Hz,1H),7.64–7.57(m,1H),7.56–7.48(m,1H). 13 C NMR (126MHz, CDCl3) δ164.89,154.26,149.89,149.28,138.41,135.45,130.1 1,130.08,128.26,126.84,126.25,126.15,125.06,124.19,122.28,121.72.

[0387] Embodiment 68

[0388]

[0389] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (61% yield).

[0391] 1 H NMR (500MHz, CDCl3) δ8.98(dd,J=4.3,1.7Hz,1H),8.56(d,J=2.0Hz,1H),8.44(dd,J=8.8,2.0Hz,1H),8.28(dd,J=8.3,1.7Hz,1H),8.22(d,J =8.8Hz,1H),8.13(d,J=8.2Hz,1H),7.95(d,J=7.8Hz,1H),7.53(ddd,J=8.3,7.2,1.2Hz,1H),7.48(dd,J=8.3,4.1Hz,1H),7.45–7.40(m,1H).13 C NMR (126MHz, CDCl3) δ167.11,154.30,151.77,149.41,136.89,135.35,131.77,130.53,128.3 1,128.29,127.24,126.67,125.63,123.52,122.14,121.82.HRMS(ESI+)m / z:[M+H]+Calcd.for C 16 H 11 N2S+263.0637, found 263.0630.

[0392] Embodiment 69

[0393]

[0394] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (53% yield).

[0396] 1 H NMR (500MHz, CDCl3) δ8.08(d,J=8.2Hz,1H),7.91–7.81(m,4H),7.51–7.47(m,1H),7.40(td,J=7.6,6.7,3.8Hz,3H). 13 C NMR (126MHz, CDCl3) δ161.57,153.79,140.92,139.64,137.26,135.09,126.67,126.26,125.73,125.40,125.10,124.68,123.44,122.72,121.63.

[0397] Embodiment 70

[0398]

[0399] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (43% yield).

[0401] 1 H NMR (500MHz, CDCl3) δ8.04(d,J=6.0Hz,1H),7.86(d,J=8.0Hz,1H),7.61(s,1H),7.57–7.44(m,3H),7.42–7.28(m,3H),4.07(s,2H). 13 C NMR (126MHz, CDCl3) δ163.50,153.40,143.14,143.07,140.11,134.31,134.22,126.38,126.1 6,125.69,124.68,123.54,122.39,121.78,120.89,38.89.HRMS(ESI+)m / z:[M+H]+Calcd.for C 16 H 12 NS+250.0685, found 250.0682.

[0402] Embodiment 71

[0403]

[0404] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0405] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (68% yield).

[0406] 1 H NMR (500MHz, CDCl3) δ7.97(d,J=8.2Hz,1H),7.82(d,J=7.9Hz,1H),7.42(t,J=7.1Hz,1H),7.33(t,J=7.6Hz,1 H),6.81(t,J=4.1Hz,1H),2.71–2.64(m,2H),2.35–2.27(m,2H),1.81(p,J=6.0Hz,2H),1.72(p,J=6.0Hz,2H). 13 C NMR (126MHz, CDCl3) δ170.69,153.84,134.21,134.18,133.49,125.98,124.93,122.92,121.42,26.53,26.16,22.41,22.05.

[0407] Embodiment 72

[0408]

[0409] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide comprises the following steps:

[0410] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (41% yield).

[0411] 1H NMR (500MHz, CDCl3) δ7.99(d,J=8.1Hz,1H),7.85(d,J=8.0Hz,1H),7.46(ddd,J=8.3,7.2,1.3Hz,1 H),7.37(ddd,J=8.2,7.2,1.2Hz,1H),7.18(d,J=19.0Hz,1H),6.96(d,J=19.0Hz,1H),0.21(s,9H). 13 C NMR(126MHz, CDCl3)δ168.97,153.92,142.17,137.22,134.60,126.39,125.64,123.47,121.76,-1.47.HRMS(ESI+)m / z:[M+H]+Calcd.forC 12 H 16 NSSi+234.0767, found 234.0762.

[0412] Embodiment 73

[0413]

[0414] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide. This embodiment provides a new method for synthesizing the drug CJM, which 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, 1.0 equivalent of electrolyte LiBr were added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (78% yield).

[0416] 1 H NMR(500MHz, CDCl3) δ7.99(d,J=8.1Hz,1H),7.93–7.88(m,2H),7.85(d,J=7.8Hz,1H),7.45(d dd,J=8.3,7.2,1.2Hz,1H),7.32(ddd,J=8.2,7.2,1.1Hz,1H),6.77–6.72(m,2H),4.00(s,2H). 13C NMR (126MHz, CDCl3) δ168.59,154.36,149.31,134.69,129.25,126.16,124.55,124.08,122.60,121.51,114.88.

[0417] Embodiment 74

[0418]

[0419] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide. This embodiment provides a new method for synthesizing the drug 5F203, which specifically includes 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, 1.0 equivalent of electrolyte LiBr were added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (81% yield).

[0421] 1 H NMR(500MHz,DMSO-d6)δ8.00(dd,J=8.8,5.4Hz,1H),7.67(dd,J=10.0,2.5Hz,1H),7.64(d,J=2.6Hz,1H), 7.60(dd,J=8.3,2.3Hz,1H),7.19(td,J=9.0,2.6Hz,1H),6.67(d,J=8.3Hz,1H),5.69(s,2H),2.10(s,3H). 19 F NMR(471MHz,DMSO-d6)δ–116.33. 13 CNMR(126MHz,DMSO-d6)δ171.59,162.82(d,J=240.6Hz),155.47(d,J=12.2Hz),151.21,130.01,129.78,1 27.16, 123.62 (d, J = 10.7Hz), 121.54, 120.56, 114.10, 112.79 (d, J = 25.1Hz), 108.20 (d, J = 23.4Hz), 17.88.

[0422] Embodiment 75

[0423]

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

[0425] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (73% yield).

[0426] 1 H NMR(500MHz,DMSO-d6)δ8.14(dd,J=5.4,8.8Hz,1H),7.85(dd,J=2.6,9.8Hz,1H),7.63(m,2H ),7.39–7.28(dt,J=2.5,9.6Hz,1H),7.19–7.08(d,J=9.0Hz,1H),3.90(s,3H),3.87(s,3H). 19 F NMR(471MHz,DMSO-d6)δ–115.71. 13 C NMR(126MHz,DMSO-d6)δ170.58,162.90,160.98,155.09,155.00,152.39,149.67,130.63,125 .88,124.04,123.96,121.57,114.08,113.89,112.49,109.93,109.13,108.94,56.28,56.17.

[0427] Embodiment 76

[0428]

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

[0430] 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 to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. 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] Embodiment 77

[0433]

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

[0435] 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (49% yield).

[0436] 1H NMR (500MHz, CDCl3) δ8.45(d,J=5.6Hz,1H),7.49(d,J=4.9Hz,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=18.7,7.0Hz,9H). 13 C NMR (126MHz, CDCl3) δ158.36,153.02,152.76,150.03,141.25,138.21,135.16,133.88,122.57,118.77 ,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, found398.1949.

[0437] Embodiment 78

[0438]

[0439] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide. This embodiment provides a new method for synthesizing the drug Thioflavine T, which 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, 1.0 equivalent of electrolyte LiBr were added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, stainless steel was used as anode, nickel foam was used as cathode, and electrolysis was performed at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a light yellow solid product (78% yield).

[0441] 1 H NMR (500MHz, CDCl3) δ7.96–7.92(m,2H),7.86(d,J=8.3Hz,1H),7.63(s,1H),7.24(dd,J=8.2,2.0Hz,1H),6.77–6.72(m,2H),3.05(s,6H),2.47(s,3H). 13C NMR (126MHz, CDCl3) δ167.90,152.58,152.14,134.78,134.32,128.80,127.59,121.88,121.65,121.30,111.80,40.29,21.58.

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

[0443] 1 H NMR(500MHz,DMSO-d6)δ8.17(s,1H),8.11(d,J=8.6Hz,1H),7.79(d,J=9.0Hz,2H),7 .66(d,J=8.7Hz,1H),6.93(d,J=9.1Hz,2H),4.19(s,3H),3.08(s,6H),2.46(s,3H). 13 C NMR (126MHz, DMSO-d6) δ173.16,154.17,141.51,138.56,132.79,131.07,128.71,123.94,117.11,112.53,111.50,79.82,38.74,21.54.

[0444] Embodiment 79

[0445]

[0446] A cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide. This embodiment provides a new method for synthesizing the drug Cinchophen, which 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, 1.0 equivalent of electrolyte LiBr were added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a white solid product (76% yield).

[0448] 1 H NMR(500MHz, CDCl3)δ8.75(d,J=8.6Hz,1H),8.42(s,1H),8.26–8.19(m,3H),7.78(t,J=7.0Hz,1 H),7.64(ddd,J=8.3,6.8,1.3Hz,1H),7.55(t,J=7.5Hz,2H),7.50(d,J=7.4Hz,1H),4.08(s,3H). 13 C NMR (126MHz, CDCl3) δ166.97,156.83,149.37,138.89,135.71,130.43,130.03,129.84,129.05,127.92,127.57,125.52,124.09,120.46,52.86.

[0449] The solid was dissolved in a mixed solution of methanol and water at room temperature, 5 equivalents of potassium hydroxide were added, and then heated to 60°C until the reaction of the raw materials was complete. After acidification with dilute hydrochloric acid, the organic solvent was removed under reduced pressure rotary evaporation, and the residue was purified by silica gel column chromatography to obtain a white solid product (93% yield).

[0450] 1 H NMR(500MHz,DMSO-d6)δ8.65(d,J=8.5Hz,1H),8.45(s,1H),8.30(d,J=7.7Hz,2H),8.17(d ,J=8.5Hz,1H),7.85(t,J=7.7Hz,1H),7.70(t,J=7.7Hz,1H),7.57(dt,J=15.3,7.2Hz,3H). 13 C NMR (126MHz, DMSO-d6) δ168.29,156.35,148.93,138.68,138.48,130.74,130.52,130.29,129.54,128.24,127.75,126.02,124.03,119.54.

[0451] Embodiment 80

[0452]

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

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

[0455] 1 H NMR (500MHz, CDCl3) δ8.12(d,J=8.3Hz,1H),7.65(t,J=3.3Hz,2H),7.53(d,J=6.8Hz,2H),2.70(s,3H). 13 C NMR(126MHz, CDCl3)δ161.65,137.18,134.79,131.14,127.30,126.34,125.85,124.71,119.59,13.34.HRMS(ESI+)m / z:[M+H]+Calcd.forC 10 H9BrNS+253.9634, found 253.9626.

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

[0457] 1 H NMR(500MHz, CDCl3)δ7.99(d,J=8.5Hz,1H),7.53(d,J=8.3Hz,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 CNMR(126MHz, CDCl3)δ159.07,155.12,154.93,138.53,130.38,125.96,124.55,12 3.29,122.21,95.52,80.01,46.05,28.54,13.11.HRMS(ESI+)m / z:[M+H]+Calcd.for C 19 H 26 N3O2S+360.1740, found 360.1722.

[0458] 1 equivalent of yellow oil was dissolved in ethanol, 0.2 equivalent of sodium tungstate was added at 0°C and stirred for 5 minutes, followed by 4 equivalents of hydrogen peroxide, slowly warmed to room temperature and stirred for 10 hours. After quenching with sodium thiosulfate aqueous solution, it was extracted with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid sulfone product (80% yield).

[0459] 1 H NMR(500MHz, CDCl3)δ8.70(d,J=8.7Hz,1H),7.64(d,J=8.4Hz,1H),7.59–7.54(m,1H),7.38(ddd,J=8.7 ,6.8,1.2Hz,1H),6.96(s,1H),3.61(t,J=5.8Hz,4H),3.56(d,J=7.2Hz,4H),3.45(s,3H),1.49(s,9H). 13 C NMR (126MHz, CDCl3) δ155.01,154.78,153.42,141.05,131.35,126.23,125.54,124. 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] 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 added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam was used as the cathode. The electrolysis was carried out at a constant current of 15 mA for 10 hours. Finally, the reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain a yellow solid product (57% yield).

[0461] 1H NMR(500MHz, CDCl3)δ7.93(d,J=8.5Hz,1H),7.75–7.69(m,2H),7.65(d,J=8.3Hz,1H ),7.56–7.43(m,4H),7.21(t,J=7.0Hz,1H),6.79(s,1H),3.62(s,8H),1.49(s,9H). 13 C NMR (126MHz, CDCl3) δ159.41,155.48,154.97,140.06,139.87,130.16,129.99,128.58,128.24, 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,found412.1974.

[0462] The obtained 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, the mixture was extracted with dichloromethane, washed with a saturated sodium bicarbonate aqueous solution, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure rotary evaporation and dried with an oil pump to obtain the final yellow product perafensine (99% yield).

[0463] 1 H NMR (500MHz, CDCl3) δ7.92(d,J=8.5Hz,1H),7.74–7.70(m,2H),7.64(d,J=8.3Hz,1H),7.49(dt,J=13. 0,6.8Hz,4H),7.19(t,J=7.0Hz,1H),6.78(s,1H),3.63–3.58(m,4H),3.09–3.03(m,4H),1.68(s,1H). 13 C NMR (126MHz, CDCl3) δ159.25,156.08,140.12,140.04,130.20,129.85,128.49,128.21,1 27.68,125.94,123.23,121.60,98.45,47.35,46.09.HRMS(ESI+)m / z:[M+Na]+Calcd.for C 19 H20N3+290.1652, found 290.1637.

[0464] application

[0465]

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

[0467] 1.0 equivalent of bromoaryl sulfone compound, 10 mol% of catalyst NiBr2·diglyme and 10 mol% of ligand bipy, 1.0 equivalent of electrolyte LiBr were added to the electrolysis reaction bottle in sequence, and the solvent DMF (concentration 0.1M) was added and stirred at room temperature for 15 minutes. Then the electrochemical reaction workstation was turned on, and the zinc sheet was used as the anode and the nickel foam 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 poured into methanol, the obtained polymer solid was filtered and washed with ammonia water, and then the solid was extracted with acetone, n-hexane, and chloroform in sequence. The obtained chloroform solution was removed from the organic solvent under reduced pressure rotary evaporation, and the obtained solid was dissolved with concentrated hydrochloric acid, and the polymer solid was reprecipitated with 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 (500MHz,CDCl3)

[0469] δ8.74(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 invention are disclosed for illustrative purposes, those skilled in the art will appreciate that various substitutions, changes and modifications are possible without departing from the spirit and scope of the present invention and the appended claims. Therefore, the scope of the present invention is not limited to the contents disclosed in the embodiments.

Claims

1. A cross electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide, characterized in that: The method comprises using an aryl sulfone compound and an aryl halide as two electrophilic reagents respectively, adding a ligand and an electrolyte in sequence under a catalyst condition, adding a solvent, and coupling the two electrophilic reagents by electrochemical driving to prepare a biaromatic compound. The general reaction formula is: Among them, Ar 1 ,Ar 2 denote the same or different aromatic systems; X represents I, Br, Cl; R represents an alkyl group or an aryl group.

2. The cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide according to claim 1, characterized in that: The catalyst is a nickel (II) bromide diethylene glycol dimethyl ether complex, the electrolyte is lithium bromide, and the solvent is N,N-dimethylformamide.

3. The cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide according to claim 2, characterized in that: The ligand is 2,2'-bipyridine or 2,2'-bipyridine-5,5'-dimethyl dicarboxylate; Among them, the structural formula of 2,2'-bipyridine is The structural formula of dimethyl 2,2'-bipyridine-5,5'-dicarboxylate is 4. The cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide according to claim 3, characterized in that: The aryl sulfone compound is any one of the following compounds: Where R is an independent C1-C 15 An alkyl chain or an aryl group; Alkyl chains include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl; Aryl includes phenyl, naphthyl, and substituted aromatic groups thereof; R is also an aromatic group substituted by trifluoromethyl, difluoromethyl, or vinyl; R 1 For independent C1-C 15 alkyl chains, halogens or aryl groups; Alkyl chains include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl; Halogens include fluorine, chlorine, and bromine; Aryl includes phenyl, naphthyl, tolyl, and substituted aromatic groups thereof; R 1 It can also be a hydroxyl group, a carbonyl group, a cyano group, an amine group, an ester group, an aldehyde group, a borate group, a trifluoromethyl group, an alkoxy group, or an ester group.

5. The cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide according to claim 4, characterized in that: The aryl halide is any one of the following compounds: Wherein, X is a chlorine atom, a bromine atom or an iodine atom; Among them, R 2 For independent C1-C 15 an alkyl chain, an alkoxy chain or an aryl group, Alkyl chains include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl; Alkoxy chains include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy; Aryl includes phenyl, naphthyl, and substituted aromatic groups thereof; R 2 It may also be an aromatic group substituted by a hydroxyl group, a carbonyl group, a cyano group, an amine group, an ester group, an aldehyde group, a borate group, a trifluoromethyl group, a difluoromethyl group, or a vinyl group.

6. The cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide according to claim 5, characterized in that: The method specifically comprises the following steps: S1. Add the reactant aryl sulfone compound and aryl halide, the catalyst nickel bromide (II) diethylene glycol dimethyl ether complex, the ligand 2,2'-bipyridine or 2,2'-bipyridine-5,5'-dimethyl dicarboxylate, and the electrolyte LiBr to an electrolysis reaction bottle in sequence, and then add the solvent N,N-dimethylformamide, and stir at room temperature for 10-20 minutes; S2. Turn on the electrochemical reaction workstation, use a stainless steel sheet or zinc sheet as the anode and nickel foam as the cathode, and perform electrolysis at a constant current of 10-20 mA for 8-12 hours; S3. The reaction solution was passed through a short diatomaceous earth column, washed with dichloromethane, and the organic solvent was removed under reduced pressure rotary evaporation. The residue was purified by silica gel column chromatography to obtain the target product.

7. The cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide according to claim 6, characterized in that: 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.

8. The cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide according to claim 7, characterized in that: The eluents of the silica gel column chromatography are petroleum ether and dichloromethane, and the ratio of the petroleum ether to dichloromethane is 10:

1.

9. The cross-electrophilic coupling reaction method of an aryl sulfone compound and an aryl halide according to claim 8, characterized in that: The aryl sulfone compound and the aryl halide are cross-electrophilicly coupled to construct C(sp 2 )-C(sp 2 ).

10. Use of the cross-electrophilic coupling reaction of the aryl sulfone compound according to any one of claims 1 to 9 with an aryl halide in the preparation of an organic high molecular polymer.

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