Biarene compound and synthesis method thereof

Abstract

According to the method, aryl anhydride and aryl bromide are used as main raw materials, N, N-dimethylacetamide is used as a solvent, 10 mol% of dibenzylideneacetone palladium and 10 mol% of ethylene glycol dimethyl ether nickel bromide are used as catalysts, and the aromatic hydrocarbon compounds are synthesized through a one-step synthesis method. The method comprises the following steps: putting 20 mol% of 2-dicyclohexylphosphorus-2 '-methyl biphenyl, 10 mol% of 2, 6'-dimethyl-2, 2 '-dipyridyl, one equivalent of sodium tetrafluoroborate as an additive and two equivalent of zinc powder as a reducing agent into a reaction container in a nitrogen atmosphere, heating to 100 DEG C, and reacting for 12 hours to obtain the biarene compound I with high yield. The method has the advantages of simplicity and convenience in operation, mild reaction conditions, high yield, few additives, high selectivity and the like, and has certain feasibility for realizing industrial production.

Description

[Technical field]

[0001] The invention belongs to the field of organic synthesis catalyzed by transition metal palladium, and specifically relates to a biaryl hydrocarbon compound and a synthesis method thereof. [Background technology]

[0002] Biaryl compounds are commonly found in many natural compounds, drug intermediates, agricultural drugs, and polymer materials. For example, OTBN can be used as a common intermediate for the preparation of sartan drugs (Miller J A., et al. Tetrahedron Lett., 1998, 40, 7275–7278); Losartan is a receptor blocker of angiotensin II, clinically used to treat hypertension (Charpentier B., et al. J. Med. Chem., 1995, 38, 4993–5006); Adapalene can be used to treat acne vulgaris (Charpentier B., et al. J. Med. Chem., 1995, 38, 4993–5006). Therefore, biaryl compounds have broad application prospects.

[0003] At present, the methods for synthesizing biaryl hydrocarbon compounds usually use aryl carboxylic acids, aryl halides, aryl carboxylic acid derivatives, aryl metal compounds, aryl borate or aryl trifluoromethanesulfonic acid as reaction raw materials. When aryl carboxylic acids and aryl carboxylic acid derivatives participate in the reaction to synthesize biaryl hydrocarbons, high temperature and oxidants are often required for oxidative decarboxylation. Excessive oxidizing substrates and oxidants not only increase the reaction cost, but also reduce the tolerance of reducing substrates. In addition, it will also lead to the occurrence of oxidative side reactions, limiting the application of carboxylic acid coupling reactions (Gooβen L J., et al. J. Am. Chem. Soc., 2007, 129, 4824–4833; Gooβen L J., et al. Angew. Chem., 2008, 120, 7211–7214; Becht J M., et al. Org. Lett., 2007, 9, 1781–1783). Aryl halides are generally subjected to electrophilic-nucleophilic coupling reactions with nucleophiles to synthesize biaryl compounds. However, most nucleophiles have disadvantages such as poor stability, air sensitivity, and difficulty in storage (Ullmann. J. Org. Chem., 1977, 42, 1821-1823; Reeves J T., Org. Lett., 2010, 12, 4388–4391; Minami H., Angew. Chem. Int. Ed., 2015, 54, 4665–4668). Aryl metal compounds are generally synthesized from aryl halides, and aryl boronic acids and aryl trifluoromethanesulfonates are also usually converted from aryl metal compounds or aryl halides (Kamikawa T., et al. Tetrahedron Lett., 1997, 38, 7087-7090; Littke A F., et al. J. Am. Chem. Soc., 2000, 122, 4020-4028; Reeves E K., et al. J. Org. Chem., 2019, 84, 11799-11812). At present, there is still a lack of a method for preparing biaryl hydrocarbon compounds with wide substrate applicability, high atom economy, high selectivity and industrial application value under mild reaction conditions.

[0004] Aryl anhydrides have the special property of being both electrophilic and nucleophilic, and can be obtained from abundant aromatic carboxylic acids. Aryl halides have the advantages of being cheap, low toxicity, high stability, and storage resistance. Therefore, this patent discloses a method for synthesizing biaryl compounds by a decarbonylation cross-reduction coupling reaction catalyzed by palladium / nickel bimetallics and using aromatic anhydrides and aromatic halides as reaction substrates. This method has the advantages of mild reaction conditions, high atom economy, wide substrate application range, and high product yield, and has certain potential industrial application value. At present, there are no public documents or patents at home and abroad on the synthesis of biaryl compounds by palladium / nickel synergistic catalysis of aromatic anhydrides and aromatic bromides. [Summary of the invention]

[0005] The purpose of the present invention is to provide a new method for efficiently synthesizing biaryl hydrocarbon compounds using palladium and nickel as catalysts and aromatic anhydrides and aromatic bromides as raw materials. The method has the advantages of simple operation, mild reaction conditions, high yield, less additives, etc., and has certain feasibility for realizing its industrial production.

[0006] In order to achieve the above-mentioned object of the invention, the present invention proposes the following technical solutions:

[0007] The palladium catalyst is dibenzylideneacetone palladium, and the nickel catalyst is ethylene glycol dimethyl ether nickel bromide.

[0008] The solvent is N,N-dimethylacetamide.

[0009] A biaryl hydrocarbon compound and a synthesis method thereof, wherein the biaryl hydrocarbon compound I has the following general structural formula:

[0010] Ar 1 -Ar 2

[0011] I

[0012] wherein Ar 1 Ar is phenyl, 4-methylphenyl, 2-methylphenyl, 4-cyclohexylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-phenylphenyl, 3-phenylphenyl, 4-methyl-2-phenylphenyl, 2-naphthyl, 4-chlorophenyl, 4-trifluoromethylphenyl. 2It is 4-phenylphenyl, 3-phenylphenyl, 4-methylphenyl, 4-methylphenyl, 3,4-dimethylphenyl, 4-ethylformatephenyl, 4-acetylphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-cyanophenyl, 4-fluorophenyl, 4-trifluoromethoxyphenyl, 4-trifluoromethylphenyl, 2-benzophenone, 7-quinoline, 2-fluorenyl, 2-naphthyl, 1-naphthyl, 4-(4-bromophenyl)pyridine, 5-benzofuran, 5-N-methylindolyl, 3-ethoxypyridine, and 3,4-dioxyphenyl.

[0013] The synthesis method of compound I is characterized by using aromatic anhydride II and aromatic bromide III as raw materials, N,N-dimethylacetamide as solvent, dibenzylideneacetone palladium and ethylene glycol dimethyl ether nickel bromide as catalysts, 2-dicyclohexylphospho-2'-methylbiphenyl and 2,6'-dimethyl-2,2'-bipyridine as ligands, sodium tetrafluoroborate as additive, zinc powder as reducing agent, and reacting at 100°C for 12 hours to obtain the biaryl compound I in high yield.

[0014] In the above-mentioned synthesis method, the structural formulas of the raw materials aryl anhydride ⅠⅠ and aryl bromide Ⅲ are as follows:

[0015]

[0016] Ar 1 Ar is phenyl, 4-methylphenyl, 2-methylphenyl, 4-cyclohexylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-phenylphenyl, 3-phenylphenyl, 4-methyl-2-phenylphenyl, 2-naphthyl, 4-chlorophenyl, 4-trifluoromethylphenyl. 2 It is 4-phenylphenyl, 3-phenylphenyl, 4-methylphenyl, 4-methylphenyl, 3,4-dimethylphenyl, 4-ethylformatephenyl, 4-acetylphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-cyanophenyl, 4-fluorophenyl, 4-trifluoromethoxyphenyl, 4-trifluoromethylphenyl, 2-benzophenone, 7-quinoline, 2-fluorenyl, 2-naphthyl, 1-naphthyl, 4-(4-bromophenyl)pyridine, 5-benzofuran, 5-N-methylindolyl, 3-ethoxypyridine, and 3,4-dioxyphenyl.

[0017] The synthesis method of the biaryl hydrocarbon compound provided by the present invention is a green and efficient synthesis route, and has the advantages of high yield of target product, less additives, mild reaction conditions, simple reaction operation and high selectivity.

Brief Description of the Drawings

[0018] Attached photos Figure 1 Shown is a route map for preparing biaryl hydrocarbon compounds provided by the present invention. [Specific implementation method]

[0019] The present invention provides a method for synthesizing a biaryl hydrocarbon compound, as shown in the attached figure: aromatic anhydride and aromatic bromide are used as raw materials, N,N-dimethylacetamide is used as solvent, 10 mol% of dibenzylideneacetone palladium and 10 mol% of ethylene glycol dimethyl ether nickel bromide are used as catalysts, 20 mol% of 2-dicyclohexylphospho-2'-methylbiphenyl and 10 mol% of 2,6'-dimethyl-2,2'-bipyridine, one equivalent of sodium tetrafluoroborate is used as additive, two equivalents of zinc powder is used as reducing agent, and the mixture is placed in a reaction container under a nitrogen atmosphere, heated to 100°C, reacted for 12 hours, and after the reaction is completed, separated and purified by column chromatography to obtain the corresponding target product.

[0020] The present invention will be further described below in conjunction with specific preparation examples:

[0021] Preparation Example 1

[0022] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 4-bromobiphenyl, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 84%. 1 H NMR (400MHz, CDCl3): δ7.68–7.64(m,8H),7.46(t,J=8.0Hz, 4H), 7.36(t,J=8.0Hz 2H). 13 CNMR (100MHz, CDCl3) δ140.8,140.2,128.9,127.5,127.4,127.1.

[0023] Preparation Example 2

[0024] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 3-bromobiphenyl, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 90%. 1 H NMR (400MHz, CDCl3) δ7.87 (s, 1H), 7.71 (d, J = 8.0Hz, 4H), 7.63 (d, J = 8.0Hz, 2H), 7.59–7.48 (m, 5H), 7.42 (t, J = 8.0Hz, 2H). 13 C NMR (100MHz, CDCl3) δ141.8,141.2,129.2,128.8,127.4,127.3,126.2,126.2.

[0025] Preparation Example 3

[0026] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 4-methyl bromobenzene acetate, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 74%. 1 H NMR (400MHz, CDCl3) δ8.15(d,J=8.0Hz,2H),7.70(d,J=8.0Hz,2H),7.66(d,J=8. 0Hz,2H),7.51(t,J=8.0Hz,2H),7.43(t,J=8.0Hz,1H),7.30(s,1H),3.98(s,3H). 13C NMR (100MHz, CDCl3) δ130.1,128.9,128.2,127.3,127.1,52.2,29.7.

[0027] Preparation Example 4

[0028] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 4-methyl bromobenzene acetate, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 74%. 1 H NMR (400MHz, CDCl3) δ7.62(t,J=8.0Hz,4H),7.48(t,J=8.0Hz,2H),7.42–7.36(m,3H),3.76(s,3H),3.72(s,2H). 13 C NMR (100MHz, CDCl3) δ172.1,140.8,140.2,133.0,129.7,128.8,127.4,127.3,127.1,52.2,40.9.

[0029] Preparation Example 5

[0030] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 4-acetyl bromobenzene, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 61%. 1H NMR (400MHz, CDCl3) δ8.07(d,J=8.4Hz,2H),7.72(d,J=8.4Hz,2H),7.67(d,J=7.2Hz,2H),7.51(t,J=7.4Hz,2H),7.44(t,J=7.4Hz,1H),2.68(s,3H). 13 C NMR (100MHz, CDCl3) δ197.8,145.8,139.9,135.9,129.0,128.9,128.3,127.3,127.3,26.7.

[0031] Preparation Example 6

[0032] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 4-methoxybromobenzene, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 34%. 1 H NMR (400MHz, CDCl3) δ7.59 (t, J = 8.0 Hz, 4H), 7.46 (t, J = 8.0 Hz, 2H), 7.35 (t, J = 8.0 Hz, 1H), 7.03 (d, J = 8.0 Hz, 2H), 3.90 (s, 3H). 13 C NMR (100MHz, CDCl3) δ159.2,140.9,133.8,128.8,128.2,126.8,126.7,114.2,55.4.

[0033] Preparation Example 7

[0034] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 3-methoxybromobenzene, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 43%. 1 H NMR(400MHz, CDCl3)δ7.64(d,J=8.0Hz,2H),7.48(td,J=8.0,4.0Hz,2H),7.43–7.38(m,2H) ,7.24(d,J=8.0Hz,1H),7.18(d,J=4.0Hz,1H),6.95(d,J=8.0Hz,1H),3.91(d,J=4.0Hz,3H). 13 C NMR (100MHz, CDCl3) δ160.0,142.8,141.1,129.8,128.8,127.5,127.3,119.7,112.9,112.7,55.3.

[0035] Preparation Example 8

[0036] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 2-methoxybromobenzene, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 41%. 1 H NMR (400MHz, CDCl3) δ7.46 (d, J = 8.0 Hz, 2H), 7.34 (t, J = 8.0 Hz, 2H), 7.28–7.22 (m, 3H), 6.98–6.90 (m, 2H), 3.74 (s, 3H). 13C NMR (100MHz, CDCl3) δ156.5,138.6,130.9,130.8,129.6,128.6,128.0,126.9,120.9,111.3,55.6,29.7.

[0037] Preparation Example 9

[0038] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 4-cyanobenzene bromide, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 60%. 1 H NMR (400MHz, CDCl3) δ7.74(q,J=8.0Hz,4H),7.63(d,J=8.0Hz,2H),7.52(t,J=8.0Hz,2H),7.46(t,J=8.0Hz,1H). 13 C NMR (100MHz, CDCl3) δ145.7,139.2,132.6,129.1,128.7,127.8,127.3,119.0,110.9.

[0039] Preparation Example 10

[0040] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 4-fluorobromobenzene, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 62%. 1H NMR (400MHz, CDCl3) δ7.64–7.55(m,4H),7.48(t,J=7.6Hz,2H),7.43–7.37(m,1H),7.17(t,J=8.8Hz,2H). 13 C NMR(100MHz,CDCl3)δ162.5(d,J CF =246.2Hz),140.3,137.4(d,J CF =3.1Hz),128.9,128.7(d,J CF =8.0Hz),127.3,127.1,115.6(d,J CF =21.4Hz)

[0041] Preparation Example 11

[0042] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 4-trifluoromethyl bromobenzene, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphospho-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 61%. 1 H NMR (400MHz, CDCl3) δ7.73 (s, 4H), 7.64 (d, J = 7.4Hz, 2H), 7.51 (t, J = 7.4Hz, 2H), 7.44 (t, J = 7.4Hz, 1H).

[0043] Preparation Example 12

[0044] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 2-bromobenzophenone, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 76%. 1 H NMR (400MHz, CDCl3) δ7.69 (d, J=8.0Hz, 2H), 7.63 (td, J=8.0Hz, 4.0Hz, 1H), 7. 58–7.49(m,3H),7.45(t,J=8.0Hz,1H),7.34–7.29(m,4H),7.28–7.12(m,3H). 13 CNMR (100MHz, CDCl3) δ198.9,141.2,140.2,139.0,137.4,132.9,130.4,130.1,130.0,129.1,128.8,128.2,128.1,127.4,127.1.

[0045] Preparation Example 13

[0046] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 7-bromoquinoline, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 79%. 1H NMR (400MHz, CDCl3) δ8.98(d,J=4.0Hz,1H),8.39(s,1H),8.23(d,J=8.0Hz,1H),7.93(d,J=8.0Hz, 1H),7.87(dd,J=8.0,4.0Hz,1H),7.80(d,J=8.0Hz,2H),7.54(t,J=8.0Hz,2H),7.48–7.42(m,2H). 13 C NMR (100MHz, CDCl3) δ150.7,148.3,142.5,140.3,136.1,129.1,128.3,128.0,127.5,126.9,126.4.

[0047] Preparation Example 14

[0048] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 2-bromofluorene, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 74%. 1 H NMR(400MHz, CDCl3)δ7.89(d,J=8.0Hz,1H),7.85(d,J=8.0Hz,1H),7.82,7.71–7.65( m,3H),7.60(d,J=8.0Hz,1H),7.50(t,J=8.0Hz,2H),7.45–7.34(m,3H),4.01(s,2H). 13 C NMR (100MHz, CDCl3) δ143.9,143.5,141.6,141.5,141.0,139.9,128.8,127.2,127.2,126.9,126.8,126.1,125.1,123.9,120.2,120.0,37.1.

[0049] Preparation Example 15

[0050] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 1-bromonaphthalene, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 52%. 1 H NMR (400MHz, CDCl3) δ8.05 (s, 1H), 7.89 (dt, J = 9.0, 5.2Hz, 3H), 7.75 (dd, J = 13.4, 4.8Hz, 3H), 7.53–7.46 (m, 4H), 7.38 (t, J = 7.4Hz, 1H). 13 C NMR (100MHz, CDCl3) δ141.2,138.6,133.7,132.6,128.9,128.4,128.2,127.7,127.5,127.4,126.3,126.0,125.8,125.6.

[0051] Preparation Example 16

[0052] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 2-bromonaphthalene, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 82%. 1 H NMR (400MHz, CDCl3) δ8.09 (s, 1H), 7.98–7.90 (m, 3H), 7.79 (t, J = 8.0Hz 3H), 7.57–7.50 (m, 4H), 7.43 (t, J = 8.0Hz, 1H). 13C NMR (100MHz, CDCl3) δ141.2,138.6,133.7,132.7,128.9,128.5,128.2,127.7,127.5,127.4,126.3,126.0,125.8,125.6.

[0053] Preparation Example 17

[0054] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 4-(4-bromophenyl)pyridine, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 51%. 1 H NMR(400MHz, CDCl3)δ8.65(dt,J=8.0,4.0Hz,1H),8.02(dt,J=12.0,4.0Hz,2H),7.74–7.69(m,2H),7.65(dt, J=8.0,4.0Hz,2H),7.59(dt,J=8.0,4.0Hz,2H),7.39(t,J=8.0Hz,2H),7.32–7.28(m,1H),7.20–7.16(m,1H). 13 C NMR (100MHz, CDCl3) δ156.8,149.3,142.0,140.5,137.6,137.4,128.9,127.6,127.6,127.5,127.2,122.3,120.8.

[0055] Preparation Example 18

[0056] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 5-bromobenzofuran, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 47%. 1 H NMR (400MHz, CDCl3) δ8.08(d,J=4.0Hz,1H),7.99(d,J=8.0Hz,1H),7.71(d,J=8.0Hz, 2H),7.64(dd,J=8.0,4.0Hz,1H),7.52(t,J=8.0Hz,3H),7.42(dd,J=12.0,4.0Hz,2H). 13 C NMR (101MHz, CDCl3) δ141.4,140.2,138.8,137.8,128.9,127.5,127.2,127.1,124.1,123.9,122.7,122.0.

[0057] Preparation Example 19

[0058] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 5-bromo-1-methylindole, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 21%. 1H NMR(400MHz, CDCl3)δ7.77(d,J=1.2Hz,1H),7.62–7.56(m,2H),7.43–7.29(m,4H),7. 23(t,J=7.4Hz,1H),7.01(d,J=3.2Hz,1H),6.47(dd,J=3.2,1.0Hz,1H),3.75(s,3H). 13 C NMR (100MHz, CDCl3) δ142.6,136.3,132.9,129.5,128.9,128.6,127.4,126.3,121.4,119.4,109.4,101.3,33.0,29.7.

[0059] Preparation Example 20

[0060] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 2-bromo-4-ethoxypyridine, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 50%. 1 H NMR (400MHz, CDCl3) δ8.42(d,J=4.0Hz,1H),7.82(dd,J=12.0,4.0Hz,1H),7.56(d,J=8.0Hz,2H),7.48(t, J=8.0Hz,2H),7.38(t,J=8.0Hz,1H),6.84(d,J=8.0Hz,1H),4.45(q,J=8.0Hz,2H),1.47(t,J=8.0Hz,3H). 13 C NMR (100MHz, CDCl3) δ163.4,145.0,138.0,137.5,130.0,129.0,127.3,126.7,111.0,61.9,14.7.

[0061] Preparation Example 21

[0062] To a 25 mL tubular reactor, 0.2 mmol of benzoic anhydride, 0.8 mmol of 3,4-dioxybromobenzene, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 44%. 1 H NMR (400MHz, CDCl3) δ7.55(d,J=7.4Hz,2H),7.44(t,J=7.6Hz,2H),7.35(t,J=7.4Hz,1H),7.13–7.07(m,2H),6.92(d,J=7.8Hz,1H),6.04(s,2H). 13 C NMR (100MHz, CDCl3) δ148.1,147.1,140.9,135.6,128.8,126.9,126.9,120.7,108.6,107.7,101.2.

[0063] Preparation Example 22

[0064] To a 25 mL tubular reactor, 0.2 mmol of p-toluic anhydride, 0.8 mmol of 4-bromobiphenyl, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 59%. 1 H NMR (400MHz, CDCl3) δ7.73–7.66(m,6H),7.59(d,J=8.0Hz,2H),7.50(t,J=8.0Hz,2H),7.40(t,J=8.0Hz,1H),7.31(d,J=8.0Hz,2H),2.45(s,3H). 13C NMR (100MHz, CDCl3) δ140.8,140.1,139.9,137.9,137.2,129.6,128.8,127.5,127.3,127.1,126.9,21.2.

[0065] Preparation Example 23

[0066] To a 25 mL tubular reactor, 0.2 mmol of p-tert-butylbenzoic anhydride, 0.8 mmol of 4-bromobiphenyl, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 59%. 1 H NMR (400MHz, CDCl3) δ7.76–7.67(m,6H),7.64(d,J=8.0Hz,2H),7.52(dd,J=16.0,8.0Hz,4H),7.41(t,J=8.0Hz,1H),1.43(s,9H). 13 C NMR (100MHz, CDCl3) δ150.4,140.8,140.0,139.7,137.8,128.8,127.5; 127.4,127.1,127.1,126.7,125.8,34.6,31.4.

[0067] Preparation Example 24

[0068] 0.2 mmol of 4-chlorobenzoic anhydride, 0.8 mmol of 4-bromobiphenyl, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added to a 25 mL tubular reactor, and heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 66%. 1H NMR (400MHz, CDCl3) δ7.70 (dd, J=16.0, 8.0Hz, 6H), 7.61 (d, J=8.0Hz, 2H), 7.53–7.45 (m, 4H), 7.41 (t, J=8.0Hz, 1H). 13 C NMR (100MHz, CDCl3) δ140.5,140.5,139.2,138.9,133.5,129.0,128.9,128.3,127.6,127.5,127.4,127.1.

[0069] Preparation Example 25

[0070] 0.2 mmol of 4-trifluoromethylbenzoic anhydride, 0.8 mmol of 4-bromobiphenyl, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added to a 25 mL tubular reactor, and the mixture was heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 37%. 1 H NMR (400MHz, CDCl3) δ7.78(d,J=8.0Hz,4H),7.75(d,J=4.0Hz,4H),7.70(d,J=8.0Hz,2H),7.53(t,J=8.0Hz,2H),7.44(t,J=8.0Hz,1H).

[0071] Preparation Example 26

[0072] 0.2 mmol of 4-methylbiphenyl-2-anhydride, 0.8 mmol of 4-bromobiphenyl, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added to a 25 mL tubular reactor, and heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 37%.1 H NMR (400MHz, CDCl3) δ7.64(d,J=8.0Hz,1H),7.51(d,J=8.0Hz,1H),7.46(t,J=8.0Hz, 1H),7.36(t,J=8.0Hz,1H),7.26(d,J=8.0Hz,1H),7.09(q,J=8.0Hz,1H),2.35(s,1H). 13 C NMR (100MHz, CDCl3) δ140.7,140.7,140.6,140.1,139.0,138.5,136.2,130.7 ,130.6,130.3,129.8,128.8,128.7,127.5,127.3,127.2,127.0,126.5,21.2.

[0073] Preparation Example 27

[0074] 0.2 mmol of 2-naphthoic anhydride, 0.8 mmol of 4-bromobiphenyl, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added to a 25 mL tubular reactor, and heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 58%. 1 H NMR (400MHz, CDCl3) δ8.05(d,J=8.0Hz,1H),7.96(dd,J=16.0,8.0Hz,2H),7.77(dd,J=16.0,8.0Hz,4H),7.66–7.48(m,8H),7.44(t,J=8.0Hz,1H). 13 C NMR (100MHz, CDCl3) δ140.88,140.2,139.9,133.8,131.7,130.6,128.9,128.4,127.8,127.4,127.2,127.1,127.0,126.1,126.1,125.9,125.5.

[0075] Preparation Example 28

[0076] 0.2 mmol of 2-methylbenzoic anhydride, 0.8 mmol of 4-bromobiphenyl, dibenzylideneacetone palladium (10 mol%, 0.02 mmol), ethylene glycol dimethyl ether nickel bromide (10 mol%, 0.02 mmol), 2-dicyclohexylphosphine-2'-methylbiphenyl (20 mol%, 0.04 mmol), 2,6'-dimethyl-2,2'-bipyridine (10 mol%, 0.02 mmol), sodium tetrafluoroborate (1 equiv, 0.2 mmol), zinc powder (2 equiv, 0.4 mmol), N,N-dimethylacetamide (1 mL) were added to a 25 mL tubular reactor, and heated to 100° C. for 12 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 79%. 1 H NMR (400MHz, CDCl3) δ7.62–7.55(m,4H),7.42–7.36(m,2H),7.36–7.25(m,3H),7.21(d,J=2.8Hz,4H),2.26(s,3H). 13 C NMR (100MHz, CDCl3) δ141.5,141.1,141.1,139.6,135.5,130.4,129.9,129.7,128.9,127.4,127.4,127.1,126.8,125.9,20.6.

[0077] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be based on the attached claims.

Claims

1. A biaryl hydrocarbon compound and a synthesis method thereof, wherein the palladium catalyst is dibenzylideneacetone palladium and the nickel catalyst is ethylene glycol dimethyl ether nickel bromide.

2. The solvent is N,N-dimethylacetamide.

3. The general structural formula of the biaryl hydrocarbon compound I is as follows: Ar 1 -On 2 I 4. Wherein the Ar 1 Ar is phenyl, 4-methylphenyl, 2-methylphenyl, 4-cyclohexylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-phenylphenyl, 3-phenylphenyl, 4-methyl-2-phenylphenyl, 2-naphthyl, 4-chlorophenyl, 4-trifluoromethylphenyl. 2 It is 4-phenylphenyl, 3-phenylphenyl, 4-methylphenyl, 4-methylphenyl, 3,4-dimethylphenyl, 4-ethylformatephenyl, 4-acetylphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-cyanophenyl, 4-fluorophenyl, 4-trifluoromethoxyphenyl, 4-trifluoromethylphenyl, 2-benzophenone, 7-quinoline, 2-fluorenyl, 2-naphthyl, 1-naphthyl, 4-(4-bromophenyl)pyridine, 5-benzofuran, 5-N-methylindolyl, 3-ethoxypyridine, and 3,4-dioxyphenyl.

5. The synthesis method according to claim 1, characterized in that Using aromatic anhydride II and aromatic bromide III as raw materials, N,N-dimethylacetamide as solvent, dibenzylideneacetone palladium and ethylene glycol dimethyl ether nickel bromide as catalysts, 2-dicyclohexylphospho-2'-methylbiphenyl and 2,6'-dimethyl-2,2'-bipyridine as ligands, sodium tetrafluoroborate as additive, zinc powder as reducing agent, and effective reaction at 100°C for 12 hours, biaryl hydrocarbon compound I can be obtained in high yield. In the above synthesis method, the structural formulas of the raw materials aryl anhydride II and aryl bromide III are as follows: wherein Ar 1 Ar is phenyl, 4-methylphenyl, 2-methylphenyl, 4-cyclohexylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-phenylphenyl, 3-phenylphenyl, 4-methyl-2-phenylphenyl, 2-naphthyl, 4-chlorophenyl, 4-trifluoromethylphenyl. 2 It is 4-phenylphenyl, 3-phenylphenyl, 4-methylphenyl, 4-methylphenyl, 3,4-dimethylphenyl, 4-ethylformatephenyl, 4-acetylphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-cyanophenyl, 4-fluorophenyl, 4-trifluoromethoxyphenyl, 4-trifluoromethylphenyl, 2-benzophenone, 7-quinoline, 2-fluorenyl, 2-naphthyl, 1-naphthyl, 4-(4-bromophenyl)pyridine, 5-benzofuran, 5-N-methylindolyl, 3-ethoxypyridine, and 3,4-dioxyphenyl.

6. The synthesis method according to claim 1, characterized in that With aromatic anhydride and aromatic bromide as raw materials, N,N-dimethylacetamide as solvent, 10 mol% dibenzylideneacetone palladium and 10 mol% ethylene glycol dimethyl ether nickel bromide as catalysts, 20 mol% 2-dicyclohexylphospho-2'-methylbiphenyl and 10 mol% 2,6'-dimethyl-2,2'-bipyridine as ligands, one equivalent of sodium tetrafluoroborate as additive, two equivalents of zinc powder as reducing agent, placed in a reaction container under a nitrogen atmosphere, heated to 100°C, and reacted for 12 hours.

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