1. The invention relates to a cyclic organic antimony compound I, II, III, IV, V, VI, VII and VIII and a synthesis method thereof, wherein the structural formula is as follows:

wherein R is₁The radicals are hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-pentylOne or more of hexyl, cyclohexyl, n-heptyl, n-octyl, benzyl and phenyl; r₂、R₃The group is one or more of hydrogen, methyl, ethyl, methoxy, fluorine and tert-butyl; x₁Is O or S, R₄The group is one of tert-butyloxycarbonyl, methoxycarbonyl, ethoxycarbonyl, trimethylsilyl and nitro, R₅The group is one of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl and phenyl, R₆And R₇The group is one or more of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, benzyl and phenyl.

2. The compound according to claim 1, wherein the cyclic organic antimony compound is obtained in high yield and high selectivity by using tetrahydrofuran, a common organic solvent, 1, 2-bis (diphenylphosphino) ethane nickel chloride, a catalyst and diphenyl antimony chloride and iodoaromatic hydrocarbons containing a bridged nitrogen ligand as raw materials.

3. The compound according to claim 1, wherein the cyclic organic antimony compound is obtained in high yield and high selectivity by using tetrahydrofuran, a common organic solvent, 1, 2-bis (diphenylphosphino) ethane nickel chloride, a catalyst and diphenyl antimony bromide and iodo aromatic hydrocarbons containing a bridged nitrogen ligand as raw materials.

4. The compound according to claim 1, wherein the cyclic organic antimony compound is obtained in high yield and high selectivity by using tetrahydrofuran, a common organic solvent, 1, 2-bis (diphenylphosphino) ethane nickel chloride, a catalyst and diphenyl antimony iodide and iodohydrocarbon containing a bridged nitrogen ligand as raw materials.

5. The compound according to claim 1, wherein the cyclic organic antimony compound is obtained in high yield and high selectivity by using a commonly used organic solvent N, N-Dimethylformamide (DMF) as a reaction solvent, 1, 2-bis (diphenylphosphino) ethane nickel chloride as a catalyst, and diphenyl antimony chloride containing a bridged nitrogen atom ligand and a brominated aromatic hydrocarbon as raw materials.

6. The compound according to claim 1, wherein the cyclic organic antimony compound is obtained in high yield and high selectivity by using a commonly used organic solvent N, N-Dimethylformamide (DMF) as a reaction solvent, 1, 2-bis (diphenylphosphino) ethane nickel chloride as a catalyst, and diphenyl antimony bromide and brominated aromatic hydrocarbons containing a bridged nitrogen atom ligand as raw materials.

7. The compound of claim 1, wherein the cyclic organic antimony compound is obtained in high yield and high selectivity by using a commonly used organic solvent N, N-Dimethylformamide (DMF) as a reaction solvent, 1, 2-bis (diphenylphosphino) ethane nickel chloride as a catalyst, and diphenyl antimony iodide and brominated aromatic hydrocarbon containing a bridged nitrogen atom ligand as raw materials.

8. The compound of claim 1, wherein the cyclic organic antimony compound is obtained in high yield and high selectivity by using a commonly used organic solvent N, N-Dimethylformamide (DMF) as a reaction solvent, 1, 2-bis (diphenylphosphino) ethane nickel chloride as a catalyst, and diphenyl antimony iodide and chloroarene containing a bridged nitrogen atom ligand as raw materials.

9. The compound according to claim 1, wherein the cyclic organic antimony compound is obtained in high yield and high selectivity by using a commonly used organic solvent N, N-Dimethylformamide (DMF) as a reaction solvent, 1, 2-bis (diphenylphosphino) ethane nickel chloride as a catalyst, and diphenyl antimony bromide and chloroarene containing a bridged nitrogen atom ligand as raw materials.

10. The compound according to claim 1, wherein the cyclic organic antimony compound is obtained in high yield and high selectivity by using a commonly used organic solvent N, N-Dimethylformamide (DMF) as a reaction solvent, 1, 2-bis (diphenylphosphino) ethane nickel chloride as a catalyst, and diphenyl antimony chloride containing a bridged nitrogen atom ligand and chlorinated aromatic hydrocarbon as raw materials.

[ background of the invention ]

In recent years, organic antimony chemistry has attracted attention from many synthetic chemists. As a heavy phosphine analog, organoantimony compounds have many unusual characteristics and have been used as unique ligands, synthesis reagents, gas capture agents and bioactive molecules. For example, organic antimony compounds can be used as ligands to coordinate with metals such as Pd, Pt, Au, Hg, Ni and the like to form stable complex complexes, and the compounds show good catalytic activity. The conventional synthesis process of organic antimony compounds involves a Grignard reagent and an organolithium reagent, which are unstable to air and water, resulting in inconvenient experimental operations. In addition, the tolerance of the functional group and the poor universality of the substrate greatly limit the further application of the organic antimony compound. Therefore, the development of efficient and simple synthetic methods is now urgently needed.

Cross-coupling reactions are important methods for forming carbon-carbon bonds and have been widely used in organic synthesis as well as in the synthesis of pharmaceutical intermediates or drug molecules. However, the study of the synthesis of carbon-metal containing bonds using cross-coupling reactions is still in the beginning. Recently, a new method for efficiently preparing a stable organic antimony compound has been developed, and the method has the characteristics of simple operation and high efficiency.

[ summary of the invention ]

The invention aims to provide a cyclic organic antimony compound and a preparation method thereof. The catalytic synthesis method takes 1, 2-bis (diphenylphosphino) ethane nickel chloride as a catalyst, tetrahydrofuran or N, N-dimethylformamide as a solvent, and diphenyl antimony halide and halogenated aromatic hydrocarbon containing a bridged nitrogen atom ligand as raw materials, and the cyclic organic antimony compound is directly synthesized by cross coupling under the air atmosphere. The method has the advantages of low cost, high yield, simple operation and the like. In order to achieve the above purpose, the invention provides the following technical scheme:

a cyclic organic antimony compound I, II, III, IV, V, VI, VII and VIII and a synthesis method thereof, wherein the structural formula is as follows:

wherein R is₁The group is one or more of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, benzyl and phenyl；R₂、R₃The group is one or more of hydrogen, methyl, ethyl, methoxy, fluorine and tert-butyl; x₁Is O or S, the R4 group is one of tert-butyloxycarbonyl, methoxycarbonyl, ethoxycarbonyl, trimethylsilyl and cyano, R₅The group is one or more of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl and phenyl, R₆And R₇The group is one or more of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, benzyl and phenyl.

The method for synthesizing the cyclic organic antimony compound has the advantages of high efficiency and good selectivity.

In the synthesis method, the structural formulas of diphenyl antimony halide IX, X, XI and aryl iodide XII containing bridged nitrogen atom ligands are as follows:

R₁the group is one or more of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, benzyl and phenyl; r₂、R₃The group is one or more of hydrogen, methyl, ethyl, methoxy, fluorine and tert-butyl;

R₄、R₅、R₆the group is one or more of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, benzyl, formyl, acetyl, carboxyl, ester group, trimethylsilyl, vinyl, ethynyl, fluorine, chlorine, bromine, cyano, nitro, thiomethyl, trifluoromethyl, trifluoromethoxy, methoxy, ethoxy and phenyl.

In the above synthesis method, the method is characterized byTetrahydrofuran (THF) as reaction solvent, diphenyl antimony chloride I containing bridged nitrogen atom ligand_XAnd iodo arene XII as raw material, and through catalytic reaction with 1, 2-bis (diphenylphosphino) ethane and nickel chloride to obtain the cyclic organic antimony compound in high yield and high selectivity.

The synthesis method is characterized in that Tetrahydrofuran (THF) is used as a reaction solvent, diphenyl antimony bromide X and iodo arene XII containing a bridged nitrogen atom ligand are used as raw materials, 1, 2-bis (diphenylphosphino) ethane nickel chloride is adopted for catalytic reaction, and the cyclic organic antimony compound is obtained with high yield and high selectivity.

The synthesis method is characterized in that Tetrahydrofuran (THF) is used as a reaction solvent, diphenyl antimony iodide XI and iodo arene XII containing a bridged nitrogen atom ligand are used as raw materials, 1, 2-bis (diphenylphosphino) ethane nickel chloride is adopted for catalytic reaction, and the cyclic organic antimony compound is obtained with high yield and high selectivity.

The synthesis method is characterized in that N, N-Dimethylformamide (DMF) is used as a reaction solvent, diphenyl antimony chloride IX containing a bridged nitrogen atom ligand and brominated aromatic hydrocarbon XIII are used as raw materials, 1, 2-bis (diphenylphosphino) ethane nickel chloride is adopted for catalytic reaction, and the cyclic organic antimony compound is obtained with high yield and high selectivity.

The synthesis method is characterized in that N, N-Dimethylformamide (DMF) is used as a reaction solvent, diphenyl antimony X containing a bridged nitrogen atom ligand and bromo-arene XIII are used as raw materials, 1, 2-bis (diphenylphosphine) ethane nickel chloride is adopted for catalytic reaction, and the cyclic organic antimony compound is obtained with high yield and high selectivity.

The synthesis method is characterized in that N, N-Dimethylformamide (DMF) is used as a reaction solvent, diphenyl antimony iodide XI containing a bridged nitrogen atom ligand and bromo-arene XIII are used as raw materials, 1, 2-bis (diphenylphosphino) ethane nickel chloride is adopted for catalytic reaction, and the cyclic organic antimony compound is obtained with high yield and high selectivity.

The synthesis method is characterized in that N, N-Dimethylformamide (DMF) is used as a reaction solvent, diphenyl antimony chloride IX and chloroarene XIV containing a bridged nitrogen atom ligand are used as raw materials, 1, 2-bis (diphenylphosphino) ethane nickel chloride is adopted for catalytic reaction, and the cyclic organic antimony compound is obtained with high yield and high selectivity.

The synthesis method is characterized in that N, N-Dimethylformamide (DMF) is used as a reaction solvent, diphenyl antimony X containing a bridged nitrogen atom ligand and chloroarene XIV are used as raw materials, 1, 2-bis (diphenylphosphine) ethane nickel chloride is adopted for catalytic reaction, and the cyclic organic antimony compound is obtained with high yield and high selectivity.

The synthesis method is characterized in that N, N-Dimethylformamide (DMF) is used as a reaction solvent, diphenyl antimony iodide XI containing a bridged nitrogen atom ligand and chloroarene XIV are used as raw materials, 1, 2-bis (diphenylphosphine) ethane nickel chloride is adopted for catalytic reaction, and the cyclic organic antimony compound is obtained with high yield and high selectivity.

[ description of the drawings ]

FIG. 1 is a schematic diagram showing the preparation of cyclic organic antimony compounds according to the present invention.

[ detailed description ] embodiments

The invention provides a high-efficiency synthesis method of a cyclic organic antimony compound, which is shown in the attached drawing: adding diphenyl antimony halide containing a bridged nitrogen atom ligand, halogenated aromatic hydrocarbon (R-X, X ═ Br, I), 1, 2-bis (diphenylphosphine) ethane nickel chloride, 1, 1 '-binaphthyl-2, 2' -bis-diphenylphosphine, zinc powder and lithium iodide into a reactor, vacuumizing and backfilling with nitrogen for 3 times, then adding a solvent into the reactor, and reacting for 8-12 hours. After the reaction is finished, quenching the reaction product by using a proper amount of 1N dilute hydrochloric acid solution, and then carrying out neutralization, washing, drying and concentration on the reaction product to obtain a crude product. Finally, the pure compound is obtained through column chromatography separation.

The invention is further illustrated below with reference to specific preparation examples:

preparation example 1

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu， R₂，R₃H), 0.3mmol iodobenzene (R)₄H), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisDiphenylphosphine, 0.6mmol zinc powder and 0.6mmol lithium iodide, and the mixture was back-filled with nitrogen three times under vacuum, and 3mL Tetrahydrofuran (THF) was added under nitrogen atmosphere to react at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure compound, and the yield is 85%.

Preparation example 2

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂, R₃H), 0.3mmol 4-methyliodobenzene (R)₄4-Me), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under a nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure compound, and the yield is 90%.

Preparation example 3

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂, R₃H), 0.3mmol of 3-methyliodobenzene (R)₄3-Me), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under a nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is purified by column chromatography to obtain a pure compound with the yield of 88%.

Preparation example 4

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂， R₃H), 0.3mmol 2-methyliodobenzene (R)₄2-Me), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under a nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure compound, and the yield is 85%.

Preparation example 5

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂， R₃H), 0.3mmol 4-cyanoiodobenzene (R)₄4-CN), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under a nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure compound, and the yield is 80%.

Preparation example 6

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂，R₃H), 0.3mmol 3-cyanoiodobenzene (R)₄3-CN), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, and extractingNitrogen was backfilled in vacuo three times, and 3mL Tetrahydrofuran (THF) was added under nitrogen and reacted at 100 deg.C for 12 h. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is purified by column chromatography to obtain a pure compound with the yield of 82%.

Preparation example 7

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂， R₃H), 0.3mmol 2-cyanoiodobenzene (R)₄2-CN), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under a nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to give pure compound with a yield of 75%.

Preparation example 8

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝Ph,R₂, R₃H), 0.3mmol 4-ethoxycarbonyliodobenzene (R)₄4-COOEt), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under a nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure compound with the yield of 89%.

Preparation example 9

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂， R₃H), 0.3mmol of 3-iodofuran (R)₄3-Furan), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure compound, and the yield is 90%.

Preparation example 10

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂, R₃H), 0.3mmol of 3-iodothiophene (R)₄3-Thiophene), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure compound, and the yield is 85%.

Preparation example 11

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂, R₃H), 0.3mmol of 2-iodofuran (R)₄2-Furan), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, and vacuum-filling with nitrogen gas three times under nitrogen atmosphere3mL of Tetrahydrofuran (THF) was added and reacted at 100 ℃ for 12 h. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to give a pure compound with a yield of 86%.

Preparation example 12

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂, R₃H), 0.3mmol 2-iodothiophene (R)₄2-Thiophene), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure compound, and the yield is 81%.

Preparation example 13

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂, R₃H), 0.3mmol 2-iodobenzofuran (R)₄2-Benzofuran), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to give a pure compound with a yield of 84%.

Preparation example 14

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂, R₃H), 0.3mmol 2-iodobenzothiophene (R)₄2-Thianaphthene), 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure compound, and the yield is 79%.

Preparation example 15

0.3mmol of diphenylantimony chloride IX (R) containing a bridged nitrogen ligand was added to a 25mL reaction tube₁＝n-Bu,R₂， R₃H), 0.3mmol of 3-iodo-9-methylcarbazole, 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to give a pure compound with a yield of 83%.

Preparation example 16

0.3mmol of diphenylantimony bromide X (R) containing bridged nitrogen ligands was added to a 25mL reaction tube₁＝n-Bu,R₂, R₃H), 0.3mmol of 1-iodo-4-butylbenzene, 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of Tetrahydrofuran (THF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours.After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to give a pure compound with a yield of 84%.

Preparation example 17

0.3mmol of diphenylantimony bromide X (R) containing bridged nitrogen ligands was added to a 25mL reaction tube₁＝n-Bu,R₂, R₃H), 0.3mmol of 3-bromo-9-methylcarbazole, 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of N, N-Dimethylformamide (DMF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to give a pure compound with a yield of 84%.

Preparation example 18

0.3mmol of diphenylantimony bromide X (R) containing bridged nitrogen ligands was added to a 25mL reaction tube₁＝n-Bu,R₂, R₃H), 0.3mmol of 1-bromo-4-butylbenzene 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of N, N-Dimethylformamide (DMF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure compound, and the yield is 81%.

Preparation example 19

Adding 0.3mmol of ligand containing bridged nitrogen atom into a 25mL reaction tubeDiphenylantimony iodine XI (R) of₁＝n-Bu,R₂, R₃H), 0.3mmol of 3-cyanobenzene, 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen gas three times, adding 3mL of N, N-Dimethylformamide (DMF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to give pure compound with a yield of 75%.

Preparation example 20

A25 mL reaction tube was charged with 0.3mmol of diphenylantimony iodine XI (R) containing a bridged nitrogen ligand₁＝n-Bu,R₂, R₃H), 0.3mmol of 4-ethoxycarbonylbromobenzene, 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of N, N-Dimethylformamide (DMF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to give a pure compound with a yield of 65%.

Preparation example 21

A25 mL reaction tube was charged with 0.3mmol of diphenylantimony iodine XI (R) containing a bridged nitrogen ligand₁＝n-Bu,R₂, R₃H), 0.3mmol of 4-ethoxycarbonylchlorobenzene, 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of N, N-Dimethylformamide (DMF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction, the reaction solution was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each time), and then saturated hydrogen carbonate was addedThe sodium solution was neutralized to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a pure compound, and the yield is 85%.

Preparation example 22

A25 mL reaction tube was charged with 0.3mmol of diphenylantimony iodine XI (R) containing a bridged nitrogen ligand₁＝n-Bu,R₂, R₃H), 0.3mmol of 3-cyanochlorobenzene, 0.03mmol of 1, 2-bis (diphenylphosphino) ethane nickel chloride, 0.03mmol of 1, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 0.6mmol of zinc powder and 0.6mmol of lithium iodide, vacuum-pumping and backfilling with nitrogen three times, adding 3mL of N, N-Dimethylformamide (DMF) under nitrogen atmosphere, and reacting at 100 ℃ for 12 hours. After the reaction was complete, the reaction mixture was washed three times with 9mL of 1N diluted hydrochloric acid solution (3 mL each), and then neutralized with saturated sodium bicarbonate solution to PH 7. Separating to obtain an organic phase, washing with water, drying, and concentrating under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to give a pure compound with a yield of 86%.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.