A C3-phenoxy-substituted quinoline compound and its synthesis method and application

Abstract

The invention discloses a quinoline compound substituted with phenoxy group at position C3 and a synthesis method and application thereof, belonging to the field of organic synthesis. The quinoline compound substituted with phenoxy group at position C3 is synthesized by a one-pot method, and the structural formula is shown in the following formula. The specific synthesis method is: o-aminobenzyl alcohol compound, aromatic ketone, transition metal salt catalyst and additive are placed in an organic solvent, and heated to react under an argon atmosphere. After the reaction is completed, the reaction liquid is post-treated to obtain the quinoline compound substituted with phenoxy group at position C3; preferably, the reaction raw material also includes benzoquinone; the above-mentioned synthesis method has simple steps, a wide range of raw materials, good functional group compatibility, relatively mild reaction conditions, high reaction yield, and green economy; the quinoline compound substituted with phenoxy group at position C3 can be used as an intermediate, and has broad application prospects in the field of organic synthesis, and also has potential application prospects in the fields of pesticides, medicines or dyes. #imgabs0#

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis, and specifically relates to a C3-phenoxy-substituted quinoline compound and a synthesis method and application thereof. Background Art

[0002] Quinoline is an important class of nitrogen-containing heterocyclic compounds. This structure is one of the most common nitrogen-containing heterocyclic compounds in natural products and drug molecules. It is widely used in medicine, pesticides, and chemical industries. Therefore, it is of great significance to study its synthesis method. Classical synthesis methods include Pfitzinger and Conrad–Limpach synthesis methods (Katritzky, Alan R.; Ramsden, Christopher A.; Scriven, Eric FV; Taylor, Richard JK; Padwa, Albert. Comprehensive Heterocyclic Chemistry, New York, 5th edn, 1984, vol. 2, pp. 395–524), but they require multiple steps of synthesis and have low synthesis efficiency. The synthetic method uses o-aminobenzaldehyde and ketone as raw materials to efficiently obtain 2-substituted quinoline products (Maco-Contelles, J.; E.;Samadi,A.;Carreiras,MdC;Soriano,E.,Recent Advances in the Reaction.Chem.Rev.2009,109,2652–2671), but benzaldehyde is unstable, so chemists have also developed a method for synthesizing 2-substituted quinolines using o-aminobenzene alcohols and ketones as raw materials (Motokura, K.; Ozawa, N.; Sato, R.; Manaka, Y.; Chun, WJ, Porous FeO(OH)Dispersed on Mg-Al Hydrotalcite Surface for One-Pot Synthesis of Quinoline Derivatives. ChemCatChem 2021,13,2915–2921.).

[0003] Although 3-oxygen-substituted quinoline has a special structure and potential application value in the fields of medicine and materials, its synthesis method is rarely reported. The existing synthesis method requires multiple steps, which is time-consuming, labor-intensive and inefficient. The reported synthesis methods also include the etherification reaction of 3-bromoquinoline (Liu, YY; Liang, D.; Lu, LQ; Xiao, WJ, Pracyical heterogeneous photoredex / nickel dual catalysis for CN and CO coupling reactions. Chem. Commun. 2019, 55, 4853-4856), and the hydroxylation reaction of 3-boronic acid substituted quinoline (Wei, PF; Qi, MZ; Wang, ZP; Ding, SY; Yu, W.; Liu, Q.; Wang, LK; Wang, HZ; An, WK; Wang, W., Benzoxazole-Linked Ultrastable Covalent Organic Frameworks for Photocatalysis. J. Am. Chem. Soc., 2018, 140, 4623-4631.), but the examples are very limited and the reaction atom economy is low. The recently reported nickel-catalyzed hydroamination / cyclization reaction of o-aminobenzonitrile and alkyne can produce 3-ethoxy-substituted quinoline with a yield of 65% (Gao, Y.; Yang, SM; Huo, YP; Chen, Q.; Li, XW; Hu, XQ; NiH-Catalyzed Hydroamination / Cyclization Cascade: Rapid Acess to Quinolines. ACS Catal. 2021, 11, 7772-7779), but only this one compound is synthesized, which is not suitable for a wide range of 3-oxygen-substituted quinoline synthesis and the establishment of a molecular library. In the prior art, there is no report on the synthesis technology of quinoline compounds substituted with phenoxy at the C3 position.

[0004] It can be seen that it is of great significance to develop a green and efficient synthesis method for C3-phenoxy-substituted quinoline compounds starting from simple raw materials. Summary of the invention

[0005] The invention provides a quinoline compound substituted with a phenoxy group at the C3 position. The quinoline compound is synthesized by a one-pot method, and the synthesis method has simple steps, a wide range of raw material applications, good functional group compatibility, relatively mild reaction conditions, high reaction yield, and is green and economical. The quinoline compound substituted with a phenoxy group at the C3 position can be used as an intermediate, has broad application prospects in the field of organic synthesis, and also has potential application prospects in the fields of pesticides, medicines or dyes.

[0006] The specific technical solutions adopted are as follows:

[0007] A quinoline compound substituted with a phenoxy group at position C3, the structural formula of which is shown in formula (I):

[0008]

[0009] In formula (I), R 1 is any one of hydrogen, naphthalene, halogen or methyl; R 2 is any one of hydrogen, methoxy or trifluoromethyl, mono- or di-substituted on the phenoxy structure; R 3 It is any of methyl, phenyl, phenyl substituted with halogen or phenyl substituted with methoxy.

[0010] Preferably, R 1 wherein halogen is selected from fluorine, chlorine or bromine; R 3 In the above, the phenyl group substituted by halogen is a phenyl group substituted by chlorine or bromine.

[0011] More specifically, the C3 phenoxy-substituted quinoline compounds include: 3-phenoxy-2-phenylquinoline, 2-(4-chlorophenyl)-3-phenoxyquinoline, 2-(2-chlorophenyl)-3-phenoxyquinoline, 2-(4-bromophenyl)-3-phenoxyquinoline, 2-(3-methoxyphenyl)-3-phenoxyquinoline, 2-(4-methoxyphenyl)-3-phenoxyquinoline, 2-(2,5-dimethoxyphenyl)-3-phenoxyquinoline, 2-methyl-3-phenoxyquinoline, 2-phenyl-3-(4-(trifluoromethyl)phenoxy)quinoline, 3-(4-methoxyphenoxy)-2-phenylquinoline, 3-(3,4-dimethoxyphenoxy)-2-phenylquinoline, 2-(4-bromophenyl)-3-phenoxyquinoline -3-(4-methoxyphenoxy)quinoline, 2-(4-chlorophenyl)-3-(4-methoxyphenoxy)quinoline, 2-(2-chlorophenyl)-3-(3,4-dimethoxyphenoxy)quinoline, 3-(4-methoxyphenoxy)-2-(3-methoxyphenyl)quinoline, 3-(3,4-dimethoxyphenoxy)-2-(3-methoxyphenyl)quinoline, 2-(2,5-dimethoxyphenyl)-3-(4-methoxyphenoxy)quinoline, 3-(3,4-dimethoxyphenoxy)-2-(2,5-dimethoxyphenyl)quinoline, 6-chloro-3-phenoxy-2-phenylquinoline, 6-bromo-3-phenoxy-2-phenylquinoline, 6-fluoro-3-phenoxy-2-phenylquinoline, 7-methyl-3- Phenoxy-2-phenylquinoline, 6-methyl-3-phenoxy-2-phenylquinoline, 5-chloro-3-phenoxy-2-phenylquinoline, 8-methyl-3-phenoxy-2-phenylquinoline, 3-phenoxy-2-phenylbenzo[g]quinoline, 6-chloro-2-(4-chlorophenyl)-3-phenoxyquinoline, 6-chloro-2-(2,5-dimethoxyphenyl)-3-phenoxyquinoline, 6-bromo-2-(2,5-dimethoxyphenyl)-3-phenoxyquinoline, 6-bromo-3-(4-methoxyphenoxy)-2-phenylquinoline, 6-chloro-3-(3,4-dimethoxyphenoxy)-2-phenylquinoline, 6-chloro-3-(4-methoxyphenoxy)-2-phenylquinoline, 6-bromo-3-(4-methoxyphenoxy)- Quinoline, 6-bromo-2-(2,5-dimethoxyphenyl)-3-(4-methoxyphenoxy)quinoline, 6-chloro-2-(2,5-dimethoxyphenyl)-3-(4-methoxyphenoxy)quinoline, 2-(4-bromophenyl)-6-chloro-3-(4-methoxyphenoxy)quinoline, 6-chloro-2-(4-chlorophenyl)-3-(4-methoxyphenoxy)quinoline, 6-bromo-3-(3,4-dimethoxyphenoxy)-2-(2,5-dimethoxyphenyl)quinoline, 6-bromo-2-(2-chlorophenyl)-3-(3,4-dimethoxyphenoxy)quinoline or 6-chloro-2-(2-chlorophenyl)-3-(3,4-dimethoxyphenoxy)quinoline.

[0012] The present invention also provides a method for synthesizing the C3-phenoxy-substituted quinoline compound, which specifically comprises the following steps:

[0013] placing an o-aminobenzyl alcohol compound, an aromatic ketone, a transition metal salt catalyst and an additive in an organic solvent, heating the mixture under an argon atmosphere for reaction, and after the reaction is completed, performing post-treatment on the reaction solution to obtain the C3-phenoxy-substituted quinoline compound;

[0014] The structural formula of the o-aminobenzyl alcohol compound is shown in formula (II), and the structural formula of the aromatic ketone is shown in formula (III).

[0015]

[0016] In formula (II) and (III), R 1 , R 2 and R 3 The definition of is consistent with that in formula (I).

[0017] Specifically, the reaction equation is shown below:

[0018]

[0019] The present invention starts from o-aminobenzyl alcohol compounds and aromatic ketones, combines hydrogen transfer reaction and aldol condensation reaction under the action of a catalyst, and realizes a technology for synthesizing C3-phenoxy-substituted quinoline compounds by a "one-pot method". Raw materials such as o-aminobenzyl alcohol and aromatic ketones are widely available and have low costs. The substrates and functional groups of the method of the present invention have wide applicability, and the yield can reach up to more than 90%, which is conducive to the synthesis of large-scale molecular libraries.

[0020] The general mechanism of the above reaction is as follows: o-aminobenzyl alcohol compounds undergo hydrogen transfer reaction in the presence of a catalyst to generate benzaldehyde, benzaldehyde and aromatic ketones such as phenoxyacetophenone undergo aldol condensation under alkaline conditions, remove a molecule of water, and obtain α, β-unsaturated ketone, and finally undergo condensation reaction between the amino group and the carbonyl group, and dehydrate to obtain the quinoline product.

[0021] Preferably, the reaction raw materials also include benzoquinone. Benzoquinone acts as an oxidant to receive hydrogen generated after the oxidation of benzyl alcohol, which can effectively promote the reaction, improve the reaction efficiency, and greatly reduce the reaction cost.

[0022] The transition metal salt catalyst is an iridium complex; the additive is a cesium salt.

[0023] Further preferably, the transition metal salt catalyst is dichloro(pentamethylcyclopentadienyl)iridium dimer; and the additive is cesium carbonate.

[0024] The organic solvent includes but is not limited to diethyl ether, tetrahydrofuran or ethylene glycol dimethyl ether.

[0025] Preferably, the molar ratio of the o-aminobenzyl alcohol compound, the aromatic ketone, the transition metal salt catalyst and the additive is 1:1-1.5:0.02-0.07:1-2.

[0026] Preferably, the molar ratio of the o-aminobenzyl alcohol compound, the aromatic ketone, the transition metal salt catalyst, the additive and the benzoquinone is 1:1-1.5:0.02-0.07:1-2:1-1.5.

[0027] Preferably, the volume usage of the organic solvent is 5-15 L / mol based on the amount of the o-aminobenzyl alcohol compound.

[0028] The temperature of the heating reaction is 80-130° C., and the reaction time is 12-16 hours.

[0029] The post-treatment is to load the reaction liquid into a column, dissolve and transfer the remaining reaction liquid with dichloromethane, separate it by column chromatography with silica gel, use a mixture of ethyl acetate and petroleum ether as the eluent, collect the eluate containing the target compound, and concentrate and dry it to obtain the C3-position phenoxy-substituted quinoline compound.

[0030] The present invention also provides the use of the C3-phenoxy substituted quinoline compound in an organic synthesis reaction, wherein the organic synthesis reaction includes a Suzuki coupling reaction or a condensation reaction; the C3-phenoxy substituted quinoline compound can be used as an important intermediate in organic synthesis and has broad application prospects in the field of organic synthesis. In addition, the C3-phenoxy substituted quinoline compound also has potential application prospects in the fields of pesticides, medicines or dyes.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] (1) The present invention provides a quinoline compound substituted with a phenoxy group at the C3 position, which contains a methoxy group, a halogen group, a methyl group or a naphthyl group. The synthesis of such special compounds is rarely reported. The synthesis method provided by the present invention is simple to operate, the reaction conditions are relatively mild, the reaction yield is high, and the maximum reaction yield can reach 90%. It is economical and green, and the by-products are only water and p-diphenol.

[0033] (2) The synthetic raw materials used in the synthetic method provided by the present invention, such as o-aminobenzyl alcohol, phenoxyacetophenone, etc., are economical and readily available, and the iridium catalytic system has the characteristics of good regioselectivity, wide substrate range, and high efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1This is the hydrogen nuclear magnetic resonance spectrum of 2-(4-bromophenyl)-3-phenoxyquinoline in Example 4.

[0035] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of 2-(4-chlorophenyl)-3-(4-methoxyphenoxy)quinoline in Example 13. DETAILED DESCRIPTION

[0036] The present invention will be further described below in conjunction with the accompanying drawings and embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0037] The drugs used in the following examples were all purchased from the market, wherein the transition metal salt catalysts were all dichloro(pentamethylcyclopentadienyl)iridium(III) dimer; and the additives were all cesium carbonate.

[0038] The post-treatment steps of the reaction solution in the embodiment are: loading the reaction solution into a column, dissolving and transferring the remaining reaction solution with dichloromethane, performing column chromatography separation with 300 mesh silica gel, and using a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:90 as the eluent, collecting the eluate containing the target compound, and concentrating and drying to obtain the C3-phenoxy-substituted quinoline compound.

[0039] Example 1

[0040] Preparation of 3-phenoxy-2-phenylquinoline

[0041] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro (pentamethylcyclopentadienyl) iridium (III) dimer ([IrCp*Cl2]2, 7.9 mg, 5 mol%), cesium carbonate (Cs2CO3, 110.0 mg, 0.34 mmol), benzoquinone (BQ, 23.7 mg, 0.22 mmol) and ether (Et2O, 2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol) and phenoxyacetophenone (46.7 mg, 0.22 mmol). After heating at 130°C under argon for 16 hours, the reaction solution is post-treated to obtain the target product as a white oily liquid (41.6 mg, yield 70%). The reaction formula is as follows:

[0042]

[0043] The characterization results of the reaction product are as follows:

[0044] 1H NMR (500MHz, CDCl3): δ=8.17–8.15(m,1H),8.06–8.03(m,2H),7.65–7.62(m,2H),7.57(s,1H),7.50–7.4 8(m,1H),7.47–7.45(m,2H),7.43–7.40(m,1H),7.39–7.34(m,2H),7.17–7.14(m,1H),7.08–7.05(m,2H).

[0045] 13 C NMR (125MHz, CDCl3): δ=155.4,151.9,148.7,143.7,136.3,129.0,128.6,128.4,128.0,127.3,127.2,127.1,125.9,125.5,123.0,120.8,118.3.

[0046] HRMS(ESI):m / z for C 21 H 15 NO[M+H] + :298.1226,found:298.1223.

[0047] FTIR(KBr,cm -1 ):3447.42,2952.91,2831.23,2713.57,1597.87,1364.70,1069.10,776.17.

[0048] Example 2

[0049] Preparation of 2-(4-chlorophenyl)-3-phenoxyquinoline

[0050] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro (pentamethylcyclopentadienyl) iridium (III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 1-(4-chlorophenyl)-2-phenoxyethyl-1-one (54.2 mg, 0.22 mmol), heat the reaction at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (19.1 mg, yield 58%). The reaction formula is as follows:

[0051]

[0052] The characterization results of the reaction product are as follows:

[0053] 1 H NMR (500MHz, CDCl3): δ=8.15–8.13(m,1H),8.05–8.02(m,2H),7.65–7.62(m,2H),7.57(s,1H),7. 49(t,J=7.5Hz,1H),7.44–7.42(m,2H),7.39–7.35(m,2H),7.19–7.15(m,1H),7.06–7.03(m,2H).

[0054] 13 C NMR (125MHz, CDCl3): δ=155.2,150.4,148.6,143.6,134.7,134.1,130.0,129.1,128.4,127.4,127.3,127.3,126.1,125.5,123.2,121.0,118.2.

[0055] HRMS(ESI):m / z for C 21 H 14 ClNO[M+H] + :332.0837,found:332.0834.

[0056] FTIR(KBr,cm -1 ):3450.47,2962.62,2830.84,2721.50,1597.20,1367.29,1072.90,778.50.

[0057] Example 3

[0058] Preparation of 2-(2-chlorophenyl)-3-phenoxyquinoline

[0059] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 1-(2-chlorophenyl)-2-phenoxyethyl-1-one (54.2 mg, 0.22 mmol), heat the reaction at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (25.1 mg, yield 76%). The reaction formula is as follows:

[0060]

[0061] The characterization results of the reaction product are as follows:

[0062] 1 H NMR (500MHz, CDCl3): δ = 8.15 (d, J = 8.4Hz, 1H), 7.67 (d, J = 8.2Hz, 1H), 7.65-7.62 (m, 1H), 7.54-7.5 2(m,2H),7.50(s,1H),7.48–7.44(m,1H),7.38-7.34(m,4H),7.18–7.14(m,1H),7.09–7.05(m,2H).

[0063] 13 C NMR (125MHz, CDCl3): δ=154.7,151.2,149.4,143.0,136.0,132.5,130.1,128.9 ,128.8,128.4,127.7,126.9,126.3,125.8,125.6,123.4,119.0,118.6,113.6.

[0064] HRMS(ESI):m / z for C 21 H 14 ClNO[M+H] + :332.0837,found:332.0838.

[0065] FTIR(KBr,cm -1 ):3453.27,2959.81,2830.84,2718.69,1602.80,1364.49,1072.09,775.78.

[0066] Example 4

[0067] Preparation of 2-(4-bromophenyl)-3-phenoxyquinoline

[0068] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 1-(4-bromophenyl)-2-phenoxyethyl-1-one (64.0 mg, 0.22 mmol), heat the reaction at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow powder solid (20.0 mg, yield 53%). The reaction formula is as follows:

[0069]

[0070] The characterization results of the reaction product are as follows:

[0071] 1 H NMR (500MHz, CDCl3): δ=8.15–8.13(m,1H),7.98–7.96(m,2H),7.65–7.62(m,2H),7.60–7.57(m, 2H),7.56(s,1H),7.51–7.48(m,1H),7.40–7.35(m,2H),7.19–7.15(m,1H),7.06–7.04(m,2H).( Figure 1 )

[0072] 13 C NMR (125MHz, CDCl3): δ=155.1,150.4,148.6,143.7,135.2,130.3,130.2,129.1,128.4,127.3,127.3,126.1,125.5,123.2,122.6,121.0,118.2.

[0073] HRMS(ESI):m / z for C 21 H 14 BrNO[M+H] + :376.0332,found:376.0331.

[0074] FTIR(KBr,cm -1 ):3447.66,2957.01,2830.84,2718.69,1599.28,1364.35,1067.29,775.70.

[0075] Example 5

[0076] Preparation of 2-(3-methoxyphenyl)-3-phenoxyquinoline

[0077] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 1-(3-methoxyphenyl)-2-phenoxyethyl-1-one (53.4 mg, 0.22 mmol), heat the reaction at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (17.6 mg, yield 54%). The reaction formula is as follows:

[0078]

[0079] The characterization results of the reaction product are as follows:

[0080] 1 H NMR (500MHz, CDCl3): δ = 8.16 (d, J = 8.6Hz, 1H), 7.66–7.62 (m, 3H), 7.60–7.58 (m, 2H), 7.51–7.47 ( m,1H),7.38–7.35(m,3H),7.17–7.14(m,1H),7.07–7.05(m,2H),6.98–6.96(m,1H),3.84(s,3H).

[0081] 13 C NMR (125MHz, CDCl3): δ=158.4,155.5,151.7,148.6,143.6,137.6,129.0,128.4,1 28.1,127.3,127.2,125.9,125.5,122.9,121.1,121.1,118.2,114.1,113.8,54.3.

[0082] HRMS(ESI):m / z for C 22 H 17 NO2[M+H] + :328.1332,found:328.1341.

[0083] FTIR(KBr,cm -1 ):3477.66,2959.81,2829.66,2718.69,1599.10,1364.87,1070.09,775.54.

[0084] Example 6

[0085] Preparation of 2-(4-methoxyphenyl)-3-phenoxyquinoline

[0086] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 1-(4-methoxyphenyl)-2-phenoxyethyl-1-one (53.2 mg, 0.22 mmol), heat the reaction at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (21.2 mg, yield 65%). The reaction formula is as follows:

[0087]

[0088] The characterization results of the reaction product are as follows:

[0089] 1 H NMR (500MHz, CDCl3): δ=8.17–8.13(m,1H),8.10–8.06(m,2H),7.65–7.61(m,2H),7.55(s,1H),7.47(td,J=7.5,7. 0,1.2Hz,1H),7.40–7.36(m,2H),7.16(td,J=7.4,1.1Hz,1H),7.09–7.06(m,2H),7.01–6.98(m,2H),3.86(s,3H).

[0090] 13 C NMR (125MHz, CDCl3): δ=160.4,156.5,152.4,149.7,144.7,131.1,130.1,129.9, 129.2,128.1(d,J=4.4Hz),126.6,126.5,124.0,122.0,119.3,113.7,55.3,29.7.

[0091] HRMS(ESI):m / z for C 22 H 17 NO2[M+H] + :328.1332,found:328.1332.

[0092] FTIR(KBr,cm -1 ):3439.38,2959.95,2830.97,2718.83,1622.57,1373.04,1064.64,773.05.

[0093] Example 7

[0094] Preparation of 2-(2,5-dimethoxyphenyl)-3-phenoxyquinoline

[0095] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 1-(2,5-dimethoxyphenyl)-2-phenoxyethyl-1-one (59.8 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (31.4 mg, yield 88%). The reaction formula is as follows:

[0096]

[0097] The characterization results of the reaction product are as follows:

[0098] 1 H NMR (500MHz, CDCl3): δ = 8.16 (d, J = 8.4Hz, 1H), 7.65 (d, J = 8.1Hz, 1H), 7.63–7.60 (m, 1H), 7.51 (s, 1H), 7.50–7.47 ( m,1H),7.36–7.32(m,2H),7.08–7.06(m,3H),6.96–6.92(m,2H),6.87(d,J=9.0Hz,1H),3.79(s,3H),3.63(s,3H).

[0099] 13 C NMR (125MHz, CDCl3): δ=155.7,152.6,150.8,149.6,143.4,128.7,128.4,128. 3,126.7,125.8,125.6,122.8,118.4,115.1,114.5,113.6,111.0,55.0,54.8.

[0100] HRMS(ESI):m / z for C 23 H 19 NO3[M+H] + :358.1438,found:358.1436.

[0101] FTIR(KBr,cm -1):3444.99,2957.14,2830.15,2718.83,1601.09,1364.61,1073.05,775.89.

[0102] Example 8

[0103] Preparation of 2-methyl-3-phenoxyquinoline

[0104] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 1-phenoxypropyl-2-ketone (33.0 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (28.4 mg, yield 60%). The reaction formula is as follows:

[0105]

[0106] The characterization results of the reaction product are as follows:

[0107] 1 H NMR (500MHz, CDCl3): δ=7.94(d,J=8.4Hz,1H),7.53–7.47(m,2H),7.38–7.28(m,4H),7.09(t,J=7.4Hz,1H),6.97–6.93(m,2H),2.64(s,3H).

[0108] 13 C NMR (125MHz, CDCl3): δ = 156.3, 154.0, 150.1, 144.2, 130.1, 128.3, 127.9, 126.7, 126.3, 124.1, 120.2, 119.0, 114.9, 20.5.

[0109] HRMS(ESI):m / z for C 16 H 13 NO[M+H] + :236.1070,found:236.1065.

[0110] FTIR(KBr,cm -1 ):3450.59,2962.75,2828.17,2718.83,1608.56,1370.24,1067.44,773.05.

[0111] Example 9

[0112] Preparation of 2-phenyl-3-(4-(trifluoromethyl)phenoxy)quinoline

[0113] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 1-phenyl-2-(4-(trifluoromethyl)phenoxy)ethyl-1-one (61.2 mg, 0.22 mmol), heat the reaction at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (18.7 mg, yield 51%). The reaction formula is as follows:

[0114]

[0115] The characterization results of the reaction product are as follows:

[0116] 1 H NMR (500MHz, CDCl3): δ = 8.21 (d, J = 8.5Hz, 1H), 7.97 (dd, J = 8.0, 1.6Hz, 2H), 7. 76–7.66(m,3H),7.59–7.52(m,3H),7.48–7.39(m,3H),7.06(d,J=8.4Hz,2H).

[0117] 13 C NMR (125MHz, CDCl3): δ=159.7,153.3,147.9,145.5,136.9,129.6,129.4,129.2,128.9,128.3,12 8.2, 127.4 (q, J = 3.7Hz), 127.2, 126.7, 125.5 (d, J = 32.8Hz), 124.5, 124.0 (d, J = 271.6Hz), 118.0.

[0118] HRMS(ESI):m / z for C 22 H 14 F3NO[M+H] + :366.1100,found:366.1108.

[0119] FTIR(KBr,cm -1):3470.22,2962.75,2830.97,2718.83,1608.56,1367.44,1078.65,775.85.

[0120] Example 10

[0121] Preparation of 3-(4-methoxyphenoxy)-2-phenylquinoline

[0122] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol) and benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 2-(4-methoxyphenoxy)-1-phenylethyl-1-one (93.0 mg, 0.22 mmol), heat the reaction at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow powder solid (23.0 mg, yield 70%). The reaction formula is as follows:

[0123]

[0124] The characterization results of the reaction product are as follows:

[0125] 1 H NMR (500MHz, CDCl3): δ = 8.14 (d, J = 8.7Hz, 1H), 8.09–8.07 (m, 2H), 7.62–7.58 (m, 2H), 7. 50–7.46(m,3H),7.45–7.42(m,2H),7.06–7.03(m,2H),6.94–6.91(m,2H),3.82(s,3H).

[0126] 13 C NMR (125MHz, CDCl3): δ=155.4,151.3,150.0,148.2,143.2,136.5,128.6,1 28.3,127.9,127.3,127.1,126.7,125.8,125.4,120.2,118.7,114.1,54.6.

[0127] HRMS(ESI):m / z for C 22 H 17 NO2[M+H] + :328.1332,found:328.1338.

[0128] FTIR(KBr,cm-1 ):3453.27,2957.01,2830.46,2718.69,1608.41,1364.49,1067.29,776.01.

[0129] Embodiment 11

[0130] Preparation of 3-(3,4-dimethoxyphenoxy)-2-phenylquinoline

[0131] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol) and benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 2-(3,4-dimethoxyphenoxy)-1-phenylethyl-1-one (60.0 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (24.2 mg, yield 68%). The reaction formula is as follows:

[0132]

[0133] The characterization results of the reaction product are as follows:

[0134] 1 H NMR (500MHz, CDCl3): δ = 8.15 (d, J = 8.4Hz, 1H), 8.09–8.07 (m, 2H), 7.64–7.59 (m, 2H), 7.51–7.42 (m, 5H) ),6.86(d,J=8.7Hz,1H),6.68(d,J=2.7Hz,1H),6.64(dd,J=8.6,2.7Hz,1H),3.89(s,3H),3.83(s,3H).

[0135] 13 C NMR (125MHz, CDCl3): δ=151.3,149.9,149.1,148.5,145.0,143.3,136.43,128.6,128 .4,128.0,127.3,127.2,126.8,125.9,125.4,119.0,110.8,110.2,103.7,55.3,55.0.

[0136] HRMS(ESI):m / z for C 23 H 19 NO3[M+H] +:358.1438,found:358.1436.

[0137] FTIR(KBr,cm -1 ):3450.47,2955.40,2830.84,2713.57,1600.00,1367.29,1070.09,772.90.

[0138] Example 12

[0139] Preparation of 2-(4-bromophenyl)-3-(4-methoxyphenoxy)quinoline

[0140] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 1-(4-bromophenyl)-2-(4-methoxyphenoxy)ethyl-1-one (70.6 mg, 0.22 mmol), heat the reaction at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow powder solid (16.7 mg, yield 41%). The reaction formula is as follows:

[0141]

[0142] The characterization results of the reaction product are as follows:

[0143] 1 H NMR (500MHz, CDCl3): δ=8.13–8.11(m,1H),8.01–7.98(m,2H),7.63–7.59(m,4H),7 .49–7.46(m,1H),7.43(s,1H),7.05–7.01(m,2H),6.95–6.92(m,2H),3.83(s,3H).

[0144] 13 C NMR (125MHz, CDCl3): δ=155.5,149.9,148.0,143.2,135.3,130.3,130.3,128.3,127.4,126.9,126.0,125.4,122.5,120.1,118.9,114.2,54.7.

[0145] HRMS(ESI):m / z for C 22 H 16 BrNO2[M+H]+ :406.0437,found:406.0438.

[0146] FTIR(KBr,cm -1 ):3444.86,2959.81,2828.04,2715.89,1594.18,1363.79,1072.90,772.90.

[0147] Example 13

[0148] Preparation of 2-(4-chlorophenyl)-3-(4-methoxyphenoxy)quinoline

[0149] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 1-(4-chlorophenyl)-2-(4-methoxyphenoxy)ethyl-1-one (60.8 mg, 0.22 mmol), heat the reaction at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (19.9 mg, yield 55%). The reaction formula is as follows:

[0150]

[0151] The characterization results of the reaction product are as follows:

[0152] 1 H NMR (500MHz, CDCl3): δ=8.13–8.11(m,1H),8.08–8.05(m,2H),7.63–7.59(m,2H),7 .49–7.44(m,3H),7.43(s,1H),7.05–7.01(m,2H),6.95–6.92(m,2H),3.83(s,3H).( Figure 2 )

[0153] 13 C NMR (125MHz, CDCl3): δ=155.5,149.9,149.9,148.0,143.2,134.9,134.1,1 30.1,128.3,127.4,127.3,126.9,126.0,125.4,120.1,118.9,114.2,54.7.

[0154] HRMS(ESI):m / z for C 22 H16 ClNO2[M+H] + :362.0942,found:362.0940.

[0155] FTIR(KBr,cm -1 ):3447.66,2959.81,2836.45,2721.50,1600.36,1364.54,1070.09,778.50.

[0156] Embodiment 14

[0157] Preparation of 2-(2-chlorophenyl)-3-(3,4-dimethoxyphenoxy)quinoline

[0158] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 1-(2-chlorophenyl)-2-(3,4-dimethoxyphenoxy)ethyl-1-one (67.4 mg, 0.22 mmol), heat the reaction at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a brown oily liquid (27.8 mg, yield 71%). The reaction formula is as follows:

[0159]

[0160] The characterization results of the reaction product are as follows:

[0161] 1 H NMR (500MHz, CDCl3): δ=8.14(d,J=8.4Hz,1H),7.67(d,J=8.1Hz,1H),7.64–7.61(m,1H),7.56–7.54(m,1H),7.53–7.51(m,1 H),7.49–7.48(m,1H),7.43(s,1H),7.41–7.36(m,2H),6.85(d,J=8.3Hz,1H),6.69–6.65(m,2H),3.89(s,3H),3.81(s,3H).

[0162] 13C NMR (125MHz, CDCl3): δ = 150.7, 150.3, 149.0, 148.0, 145.2, 142.8, 136.1, 132.5, 130.1, 128. 8,128.4,128.3,127.8,126.7,126.3,125.9,125.6,117.3,110.7,110.7,104.0,55.2,55.0.

[0163] HRMS(ESI):m / z for C 23 H 18 ClNO3[M+H] + :392.1048,found:392.1054.

[0164] FTIR(KBr,cm -1 ):3464.49,2959.81,2833.64,2715.89,1599.49,1365.01,1067.29,775.68.

[0165] Embodiment 15

[0166] Preparation of 3-(4-methoxyphenoxy)-2-(3-methoxyphenyl)quinoline

[0167] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol) and benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 2-(4-methoxyphenoxy)-1-(3-methoxyphenyl)ethyl-1-one (60.0 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (18.6 mg, yield 52%). The reaction formula is as follows:

[0168]

[0169] The characterization results of the reaction product are as follows:

[0170] 1H NMR (500MHz, CDCl3): δ=8.15–8.13(m,1H),7.68–7.66(m,1H),7.64–7.59(m,3H),7.48–7.45(m,1H),7.43(s,1 H),7.39(t,J=8.0Hz,1H),7.05–7.02(m,2H),7.00–6.98(m,1H),6.94–6.91(m,2H),3.87(s,3H),3.82(s,3H).

[0171] 13 C NMR (125MHz, CDCl3): δ=158.4,155.4,151.1,150.0,148.2,143.2,137.7,128.3,1 28.1,127.3,126.8,125.9,125.4,121.2,120.1,118.9,114.1,114.0,54.6,54.3.

[0172] HRMS(ESI):m / z for C 23 H 19 NO3[M+H] + :358.1438,found:358.1436.

[0173] FTIR(KBr,cm -1 ):3464.49,2959.81,2830.84,2718.69,1602.80,1367.29,1070.09,778.50.

[0174] Example 16

[0175] Preparation of 3-(3,4-dimethoxyphenoxy)-2-(3-methoxyphenyl)quinoline

[0176] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 2-(3,4-dimethoxyphenoxy)-1-(3-methoxyphenyl)ethyl-1-one (66.6 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (24.7 mg, yield 64%). The reaction formula is as follows:

[0177]

[0178] The characterization results of the reaction product are as follows:

[0179] 1 H NMR (500MHz, CDCl3): δ = 8.15 (d, J = 8.4Hz, 1H), 7.68–7.66 (m, 1H), 7.64–7.60 (m, 3H), 7.49–7.46 (m, 2H), 7.39 (t, J = 8.0Hz, 1H), 7. 01–6.98(m,1H),6.86(d,J=8.7Hz,1H),6.68(d,J=2.7Hz,1H),6.63(dd,J=8.7,2.7Hz,1H),3.89(s,3H),3.87(s,3H),3.83(s,3H).

[0180] 13 C NMR (125MHz, CDCl3): δ=158.4,151.1,149.8,149.1,148.6,145.0,143.2,137.7,128.4,128.1, 127.3,126.9,125.9,125.4,121.2,119.2,114.0,113.9,110.8,110.1,103.6,55.3,55.0,54.3.

[0181] HRMS(ESI):m / z for C 24 H 21 NO4[M+H] + :388.1543,found:388.1548.

[0182] FTIR(KBr,cm -1 ):3453.27,2957.01,2937.38,2828.04,2721.50,1602.80,1367.29,1072.90,778.50.

[0183] Embodiment 17

[0184] Preparation of 2-(2,5-dimethoxyphenyl)-3-(4-methoxyphenoxy)quinoline

[0185] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 1-(2,5-dimethoxyphenyl)-2-(4-methoxyphenoxy)ethyl-1-one (66.5 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (29.9 mg, yield 78%). The reaction formula is as follows:

[0186]

[0187] The characterization results of the reaction product are as follows:

[0188] 1 H NMR (500MHz, CDCl3): δ = 8.14 (d, J = 8.4Hz, 1H), 7.63–7.57 (m, 2H), 7.48–7.45 (m, 1H), 7.37 (s, 1H), 7.09 (d, J=3.0Hz,1H),7.05–7.02(m,2H),6.95(dd,J=8.9,3.0Hz,1H),6.91-6.89(m,3H),3.81(s,6H),3.70(s,3H).

[0189] 13 C NMR (125MHz, CDCl3): δ=155.2,152.7,151.1,150.8,148.6,143.0,128.3,127.6,127.1, 126.4,125.8,125.5,120.2,117.4,115.1,114.6,114.4,113.9,111.2,55.1,54.8,54.6.

[0190] HRMS(ESI):m / z for C 24 H 21 NO4[M+H] + :388.1543,found:388.1549.

[0191] FTIR(KBr,cm -1 ):3456.07,2957.01,2829.53,2715.89,1602.80,1364.49,1072.90,775.49.

[0192] Embodiment 18

[0193] Preparation of 3-(3,4-dimethoxyphenoxy)-2-(2,5-dimethoxyphenyl)quinoline

[0194] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol) and benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add o-aminobenzyl alcohol (24.6 mg, 0.2 mmol), 2-(3,4-dimethoxyphenoxy)-1-(2,5-dimethoxyphenyl)ethyl-1-one (73.2 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (37.4 mg, yield 90%). The reaction formula is as follows:

[0195]

[0196] The characterization results of the reaction product are as follows:

[0197] 1 H NMR (500MHz, CDCl3): δ = 8.07 (d, J = 8.4Hz, 1H), 7.57 (d, J = 8.2Hz, 1H), 7.52 (ddd, J = 8.4, 6.8, 1.4Hz, 1H), 7.40 (t, J = 7.0Hz, 1H), 7.35 (s, 1H), 7.02 (d ,J=3.0Hz,1H),6.87(dd,J=9.0,3.0Hz,1H),6.83(d,J=9.0Hz,1H),6.77(d ,J=8.5Hz,1H),6.61–6.55(m,2H),3.81(s,3H),3.74(s,6H),3.63(s,3H).

[0198] 13 C NMR (125MHz, CDCl3): δ=153.7,152.1,151.8,151.7,150.0,150.0,145.9,144.1,129.3,128.6,128 .0,127.6,126.9,126.6,118.8,116.2,115.5,112.2,111.7,111.4,104.8,56.3,56.2,56.0,55.8.

[0199] HRMS(ESI):m / z for C 25 H 23 NO5[M+Na] +:440.1468,found:440.1475.

[0200] FTIR(KBr,cm -1 ):3450.47,2957.01,2836.45,2715.89,1600.00,1367.29,1072.90,775.82.

[0201] Embodiment 19

[0202] Preparation of 6-chloro-3-phenoxy-2-phenylquinoline

[0203] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-chlorophenyl)methanol (31.6 mg, 0.2 mmol), phenoxyacetophenone (46.7 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (23.3 mg, yield 70%). The reaction formula is as follows:

[0204]

[0205] The characterization results of the reaction product are as follows:

[0206] 1 H NMR (500MHz, CDCl3): δ = 8.06 (t, J = 8.7Hz, 3H), 7.61 (d, J = 2.2Hz, 1H), 7.56–7.53 (m ,1H),7.48–7.43(m,3H),7.41–7.37(m,3H),7.20–7.17(m,1H),7.08–7.07(m,2H).

[0207] 13 C NMR (125MHz, CDCl3): δ=154.8,151.8,149.8,141.8,136.0,131.7,129.9,129.2,128.6,128.2,127.9,127.9,127.2,124.1,123.5,119.0,118.7.

[0208] HRMS(ESI):m / z for C 21 H 14 ClNO[M+H] + :388.1377,for C21 H 14 ClNO[M+H] + :332.0837,found:332.0842.

[0209] FTIR(KBr,cm -1 ):3566.21,2928.97,2828.04,2721.50,1610.12,1359.27,1207.76,1073.13,778.50.

[0210] Embodiment 20

[0211] Preparation of 6-bromo-3-phenoxy-2-phenylquinoline

[0212] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-bromophenyl)methanol (40.4 mg, 0.2 mmol), phenoxyacetophenone (46.7 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (28.2 mg, yield 75%). The reaction formula is as follows:

[0213]

[0214] The characterization results of the reaction product are as follows:

[0215] 1 H NMR (500MHz, CDCl3): δ=8.08–8.06(m,2H),8.02(d,J=9.0Hz,1H),7.81(d,J=2.1Hz,1H),7.69(dd ,J=9.0,2.2Hz,1H),7.50–7.45(m,3H),7.44–7.38(m,3H),7.22–7.19(m,1H),7.10-7.07(m,2H).

[0216] 13 C NMR (125MHz, CDCl3): δ=154.7,152.0,149.7,142.0,136.0,130.4,130.0,129.2, 128.6,128.4,128.2,127.4,127.2,123.5,119.9,118.9,118.7,76.2,76.0,75.7.

[0217] HRMS(ESI):m / z for C 21 H 14 BrNO[M+H] + :376.0332,found:376.0333.

[0218] FTIR(KBr,cm -1 ):3424.23,2833.37,2357.20,2337.26,1594.33,1359.98,771.62,669.41.

[0219] Embodiment 21

[0220] Preparation of 6-fluoro-3-phenoxy-2-phenylquinoline

[0221] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-fluorophenyl)methanol (28.2 mg, 0.2 mmol), phenoxyacetophenone (46.7 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow powder solid (36.8 mg, yield 58%). The reaction formula is as follows:

[0222]

[0223] The characterization results of the reaction product are as follows:

[0224] 1 H NMR (500MHz, CDCl3): δ = 8.13 (dd, J = 9.3, 5.4Hz, 1H), 8.07–8.01 (m, 2H), 7.50–7.32 (m, 7H), 7.25–7.15 (m, 2H), 7.09–7.05 (m, 2H).

[0225] 13C NMR (125MHz, CDCl3): δ = 161.9, 159.9, 155.9, 152.0 (d, J = 3.0Hz), 150.8, 141.7, 137.1, 131.9 (d, J = 9.5Hz), 130.2 ,129.6,129.1(d,J=8.5Hz),128.2,124.5,120.5(d,J=5.3Hz),119.7,118.2(d,J=25.8Hz),109.6(d,J=22.3Hz).

[0226] HRMS(ESI):m / z for C 21 H 14 FNO[M+H] + :316.1132,found:316.1130.

[0227] FTIR(KBr,cm -1 ):3461.68,2830.84,2718.69,1611.21,1367.29,1067.29,775.70. Example 22

[0228] Preparation of 7-methyl-3-phenoxy-2-phenylquinoline

[0229] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-4-methylphenyl)methanol (27.4 mg, 0.2 mmol), phenoxyacetophenone (46.7 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (23.1 mg, yield 74%). The reaction formula is as follows:

[0230]

[0231] The characterization results of the reaction product are as follows:

[0232] 1 H NMR (500MHz, CDCl3): δ=8.07–8.02(m,2H),7.97(s,1H),7.57(d,J=8.4Hz,2H),7.49–7.40( m,3H),7.38–7.32(m,3H),7.14(t,J=7.4Hz,1H),7.05(dd,J=8.7,1.1Hz,2H),2.57(s,1H).

[0233] 13 C NMR (125MHz, CDCl3): δ=156.7,152.8,149.0,145.1,138.4,137.5,130.0,129. 6,129.2,128.9,128.5,128.2,126.2(d,J=3.6Hz),123.8,122.3,119.0,21.8.

[0234] HRMS(ESI):m / z for C 22 H 17 NO[M+H] + :312.1383,found:312.1389.

[0235] FTIR(KBr,cm -1 ):3419.63,2957.01,2825.23,2721.50,1611.21,1364.49,1075.70,775.70.

[0236] Embodiment 23

[0237] Preparation of 6-methyl-3-phenoxy-2-phenylquinoline

[0238] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-methylphenyl)methanol (27.4 mg, 0.2 mmol), phenoxyacetophenone (46.7 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (17.8 mg, yield 57%). The reaction formula is as follows:

[0239]

[0240] The characterization results of the reaction product are as follows:

[0241] 1 H NMR (500MHz, CDCl3): δ=8.09–8.02(m,3H),7.52–7.33(m,8H),7.15(t,J=7.4Hz,1H),7.06(d,J=7.6Hz,2H),2.51(s,3H).

[0242] 13C NMR (125MHz, CDCl3): δ=156.6,152.0,149.7,143.4,137.5,136.9,130.5,1 30.0,129.6,129.1,128.8,128.4,128.2,125.5,123.9,121.6,119.2,21.6.

[0243] HRMS(ESI):m / z for C 22 H 17 NO[M+H] + :312.1383,found:312.1385.

[0244] FTIR(KBr,cm -1 ):3436.45,2828.04,2718.69,1611.21,1361.68,1072.90,778.50. Example 24

[0245] Preparation of 5-chloro-3-phenoxy-2-phenylquinoline

[0246] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-6-chlorophenyl)methanol (31.5 mg, 0.2 mmol), phenoxyacetophenone (46.7 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow powder solid (41.4 mg, yield 62%). The reaction formula is as follows:

[0247]

[0248] The characterization results of the reaction product are as follows:

[0249] 1 H NMR (500MHz, CDCl3): δ=8.12–8.06(m,3H),7.96(d,J=0.8Hz,1H),7.59–7.52(m, 2H),7.51–7.45(m,3H),7.42–7.38(m,2H),7.21–7.16(m,1H),7.11–7.08(m,2H).

[0250] 13C NMR (125MHz, CDCl3): δ=156.0,153.6,150.6,145.1,136.8,130.2,129.9,129.7,129.4,128.6,128.3,127.7,126.8,126.6,124.4,119.3,118.8.

[0251] HRMS(ESI):m / z for C 21 H 14 ClNO[M+H] + :332.0837,found:332.0841.

[0252] FTIR(KBr,cm -1 ):3456.07,2828.04,2715.89,1602.08,1357.27,1078.50,775.70. Example 25

[0253] Preparation of 8-methyl-3-phenoxy-2-phenylquinoline

[0254] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-3-methylphenyl)methanol (27.4 mg, 0.2 mmol), phenoxyacetophenone (46.7 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow powder solid (32.7 mg, yield 53%). The reaction formula is as follows:

[0255]

[0256] The characterization results of the reaction product are as follows:

[0257] 1 H NMR (500MHz, CDCl3): δ=8.22–8.19(m,2H),7.57(s,1H),7.50–7.46(m,4H),7.45–7 .42(m,1H),7.40–7.36(m,3H),7.17–7.13(m,1H),7.08–7.06(m,2H),2.89(s,3H).

[0258] 13C NMR (125MHz, CDCl3): δ=156.7,150.8,149.6,143.8,137.8,137.6,130.0,1 29.9,128.9,128.3,128.3,128.1,126.8,124.5,123.8,122.6,119.1,18.1.

[0259] HRMS(ESI):m / z for C 22 H 17 NO[M+H] + :312.1383,found:312.1383.

[0260] FTIR(KBr,cm -1 ):3444.99,2833.78,2833.64,2718.83,1605.75,1359.03,1078.65,775.70.

[0261] Embodiment 26

[0262] Preparation of 3-phenoxy-2-phenylbenzo[g]quinoline

[0263] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (3-aminonaphthalene-2-yl)methanol (24.6 mg, 0.2 mmol) and phenoxyacetophenone (46.7 mg, 0.22 mmol). After heating at 130°C under argon for 16 hours, the reaction solution is post-treated to obtain the target product as a yellow powder solid (18.1 mg, yield 52%). The reaction formula is as follows:

[0264]

[0265] The characterization results of the reaction product are as follows:

[0266] 1 H NMR (500MHz, CDCl3): δ = 8.77 (s, 1H), 8.18 (s, 1H), 8.15–8.11 (m, 2H), 8.08 (dd, J = 6.4, 3.4Hz, 1H), 7.94 (dd, J=6.3,3.4Hz,1H),7.62(s,1H),7.53–7.46(m,5H),7.44–7.39(m,2H),7.23–7.19(m,1H),7.16–7.12(m,2H).

[0267] 13 C NMR (125MHz, CDCl3): δ=156.0,154.7,149.7,141.8,137.5,133.1,132.2,130.1,129.7 ,129.3,128.7,128.2,127.7,127.5,126.7,126.2,125.7,124.8,124.4,119.8,119.7.

[0268] HRMS(ESI):m / z for C 25 H 17 NO[M+H] + :338.1383,found:348.1376.

[0269] FTIR(KBr,cm -1 ):3442.06,2957.01,2828.04,2715.89,1616.82,1364.49,1064.49,772.90.

[0270] Embodiment 27

[0271] Preparation of 6-chloro-2-(4-chlorophenyl)-3-phenoxyquinoline

[0272] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-chlorophenyl)methanol (31.5 mg, 0.2 mmol), 1-(4-chlorophenyl)-2-phenoxyethyl-1-one (54.3 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow powder solid (20.3 mg, yield 55%). The reaction formula is as follows:

[0273]

[0274] The characterization results of the reaction product are as follows:

[0275] 1H NMR (500MHz, CDCl3): δ = 8.07 (d, J = 9.0Hz, 1H), 7.63 (d, J = 2.3Hz, 1H), 7.53 (dd, J = 9.0, 2.3Hz, 1H), 7.38–7.34 (m, 3H), 7 .16(t,J=7.4Hz,1H),7.08–7.06(m,3H),6.94(dd,J=9.0,3.1Hz,1H),6.88(d,J=9.0Hz,1H),3.80(s,3H),3.66(s,3H).

[0276] 13 C NMR (125MHz, CDCl3): δ=155.2,1527,151.7,150.7,150.6,141.6,131.6,129.9,128. 9,128.2,127.5,126.5,124.2,123.2,118.7,117.6,115.0,114.6,111.1,55.0,54.8.

[0277] HRMS(ESI):m / z for C 21 H 13 Cl2NO[M+Na] + :414.0867,found:414.0870.

[0278] FTIR(KBr,cm -1 ):3456.07,2959.81,2828.04,2718.69,1598.18,1365.15,1070.09,778.81.

[0279] Embodiment 28

[0280] Preparation of 6-chloro-2-(2,5-dimethoxyphenyl)-3-phenoxyquinoline

[0281] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-chlorophenyl)methanol (31.6 mg, 0.2 mmol), 1-(2,5-dimethoxyphenyl)-2-phenoxyethyl-1-one (59.9 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (30.9 mg, yield 79%). The reaction formula is as follows:

[0282]

[0283] The characterization results of the reaction product are as follows:

[0284] 1 H NMR (500MHz, CDCl3): δ = 8.07 (d, J = 9.0Hz, 1H), 7.63 (d, J = 2.3Hz, 1H), 7.53 (dd, J = 9.0, 2.3Hz, 1H), 7.38–7.34 (m, 3H), 7 .16(t,J=7.4Hz,1H),7.08–7.06(m,3H),6.94(dd,J=9.0,3.1Hz,1H),6.88(d,J=9.0Hz,1H),3.80(s,3H),3.66(s,3H).

[0285] 13 C NMR (125MHz, CDCl3): δ=155.15,152.65,151.74,150.73,150.56,141.58,131.61,129.85,128.88 ,128.23,127.50,126.51,124.17,123.24,118.72,117.63,115.02,114.64,111.05,55.00,54.80.

[0286] HRMS(ESI):m / z for C 23 H 18 ClNO3[M+Na] + :414.0867,found:414.0870.

[0287] FTIR(KBr,cm -1 ):3456.07,2959.81,2828.04,2718.69,1598.18,1365.15,1070.09,778.81.

[0288] Embodiment 29

[0289] Preparation of 6-bromo-2-(2,5-dimethoxyphenyl)-3-phenoxyquinoline

[0290] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-bromophenyl)methanol (40.4 mg, 0.2 mmol), 1-(2,5-dimethoxyphenyl)-2-phenoxyethyl-1-one (59.9 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (33.6 mg, yield 77%). The reaction formula is as follows:

[0291]

[0292] The characterization results of the reaction product are as follows:

[0293] 1 H NMR (500MHz, CDCl3): δ=8.02–7.98(m,1H),7.81(d,J=1.8Hz,1H),7.66(dd,J=9.0,2.1Hz,1H),7.38–7.35(m,3H),7. 17(t,J=7.1Hz,1H),7.08–7.04(m,3H),6.95(dd,J=8.9,3.1Hz,1H),6.88(d,J=9.0Hz,1H),3.81(s,3H),3.66(s,3H).

[0294] 13 C NMR (125MHz, CDCl3): δ=155.1,152.7,151.9,150.7,150.5,141.8,130.0,130.0,128. 9,128.7,127.5,126.5,123.3,119.8,118.7,117.5,115.0,114.7,111.1,55.0,54.8.

[0295] HRMS(ESI):m / z for C 23 H 18 BrNO3[M+H] + :436.0543,found:436.0539.

[0296] FTIR(KBr,cm -1 ):3453.27,2959.81,2833.64,2715.89,1596.76,1364.18,1067.29,775.61.

[0297] Embodiment 30

[0298] Preparation of 6-bromo-3-(4-methoxyphenoxy)-2-phenylquinoline

[0299] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-bromophenyl)methanol (40.4 mg, 0.2 mmol), 2-(4-methoxyphenoxy)-1-phenylethyl-1-one (53.3 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (30.2 mg, yield 74%). The reaction formula is as follows:

[0300]

[0301] The characterization results of the reaction product are as follows:

[0302] 1 H NMR (500MHz, CDCl3): δ=8.09–8.07(m,2H),7.98(d,J=8.9Hz,1H),7.76(d,J=2.1Hz,1H),7.65(dd,J= 8.9,2.2Hz,1H),7.51–7.44(m,3H),7.28(s,1H),7.06–7.03(m,2H),6.96–6.93(m,2H),3.83(s,3H).

[0303] 13 C NMR (125MHz, CDCl3): δ=155.7,151.5,150.9,147.6,141.6,136.1,130.1,1 30.0,128.6,128.5,128.2,127.4,127.2,120.5,119.8,117.0,114.3,54.7.

[0304] HRMS(ESI):m / z for C 22 H 16 BrNO2[M+H] + :406.0437,found:406.0433.

[0305] FTIR(KBr,cm -1):3481.31,2828.04,2721.50,1600.16,1365.01,1067.29,778.95. Example 31

[0306] Preparation of 6-chloro-3-(3,4-dimethoxyphenoxy)-2-phenylquinoline

[0307] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-chlorophenyl)methanol (31.6 mg, 0.2 mmol), 2-(3,4-dimethoxyphenoxy)-1-phenylethyl-1-one (60.0 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (24.1 mg, yield 61%). The reaction formula is as follows:

[0308]

[0309] The characterization results of the reaction product are as follows:

[0310] 1 H NMR (500MHz, CDCl3): δ=8.09–8.05(m,3H),7.60(d,J=2.3Hz,1H),7.54–7.44(m,4H),7.33(s,1H),6 .88(d,J=8.6Hz,1H),6.68(d,J=2.7Hz,1H),6.65(dd,J=8.6,2.7Hz,1H),3.91(s,3H),3.84(s,3H).

[0311] 13 C NMR (125MHz, CDCl3): δ=151.3,150.8,149.2,147.9,145.3,141.5,136.1,131.6,129. 9,128.6,128.2,128.0,127.6,127.2,124.1,117.3,110.8,110.5,103.8,55.3,55.0.

[0312] HRMS(ESI):m / z for C 23 H 18 ClNO3[M+H] + :392.1048,found:392.1042.

[0313] FTIR(KBr,cm -1 ):3447.66,2952.91,2829.88,2718.69,1599.64,1363.38,1072.90,775.70.

[0314] Embodiment 32

[0315] Preparation of 6-chloro-3-(4-methoxyphenoxy)-2-phenylquinoline

[0316] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol) and benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-chlorophenyl)methanol (31.6 mg, 0.2 mmol), 2-(4-methoxyphenoxy)-1-phenylethyl-1-one (53.3 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (25.6 mg, yield 71%). The reaction formula is as follows:

[0317]

[0318] The characterization results of the reaction product are as follows:

[0319] 1 H NMR (500MHz, CDCl3): δ = 8.09–8.04 (m, 3H), 7.59 (d, J = 2.3Hz, 1H), 7.53–7. 45(m,4H),7.28(s,1H),7.07–7.03(m,2H),6.96–6.93(m,2H),3.83(s,3H).

[0320] 13 C NMR (125MHz, CDCl3): δ=155.7,151.3,151.0,147.6,141.4,136.1,131.6,1 29.9,128.6,128.2,128.0,127.5,127.2,124.0,120.4,117.1,114.3,54.7.

[0321] HRMS(ESI):m / z for C 22 H 16 ClNO2[M+H] + :362.0942,found:362.0948.

[0322] FTIR(KBr,cm -1 ):3436.45,2836.45,2721.50,1599.28,1364.49,1072.90,775.70. Example 33

[0323] Preparation of 6-bromo-3-(4-methoxyphenoxy)-2-(3-methoxyphenyl)quinoline

[0324] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-bromophenyl)methanol (40.4 mg, 0.2 mmol), 2-(4-methoxyphenoxy)-1-(3-methoxyphenyl)ethyl-1-one (59.9 mg, 0.22 mmol), heat and react at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (22.5 mg, yield 52%). The reaction formula is as follows:

[0325]

[0326] The characterization results of the reaction product are as follows:

[0327] 1 H NMR (500MHz, CDCl3): δ=7.98(d,J=8.9Hz,1H),7.76(d,J=2.1Hz,1H),7.68–7.66(m,1H),7.66–7.63(m,2H),7.40( t,J=8.0Hz,1H),7.28(s,1H),7.06–7.02(m,2H),7.02–6.99(m,1H),6.95–6.92(m,2H),3.87(s,3H),3.83(s,3H).

[0328] 13 C NMR (125MHz, CDCl3): δ=158.4,155.7,151.3,150.9,147.6,141.5,137.3,130.1,130. 0,128.5,128.2,127.4,121.2,120.4,119.9,117.1,114.3,114.1,114.0,54.7,54.3.

[0329] HRMS(ESI):m / z for C 23 H 18BrNO3[M+H] + :436.0543,found:436.0548.

[0330] FTIR(KBr,cm -1 ):3447.66,2962.62,2830.84,2715.89,1608.41,1364.49,1070.09,775.70.

[0331] Embodiment 34

[0332] Preparation of 6-bromo-2-(2,5-dimethoxyphenyl)-3-(4-methoxyphenoxy)quinoline

[0333] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-bromophenyl)methanol (40.4 mg, 0.2 mmol), 1-(2,5-dimethoxyphenyl)-2-(4-methoxyphenoxy)ethyl-1-one (66.5 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a brown oily liquid (32.3 mg, yield 70%). The reaction formula is as follows:

[0334]

[0335] The characterization results of the reaction product are as follows:

[0336] 1 H NMR (500MHz, CDCl3): δ=7.98 (d, J=8.9Hz, 1H), 7.77 (d, J=2.1Hz, 1H), 7.63 (dd, J=8.9, 2.2Hz, 1H), 7.22 (s, 1H), 7.08 (d ,J=3.0Hz,1H),7.04–7.01(m,2H),6.96(dd,J=9.0,3.0Hz,1H),6.93–6.89(m,3H),3.82(d,J=1.6Hz,6H),3.72(s,3H).

[0337] 13C NMR (125MHz, CDCl3): δ=155.5,152.7,151.6,151.5,150.7,148.1,141.4,129.9,129.7, 128.8,127.4,126.7,120.4,119.7,115.8,115.0,114.6,114.0,111.2,55.1,54.8,54.6.

[0338] HRMS(ESI):m / z for C 24 H 20 BrNO4[M+H] + :466.0648,found:466.0655.

[0339] FTIR(KBr,cm -1 ):3447.66,2957.01,2830.84,2713.57,1602.80,1367.29,1072.90,773.96.

[0340] Embodiment 35

[0341] Preparation of 6-chloro-2-(2,5-dimethoxyphenyl)-3-(4-methoxyphenoxy)quinoline

[0342] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-chlorophenyl)methanol (31.5 mg, 0.2 mmol), 1-(2,5-dimethoxyphenyl)-2-(4-methoxyphenoxy)ethyl-1-one (66.5 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (25.6 mg, yield 61%). The reaction formula is as follows:

[0343]

[0344] The characterization results of the reaction product are as follows:

[0345] 1H NMR (500MHz, CDCl3): δ = 8.05 (d, J = 8.9Hz, 1H), 7.60 (d, J = 2.3Hz, 1H), 7.50 (dd, J = 8.9, 2.3Hz, 1H), 7.23 (s, 1H), 7.08 (d ,J=3.0Hz,1H),7.04–7.01(m,2H),6.96(dd,J=9.0,3.0Hz,1H),6.93–6.90(m,3H),3.82(d,J=1.6Hz,6H),3.72(s,3H).

[0346] 13 C NMR (125MHz, CDCl3): δ=155.5,152.7,151.7,151.3,150.8,148.1,141.2,131.5,129.8, 128.3,127.2,126.7,124.1,120.4,115.9,115.0,114.6,114.0,111.2,55.1,54.8,54.6.

[0347] HRMS(ESI):m / z for C 24 H 20 ClNO4[M+H] + :422.1154,found:422.1157.

[0348] FTIR(KBr,cm -1 ):3458.88,2962.62,2828.25,2721.50,1600.00,1364.82,1072.90,776.45.

[0349] Embodiment 36

[0350] Preparation of 2-(4-bromophenyl)-6-chloro-3-(4-methoxyphenoxy)quinoline

[0351] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-chlorophenyl)methanol (31.5 mg, 0.2 mmol), 1-(4-bromophenoxy)-2-(4-methoxyphenoxy)ethyl-1-one (70.7 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (15.9 mg, yield 41%). The reaction formula is as follows:

[0352]

[0353] The characterization results of the reaction product are as follows:

[0354] 1 H NMR (500MHz, CDCl3): δ=8.03(d,J=9.0Hz,1H),8.01–7.98(m,2H),7.63–7.60(m,2H),7.58(d,J=2.3H z,1H),7.52(dd,J=9.0,2.3Hz,1H),7.28(s,1H),7.05–7.02(m,2H),6.96–6.93(m,2H),3.84(s,3H).

[0355] 13 C NMR (125MHz, CDCl3): δ=155.8,150.8,149.9,147.4,141.4,135.0,131.8,1 30.4,130.3,129.8,128.1,127.7,124.1,122.7,120.4,117.3,114.3,54.7.

[0356] HRMS(ESI):m / z for C 22 H 15 BrClNO2[M+H] + :440.0047,found:440.0042.

[0357] FTIR(KBr,cm -1 ):3442.06,2957.01,2828.04,2715.89,1600.70,1364.98,1072.90,775.70.

[0358] Embodiment 37

[0359] Preparation of 6-chloro-2-(4-chlorophenyl)-3-(4-methoxyphenoxy)quinoline

[0360] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-chlorophenyl)methanol (31.5 mg, 0.2 mmol), 1-(4-chlorophenyl)-2-(4-methoxyphenoxy)ethyl-1-one (60.8 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (19.5 mg, yield 49%). The reaction formula is as follows:

[0361]

[0362] The characterization results of the reaction product are as follows:

[0363] 1 H NMR (500MHz, CDCl3): δ=8.08–8.05(m,2H),8.03(d,J=9.0Hz,1H),7.58(d,J=2.2Hz,1H),7.52(dd,J= 9.0,2.3Hz,1H),7.47–7.44(m,2H),7.28(s,1H),7.05–7.02(m,2H),6.96–6.93(m,2H),3.83(s,3H).

[0364] 13 C NMR (125MHz, CDCl3): δ=155.8,150.9,149.9,147.4,141.3,134.5,134.3,1 31.8,130.1,129.8,128.0,127.7,127.4,124.0,120.4,117.3,114.3,54.7.

[0365] HRMS(ESI):m / z for C 22 H 15 Cl2NO2[M+H] + :396.0553,found:396.0548.

[0366] FTIR(KBr,cm -1 ):3444.86,2957.01,2833.64,2721.50,1600.00,1364.49,1081.31,772.90.

[0367] Embodiment 38

[0368] Preparation of 6-bromo-3-(3,4-dimethoxyphenoxy)-2-(2,5-dimethoxyphenyl)quinoline

[0369] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-bromophenyl)methanol (40.4 mg, 0.2 mmol), 2-(3,4-dimethoxyphenoxy)-1-(2,5-dimethoxyphenyl)ethyl-1-one (73.1 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white oily liquid (36.0 mg, yield 73%). The reaction formula is as follows:

[0370]

[0371] The characterization results of the reaction product are as follows:

[0372] 1 H NMR (500MHz, CDCl3): δ=7.99(d,J=8.9Hz,1H),7.80(d,J=1.9Hz,1H),7.64(dd,J=8.9,2.1Hz,1H),7.27(d,J=11.5Hz,1H),7.09(d,J=2.9Hz,1H), 6.96(dd,J=9.0,3.0Hz,1H),6.91(d,J=9.0Hz,1H),6.86(d,J=8.2Hz,1H) ,6.67–6.64(m,2H),3.89(s,3H),3.82(s,3H),3.80(s,3H),3.72(s,3H).

[0373] 13 C NMR (125MHz, CDCl3): δ=152.7,151.5,151.4,150.7,149.0,148.4,145.1,141.4,129.9,129.8,128 .8,127.5,126.5,119.8,116.2,115.1,114.6,111.2,110.7,110.6,103.8,55.2,55.2,55.0,54.8.

[0374] HRMS(ESI):m / z for C 25 H 22 BrNO5[M+H] +:496.0754,found:496.0760.

[0375] FTIR(KBr,cm -1 ):3450.47,2957.01,2830.84,2718.69,1597.20,1370.09,1072.90,781.31.

[0376] Embodiment 39

[0377] Preparation of 6-bromo-2-(2-chlorophenyl)-3-(3,4-dimethoxyphenoxy)quinoline

[0378] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-bromophenyl)methanol (40.4 mg, 0.2 mmol), 1-(2-chlorophenyl)-2-(3,4-dimethoxyphenoxy)ethyl-1-one (67.5 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a brown oily liquid (29.4 mg, yield 62%). The reaction formula is as follows:

[0379]

[0380] The characterization results of the reaction product are as follows:

[0381] 1 H NMR (500MHz, CDCl3): δ=7.98 (d, J=8.9Hz, 1H), 7.83 (d, J=2.1Hz, 1H), 7.67 (dd, J=8.9, 2.1Hz, 1H), 7.56–7.54 (m, 1H) ,7.50–7.47(m,1H),7.43–7.37(m,2H),7.29(s,1H),6.87–6.85(m,1H),6.68–6.65(m,2H),3.90(s,3H),3.82(s,3H).

[0382] 13C NMR (125MHz, CDCl3): δ=151.1,151.0,149.1,147.5,145.4,141.2,135.8,132.4,130. 1,130.0,129.0,128.5,127.6,125.9,120.3,115.7,110.9,110.7,104.0,55.2,55.0.

[0383] HRMS(ESI):m / z for C 23 H 17 BrClNO3[M+H] + :470.0153,found:470.0148.

[0384] FTIR(KBr,cm -1 ):3450.59,2954.34,2825.76,2718.83,1600.15,1367.44,1070.24,775.73.

[0385] Embodiment 40

[0386] Preparation of 6-chloro-2-(2-chlorophenyl)-3-(3,4-dimethoxyphenoxy)quinoline

[0387] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (7.9 mg, 5 mol%), cesium carbonate (110.0 mg, 0.34 mmol), benzoquinone (23.7 mg, 0.22 mmol) and ether (2.0 ml). Then, add (2-amino-5-chlorophenyl)methanol (31.5 mg, 0.2 mmol), 1-(2-chlorophenyl)-2-(3,4-dimethoxyphenoxy)ethyl-1-one (67.5 mg, 0.22 mmol), heat at 130°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a yellow oily liquid (29.4 mg, yield 62%). The reaction formula is as follows:

[0388]

[0389] The characterization results of the reaction product are as follows:

[0390] 1H NMR (500MHz, CDCl3): δ = 8.05 (d, J = 9.0Hz, 1H), 7.65 (d, J = 2.3Hz, 1H), 7.56–7.53 (m, 2H), 7.50–7.47 (m ,1H),7.43–7.37(m,2H),7.30(s,1H),6.87–6.85(m,1H),6.69–6.66(m,2H),3.90(s,3H),3.82(s,3H).

[0391] 13 C NMR (125MHz, CDCl3): δ=151.2,150.9,149.1,147.5,145.4,141.0,135.8,132.4,132.1,130. 0,129.9,129.0,128.5,128.4,127.5,125.9,124.2,115.9,110.9,110.7,104.0,55.2,55.0.

[0392] HRMS(ESI):m / z for C 23 H 17 Cl2NO3[M+H] + :426.0658,found:426.0659.

[0393] FTIR(KBr,cm -1 ):3464.49,2959.81,2830.84,2718.69,1597.20,1364.82,1072.90,773.96.

[0394] Embodiment 41

[0395] Preparation of 3-phenoxy-2-phenylquinoline

[0396] Take a clean reaction bottle, add a small magnetic bar, dry it, add dichloro (pentamethylcyclopentadienyl) iridium (III) dimer ([IrCp*Cl2]2, 3.9 mg, 5 mol%), cesium carbonate (Cs2CO3, 55.4 mg, 0.17 mmol) and ether (Et2O, 1.0 ml). Then, add o-aminobenzyl alcohol (12.3 mg, 0.1 mmol) and phenoxyacetophenone (23.3 mg, 0.11 mmol). After heating at 130°C under argon for 16 hours, the reaction solution is post-treated to obtain the target product as a white oily liquid (17.2 mg, yield 58%). The reaction formula is as follows:

[0397]

[0398] The characterization results of the reaction product are as follows:

[0399] 1H NMR (500MHz, CDCl3): δ=8.17–8.15(m,1H),8.06–8.03(m,2H),7.65–7.62(m,2H),7.57(s,1H),7.50–7.4 8(m,1H),7.47–7.45(m,2H),7.43–7.40(m,1H),7.39–7.34(m,2H),7.17–7.14(m,1H),7.08–7.05(m,2H).

[0400] 13C NMR (125MHz, CDCl3): δ=155.4,151.9,148.7,143.7,136.3,129.0,128.6,128.4,128.0,127.3,127.2,127.1,125.9,125.5,123.0,120.8,118.3.

[0401] HRMS(ESI):m / z for C 21 H 15 NO[M+H]+:298.1226,found:298.1223.

[0402] FTIR(KBr,cm-1):3447.42,2952.91,2831.23,2713.57,1597.87,1364.70,1069.10,776.17.

[0403] Application Example 1

[0404] Preparation of 3-phenoxy-2,6-diphenylquinoline

[0405] Take a clean reaction bottle, add a small magnetic bar, dry it, add tetrakistriphenylphosphine palladium (Pd(PPh3)4, 2.8 mg, 5 mol%), potassium carbonate (K2CO3, 26.4 mg, 0.19 mmol), toluene (toluene, 0.19 mL), water (H2O, 0.09 mL) and ethanol (EtOH, 0.05 mL). Then, add 6-bromo-3-phenoxy-2-phenylquinoline (prepared in Example 20, 17.9 mg, 0.05 mmol), phenylboric acid (8.8 mg, 0.07 mmol), heat the reaction at 95°C under argon for 16 hours, and the reaction solution is post-treated to obtain the target product as a white solid (11.6 mg, yield 65%). The reaction formula is as follows:

[0406]

[0407] The characterization results of the reaction product are as follows:

[0408] 1 H NMR (400MHz, CDCl3) δ = 8.22 (d, J = 8.7Hz, 1H), 8.10–8.05 (m, 2H), 7.90 (dd, J = 8.7, 2.0Hz, 1H), 7.84 (s, 1H), 7.70 (d, J=8.7Hz,2H),7.60(s,1H),7.51–7.43(m,5H),7.39(t,J=7.9Hz,3H),7.17(t,J=7.4Hz,1H),7.09(d,J=8.8Hz,2H).

[0409] 13 C NMR (101MHz, CDCl3) δ = 156.3, 152.7, 150.2, 144.1, 140.3, 139.6, 137.4, 130.1, 129.8 ,129.6,129.1,129.0,128.6,128.2,127.9,127.8,127.4,124.3,124.2,121.8,119.5.

[0410] HRMS(ESI):m / z:for C 27 H 19 NO[M+H] + 374.1545, found 374.1577.

[0411] FTIR(KBr,cm -1 ):3453.40,2830.97,2716.02,1602.95,1367.44,773.05.

[0412] Application Example 2

[0413] Preparation of (E)-3-phenoxy-2-phenylvinylquinoline

[0414] Take a clean reaction bottle, add a small magnetic bar, dry it, add p-toluenesulfonamide (p-Toluenesulfonamide, 34.2 mg, 0.2 mmol) and toluene (toluene, 0.19 mL). Then, add 2-methyl-3-phenoxyquinoline (prepared in Example 8, 34.6 mg, 0.2 mmol) and benzaldehyde (21.2 mg, 0.2 mmol). After heating at 120°C under argon for 12 hours, the reaction solution is post-treated to obtain the target product as a white solid (35.3 mg, yield 55%). The reaction formula is as follows:

[0415]

[0416] The characterization results of the reaction product are as follows:

[0417] 1 H NMR (400MHz, CDCl3) δ=8.07–7.99(m,2H),7.67(d,J=16.0Hz,1H),7.57(d,J=7.1Hz,2H),7.51( t,2H),7.37–7.27(m,6H),7.23(d,J=7.2Hz,1H),7.12(t,J=7.4Hz,1H),7.04(d,J=7.4Hz,2H).

[0418] 13 C NMR(101MHz, CDCl3)δ=155.5,148.6,148.6,143.7,135.8,134.6,129.1,128.0 ,127.6,127.6,127.3,127.1,126.5,125.6,125.4,123.2,120.7,119.8,118.3.

[0419] HRMS(ESI)m / z:for C 23 H 17 NO[M+H] + 324.1388, found 324.1445.

[0420] FTIR(KBr,cm -1 ):3453.40,2962.62,2833.64,2715.89,1605.61,1361.68,1067.29,778.50.

[0421] It can be seen from the examples that the synthesis method of the present invention is simple to operate and is applicable to various group-substituted o-aminobenzyl alcohols, including halogen-substituted o-aminobenzyl alcohols, methyl-substituted o-aminobenzyl alcohols and naphthyl-substituted o-aminobenzyl alcohols; it is also applicable to various group-substituted phenoxyacetophenones, including halogen-substituted phenoxyacetophenones, methoxy-substituted phenoxyacetophenones, and halogen- and methoxy-disubstituted phenoxyacetophenones; and it has good functional group compatibility and is applicable to fluorine, chlorine, bromine and trifluoromethyl. The addition of benzoquinone and cesium carbonate can also efficiently promote the reaction and greatly reduce the cost, with the highest yield reaching 90%.

[0422] The embodiments described above provide a detailed description of the technical solutions of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, supplements or similar substitutions made within the scope of the principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for synthesizing a quinoline compound substituted with a phenoxy group at position C3, characterized in that: The following steps are involved: Placing an o-aminobenzyl alcohol compound, an aromatic ketone, a transition metal salt catalyst and an additive in an organic solvent, heating the mixture under an argon atmosphere for reaction, and after the reaction is completed, post-treating the reaction solution to obtain the C3-position phenoxy-substituted quinoline compound; the reaction raw materials also include an oxidant benzoquinone; the transition metal salt catalyst is dichloro(pentamethylcyclopentadienyl)iridium dimer; the additive is cesium carbonate; the molar ratio of the o-aminobenzyl alcohol compound, the aromatic ketone, the transition metal salt catalyst, the additive and the benzoquinone is 1:1-1.5:0.02-0.07:1-2:1-1.5; The quinoline compound substituted with phenoxy at position C3 has a structural formula as shown in formula (I): ； （Ⅰ）； In formula (I), R 1 is any one of hydrogen, naphthalene, halogen or methyl, halogen is selected from fluorine, chlorine or bromine; R 2 is any one of hydrogen, methoxy or trifluoromethyl; R 3 is any one of methyl, phenyl, halogen-substituted phenyl or methoxy-substituted phenyl, and the halogen-substituted phenyl is chlorine- or bromine-substituted phenyl; The structural formula of the o-aminobenzyl alcohol compound is shown in formula (II), and the structural formula of the aromatic ketone is shown in formula (III). ； （Ⅱ）； ； （Ⅲ）； In formula (II) and (III), R 1 , R 2 and R 3 The definition of is consistent with that in formula (I).

2. The method for synthesizing a C3-phenoxy-substituted quinoline compound according to claim 1, characterized in that: The organic solvent is diethyl ether, tetrahydrofuran or ethylene glycol dimethyl ether.

3. The method for synthesizing a C3-phenoxy-substituted quinoline compound according to claim 1, characterized in that: The volume dosage of the organic solvent is 5-15 L / mol based on the amount of the o-aminobenzyl alcohol compound.

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