A process for the synthesis of alkyl aryl ethers

Abstract

The application discloses a simple method for synthesizing alkyl aryl ethers. The method uses cheap and abundant aryl or heteroaryl halides and alcohols as substrates, and successfully realizes a carbon-oxygen bond coupling reaction catalyzed by a cheap transition metal nickel in the presence of a reducing agent and an organic base, so that a series of alkyl aryl ether compounds are prepared in a high yield under mild conditions. The raw materials are simple and easy to obtain, the reaction process is simple and easy to operate, the conditions are mild, the yield is high, the substrate range is wide, the use of traditional noble metal catalysts and inorganic bases is avoided, and problems such as a complex catalytic system reaction and poor functional group compatibility caused by the use of the noble metal catalysts and the inorganic bases are avoided. The method is a simple and efficient method for synthesizing alkyl aryl ethers, and has a good application prospect.

Description

Technical Field

[0001] This invention relates to a simple method for synthesizing alkyl aryl ethers, specifically a method for etherifying aryl or heteroaryl halides using an inorganic nickel salt as a catalyst, belonging to the field of organic synthesis technology. Background Technology

[0002] Alkyl aryl ethers are widely found in molecules used in pharmaceuticals, pesticides, and natural products, possessing significant application value. Their synthesis has long been a crucial research area in organic synthesis. In fact, over the past few decades, palladium-catalyzed etherification of alkyl aryl ethers and copper-catalyzed Ullmann coupling have been widely applied in their synthesis. Although these reactions exhibit high reactivity, certain limitations remain: the use of insoluble strong inorganic bases and complex ligands restricts large-scale scale-up, affects functional group compatibility, and reduces resource utilization in the synthesis process. Therefore, chemists have been searching for alternative, high-yield, economical, and environmentally friendly novel catalytic systems. Nickel is abundant, inexpensive, and easily commercialized, showing promising industrial application prospects. Consequently, nickel-catalyzed aryl CO bond coupling of aryl halides and alcohols has attracted widespread attention from chemists. The MacMillan group first reported the combination of photocatalysis and nickel catalysis to achieve the etherification of alkyl aryl halides and alcohols (Nature 2015, 524, 330). Since then, the photocatalytic nickel-co-catalyzed strategy has been widely applied to CO bond coupling reactions. However, this catalytic system requires expensive metal photosensitizers and the substrates are only applicable to brominated aromatics. Stradiotto's group achieved nickel-catalyzed CO bond coupling reactions of aryl electrophiles with alcohols (J. Am. Chem. Soc. 2018, 140, 5023). This work mainly promoted the formation of aryl CO bond coupling products by cleverly designing phosphine ligands PAd-DalPhos or CyPAd-DalPhos. However, this catalytic system still requires the design of specific and complex phosphine ligands and the use of highly basic metal alkoxides. Xue's group reported a photo-promoted nickel-catalyzed aryl CO bond coupling reaction (Angew. Chem. Int. Ed. 2020, 59, 12714), which does not require the addition of an additional photosensitizer. Subsequently, Baran's group also achieved electrocatalyzed nickel-catalyzed aryl-CO coupling reactions (Angew. Chem. Int. Ed. 2021, 60, 20700). Although significant progress has been made in directly promoting nickel-catalyzed aryl-CO bond coupling reactions via photo / electrochemistry, unresolved issues remain: 1) electron-rich haloarynes exhibit poor reactivity; 2) in photo-induced nickel catalysis systems, specific nickel complexes that can be excited by short-wavelength light (390-395 nm) need to be designed, resulting in poor functional group tolerance and reaction diversity; in electrocatalysis systems, there are issues of complex operation and easy deactivation of active intermediates. Therefore, developing simpler and cheaper methods for synthesizing alkylaryl ethers remains a significant challenge. Summary of the Invention

[0003] The purpose of this invention is to provide a method for synthesizing alkylaryl ether compounds by reacting aryl or heteroaryl halides with alcohols using abundant and inexpensive inorganic nickel salts as catalysts. This method has readily available raw materials, simple process, good substrate applicability, and good yield.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] A method for synthesizing alkyl aryl ether compounds, characterized in that: the compound shown in Formula I and the compound shown in Formula II are used as reaction substrates, and a divalent nickel salt, a ligand, an organic base, a silane reagent, and an organic solvent are added. Under an inert atmosphere and heating conditions, an etherification reaction of the haloaromatic hydrocarbon occurs to obtain the alkyl aryl ether compound shown in Formula III.

[0006]

[0007] In the formula, Ar represents the aromatic hydrocarbon obtained by mono- or poly-substituted ortho-, meta-, or para-substituted groups on the benzene ring, wherein the substituents are selected from C1 to C2. 12 Alkyl, C1-C 12 Alkoxy, C2-C 12 Acyl, halogen, cyano, cyclopropanecyano, trifluoromethoxy, methyl sulfone, trifluoromethyl, furanyl, quinoxalinyl, thiophene, adamantyl, methylenedioxy, dioxane, pyridyl, methylpyridyl, trifluoromethylpyridyl, thiophene, benzothiophene, furanyl, benzofuranyl, carbazole, valeronyl; R is selected from C1 to C2. 18 Alkyl, C1-C 18 Alkoxy, C4~C 15 alkenyl, C3~C 10 cycloalkyl, C2-C 10 Alkyl hydroxyl, trifluoroethyl, benzyl, naphthyl, C1-C4 alkyl-substituted phenylethyl, halogen-substituted phenylethyl, thiophene methyl, furanyl methyl, piperidine methyl; X represents Br or Cl;

[0008] The ligand is the compound shown in structure IV.

[0009]

[0010] In the formula, R' is selected from hydrogen atom, halogen atom, phenyl, C1-C4 alkyl, methoxy, ester group, and amino.

[0011] The divalent nickel salt is an inorganic nickel salt used as a catalyst, and is mainly selected from nickel bromide, nickel bromide trihydrate, or nickel chloride.

[0012] The organic base is selected from tetramethylguanidine (TMG), tert-butyltetramethylguanidine (TMG), etc. tBu-TMG), 1,5,7-triazonibicyclo[4.4.0]dec-5-ene (TBD), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabispirocyclo[5.4.0]undec-7-ene (DBU), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD).

[0013] The silane reagent is a reducing agent, mainly selected from PhSiH3, Ph3SiH, and Et2SiH2.

[0014] The organic solvent is selected from N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, 1,4-dioxane, toluene, and acetonitrile.

[0015] The reaction temperature is 80–120℃, and the reaction time is 12–24 h.

[0016] This invention utilizes inexpensive and readily available inorganic nickel salts as catalysts to achieve the etherification reaction of aryl or heterocyclic aryl halides under heating conditions, yielding a series of alkyl aryl ether compounds. The preparation method is simple, with high yield and good selectivity. It not only solves the problem that low-activity aryl halides cannot participate in the reaction, but also avoids the use of complex ligands and inorganic bases in transition metal catalysis. Furthermore, this invention overcomes the shortcomings of limited substrate scope, expensive raw materials and reagents, complex reaction systems, and is economical and inexpensive, aligning with the concept of environmentally friendly, economical, and green chemical synthesis, and possesses significant application prospects. Detailed Implementation

[0017] The present invention will be further described in detail below with reference to the embodiments, but the scope of protection of the present invention is not limited to these embodiments.

[0018] Example 1

[0019] Under an argon atmosphere, p-methylbromobenzene (0.5 mmol), phenylbutanol (1.0 mmol), bipyridine (0.025 mmol), nickel bromide (0.025 mmol), DBU (0.75 mmol), phenylsilane (0.15 mmol), toluene (1.0 mL), and a magnetic stir bar were added to a reaction tube. The reaction was stirred in an oil bath at 120 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solvent was removed by vacuum distillation to obtain the crude product. The crude product was purified by column chromatography using petroleum ether and ethyl acetate as eluents to obtain the target product in 79% yield. The product structure was determined by... 1 HNMR, 13 Confirmed by C NMR and HRMS.

[0020]

[0021] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows:1 H NMR (400MHz, CDCl3) δ7.29-7.25(m,2H),7.19-7.15(m,3H),7.05(d,J=8.0Hz,2H),6.77 (d,J=8.0Hz,2H),3.93-3.90(m,2H),2.68-2.65(m,2H),2.27(s,3H),1.80-1.77(m,4H); 13 C NMR (100MHz, CDCl3) δ157.05,142.37,129.96,129.79,128.55,128.43,125.88,114.45,67.88,35.72,29.05,28.01,20.58.HRMS(ESI)m / zC 17 H 21 O[M+H] + Theoretical value: 241.1587, measured value: 241.1597.

[0022] Example 2

[0023] In this embodiment, equimolar 4-methoxybromobenzene was used to replace p-methylbromobenzene in Example 1, and 1,4-dioxane was used to replace toluene. Other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 75%.

[0024]

[0025] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.30-7.25(m,2H),7.20-7.16(m,3H),6.82(s,4H),3.93-3.90(m,2H),3.76(s,3H),2.71-2.66(m,2H),1.82-1.78(m,4H); 13 C NMR (100MHz, CDCl3) δ153.90,153.42,142.42,128.58,128.46,125.92,115.63,114.80,68.61,55.90,35.77,29.15,28.02.HRMS(ESI)m / z C 17 H 21 O2[M+H] + Theoretical value: 257.1536, measured value: 257.1536.

[0026] Example 3

[0027] In this embodiment, equimolar 4-tert-butylbromobenzene was used to replace p-methylbromobenzene in Example 1, and nickel bromide trihydrate was used to replace nickel bromide. Other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 81%.

[0028]

[0029] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz, CDCl3)δ7.30-7.26(m,4H),7.20-7.17(m,3H),6.84-6.80(m, 2H),3.96-3.93(m,2H),2.69-2.66(m,2H),1.82-1.78(m,4H),1.29(s,9H); 13 CNMR(100MHz, CDCl3)δ156.93,143.32,142.42,128.58,128.45,126.32,125.90,114.05,67.82,35.74,34.19,31.68,29.09,28.04.HRMS(ESI)m / z C 20 H 27 O[M+H] + Theoretical value: 283.2056, measured value: 283.2059.

[0030] Example 4

[0031] In this embodiment, equimolar amounts of 4-benzyloxybromobenzene were used to replace p-methylbromobenzene in Example 1, and 4,4'-di-tert-butylbipyridine were used to replace bipyridine. The other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 82%.

[0032]

[0033] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz, CDCl3)δ7.44-7.36(m,5H),7.33-7.27(m,2H),7.21-7.19(m,3H),6.92 -6.81(m,4H),5.02(s,2H),3.94-3.91(m,2H),2.71-2.67(m,2H),1.82-1.79(m,4H); 13C NMR (100MHz, CDCl3) δ153.63,153.08,142.40,137.51,128.67,128.57,128.46,127.9 9,127.61,125.91,116.00,115.59,70.88,68.55,35.75,29.13,28.01.HRMS(ESI)m / z C 23 H 25 O2[M+H] + Theoretical value: 333.1849, measured value: 333.1857.

[0034] Example 5

[0035] In this embodiment, equimolar amounts of 4-bromobiphenyl were used to replace p-methylbromobenzene in Example 1, and 4,4'-dimethoxybipyridine were used to replace bipyridine. The other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 79%.

[0036]

[0037] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.58-7.49(m,4H),7.40(t,J=7.4Hz,2H),7.29(t,J=7.6Hz,3H),7.23-7. 17(m,3H),6.97-6.94(m,2H),4.01(t,J=5.6Hz,2H),2.70(t,J=6.6Hz,2H),1.87-1.81(m,4H); 13 C NMR (100MHz, CDCl3) δ158.82,142.35,141.03,133.78,128.84,128.58,128.48,12 8.26,126.86,126.75,125.95,114.94,68.01,35.75,29.05,28.01.HRMS(ESI)m / z C 22 H 23 O[M+H] + Theoretical value: 303.1743, measured value: 303.1744.

[0038] Example 6

[0039] In this embodiment, equimolar amounts of 1-(4-bromophenyl)-cyclopropaneformonitrile were used to replace p-methylbromobenzene in Example 1, and nickel bromide trihydrate was used to replace nickel bromide. Other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 65%.

[0040]

[0041] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.32-7.28(m,2H),7.23-7.20(m,5H),6.88-6.84(m,2H),3.97-3.95(m,2H) ,2.72-2.69(m,2H),1.83-1.81(m,4H),1.66(dd,J=7.6,4.8Hz,2H),1.33(dd,J=7.6,4.8Hz,2H); 13 C NMR (100MHz, CDCl3) δ158.73,142.20,128.50,128.42,127.87,127.66,125. 90,123.08,114.92,67.97,35.64,28.86,27.89,17.46,13.23.HRMS(ESI)m / z C 20 H 22 NO[M+H] + Theoretical value: 292.1696, measured value: 292.1703.

[0042] Example 7

[0043] In this embodiment, equimolar 4-bromobenzonitrile was used to replace p-methylbromobenzene in Example 1, tetrahydrofuran was used to replace toluene, and other steps were the same as in Example 1, to obtain the target product with the following structural formula, with a yield of 65%.

[0044]

[0045] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz,CD3OD)δ7.58-7.56(m,2H),7.32-7.27(m,2H),7.21-7.19(m,3H) ,6.93-6.91(m,2H),4.02-3.99(m,2H),2.72-2.68(m,2H),1.87-1.79(m,4H); 13 C NMR (100MHz, CDCl3) δ162.52,142.05,134.11,128.54,126.06,119.42,115.32,103.93,68.33,35.64,28.70,27.82.HRMS(ESI)m / z C 17 H 18 NO[M+H] + Theoretical value: 252.1383, measured value: 252.1383.

[0046] Example 8

[0047] In this embodiment, equimolar amounts of 4-bromoacetophenone were used to replace p-methylbromobenzene and tert-butyltetramethylguanidine in Example 1. t Replacing tetramethylguanidine with Bu-TMG, the other steps were the same as in Example 1, yielding the target product with the following structure in 87% yield.

[0048]

[0049] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.93 (d, J = 8.8Hz, 2H), 7.32-7.28 (m, 2H), 7.22-7.18 (m, 3H), 6.91 (d, J=8.8Hz,2H),4.03(t,J=5.8Hz,2H),2.70(t,J=7.0Hz,2H),2.56(s,3H),1.88-1.81(m,4H); 13 C NMR (100MHz, CDCl3) δ196.90,163.15,142.13,130.70,130.30,128.52,128.48,125.98,114.24,68.12,35.65,28.79,27.87,26.44.HRMS(ESI)m / z C 18 H 21 O2[M+H] + Theoretical value: 269.1536, measured value: 269.1538.

[0050] Example 9

[0051] In this embodiment, equimolar amounts of 4-fluorobromobenzene were used to replace p-methylbromobenzene in Example 1, and 4,4'-diphenyl-2,2'-bipyridine were used to replace bipyridine. The other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 80%.

[0052]

[0053] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.32-7.28(m,2H),7.22-7.18(m,3H),6.99-6.94(m,2H) ,6.85-6.80(m,2H),3.95-3.92(m,2H),2.72-2.68(m,2H),1.83-1.80(m,4H); 13C NMR (100MHz, CDCl3) δ157.31 (d, J = 236.4Hz), 156.12, 155.35 (d, J = 2.1Hz), 142.31, 128.56, 12 8.48, 125.96, 115.87 (d, J = 22.8Hz), 115.58 (d, J = 7.9Hz), 68.12, 35.65, 28.79, 27.87, 26.44.

[0054] Example 10

[0055] In this embodiment, equimolar amounts of 4-trifluoromethoxybromobenzene were used to replace p-methylbromobenzene in Example 1, and 5,5'-dimethyl-2,2'-bipyridine were used to replace bipyridine. The other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 90%.

[0056]

[0057] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (600MHz, CDCl3) δ7.33-7.29(m,2H),7.23-7.19(m,3H),7.15-7.13(m,2H),6. 89-6.85(m,2H),3.96(t,J=5.8Hz,2H),2.71(t,J=7.0Hz,2H),1.85-1.81(m,4H); 13 C NMR (100MHz, CDCl3) δ157.76, 142.77, 142.25, 128.57, 128.51, 125.99, 122.51, 120.75 (d, J = 254.0Hz), 115.35, 68.38, 35.71, 28.93, 27.93.

[0058] Example 11

[0059] In this embodiment, equimolar amounts of 4-bromophenyl sulfone were used to replace p-methylbromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in the target product with the following structural formula and a yield of 96%.

[0060]

[0061] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.85 (d, J = 8.8Hz, 2H), 7.31-7.28 (m, 2H), 7.21-7.19 (m, 3H), 6.99 (d, J=8.8Hz,2H),4.04(t,J=5.8Hz,2H),3.03(s,3H),2.70(t,J=7.0Hz,2H),1.84-1.81(m,4H); 13 C NMR (100MHz, CDCl3) δ163.38,142.05,132.32,129.66,128.53,126.06,115.07,68.50,45.00,35.64,28.71,27.81..HRMS(ESI)m / zC 17 H 21 O3S[M+H] + Theoretical value: 305.1206, measured value: 305.1206.

[0062] Example 12

[0063] In this embodiment, p-methylbromobenzene in Example 1 was replaced with equimolar m-bromotrifluorotoluene, and bipyridine was replaced with 6,6'-diamino-2,2'-bipyridine. The other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 56%.

[0064]

[0065] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.38(t,J=8.0Hz,1H),7.33-7.29(m,2H),7.21(t,J=7.6Hz,4H),7.12(t,J=2.0 Hz,1H),7.06(dd,J=8.4,2.4Hz,1H),4.01(t,J=5.8Hz,2H),2.71(t,J=7.0Hz,2H),1.87-1.82(m,4H); 13 C NMR (100MHz, CDCl3) δ159.32, 142.20, 131.9 (q, J = 32Hz), 130.03, 128.55, 128.50, 126.00, 124.1 6(q,J=270.7Hz),118.11,117.32(q,J=3.9Hz),111.31(q,J=3.9Hz),68.15,35.68,28.84,27.91. 19 F NMR (376MHz, CDCl3) δ-62.62 (s, 3F).

[0066] Example 13

[0067] In this embodiment, equimolar m-bromoanisole was used to replace p-methylbromobenzene in Example 1, and nickel bromide trihydrate was used to replace nickel bromide. Other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 80%.

[0068]

[0069] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz,CD3OD)δ7.33-7.29(m,2H),7.23-7.17(m,4H),6.54-6.48(m,3H) ,3.98(t,J=5.8Hz,2H),3.81(s,3H),2.71(t,J=7.0Hz,2H),1.85-1.81(m,4H); 13 C NMR (100MHz, CDCl3) δ160.99,160.51,142.37,129.97,128.58,128.47,125.9 3,106.87,106.32,101.13,67.91,55.40,35.74,29.02,28.01.HRMS(ESI)m / zC 17 H 21 O2[M+H] + Theoretical value: 257.1536, measured value: 257.1536.

[0070] Example 14

[0071] In this embodiment, equimolar amounts of 2-(1-adamantyl)-4-bromoanisole were used to replace p-methylbromobenzene in Example 1, and 1,8-diazobicyclo[5.4.0]undec-5-ene (TBD) were used to replace 1,8-diazobispirocyclo[5.4.0]undec-7-ene (DBU). The other steps were the same as in Example 1, and the target product with the following structure was obtained in 82% yield.

[0072]

[0073] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.30-7.26(m,2H),7.21-7.16(m,3H),6.81(d,J=3.2Hz,2H),6.65(dd,J=8.8,3.2Hz,1H),3. 90(t,J=5.8Hz,2H),3.77(s,3H),2.68(t,J=7.0Hz,2H),2.08-2.04(m,9H),1.81-1.78(m,4H),1.76-1.75(m,6H); 13 C NMR (100MHz, CDCl3) δ153.28,153.16,142.47,140.21,128.59,128.45,125.89,114.86, 112.67,110.76,68.37,55.80,40.70,37.27,37.18,35.79,29.26,28.06.HRMS(ESI)m / z C 27 H 35 O2[M+H] + Theoretical value: 391.2632, measured value: 391.2630.

[0074] Example 15

[0075] In this embodiment, equimolar amounts of 3,5-di-tert-butylbromobenzene were used to replace p-methylbromobenzene in Example 1, and 1,4-dioxane was used to replace toluene. The other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 79%.

[0076]

[0077] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.30-7.25(m,3H),7.21-7.16(m,3H),7.01(s,1H),6.74(s,1 H),3.97(t,J=5.2Hz,2H),2.69(t,J=6.0Hz,2H),1.86-1.81(m,4H),1.31(s,18H); 13 C NMR (100MHz, CDCl3) δ158.79,152.28,142.46,128.59,128.46,125.91,115.01,108.99,67.72,35.79,35.13,31.61,29.26,28.06.HRMS(ESI)m / zC 24 H 35 O[M+H] +Theoretical value: 339.2682, measured value: 338.2685.

[0078] Example 16

[0079] In this embodiment, equimolar amounts of 6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene were used to replace p-methylbromobenzene in Example 1, and N,N-dimethylformamide was used to replace toluene. The other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 51%.

[0080]

[0081] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.29-7.26(m,2H),7.21-7.17(m,4H),6.81(d,J=2.8Hz,1H),6.69(dd,J=8.4,2.8Hz,1 H),3.93(t,J=5.8Hz,2H),2.68(t,J=7.0Hz,2H),1.82-1.80(m,4H),1.66(s,4H),1.26(s,6H),1.25(s,6H); 13 C NMR (100MHz, CDCl3) δ156.91,146.40,142.44,137.24,128.59,128.45,127.56,125.90,112 .51,111.88,67.71,35.78,35.36,34.61,33.81,32.16,31.98,29.20,28.05.HRMS(ESI)m / z C 24 H 33 O[M+H] + Theoretical value: 337.2526, measured value: 337.2525.

[0082] Example 17

[0083] In this embodiment, equimolar amounts of 3,4-dimethoxybromobenzene were used to replace p-methylbromobenzene in Example 1, and acetonitrile was used to replace toluene. The other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 54%.

[0084]

[0085] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CD3OD) δ7.30-7.26(m,2H),7.21-7.17(m,3H),6.76(d,J=8.4Hz,1H),6.50(d,J=2.8Hz,1H),6.37(d d,J=8.4,2.8Hz,1H),3.94(t,J=5.8Hz,2H),3.85(s,3H),3.83(s,3H),2.69(t,J=7.0Hz,2H),1.82-1.80(m,4H); 13 C NMR (100MHz, CDCl3) δ153.90,150.04,143.58,142.37,128.57,128.47,125.93,1 12.07,103.92,101.08,68.44,56.64,55.97,35.77,29.15,28.03.HRMS(ESI)m / z C 18 H 23 O3[M+H] + Theoretical value: 287.1642, measured value: 287.1644.

[0086] Example 18

[0087] In this embodiment, equimolar amounts of 4-bromo-1,2-methylenedioxybenzene were used to replace p-methylbromobenzene in Example 1, the amounts of nickel catalyst and bipyridine were increased to 10.0 mol%, and the other steps were the same as in Example 1, to obtain the target product with the following structural formula in a yield of 48%.

[0088]

[0089] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.30-7.26(m,2H),7.20-7.17(m,3H),6.69(d,J=8.8Hz,1H),6.47(d,J=2.4Hz,1 H),6.30(dd,J=8.8,2.4Hz,1H),5.90(s,2H),3.90-3.87(m,2H),2.69-2.66(m,2H),1.80-1.76(m,4H); 13 C NMR (100MHz, CDCl3) δ154.78,148.36,142.36,141.64,128.56,128.47,125.9 3,108.07,105.86,101.20,98.23,68.89,35.74,29.06,27.99.HRMS(ESI)m / z C 17 H19 O3[M+H] + Theoretical value: 271.1329, measured value: 271.1327.

[0090] Example 19

[0091] In this embodiment, equimolar amounts of 6-bromo-1,4-benzodioxane were used to replace p-methylbromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in the target product with the following structural formula, with a yield of 42%.

[0092]

[0093] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.32-7.28(m,2H),7.22-7.19(m,3H),6.78(d,J=8.8Hz,1H),6.46-6.41(m,2H), 4.26-4.24(m,2H),4.22-4.20(m,2H),3.90(t,J=5.4Hz,2H),2.69(t,J=6.8Hz,2H),1.82-1.79(m,4H); 13 C NMR (100MHz, CDCl3) δ153.76,143.76,142.26,137.57,128.43,128.31,125.77,1 17.35,107.99,103.47,68.36,64.62,64.16,35.60,28.92,27.85.HRMS(ESI)m / z C 18 H 21 O3[M+H] + Theoretical value: 285.1485, measured value: 285.1485.

[0094] Example 20

[0095] In this embodiment, equimolar amounts of 5-bromobenzofuran were used to replace p-methylbromobenzene in Example 1, the amounts of nickel catalyst and bipyridine were increased to 10.0 mol%, and the other steps were the same as in Example 1, yielding the target product with the following structural formula in 53% yield.

[0096]

[0097] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.59-7.57(m,1H),7.39(d,J=9.2Hz,1H),7.32-7.28(m,2H),7.23-7.18(m,3H),7.04(d,J=2. 4Hz,1H),6.90(dd,J=8.8,2.4Hz,1H),6.70(s,1H),4.01(t,J=5.8Hz,2H),2.71(t,J=7.0Hz,2H),1.86-1.83(m,4H); 13 CNMR(100MHz,CDCl3)δ155.55,150.11,145.79,142.42,128.59,128.47,128.09,12 5.93,113.82,111.88,106.81,104.71,68.82,35.78,29.16,28.05.HRMS(ESI)m / zC 18 H 19 O2[M+H] + Theoretical value: 267.1380, measured value: 267.1386.

[0098] Example 21

[0099] In this embodiment, equimolar amounts of 6-bromoquinoxaline were used to replace p-methylbromobenzene in Example 1, the amount of nickel catalyst and bipyridine was increased to 10.0 mol%, and the other steps were the same as in Example 1, to obtain the target product with the following structural formula, with a yield of 61%.

[0100]

[0101] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ8.75(s,1H),8.69(s,1H),7.98(d,J=9.2Hz,1H),7.43-7.40(m,1H),7.35-7.34(m,1 H),7.31-7.28(m,2H),7.23-7.16(m,3H),4.15(t,J=6.0Hz,2H),2.72(t,J=7.2Hz,2H),1.94-1.84(m,4H); 13 C NMR (100MHz, CDCl3) δ160.42,144.95,144.81,142.44,142.17,139.37,130.54,12 8.57,128.52,126.02,123.92,107.37,68.55,35.71,28.74,27.98.HRMS(ESI)m / z C 18 H19 N₂O[M+H] + Theoretical value: 279.1492, measured value: 279.1488.

[0102] Example 22

[0103] In this embodiment, equimolar 5-bromobenzothiophene was used to replace p-methylbromobenzene in Example 1, and 4,4'-dichloro-2,2'-bipyridine was used to replace bipyridine. The other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 44%.

[0104]

[0105] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.72(d,J=8.4Hz,1H),7.42(d,J=5.2Hz,1H),7.31-7.17(m,7H),6.9 8(dd,J=8.8,2.8Hz,1H),4.03(t,J=5.8Hz,2H),2.71(t,J=7.0Hz,2H),1.87-1.82(m,4H); 13 C NMR (100MHz, CDCl3) δ157.08,142.38,140.84,132.21,128.59,128.48,127.54,12 5.95,123.74,123.17,115.24,106.71,68.32,35.76,29.06,28.04.HRMS(ESI)m / z C 18 H 19 OS[M+H] + Theoretical value: 283.1151, measured value: 283.1158.

[0106] Example 23

[0107] In this embodiment, equimolar 6-bromo-2-methylquinoline was used to replace p-methylbromobenzene in Example 1, and tetramethylguanidine (TMG) was used to replace 1,8-diazobispiro[5.4.0]undec-7-ene (DBU). The other steps were the same as in Example 1, and the target product with the following structure was obtained with a yield of 68%.

[0108]

[0109] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.90 (d, J = 8.4Hz, 2H), 7.31 (dd, J = 9.2, 3.2Hz, 1H), 7.19 (d, J = 8.4Hz, 1H), 7.0 (d, J = 2.8Hz, 1H), 3.87 (s, 3H), 2.68 (s, 3H); 13 C NMR (100MHz, CDCl3) δ157.19,156.39,143.93,135.11,130.05,127.37,122.30,121.94,105.27,55.54,25.09.HRMS(ESI)m / z C 11 H 12 NO[M+H] + Theoretical value: 174.0913, measured value: 174.0914.

[0110] Example 24

[0111] In this embodiment, equimolar amounts of 2-bromodibenzothiophene were used to replace p-methylbromobenzene in Example 1, and Ph3SiH was used to replace PhSiH3. The other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 50%.

[0112]

[0113] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ8.07-8.05(m,1H),7.81-7.79(m,1H),7.67(d,J=8.8Hz,1H),7.57(d,J=2.4Hz,1H),7.42-7.39(m,2H),7.3 1-7.27(m,2H),7.22-7.17(m,3H),7.05(dd,J=8.8,2.4Hz,1H),4.05(t,J=5.8Hz,2H),2.70(t,J=7.0Hz,2H),1.86-1.83(m,4H); 13 C NMR (100MHz, CDCl3) δ157.29,142.36,140.75,136.77,135.66,131.39,128.60,128.51,126.79,12 5.98,124.25,123.53,123.11,121.69,116.40,106.06,68.53,35.78,29.12,28.05.HRMS(ESI)m / z C 22 H 21 OS[M+H] +Theoretical value: 333.1308, measured value: 333.1307.

[0114] Example 25

[0115] In this embodiment, equimolar amounts of 2-bromobenzofuran were used to replace p-methylbromobenzene in Example 1, and N,N-dimethylacetamide was used to replace toluene. The other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 58%.

[0116]

[0117] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.89(d,J=7.6Hz,1H),7.53(d,J=8.0Hz,1H),7.46-7.40(m,3H),7.33-7.17(m ,6H),7.03(dd,J=8.8,2.8Hz,1H),4.07(t,J=5.8Hz,2H),2.72(t,J=7.0Hz,2H),1.93-1.83(m,4H); 13 C NMR (100MHz, CDCl3) δ157.08,155.49,151.06,142.39,128.60,128.50,127.21,125.96,124.83,12 4.68,122.53,120.69,115.89,112.19,111.88,104.93,68.97,35.79,29.18,28.06.HRMS(ESI)m / zC 22 H 21 O2[M+H] + Theoretical value: 317.1536, measured value: 317.1536.

[0118] Example 26

[0119] In this embodiment, equimolar amounts of 9-(4-bromophenyl)carbazole were used to replace p-methylbromobenzene in Example 1, and nickel chloride was used to replace nickel bromide. The other steps were the same as in Example 1, and the target product with the following structural formula was obtained with a yield of 85%.

[0120]

[0121] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ8.13 (d, J = 8.0Hz, 2H), 7.44-7.37 (m, 4H), 7.32-7.18 (m, 9H), 7. 06(d,J=8.4Hz,2H),4.05(t,J=5.8Hz,2H),2.73(t,J=7.0Hz,2H),1.88-1.83(m,4H); 13 C NMR (100MHz, CDCl3) δ158.52,142.29,141.53,130.28,128.67,128.59,128.51,126.0,12 5.96,123.24,120.37,119.75,115.72,109.85,68.28,35.74,29.01,28.0.HRMS(ESI)m / z C 28 H 26 NO[M+H] + Theoretical value: 392.2009, measured value: 392.2007.

[0122] Example 27

[0123] In this embodiment, equimolar 7-bromo-3,4-dihydroquinoline-2-one was used to replace p-methylbromobenzene in Example 1, the alcohol was increased to 4.0 equiv, and the other steps were the same as in Example 1, to obtain the target product with the following structural formula, with a yield of 82%.

[0124]

[0125] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (600MHz, CDCl3) δ8.95 (s, 1H), 7.30-7.25 (m, 2H), 7.20-7.18 (m, 3H), 7.02 (d, J = 8.4Hz, 1H), 6.50 (dd, J = 8.4, 2.4Hz, 1H), 6.3 7(d,J=2.8Hz,1H),3.93(t,J=5.8Hz,2H),2.88(t,J=7.2Hz,2H),2.68(t,J=7.0Hz,2H),2.61(t,J=7.6Hz,2H),1.81-1.76(m,4H); 13 C NMR (100MHz, CDCl3) δ172.41,158.83,142.28,138.32,128.66,128.54,128.44,125.9 1,115.73,108.88,102.40,68.06,35.68,31.19,28.93,27.93,24.67.HRMS(ESI)m / zC19 H 22 NO2[M+H] + Theoretical value: 296.1645; found: Actual value: 296.1643.

[0126] Example 28:

[0127] Under an argon atmosphere, p-bromoacetophenone (0.5 mmol), methanol (1.0 mmol), bipyridine (0.025 mmol), nickel bromide (0.025 mmol), DBU (0.75 mmol), styrene (0.15 mmol), toluene (1.0 mL), and a magnetic stir bar were added to a reaction tube. The reaction was stirred in an oil bath at 120 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solvent was removed by vacuum distillation to obtain the crude product. The crude product was purified by column chromatography using petroleum ether and ethyl acetate as eluents to obtain the target product in 76% yield. The structure of the product was determined by... 1 HNMR, 13 Confirmed by C NMR and HRMS.

[0128]

[0129] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.93 (d, J = 8.8Hz, 2H), 6.93 (d, J = 8.8Hz, 2H), 3.87 (s, 3H), 2.55 (s, 3H); 13 C NMR(100MHz, CDCl3)δ196.94,163.60,130.71,130.45,113.80,55.59,26.48.HRMS(ESI)m / z C9H 11 O2[M+H] + Theoretical value: 151.0754, measured value: 151.0753.

[0130] Example 29

[0131] In this embodiment, equimolar ethanol was used to replace methanol in Example 28, and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) was used to replace 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The other steps were the same as in Example 28, and the target product with the following structure was obtained with a yield of 57%.

[0132]

[0133] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.91 (d, J = 8.8Hz, 2H), 6.90 (d, J = 8.8Hz, 2H), 4.08 (q, J = 7.0Hz, 2H), 2.54 (s, 3H), 1.43 (t, J = 7.0Hz, 3H); 13 C NMR(100MHz, CDCl3)δ196.92,163.01,130.69,130.23,114.19,63.83,26.42,14.76.HRMS(ESI)m / zC 10 H 13 O2[M+H] + Theoretical value: 165.0910, measured value: 165.0906.

[0134] Example 30

[0135] In this embodiment, equimolar octadecyl alcohol was used to replace methanol in Example 28, and 4,4'-diamino-2,2'-bipyridine was used to replace bipyridine. The other steps were the same as in Example 28, and the target product with the following structural formula was obtained with a yield of 74%.

[0136]

[0137] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.93(d,J=8.8Hz,2H),6.92(d,J=8.8Hz,2H),4.02(t,J=6.4Hz,2H),2. 55(s,3H),1.84-1.77(m,2H),1.47-1.44(m,2H),1.37-1.26(m,28H),0.88(t,J=6.6Hz,3H); 13 C NMR (100MHz, CDCl3) δ196.87,163.29,130.71,130.29,114.29,68.47,32.07,29. 84,29.80,29.73,29.70,29.50,29.26,26.43,26.12,22.83,14.25.HRMS(ESI)m / z C 26 H 45 O2[M+H] + Theoretical value: 389.3414, measured value: 389.3418.

[0138] Example 31

[0139] In this embodiment, equimolar amounts of 4-chlorophenylethanol were used to replace methanol in Example 28, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) were used to replace 1,8-diazabispirocyclo[5.4.0]undec-7-ene (DBU). The other steps were the same as in Example 28, and the target product with the following structural formula was obtained with a yield of 69%.

[0140]

[0141] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.91 (d, J = 8.8Hz, 2H), 7.30-7.26 (m, 2H), 7.22-7.20 (m, 2H) ,6.90(d,J=8.8Hz,2H),4.21(t,J=6.8Hz,2H),3.08(t,J=6.8Hz,2H),2.54(s,3H); 13 C NMR (100MHz, CDCl3) δ196.81,162.70,136.52,132.63,130.71,130.62,130.45,128.79,114.30,68.62,35.08,26.43.HRMS(ESI)m / z C 16 H 16 ClO2[M+H] + Theoretical value: 275.0833, measured value: 275.0831.

[0142] Example 31

[0143] In this embodiment, equimolar 4-tert-butylphenylethanol was used to replace methanol in Example 28, and Et2SiH2 was used to replace PhSiH3. The other steps were the same as in Example 28, and the target product with the following structural formula was obtained with a yield of 51%.

[0144]

[0145] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.93 (d, J = 8.8Hz, 2H), 7.38-7.35 (m, 2H), 7.25-7.22 (m, 2H), 6.93 ( d,J=8.8Hz,2H),4.23(t,J=7.2Hz,2H),3.10(t,J=7.2Hz,2H),2.56(s,3H),1.33(s,9H); 13C NMR (100MHz, CDCl3) δ196.94,162.90,149.65,134.77,130.71,130.37,128.78,125.60,114.30,69.05,35.17,34.55,31.49,26.47.HRMS(ESI)m / z C 20 H 25 O2[M+H] + Theoretical value: 297.1849, measured value: 297.1848.

[0146] Example 32

[0147] In this embodiment, equimolar 3-buten-1-ol was used to replace methanol in Example 28, and nickel bromide trihydrate was used to replace nickel bromide. Other steps were the same as in Example 28, and the target product with the following structural formula was obtained with a yield of 73%.

[0148]

[0149] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.93 (d, J = 8.8Hz, 2H), 6.93 (d, J = 8.8Hz, 2H), 5.95-5.85 (m, 1H), 5.21-5.12 (m, 2H), 4.08 (t, J = 6.6Hz, 2H), 2.60-2.53 (m, 5H); 13 C NMR(100MHz, CDCl3)δ196.89,163.00,134.13,130.72,130.50,117.51,114.34,67.56,33.60,26.45.HRMS(ESI)m / z C 16 H 19 O2[M+H] + Theoretical value: 219.1380, measured value: 219.1377.

[0150] Example 33

[0151] In this embodiment, equimolar amounts of 3-methyl-2-buten-1-ol were used to replace methanol in Example 28, and the other steps were the same as in Example 28, resulting in the target product with the following structural formula, with a yield of 82%.

[0152]

[0153] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.92(d,J=8.8Hz,2H),6.93(d,J=8.8Hz,2H),5.48(t,J=7.0Hz,1H),4.57(d,J=6.8Hz,2H),2.56(s,3H),1.80(s,3H),1.75(s,3H); 13 C NMR(100MHz, CDCl3)δ196.88,162.99,139.01,130.70,130.38,119.15,114.49,65.17,26.44,25.94,18.37.HRMS(ESI)m / z C 13 H 17 O2[M+H] + Theoretical value: 205.1223, measured value: 205.1229.

[0154] Example 34

[0155] In this embodiment, methanol in Example 28 was replaced with equimolar hydroxymethylcyclopropane, and toluene was replaced with 1,4-dioxane. The other steps were the same as in Example 28, and the target product with the following structural formula was obtained with a yield of 87%.

[0156]

[0157] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.92 (d, J = 8.4Hz, 2H), 6.92 (d, J = 8.4Hz, 2H), 3.86 (d, J = 6. 8Hz,2H),2.55(s,3H),1.32-1.25(m,1H),0.69-0.64(m,2H),0.39-0.35(m,2H); 13 C NMR(100MHz, CDCl3)δ196.91,163.10,130.72,130.34,114.33,73.08,26.45,25.94,10.23,3.37.HRMS(ESI)m / z C 12 H 14 O2[M+H] + Theoretical value: 191.1067, measured value: 191.1072.

[0158] Example 35

[0159] In this embodiment, equimolar amounts of 3-(4-morpholine)-1-propanol were used to replace methanol in Example 28, and 4,4'-tert-butyl-2,2'-bipyridine were used to replace bipyridine. The other steps were the same as in Example 28, and the target product with the following structural formula was obtained with a yield of 52%.

[0160]

[0161] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.91(d,J=8.8Hz,2H),6.91(d,J=8.8Hz,2H),4.07(t,J=6.4Hz,2H),3 .71(t,J=4.6Hz,4H),2.55(s,3H),2.53-2.49(m,2H),2.47-2.44(m,4H),2.01-1.94(m,2H); 13 C NMR (100MHz, CDCl3) δ196.92,163.03,130.68,130.32,114.23,67.04,66.41,55.46,53.82,26.44,26.36.HRMS(ESI)m / z C 15 H 22 NO3[M+H] + Theoretical value: 264.1594; Found value: 264.1593.

[0162] Example 36

[0163] In this embodiment, methanol in Example 28 was replaced with equimolar 3-methoxy-3-methyl-1-butanol, and 1,8-diazobicyclo[5.4.0]undec-5-ene (TBD) was replaced with 1,8-diazobicyclo[5.4.0]undec-7-ene (DBU). The other steps were the same as in Example 28, and the target product with the following structure was obtained in 68% yield.

[0164]

[0165] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.90 (d, J = 8.4Hz, 2H), 6.91 (d, J = 8.4Hz, 2H), 4.11 (t, J = 6.8Hz, 2H), 3.20 (s, 3H), 2.53 (s, 3H), 2.00 (t, J = 7.0Hz, 2H), 1.23 (s, 6H); 13C NMR(100MHz, CDCl3)δ196.89,163.09,130.72,130.37,114.32,73.73,64.69,49.45,39.08,26.45,25.45.HRMS(ESI)m / z C 14 H 21 O3[M+H] + Theoretical value: 237.1485, measured value: 237.1491.

[0166] Example 37

[0167] In this embodiment, equimolar furfuryl alcohol was used to replace methanol in Example 28, and the other steps were the same as in Example 28, resulting in the target product with the following structural formula and a yield of 82%.

[0168]

[0169] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.94(d,J=8.4Hz,2H),7.46(s,1H),7.02(d,J=8.4Hz,2H),6.47(s,1H),6.40(s,1H),5.07(s,2H),2.56(s,3H); 13 C NMR (100MHz, CDCl3) δ196.90,162.31,149.61,143.51,130.88,130.72,114.62,110.76,110.58,62.51,26.51.HRMS(ESI)m / z C 13 H 13 O3[M+H] + Theoretical value: 217.0859, measured value: 217.0869.

[0170] Example 38

[0171] In this embodiment, equimolar myrtle alcohol was used to replace methanol in Example 28, and 4,4'-diester-2,2'-bipyridine was used to replace bipyridine. Other steps were the same as in Example 28, and the target product with the following structural formula was obtained with a yield of 58%.

[0172]

[0173] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR(400MHz, CDCl3)δ7.90(d,J=8.8Hz,2H),6.92(d,J=8.8Hz,2H),5.61(s,1H),4.45(s,2H),2.54(s,3H),2.44-2 .39(m,1H),2.36-2.23(m,2H),2.22-2.19(m,1H),2.14-2.09(m,1H),1.29(s,3H),1.21-1.16(m,1H),0.82(s,3H); 13 CNMR(100MHz,CDCl3)δ196.94,163.04,143.35,130.57,130.26,121.09,114.61 ,70.86,43.30,40.88,38.20,31.61,31.38,26.43,26.23,21.17.HRMS(ESI)m / z C 18 H 23 O2[M+H] + Theoretical value: 271.1693, measured value: 271.1690.

[0174] Example 39

[0175] In this embodiment, equimolar nerol was used to replace methanol in Example 28, and N,N-dimethylformamide was used to replace toluene. Other steps were the same as in Example 28, and the target product with the following structural formula was obtained with a yield of 74%.

[0176]

[0177] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.91(d,J=8.8Hz,2H),6.92(d,J=8.8Hz,2H),5.46(t,J=6.2Hz,1H),5.08(t,J=6. 0Hz,1H),4.60(d,J=6.8Hz,2H),2.54(s,3H),2.14-2.06(m,4H),1.74(s,3H),1.67(s,3H),1.60(s,3H); 13 C NMR (100MHz, CDCl3) δ196.83,162.96,141.97,131.98,130.64,130.28,123.78, 118.92,114.46,65.20,39.61,26.39,26.35,25.76,17.79,16.80.HRMS(ESI)m / z C 18 H 25 O2[M+H]+ Theoretical value: 273.1849, measured value: 273.1849.

[0178] Example 40

[0179] In this embodiment, equimolar citronellol was used to replace methanol in Example 28, and the other steps were the same as in Example 28, to obtain the target product with the following structural formula, with a yield of 84%.

[0180]

[0181] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.93(d,J=8.0Hz,2H),6.92(d,J=8.0Hz,2H),5.10(t,J=6.6Hz,1H),4.10-4.01(m,2H),2.56(s,3H ),2.07-1.95(m,2H),1.90-1.81(m,1H),1.71-1.61(m,8H),1.44-1.35(m,1H),1.27-1.20(m,1H),0.96(d,J=6.0Hz,3H; 13 C NMR (100MHz, CDCl3) δ196.89,163.26,131.54,130.72,130.31,124.71,114.31, 66.72,37.23,36.10,29.65,26.44,25.85,25.58,19.68,17.81.HRMS(ESI)m / zC 18 H 27 O2[M+H] + Theoretical value: 275.2006, measured value: 275.2004.

[0182] Etherification of chlorinated aromatic hydrocarbons:

[0183] Example 41:

[0184] Under an argon atmosphere, p-chloroacetophenone (0.5 mmol), phenylbutanol (2.0 mmol), bipyridine (0.025 mmol), nickel bromide (0.025 mmol), DBU (0.75 mmol), phenylsilane (0.15 mmol), toluene (1.0 mL), and a magnetic stir bar were added to a reaction tube. The reaction was stirred in an oil bath at 120 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solvent was removed by vacuum distillation to obtain the crude product. The crude product was purified by column chromatography using petroleum ether and ethyl acetate as eluents to obtain the target product in 83% yield. The structure of the product was determined by... 1 HNMR, 13 Confirmed by C NMR and HRMS.

[0185]

[0186] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.93 (d, J = 8.8Hz, 2H), 7.32-7.28 (m, 2H), 7.22-7.18 (m, 3H), 6.91 (d, J=8.8Hz,2H),4.03(t,J=5.8Hz,2H),2.70(t,J=7.0Hz,2H),2.56(s,3H),1.88-1.81(m,4H); 13 C NMR (100MHz, CDCl3) δ196.90,163.15,142.13,130.70,130.30,128.52,128.48,125.98,114.24,68.12,35.65,28.79,27.87,26.44.HRMS(ESI)m / z C 18 H 21 O2[M+H] + Theoretical value: 269.1536, measured value: 269.1538.

[0187] Example 42

[0188] In this embodiment, equimolar amounts of 2-methyl-4-chlorobenzonitrile were used to replace p-chloroacetophenone in Example 41, and nickel bromide trihydrate was used to replace nickel bromide. Other steps were the same as in Example 41, and the target product with the following structural formula was obtained with a yield of 79%.

[0189]

[0190] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (600MHz, CDCl3) δ7.50 (d, J = 8.8Hz, 1H), 7.32-7.28 (m, 2H), 7.22-7.20 (m, 3H), 6.79-6 .73(m,2H),3.99(t,J=5.6Hz,2H),2.70(t,J=7.0Hz,2H),2.50(s,3H),1.84-1.82(m,4H); 13 C NMR (100MHz, CDCl3) δ162.30,144.11,142.04,134.26,128.49,128.46,126.98,1 18.77,116.21,112.56,104.35,68.11,35.58,28.66,27.79,20.78.HRMS(ESI)m / z C 18H 20 NO[M+H] + Theoretical value: 266.1539, measured value: 266.1539.

[0191] Example 43

[0192] In this embodiment, equimolar amounts of 2-trifluoromethyl-4-chloropyridine were used to replace p-chloroacetophenone in Example 41, and 4,4'-di-tert-butyl-2,2'-bipyridine were used to replace bipyridine. The other steps were the same as in Example 41, and the target product with the following structural formula was obtained with a yield of 76%.

[0193]

[0194] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ8.52 (d, J = 6.0Hz, 1H), 7.32-7.26 (m, 2H), 7.21-7.16 (m, 4H), 6.93-6.91(m,1H),4.06(t,J=5.6Hz,2H),2.71(t,J=7.0Hz,2H),1.89-1.81(m,4H); 13 C NMR (100MHz, CDCl3) δ166.16, 151.46, 149.81 (q, J = 34.1Hz), 141.87, 128.54, 127.24 (q, J = 469. 2Hz),128.51,126.09,112.27,107.90(q,J=2.7Hz),68.53,35.55,28.41,27.69.HRMS(ESI)m / z C 16 H 17 F3NO[M+H] + Theoretical value: 296.1257, measured value: 296.1254.

[0195] Example 44

[0196] In this embodiment, equimolar amounts of 4-chlorobenzophenone were used to replace p-chloroacetophenone in Example 41, and the other steps were the same as in Example 41, resulting in the target product with the following structural formula and a yield of 61%.

[0197]

[0198] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.82 (d, J = 8.8Hz, 2H), 7.76 (d, J = 7.2Hz, 2H), 7.59-7.55 (m, 1H), 7.48 (t, J = 7.6Hz, 2H), 7.33-7. 28(m,2H),7.23-7.19(m,3H),6.95(d,J=8.8Hz,2H),4.06(t,J=5.6Hz,2H),2.72(t,J=7.0Hz,2H),1.89-1.81(m,4H); 13 CNMR (100MHz, CDCl3) δ195.69,162.89,142.14,138.44,132.69,131.97,130.07,129.8 4,128.53,128.48,128.29,125.98,114.11,68.14,35.65,28.80,27.88.HRMS(ESI)m / z C 23 H 23 O2[M+H] + Theoretical value: 331.1693, measured value: 331.1686.

[0199] Example 45

[0200] In this embodiment, equimolar fenofibrate was used to replace p-chloroacetophenone in Example 41, and the other steps were the same as in Example 41, resulting in the target product with the following structural formula and a yield of 87%.

[0201]

[0202] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (600MHz, CDCl3) δ7.78-7.76(m,2H),7.74-7.72(m,2H),7.32-7.27(m,2H),7.22-7.19(m,3H),6.95-6.92(m,2H),6.89-6.87( m,2H),5.13-5.07(m,1H),4.05(t,J=5.6Hz,2H),2.71(t,J=7.0Hz,2H),1.87-1.83(m,4H),1.67(s,6H),1.22(s,3H),1.21(s,3H); 13C NMR (100MHz, CDCl3) δ194.48,173.31,162.52,159.17,142.11,132.32,131.77,131.42,130.50,128.49, 128.43,125.93,117.29,114.01,79.40,69.34,68.07,35.61,28.77,27.84,25.46,21.60.HRMS(ESI)m / z C 30 H 35 O5[M+H] + Theoretical value: 475.2479, measured value: 475.2472.

[0203] Example 46

[0204] Under an argon atmosphere, p-chloroacetophenone (0.5 mmol), trifluoroethanol (2.0 mmol), bipyridine (0.025 mmol), nickel bromide (0.025 mmol), DBU (0.75 mmol), styrene (0.15 mmol), toluene (1.0 mL), and a magnetic stir bar were added to a reaction tube. The reaction was stirred in an oil bath at 120 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solvent was removed by vacuum distillation to obtain the crude product. The crude product was purified by column chromatography using petroleum ether and ethyl acetate as eluents to obtain the target product in 92% yield. The structure of the product was determined by... 1 H NMR, 13 Confirmed by C NMR and HRMS.

[0205]

[0206] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.97 (d, J = 8.8 Hz, 2H), 6.99 (d, J = 8.8 Hz, 2H), 4.02 (q, J = 8.8 Hz, 2H), 2.58 (s, 3H); 13 C NMR (100MHz, CDCl3) δ196.69, 160.94, 132.02, 130.82, 123.19 (q, J = 276.2Hz), 114.59, 65.65 (q, J = 35.9Hz), 26.52. 19 FNMR(376MHz,CDCl3)δ-73.80(s,3F).HRMS(ESI)m / z C 10 H 10 F3O2[M+H] + Theoretical value: 219.0627, measured value: 219.0630.

[0207] Example 47

[0208] In this embodiment, equimolar benzyl alcohol was used to replace trifluoroethanol in Example 46, and 1,4-dioxane was used to replace toluene. Other steps were the same as in Example 46, and the target product with the following structural formula was obtained with a yield of 87%.

[0209]

[0210] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.94(d,J=8.8Hz,2H),7.45-7.33(m,5H),7.01(d,J=8.8Hz,2H),5.13(s,2H),2.56(s,3H); 13 C NMR (100MHz, CDCl3) δ196.90,162.72,136.27,130.72,130.61,128.81,128.36,127.58,114.64,70.23,26.42.HRMS(ESI)m / z C 15 H 15 O2[M+H] + Theoretical value: 227.1067, measured value: 227.1065.

[0211] Example 48

[0212] In this embodiment, equimolar 2-methylphenylethanol was used to replace trifluoroethanol in Example 46, and 4,4'-di-tert-butyl-2,2'-bipyridine was used to replace bipyridine. The other steps were the same as in Example 46, and the target product with the following structural formula was obtained with a yield of 58%.

[0213]

[0214] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.93 (d, J = 8.8Hz, 2H), 7.25-7.22 (m, 1H), 7.21-7.17 (m, 3H), 6.93 ( d,J=8.8Hz,2H),4.21(t,J=7.2Hz,2H),3.08(t,J=7.2Hz,2H),2.56(s,3H),2.40(s,3H); 13C NMR (100MHz, CDCl3) δ196.88,162.90,136.62,135.99,130.74,130.57,130.5 4,129.68,127.00,126.33,114.33,68.16,33.02,26.46,19.63.HRMS(ESI)m / z C 17 H 19 O2[M+H] + Theoretical value: 255.1380, measured value: 255.1378.

[0215] Example 49

[0216] In this embodiment, equimolar 1-naphthylethanol was used to replace trifluoroethanol in Example 46, nickel chloride was used to replace nickel bromide, and other steps were the same as in Example 46, to obtain the target product with the following structural formula, with a yield of 74%.

[0217]

[0218] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ8.01(d,J=8.4Hz,1H),7.90(t,J=8.8Hz,3H),7.79(t,J=4.8Hz,1H),7.58-7.51(m,2H ),7.44(d,J=5.2Hz,2H),6.92(d,J=8.8Hz,2H),4.36(t,J=7.4Hz,2H),3.61(t,J=7.4Hz,2H),2.55(s,3H); 13 C NMR (100MHz, CDCl3) δ196.93,162.82,134.03,133.74,132.14,130.73,130.48,129.07,12 7.68,127.27,126.34,125.84,125.70,123.56,114.31,68.35,32.81,26.48.HRMS(ESI)m / z C 20 H 19 O2[M+H] + Theoretical value: 291.1380, measured value: 291.1375.

[0219] Example 50

[0220] In this embodiment, equimolar 5-hexen-1-ol was used to replace trifluoroethanol in Example 46, and 1,8-diazobicyclo[4.4.0]undec-5-ene (TBD) was used to replace 1,8-diazobicyclo[5.4.0]undec-7-ene (DBU). The other steps were the same as in Example 46, and the target product with the following structure was obtained with a yield of 67%.

[0221]

[0222] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.92(d,J=8.8Hz,2H),6.92(d,J=8.8Hz,2H),5.88-5.78(m,1H),5.07-4.96(m ,2H),4.03(t,J=6.4Hz,2H),2.55(s,3H),2.17-2.10(m,2H),1.86-1.79(m,2H),1.62-1.54(m,2H); 13 C NMR (100MHz, CDCl3) δ196.90,163.21,138.50,130.73,130.35,115.02,114.28,68.18,33.50,28.68,26.45,25.39.HRMS(ESI)m / z C 14 H 19 O2[M+H] + Theoretical value: 219.1380, measured value: 219.1377.

[0223] Example 51

[0224] In this embodiment, trifluoroethanol in Example 46 was replaced with equimolar diethylene glycol, and bipyridine was replaced with 4,4'-di-tert-butyl-2,2'-bipyridine. The other steps were the same as in Example 46, and the target product with the following structural formula was obtained with a yield of 83%.

[0225]

[0226] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.92(d,J=8.8Hz,2H),6.94(d,J=8.8Hz,2H),4.19(t,J=4.6Hz,2H),3. 88(t,J=4.6Hz,2H),3.77(t,J=4.6Hz,2H),3.67(t,J=4.6Hz,2H),2.57(s,3H),1.45(m,1H); 13C NMR(100MHz, CDCl3)δ196.96,162.68,130.72,130.66,114.34,72.75,69.55,67.65,61.86,26.49.HRMS(ESI)m / z C 12 H 17 O4[M+H] + Theoretical value: 225.1121, measured value: 225.1119.

[0227] Example 52

[0228] In this embodiment, equimolar 1,4-butanediol was used to replace trifluoroethanol in Example 46, and the other steps were the same as in Example 46, to obtain the target product with the following structural formula, with a yield of 89%.

[0229]

[0230] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz, CDCl3) δ7.92(d,J=8.8Hz,2H),6.91(d,J=8.8Hz,2H),4.06(t,J=6.2Hz,2H) ,3.73(t,J=6.2Hz,2H),2.55(s,3H),1.94-1.87(m,2H),1.79-1.72(m,2H),1.42(s,1H); 13 C NMR(100MHz, CDCl3)δ197.03,163.01,130.73,130.33,114.24,68.08,62.54,29.38,26.47,25.75.HRMS(ESI)m / z C 12 H 17 O3[M+H] + Theoretical value: 209.1172, measured value: 209.1173.

[0231] Example 53

[0232] In this embodiment, equimolar tetrahydrofurfuryl alcohol was used to replace trifluoroethanol in Example 46, and the other steps were the same as in Example 46, to obtain the target product with the following structural formula, with a yield of 74%.

[0233]

[0234] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR(400MHz, CDCl3)δ7.90(d,J=8.8Hz,2H),6.93(d,J=8.4Hz,2H),4.29-4.23(m,1H),4.01-3.99(m,2H),3 .94-3.88(m,1H),3.84-3.78(m,1H),2.52(s,3H),2.11-2.01(m,1H),1.99-1.88(m,2H),1.79-1.70(m,1H); 13 C NMR (100MHz, CDCl3) δ196.98,162.92,130.69,130.57,114.36,76.98,70.70,68.80,28.33,26.50,25.85.HRMS(ESI)m / zC 13 H 17 O3[M+H] + Theoretical value: 221.1172, measured value: 221.1170.

[0235] Example 54

[0236] In this embodiment, equimolar 2-thiopheneethanol was used to replace trifluoroethanol in Example 46, and nickel bromide trihydrate was used to replace nickel bromide. Other steps were the same as in Example 46, and the target product with the following structural formula was obtained with a yield of 86%.

[0237]

[0238] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.93(d,J=8.4Hz,2H),7.18(d,J=4.8Hz,1H),6.94(d,J=9.4Hz,4H),4.25(t,J=6.6Hz,2H),3.34(t,J=6.6Hz,2H),2.56(s,3H); 13 C NMR (100MHz, CDCl3) δ196.92,162.69,140.01,130.75,130.65,127.03,125.82,124.29,114.38,69.69,29.99,26.50.HRMS(ESI)m / z C 14 H 15 O2S[M+H] + Theoretical value: 247.0787, measured value: 247.0792.

[0239] Example 55

[0240] In this embodiment, equimolar 2-thiophene methanol was used to replace trifluoroethanol in Example 46, and acetonitrile was used to replace toluene. Other steps were the same as in Example 46, and the target product with the following structural formula was obtained with a yield of 75%.

[0241]

[0242] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, MeOD) δ77.94 (d, J = 8.8 Hz, 2H), 7.36-7.34 (m, 1H), 7.14-7.13 (m, 1H), 7.03-7.00 (m, 3H), 5.23 (s, 2H), 2.56 (s, 3H); 13 C NMR (100MHz, CDCl3) δ196.89,162.22,138.41,130.85,130.71,127.36,127.02,126.71,114.69,65.14,26.50.HRMS(ESI)m / z C 13 H 13 O2S[M+H] + Theoretical value: 233.0631, measured value: 233.0631.

[0243] Example 56

[0244] In this embodiment, trifluoroethanol in Example 46 was replaced with equimolar N-Boc-4-piperidinemethanol, and the other steps were the same as in Example 46, to obtain the target product with the following structural formula, with a yield of 81%.

[0245]

[0246] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz, CDCl3) δ7.91(d,J=8.8Hz,2H),6.89(d,J=8.8Hz,2H),4.15(s,2H),3.84(d,J=6.4Hz,2H), 2.77-2.69(m,2H),2.53(s,3H),2.00-1.92(m,1H),1.82-1.78(m,2H),1.45(s,9H),1.29-1.23(m,2H); 13 C NMR (100MHz, CDCl3) δ196.87,162.99,154.93,130.69,130.38,114.19,79.56,72.54,36.22,28.89,28.55,26.44.HRMS(ESI)m / zC 19 H28 NO4[M+H] + Theoretical value: 334.2013, measured value: 334.2015.

[0247] Example 57

[0248] In this embodiment, equimolar perillol was used to replace trifluoroethanol in Example 46, and the other steps were the same as in Example 46, to obtain the target product with the following structural formula, with a yield of 56%.

[0249]

[0250] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.92(d,J=8.8Hz,2H),6.94(d,J=8.8Hz,2H),5.85(t,J=3.2Hz,1H),4.73(d,J=7.2Hz,2H),4 .45(s,2H),2.55(s,3H),2.23-2.14(m,4H),2.04-1.96(m,1H),1.91-1.85(m,1H),1.74(s,3H),1.56-1.47(m,1H); 13 CNMR(100MHz,CDCl3)δ196.98,163.06,149.67,133.00,130.68,130.37,125.93, 114.54,108.98,72.55,41.00,30.59,27.42,26.49,26.37,20.92.HRMS(ESI)m / z C 18 H 23 O2[M+H] + Theoretical value: 271.1693, measured value: 271.1691.

[0251] Example 58

[0252] In this embodiment, trifluoroethanol in Example 46 was replaced with equimolar novoethanol, and bipyridine was replaced with 6,6'-diamino-2,2'-bipyridine. The other steps were the same as in Example 46, and the target product with the following structural formula was obtained with a yield of 59%.

[0253]

[0254] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.91(d,J=8.8Hz,2H),6.89(d,J=8.8Hz,2H),5.36-5.33(m,1H),4.02(t,J=6.8Hz,2H),4.45(s,2H),2.54(s, 3H),2.48-2.43(m,2H),2.39-2.34(m,1H),2.29-2.18(m,2H),2.09-2.08(s,2H),1.27(s,3H),1.17(d,J=8.8Hz,2H),0.82(s,3H); 13 C NMR (100MHz, CDCl3) δ196.87,163.00,144.26,130.66,130.24,119.00,114.24,66. 65,45.95,40.81,38.18,36.43,31.75,31.47,26.42,26.39,21.28.HRMS(ESI)m / zC 19 H 25 O2[M+H] + Theoretical value: 285.1849, measured value: 285.1845.

Claims

1. A method for synthesizing alkyl aryl ether compounds, characterized in that: Using the compounds shown in Formula I and Formula II as reaction substrates, nickel bromide or nickel chloride catalyst, bipyridine as ligand, base, benzylsilane as reducing agent, and organic solvent, an etherification reaction of haloaromatic hydrocarbons occurs under an inert atmosphere and heating conditions to obtain alkylaryl ether compounds shown in Formula III. In the formula, Ar represents the aromatic hydrocarbon obtained by mono- or poly-substituted ortho-, meta-, or para-substituted groups on the benzene ring, wherein the substituents are selected from C1 to C2. 12 Alkyl, C1-C 12 Alkoxy, C2-C 12 Acyl, halogen, cyano, cyclopropanecyano, trifluoromethoxy, methyl sulfone, trifluoromethyl, furanyl, quinoxalinyl, thiophene, adamantyl, methylenedioxy, dioxane, pyridyl, methylpyridyl, trifluoromethylpyridyl, thiophene, benzothiophene, furanyl, benzofuranyl, carbazole, valeronyl; R is selected from C1 to C2. 18 Alkyl, C1-C 18 Alkoxy, C4~C 15 alkenyl, C3~C 10 cycloalkyl, C2-C 10 The alkyl hydroxyl, trifluoroethyl, benzyl, naphthyl, C1-C4 alkyl-substituted phenylethyl, halogen-substituted phenylethyl, thiophene methyl, furanyl methyl, piperidine methyl; X represents Br or Cl.

2. The method for synthesizing alkylaryl ethers according to claim 1, characterized in that: The organic base is selected from tetramethylguanidine, tert-butyltetramethylguanidine, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabispirocyclo[5.4.0]undec-7-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.

3. The method for synthesizing alkylaryl ethers according to claim 1, characterized in that: The organic solvent is selected from N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, 1,4-dioxane, toluene, and acetonitrile.

4. The method for synthesizing alkylaryl ethers according to claim 1, characterized in that: The reaction temperature is 80–120℃.

5. The method for synthesizing alkylaryl ethers according to claim 1, characterized in that: The reaction time is 12–24 hours.

6. The method for synthesizing alkylaryl ethers according to claim 1, characterized in that: The method involves a reaction carried out under an inert atmosphere.

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