A photochemical cobalt catalyzed synthesis of arylamines

Abstract

The application discloses a photochemical cobalt catalytic synthesis method of arylamine compounds, uses bipyridine as a ligand, uses a cobalt salt as a catalyst, uses cheap and abundant aryl bromide and amine compounds as reactants, adds an organic base, and realizes synthesis of arylamine compounds by promoting C-N coupling reaction of aryl bromide and amine compounds through cobalt catalysis in an argon atmosphere. The reaction system is simple, the operation is simple, the reaction condition is mild, the post-treatment is simple, the target compound is good in selectivity and high in yield, the use of traditional expensive metal catalysts and inorganic bases is avoided, problems such as complicated catalytic system reaction and poor functional group compatibility are avoided, and the method has good application value and market prospect.

Description

Technical Field

[0001] This invention belongs to the field of aromatic amine synthesis technology, specifically relating to a method for synthesizing aromatic amine compounds by photochemical cobalt catalysis. Background Technology

[0002] Aromatic amines are common structural units in organic molecules (Chem. Soc. Rev., 2011, 40, 5068), widely found in natural products, pharmaceutical molecules, pesticides, fragrances, dyes, and polymer-related compounds (Eur. J. Org. Chem., 2011, 1207; Angew. Chem. Int. Ed., 1999, 38, 2096). Transition metal-catalyzed Buchwald-Hartwig and Ulman-Ma amination reactions are important methods for constructing CN bonds (Org. Process Res. Dev. 2019, 23, 1529). In these reactions, metals Pd (Chem.Soc.Rev.2013,42,9283; Org.ProcessRes.Dev.2019,23,1478; Angew.Chem.Int.Ed.2019,58,17118), Cu (Angew.Chem.Int.Ed.2009,48,6954; Chem.Soc.Rev.2014,43,3525; Angew.Chem.Int.Ed.2017,56,16136) and Ni (Org.Process Res.Dev.2022,26,2281; Org.Chem.Front.2023,10,548) are widely used as catalysts, providing a general method for the synthesis of aromatic amines. However, for different types of amine nucleophiles, it is often necessary to synthesize different types of phosphine ligands, carbene, or oxalamide ligands to stabilize the catalyst, promote reductive elimination, and achieve CN coupling reactions (Chem. Rec. 2016, 16, 1819; Chin. J. Chem. 2020, 38, 879). Therefore, developing a universal single catalyst system to achieve universal CN coupling is a major challenge.

[0003] Cobalt is abundant and has low toxicity (Org. Biomol. Chem. 2019, 17, 10119). Applying cobalt catalysts to coupling reactions (Chem. Rev. 2010, 110, 1435) has become a novel and promising strategy (Chem. Soc. Rev. 2015, 44, 3391; Chem. Eur. J., 2021, 27, 2021; Org. Biomol. Chem. 2020, 18, 7740). In 2009, Teo (Chem.Eur.J.2009,15,3072; Org.Biomol.Chem.2014,12,7478; Synlett2015,26,1697; ChemistrySelect 2018,3,4406; Catalysts 2020,10,1315; Journal of Organometallic Chem.2018,868,144) et al. developed a cobalt-catalyzed CN coupling reaction of aryl iodides and small amounts of bromides using dmeda as a ligand. However, the substrate applicability was relatively limited, the aryl bromides had low activity, and the ortho-position was significantly hindered. Toma et al. (Eur. J. Org. Chem. 2015, 4018) used phosphorus ligands to achieve cobalt-catalyzed CN coupling reactions of aryl chlorides and secondary amines, but this method suffers from high reaction temperatures (typically above 100 °C), limited substrate applicability, and the need for functional group induction. Fout's group (Chem. Sci. 2014, 5, 4831; Inorg. Chem. 2022, 61, 18019) developed a phosphorus ligand-promoted cobalt(I)-catalyzed CN coupling reaction involving aryl halides with LiN(SiMe3)2 as an N-nucleophile. Knochel et al. (Chem. Eur. J. 2013, 19, 6225; Angew. Chem. Int. Ed. 2018, 57, 1108) developed a cobalt-catalyzed electrophilic amination reaction of aryl zinc reagents with chloramines or N-hydroxylamine benzoates. However, this reaction is only applicable to activated secondary amines, limiting the substrate range of amines. Furthermore, the zinc reagent is prepared in advance from aryl halides and zinc. Although some progress has been made in the application of cobalt catalysts in aryl CN coupling reactions (Tetrahedron 2022, 104, 132582; Chem. Commun. 2008, 3221; Chem. Rev. 2010, 110, 1435), their application in synthetic chemistry is very limited due to the lack of a universal catalyst system. Therefore, developing a universal and efficient Co-catalyzed CN coupling reaction under mild conditions will provide new strategies and potential applications for the development of amination reactions. Summary of the Invention

[0004] The purpose of this invention is to provide a method for synthesizing aromatic amine compounds by using an inexpensive cobalt salt and bipyridine catalytic system to achieve CN coupling of aryl bromides and amine compounds.

[0005] To achieve the above objectives, the technical solution adopted in this invention is as follows: aryl bromide of Formula I, amine compound of Formula II, bipyridine, cobalt catalyst, and organic base are added to an organic solvent, heated and irradiated in an argon atmosphere, and the reaction is carried out. After the reaction is complete, the product is separated and purified to obtain the aromatic amine compound of Formula III.

[0006]

[0007] In the formula, Ar represents any one of aryl, substituted aryl, heterocyclic aryl, and substituted heterocyclic aryl, specifically representing any one of phenyl, thienyl, thiazolyl, pyridinyl, benzofuranyl, dibenzothienyl, pyrazolyl, piperidinyl, and quinoxalinyl, or a phenyl group containing at least one substituent from C1-C6 alkyl, C6-cycloalkyl, tert-butyldimethylsiloxy, sulfonyl, acrylyl, piperidinyl, trimethylsilyl, halogen, C1-C4 alkoxy, trifluoromethoxy, trifluoromethyl, cyano, ester, aldehyde, acyl, carbonyl, and borosilicate; HNNu represents aromatic amine, substituted aromatic amine, heterocyclic aromatic amine, aliphatic amine, pyrazole, amide, sulfonamide, etc. 15 Any of the N-labeled ammonium chlorides.

[0008] In the above synthesis method, the amount of amine compound used is preferably 1.1 to 2 times the molar amount of aryl bromide.

[0009] In the above synthesis method, the amount of bipyridine used is preferably 5% to 10% of the molar amount of aryl bromide.

[0010] In the above synthesis method, the preferred cobalt catalyst is any one of cobalt bromide, cobalt carbonate, cobalt acetate, cobalt chloride, cobalt perchlorate, etc., and its amount is 5% to 10% of the molar amount of aryl bromide.

[0011] In the above synthesis method, the preferred organic base is any one of 1,8-diazabicycloundec-7-ene (DBU), tetramethylguanidine (TMG), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (DMTHPM), etc., and its amount is 2 to 3 times the molar amount of aryl bromide.

[0012] In the above synthesis method, the preferred organic solvent is any one or two of dimethyl sulfoxide, toluene, isopropanol, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0013] In the above synthesis method, it is preferred to react at 80-90°C for 24-36 hours under an argon atmosphere and irradiated with ultraviolet light with a wavelength of 360-430 nm.

[0014] The beneficial effects of this invention are as follows:

[0015] This invention utilizes a cobalt salt and bipyridine system to synthesize aromatic amines via a CN-coupling reaction of aryl bromides and amines under light irradiation. The reaction system is simple, economically efficient, environmentally friendly, and requires minimal post-reaction processing. The resulting aromatic amines exhibit good yields and excellent functional group compatibility. This method offers a simple and efficient way to synthesize aromatic amines, aligning with current trends towards environmentally friendly, economical, and green chemistry, and possesses significant application potential. Detailed Implementation

[0016] 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.

[0017] Example 1

[0018] In an argon atmosphere, 31.4 mg (0.2 mmol) bromobenzene, 29.4 mg (0.4 mmol) n-butylamine, 1.9 mg (0.01 mmol) bipyridine, 3.6 mg (0.01 mmol) cobalt(II) perchlorate hexahydrate, 60 mg (0.6 mmol) DBU, 2 mL N,N-dimethylformamide, and a magnetic flux were added to a reaction tube. The reaction was carried out at 85 °C for 24 hours under ultraviolet light irradiation at a wavelength of 390–395 nm. After the reaction was completed, the mixture was cooled to room temperature, diluted with saturated sodium chloride aqueous solution and ethyl acetate to obtain an organic phase. The organic phase was distilled under reduced pressure to obtain a crude product. The crude product was separated by column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 100:1 to 10:1 as the eluent, yielding a pale yellow oily product with the following structural formula, in 86% yield.

[0019]

[0020] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz, CDCl3) δ7.16(dd,J=8.5,7.4Hz,2H),6.68(t,J=7.3Hz,2H),6.59(d,J=7.7Hz,1H),3 .47(br,1H),3.09(t,J=7.1Hz,2H),1.63-1.56(m,2H),1.46-1.40(m,2H),0.95(t,J=7.3Hz,3H); 13C NMR(100MHz, CDCl3)δ148.6,129.3,117.1,112.7,43.7,31.7,20.4,14.0; HRMS(ESI)m / z C 10 H 16 N + [M+H] + Theoretical value 150.1277, measured value 150.1280.

[0021] Example 2

[0022] In this embodiment, 4-tert-butylbromobenzene was used to replace the bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow oily substance with the following structural formula, with a yield of 90%.

[0023]

[0024] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz, CDCl3)δ7.19(d,J=6.8Hz,2H),6.55(d,J=6.9Hz,2H),3.65-3.19(m,1H), 3.09(m,2H),1.62-1.53(m,2H),1.46-1.38(m,2H),1.27(s,9H),0.94(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ146.3,139.9,126.0,112.5,44.0,33.9,31.9,31.6,20.4,14.0; HRMS(ESI)m / z C 14 H 24 N + [M+H] + Theoretical value: 206.1903, measured value: 206.1905.

[0025] Example 3

[0026] In this embodiment, 1-bromo-4-(trans-4-pentylcyclohexyl)benzene was used to replace the bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow oily substance with the following structural formula, with a yield of 86%.

[0027]

[0028] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.11(d,J=8.3Hz,2H),6.64(d,J=8.3Hz,2H),3.51(br,1H),3.17(t,J=7.1Hz,2H),2.48-2 .40(m,1H),1.94(t,J=9.7Hz,4H),1.74-1.61(m,2H),1.59-1.40(m,6H),1.31-1.24(m,2H),1.20-0.92(m,8H); 13 CNMR(100MHz, CDCl3)δ146.7,136.8,127.5,112.8,44.0,43.6,39.9,37.2,34.7,33.8,31.9,20.4,20.2,14.5,14.0; HRMS(ESI)m / z C19H 32 N + [M+H] + Theoretical value: 274.2529, measured value: 274.2530.

[0029] Example 4

[0030] In this embodiment, bromobenzene in Example 1 was replaced with an equimolar amount of ((4-bromobenzyl)oxy)(tert-butyl)dimethylsilane, and the other steps were the same as in Example 1, resulting in a pale yellow solid with the following structural formula, in a yield of 80%.

[0031]

[0032] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.05(d,J=7.7Hz,2H),6.50(d,J=7.1Hz,2H),4.54(s,2H),3.02(t,J=7.0Hz,2H),1.57-1.48(m,2H),1.43-1.36(m,2H),0.91 -0.86(m,12H),0.04-0.05(m,6H); 13 C NMR(100MHz, CDCl3)δ147.7,130.0,127.8,112.6,65.1,43.9,31.7,26.0,20.3,18.5,13.9,-5.1; HRMS(ESI)m / z C 17 H 32 NOSi + [M+H] + Theoretical value: 294.2248, measured value: 294.2250.

[0033] Example 5

[0034] In this embodiment, 4-bromobenzene sulfone was replaced with an equimolar amount in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow solid product with the following structural formula, in a yield of 83%.

[0035]

[0036] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.68(d,J=8.8Hz,2H),6.60(d,J=8.8Hz,2H),4.30(br,1H),3.17(d ,J=3.4Hz,2H),3.00(s,3H),1.69-1.60(m,2H),1.49-1.40(m,2H),0.97(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ152.5,129.4,126.9,111.6,45.1,43.0,31.2,20.2,13.8; HRMS(ESI)m / z C 11 H 18 NO2S + [M+H] + Theoretical value: 228.1053, measured value: 228.1055.

[0037] Example 6

[0038] In this embodiment, ethyl 4-bromobenzoate was used to replace bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow oily substance with the following structural formula, with a yield of 85%.

[0039]

[0040] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.86(d,J=8.8Hz,2H),6.53(d,J=8.8Hz,2H),4.31(q,J=7.1Hz,2H),4.13(br,1H),3.15(t,J=7.1Hz,2H),1.65-1.60(m,2H),1.47 -1.38(m,2H),1.35(t,J=7.1Hz,3H),0.95(t,J=7.3Hz,3H); 13C NMR(100MHz, CDCl3)δ166.9,152.1,131.5,118.3,111.3,60.1,43.1,31.4,20.2,14.5,13.8; HRMS(ESI)m / z C 13 H 20 NO2 + [M+H] + Theoretical value: 222.1489, measured value: 222.1490.

[0041] Example 7

[0042] In this embodiment, 1,4-dibromobenzene was used to replace the bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow oily substance with the following structural formula, with a yield of 87%.

[0043]

[0044] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz, CDCl3) δ7.23(d,J=8.8Hz,2H),6.46(d,J=8.8Hz,2H),3.60(br,1H) ,3.12-3.02(m,2H),1.61-1.56(m,2H),1.47-1.39(m,2H),0.95(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ147.5,131.9,114.2,112.7,43.7,31.5,20.3,13.9; HRMS(ESI)m / z C 10 H 15 BrN + [M+H] + Theoretical value: 228.0382, measured value: 228.0388.

[0045] Example 8

[0046] In this embodiment, 2-methoxybromobenzene was used to replace the bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow oily substance with the following structural formula, with a yield of 93%.

[0047]

[0048] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ6.78(t,J=7.6Hz,1H),6.67(d,J=7.6Hz,1H),6.63-6.47(m,2H),4.07(br,1H ),3.74(s,3H),3.03(t,J=7.1Hz,2H),1.61-1.47(m,2H),1.46-1.32(m,2H),0.88(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ146.8,138.6,121.4,116.1,109.8,109.4,55.4,43.4,31.7,20.5,14.0; HRMS(ESI)m / zC 11 H 18 NO + [M+H] + Theoretical value: 180.1383, measured value: 180.1388.

[0049] Example 9

[0050] In this embodiment, 2-hexylpropylbromobenzene was used to replace the bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow oily substance with the following structural formula, with a yield of 83%.

[0051]

[0052] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.20-7.07(m,2H),6.72(t,J=7.4Hz,1H),6.64(d,J=8.0Hz,1H),3.60(br,1H),3.15(t,J=7 .0Hz,2H),2.95-2.86(m,1H),1.76-1.63(m,2H),1.56-1.39(m,2H),1.25(d,J=6.8Hz,6H),0.97(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ145.2,131.9,126.7,124.8,116.9,110.4,43.8,31.8,27.2,22.3,20.4,14.0; HRMS(ESI)m / z C 13 H 22 N + [M+H] + Theoretical value: 192.1747, measured value: 192.1750.

[0053] Example 10

[0054] In this embodiment, 3,5-dichlorobromobenzene was used to replace the bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow oily substance with the following structural formula, with a yield of 85%.

[0055]

[0056] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz, CDCl3)δ6.63(s,1H),6.43(s,2H),3.92-3.58(m,1H),3.06(t, J=7.2Hz,2H),1.73-1.50(m,3H),1.50-1.34(m,2H),0.96(t,J=7.3Hz,3H); 13 C NMR (100MHz, CDCl3) δ150.0,135.4,116.6,110.7,43.4,31.3,20.2,13.8; HRMS (ESI) m / z C9H 15 N + [M+H] + Theoretical value 151.1230, measured value 151.1235.

[0057] Example 11

[0058] In this embodiment, 3-fluoro-5-methoxybromobenzene was used to replace the bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow oily substance with the following structural formula, with a yield of 86%.

[0059]

[0060] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ6.02-5.91 (m, 2H), 5.90 (d, J = 2.1Hz, 1H), 3.74 (s, 4H, NH, OMe) ,3.06(t,J=7.1Hz,2H),1.70-1.59(m,2H),1.56-1.46(m,2H),0.95(t,J=7.3Hz,3H); 13 C NMR (100MHz, CDCl3) δ164.8 (d, J = 240.6Hz), 161.7 (d, J = 14.0Hz), 150.6 (d, J = 13.5Hz), 9 4.2(d,J=2.1Hz),92.5(d,J=25.6Hz),90.2(d,J=26.0Hz),55.3,43.6,31.5,20.2,13.9; 19F NMR(376MHz, CDCl3)δ-112.14(s,F); HRMS(ESI)m / z C 11 H 17 FNO + [M+H] + Theoretical value: 198.1289, measured value: 198.1290.

[0061] Example 12

[0062] In this embodiment, 3,5-dimethyl-4-aldehyde bromobenzene was used to replace the bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow oily substance with the following structural formula, with a yield of 81%.

[0063]

[0064] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ10.32(br,1H),6.21(s,2H),4.18(br,1H),3.17(t,J=7.1H z,2H),2.55(s,6H),1.69-1.52(m,2H),1.52-1.40(m,2H),0.96(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ190.4,152.0,144.7,122.4,112.6,42.7,31.4,21.3,20.2,13.8; HRMS(ESI)m / z C 13 H 20 NO + [M+H] + Theoretical value: 206.1539, measured value: 206.1540.

[0065] Example 13

[0066] In this embodiment, 4-bromopyridine was used to replace bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow oily substance with the following structural formula, in a yield of 78%.

[0067]

[0068] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ8.16 (s, 2H), 6.49 (s, 2H), 5.09 (br, 1H), 3.24-3.10 (m, 2H), 1.71 -1.58 (m, 2H), 1.52 -1.41 (m, 2H), 0.95 (t, J = 7.3Hz, 3H); 13 C NMR (100MHz, CDCl3) δ154.1,148.7,107.6,42.3,31.1,20.1,13.8; HRMS (ESI) m / z C9H 15 N + [M+H] + Theoretical value 151.1230, measured value 151.1233.

[0069] Example 14

[0070] In this embodiment, 3-bromopyridine was used to replace bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow oily substance with the following structural formula, with a yield of 81%.

[0071]

[0072] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ8.01(d,J=2.7Hz,1H),7.93(d,J=3.8Hz,1H),7.16-7.02(m,1H),6.85(m,1H) ,3.78(br,1H),3.11(t,J=7.1Hz,2H),1.69-1.52(m,2H),1.49-1.32(m,2H),0.96(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ144.5,138.4,135.9,123.7,118.3,43.2,31.5,20.2,13.8; HRMS(ESI)m / z C9H 15 N2 + [M+H] + Theoretical value 151.1230, measured value 151.1235.

[0073] Example 15

[0074] In this embodiment, 5-bromobenzofuran was used to replace bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow oily substance with the following structural formula, with a yield of 72%.

[0075]

[0076] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.52(d,J=2.1Hz,1H),7.29(d,J=8.8Hz,1H),6.76(d,J=2.3Hz,1H),6.67- 6.57(m,2H),3.13(t,J=7.1Hz,2H),1.76-1.63(m,2H),1.58-1.38(m,2H),0.97(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ148.9,145.2,144.9,128.2,112.5,111.6,106.3,102.6,44.8,31.8,20.4,13.9; HRMS(ESI)m / zC 12 H 16 NO + [M+H] + Theoretical value 190.1226, measured value 190.1230.

[0077] Example 16

[0078] In this embodiment, 4-bromodibenzothiophene was replaced with an equimolar amount of bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow solid with the following structural formula, in a yield of 69%.

[0079]

[0080] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.93(d,J=7.8Hz,1H),7.87(d,J=8.5Hz,1H),7.73(d,J=7.8Hz,1H),7.36(t,J=7.4Hz,1H),7.29(t,J=7.4Hz,1H),6.96(d ,J=1.9Hz,1H),6.71(dd,J=8.5,1.9Hz,1H),3.82(br,1H),3.18(t,J=7.1Hz,2H),1.76-7.62(m,2H),1.52-1.37(m,2H),0.97(t,J=7.3Hz,3H); 13 C NMR (100MHz, CDCl3) δ148.0,141.7,137.8,136.2,126.2,124.6,124.2,122.5,122.2,120.0,112.3,103.9,43.8,31.6,20.4,13.9; HRMS (ESI) m / z C 16H 18 NS + [M+H] + Theoretical value: 256.1154, measured value: 256.1153.

[0081] Example 17

[0082] In this embodiment, 10-(4-bromobenzene)-9,9-dimethyl-9,10-dihydroacrylidine was used to replace the bromobenzene in Example 1, and the other steps were the same as in Example 1, to obtain a pale yellow solid with the following structural formula, with a yield of 70%.

[0083]

[0084] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.41(dd,J=7.6,1.1Hz,2H),7.06(d,J=8.6Hz,2H),6.99-6.92(m,2H),6.88(dd,J=10.7,4.1Hz,2H),6.74(d,J= 8.6Hz,2H),6.39(d,J=8.1Hz,2H),3.74(br,1H),3.15(t,J=7.1Hz,2H),1.71-1.58(m,8H),1.56-1.42(m,2H),0.98(t,J=7.3Hz,3H); 13 C NMR (100MHz, CDCl3) δ148.2,141.7,131.8,130.2,130.0,126.4,125.1,120.3,114.5,114.4,43.9,36.0,31.8,31.4,20.5,14.1; HRMS (ESI) m / z C 25 H 29 N2 + [M+H] + Theoretical value: 357.2325, measured value: 357.2355.

[0085] Example 18

[0086] In this embodiment, equimolar amounts of benzo[a]min were used to replace bromobenzene in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow solid with the following structural formula, with a yield of 85%.

[0087]

[0088] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.45-7.36(m,2H),7.33-7.26(m,2H),7.26-7.17(m,4H),7.16-7.06(m,3H),6.47(d,J=8.6Hz,2H),4.11(br,1H),3.47( s,2H),3.23-3.09(m,1H),3.03(t,J=7.1Hz,2H),2.65-2.31(m,8H),1. 60-1.48(m,2H),1.48-1.31(m,2H),1.29(s,9H),0.92(t,J=7.3Hz,3H); 13 C NMR (100MHz, CDCl3) δ149.9,147.5,143.7,135.0,131.2,129.0(d,J=8.4Hz),128.3,127.9,1 26.5,125.1,112.6,75.7,62.7,53.4,51.9,43.8,34.5,31.8,31.5,20.3,14.0; HRMS(ESI)m / z C 32 H 44 N3 + [M+H] + Theoretical value: 470.3530, measured value: 470.3533.

[0089] Example 19

[0090] In this embodiment, 3,5-dimethylbromobenzene was used to replace bromobenzene in Example 1, and 3-butene-1-amine was used to replace n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow oily substance with the following structural formula was obtained with a yield of 95%.

[0091]

[0092] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz, CDCl3)δ6.36(s,1H),6.24(s,2H),5.85-5.48(m,1H),5.23-5.05( m,2H),3.48(br,1H),3.15(t,J=6.7Hz,2H),2.35(q,J=6.8Hz,2H),2.23(s,6H); 13 C NMR(100MHz, CDCl3)δ148.4,138.9,136.0,119.5,117.0,110.9,42.9,33.8,21.6; HRMS(ESI)m / z C 12 H 18 N+ [M+H] + Theoretical value: 176.1434, measured value: 177.0192.

[0093] Example 20

[0094] In this embodiment, 3,5-dimethylbromobenzene was used to replace the bromobenzene in Example 1, and 2-(methanesulfonyl)ethylamine was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow oily substance with the following structural formula was obtained with a yield of 84%.

[0095]

[0096] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ6.43(s,1H),6.26(s,2H),4.10(br,1H),3.68(t,J=6.0Hz,2H),3.26(t,J=6.0Hz,2H),2.92(s,3H),2.24(s,6H); 13 CNMR(100MHz, CDCl3)δ146.7,139.3,120.6,111.2,53.7,42.0,37.9,21.5; HRMS(ESI)m / zC 11 H 18 NO2S + [M+H] + Theoretical value: 228.1053, measured value: 228.1060.

[0097] Example 21

[0098] In this embodiment, 3,5-dimethylbromobenzene was used to replace the bromobenzene in Example 1, and 2-[2-(propynyloxy)ethoxy]ethylamine was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow solid with the following structural formula was obtained with a yield of 67%.

[0099]

[0100] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ6.37 (s, 1H), 6.28 (s, 2H), 4.21 (d, J = 2.3Hz, 2H), 3.90-3.55 (m, 6H), 3.29 (t, J = 5.3Hz, 2H), 2.44 (t, J = 2.3Hz, 1H), 2.23 (s, 6H); 13C NMR(100MHz, CDCl3)δ148.3,138.8,119.6,111.1,79.6,74.6,70.1,69.8,69.1,58.4,43.5,21.5; HRMS(ESI)m / z C 15 H 22 NO2 + [M+H] + Theoretical value: 248.1645, measured value: 248.1650.

[0101] Example 22

[0102] In this embodiment, 3,5-dimethylbromobenzene was used to replace the bromobenzene in Example 1, and N,N-dimethylglycine was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow solid with the following structural formula was obtained with a yield of 60%.

[0103]

[0104] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ6.38(s,1H),6.27(s,2H),4.80(br,1H),3.84(s,2H),3.02(s,6H),2.25(s,6H); 13 C NMR (100MHz, CDCl3) δ169.2,147.6,138.9,119.5,110.9,45.3,35.8,35.7 21.5; HRMS (ESI) m / z C 12 H 19 N2O + [M+H] + Theoretical value: 207.1492, measured value: 207.1490.

[0105] Example 23

[0106] In this embodiment, 3,5-dimethylbromobenzene was used to replace the bromobenzene in Example 1, and N-butylamine was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow solid with the following structural formula was obtained with a yield of 72%.

[0107]

[0108] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.18 (dd, J=9.9, 5.7Hz, 2H), 6.72 (t, J=7.3Hz, 1H), 6.62 (d, J=7.9Hz,2H),6.39(s,1H),6.27(s,2H),3.64(br,2H),3.34(s,4H),2.23(s,6H); 13 C NMR (100MHz, CDCl3) δ148.2 (d, J = 7.2Hz), 139.1, 129.4, 119.9, 117.8, 113.1, 111.1; HRMS (ESI) m / z C 16 H 21 N2 + [M+H] + Theoretical value: 241.1699, measured value: 241.1702.

[0109] Example 24

[0110] In this embodiment, 3,5-dimethylbromobenzene was used to replace the bromobenzene in Example 1, and 2,2-difluoroethane-1-amine was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow oily substance with the following structural formula was obtained with a yield of 90%.

[0111]

[0112] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ6.44(s,1H),6.29(s,2H),5.89(tt,J=56.3,4.3Hz,1H),3.74(br,1H),3.49(td,J=14.3,4.2Hz,2H),2.24(s,6H); 13 CNMR (100MHz, CDCl3) δ146.8, 139.2, 120., 114.6 (t, J = 241.7Hz), 111.0, 46.5 (t, J = 26.2Hz), 21.5; HRMS (ESI) m / z C 10 H 14 F2N + [M+H] + Theoretical value: 186.1089, measured value: 186.1094.

[0113] Example 25

[0114] In this embodiment, 3,5-dimethylbromobenzene was used to replace bromobenzene in Example 1, and n-butylamine was used to replace n-butylamine in Example 1. Other steps were the same as in Example 1, and a pale yellow oily substance with the following structural formula was obtained with a yield of 81%.

[0115]

[0116] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz, CDCl3)δ7.89(s,1H),7.60(d,J=7.9Hz,1H),7.30(d,J=8.1Hz,1H),7.21-7.17(m,1H),7.14-7.08(m,1H),6 .95(d,J=2.3Hz,1H),6.37(s,1H),6.24(s,2H),3.60(br,1H),3.43(t,J=6.8Hz,2H),3.04(t,J=6.8Hz,2H),2.22(s,6H); 13 C NMR (100MHz, CDCl3) δ148.4,139.0,136.5,127.5,122.2,122.1,119.5,119.5,118.9,113.5,111.3,111.1,44.1,25.3,21.6; HRMS (ESI) m / zC 18 H 21 N2 + [M+H] + Theoretical value: 265.1699, measured value: 265.1701.

[0117] Example 26

[0118] In this embodiment, 3,5-dimethylbromobenzene was used to replace the bromobenzene in Example 1, and 3,3-difluorocyclobutylamine was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow oily substance with the following structural formula was obtained with a yield of 94%.

[0119]

[0120] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ6.43(s,1H),6.17(s,2H),3.88-3.77(m,1H),3.71(br,1H),3.16-2.86(m,2H),2.52-2.29(m,2H),2.23(s,6H); 13C NMR (100MHz, CDCl3) δ 146.6, 139.2, 120.5, 119.2 (dd, J = 282.5, 271.7Hz), 111.3, 43.5 (dd, J = 23.1, 21.4Hz), 38.2 (dd, J = 15.8, 7.2Hz), 21.5; HRMS (ESI) m / z C 12 H 16 F2N + [M+H] + Theoretical value: 212.1245, measured value: 212.1248.

[0121] Example 27

[0122] In this embodiment, 3,5-dimethylbromobenzene was used to replace bromobenzene in Example 1, and 2-adamantaneamine was used to replace n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow oily substance with the following structural formula was obtained with a yield of 84%.

[0123]

[0124] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ6.31(s,1H),6.23(s,2H),3.65(s,1H),3.52(s,1H),2.26(s,1H),2.22(s, 6H),2.00(s,2H),1.94-1.8-78(m,4H),1.85-1.79(m,3H),1.74(s,2H),1.57(d,J=12.6Hz,2H); 13 C NMR(100MHz, CDCl3)δ147.6,138.9,118.8,111.0,56.8,37.8,37.5,31.8,31.74,27.6,27.4,21.6; HRMS(ESI)m / zC 18 H 26 N + [M+H] + Theoretical value: 256.2060, measured value: 256.2064.

[0125] Example 28

[0126] In this embodiment, 3,5-dimethylbromobenzene was used to replace the bromobenzene in Example 1, and 2-oxa-6-azaspiro[3.3]heptane was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow oily substance with the following structural formula was obtained with a yield of 76%.

[0127]

[0128] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ6.35(s,1H),6.01(s,2H),4.74(s,4H),3.90(s,4H),2.18(s,6H); 13 C NMR(100MHz, CDCl3)δ150.4,137.7,119.1,108.6,80.3,60.7,38.1,20.4; HRMS(ESI)m / z C 13 H 18 NO + [M+H] + Theoretical value: 204.1383, measured value: 204.1389.

[0129] Example 29

[0130] In this embodiment, 3,5-dimethylbromobenzene was used to replace the bromobenzene in Example 1, and methyl p-aminobenzoate was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow solid with the following structural formula was obtained with a yield of 72%.

[0131]

[0132] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.90(d,J=8.1Hz,2H),6.96(d,J=8.1Hz,2H),6.79(s,2H),6.71(s,1H),5.94(br,1H),3.87(s,3H),2.30(s,6H); 13 CNMR(100MHz, CDCl3)δ167.0,148.4,140.7,139.2,131.5,123.0,118.3,114.6,113.0,51.7,21.4; HRMS(ESI)m / z C 16 H 18 NO2 + [M+H] + Theoretical value: 256.1332, measured value: 256.1335.

[0133] Example 30

[0134] In this embodiment, 3,5-dimethylbromobenzene was used to replace bromobenzene in Example 1, and 3,5-dimethylaniline was used to replace n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow solid with the following structural formula was obtained with a yield of 65%.

[0135]

[0136] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ6.61 (s, 4H), 6.50 (s, 2H), 5.43 (br, 1H), 2.19 (d, J = 3.1Hz, 12H); 13 C NMR(100MHz, CDCl3)δ142.3,138.0,121.7,114.7,20.4; HRMS(ESI)m / z C 16 H 20 N + [M+H] + Theoretical value: 226.1590, measured value: 226.1595.

[0137] Example 31

[0138] In this embodiment, equimolar 4-trifluoromethylbromobenzene was used to replace the bromobenzene in Example 1, and equimolar 4-octylaniline was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow solid with the following structural formula was obtained with a yield of 73%.

[0139]

[0140] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.43(d,J=8.5Hz,2H),7.14(d,J=8.3Hz,2H),7.06(d,J=8.4Hz,2H),6.97(d,J=8.5Hz,2H),5 .82(br,1H),5.22-5.20(m,1H),2.63-2.52(m,2H),1.65-1.54(m,2H),1.38-1.30(m,10H),0.88(t,J=6.7Hz,3H); 13 C NMR (100MHz, CDCl3) δ147.5,138.5,138.2,129.4,126.7(q,J=3.7Hz),124.7(q,J=26 6.7Hz),120.9,114.7,35.4,31.9,31.6,29.5,29.3,29.3,22.7,14.1; HRMS(ESI)m / zC21 H 27 F3N + [M+H] + Theoretical value 350.2090, measured value 350.2086.

[0141] Example 32

[0142] In this embodiment, 3,5-dimethylbromobenzene was used to replace the bromobenzene in Example 1, and 2-phenoxyacetamide was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow solid with the following structural formula was obtained with a yield of 74%.

[0143]

[0144] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ8.18 (s, 1H), 7.34 (dd, J = 9.4, 4.4Hz, 2H), 7.28-7.17 (m, 2H), 7.0 6(d,J=6.5Hz,1H),7.02-6.89(m,2H),6.79(s,1H),4.58(d,J=5.1Hz,2H),2.31(s,6H); 13 C NMR (100MHz, CDCl3) δ166.2,157.1,138.9,136.7,129.9,126.7,122.4,117.9,114.9,67.7,21.4; HRMS (ESI) m / zC 16 H 18 NO2 + [M+H] + Theoretical value: 256.1332, measured value: 256.1335.

[0145] Example 33

[0146] In this embodiment, 3,5-dimethylbromobenzene was used to replace the bromobenzene in Example 1, and trifluoromethylacetamide was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow solid with the following structural formula was obtained with a yield of 82%.

[0147]

[0148] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.89(s,1H),7.18(s,2H),6.87(br,1H),2.31(s,6H); 13C NMR (100MHz, CDCl3) δ154.7 (q, J = 37.2Hz), 139.2, 134.9, 128.1, 118.3, 115.8 (q, J = 288.7Hz), 21.3; 19 F NMR (376MHz, CDCl3) δ-75.77 (s, CF3); HRMS (ESI) m / z C 10 H 11 F3NO + [M+H] + Theoretical value: 218.0787, measured value: 218.0790.

[0149] Example 34

[0150] In this embodiment, 3,5-dimethylbromobenzene was used to replace the bromobenzene in Example 1, and benzenesulfonamide was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow solid with the following structural formula was obtained with a yield of 70%.

[0151]

[0152] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.79-7.70(m,2H),7.53-7.43(m,1H),7.41-7.32(m,2H),6.98(br,1H),6.67(s,1H),6.64(s,2H); 13 C NMR (100MHz, CDCl3) δ139.1,139.0,136.2,132.9,128.9,127.2,127.0,119.1,21.2; HRMS (ESI) m / zC 14 H 16 NO2S + [M+H] + Theoretical value: 262.0896, measured value: 262.0899.

[0153] Example 35

[0154] In this embodiment, 3,5-dimethylbromobenzene was used to replace the bromobenzene in Example 1, and 4-fluorobenzenesulfonamide was used to replace the n-butylamine in Example 1. The other steps were the same as in Example 1, and a pale yellow solid with the following structural formula was obtained with a yield of 70%.

[0155]

[0156] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.87-7.73(m,2H),7.11(t,J=8.6Hz,2H),6.76(br,1H),6.71(s,1H),6.68(s,2H),2.22(s,6H); 13 C NMR (100MHz, CDCl3) δ165.2 (d, J = 255.3Hz), 139.2, 135.9, 135.2, 130.0 (d, J = 9.4Hz), 127.4, 119.4, 116.2 (d, J = 22.6Hz), 21.2; HRMS (ESI) m / z C 14 H 15 FNO2S + [M+H] + Theoretical value 280.0802, measured value 280.0800.

[0157] Example 36

[0158] In this embodiment, equimolar 3-methoxypyrazole was used to replace n-butylamine in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow solid with the following structural formula, with a yield of 76%.

[0159]

[0160] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.62(d,J=7.4Hz,2H),7.58-7.54(m,1H),7.48(d,J=5.4Hz,1H),7.46-7.40(m,2H),7.30-7.21(m,1H),3.82(s,3H); 13 C NMR (100MHz, CDCl3) δ148.5,140.4,129.5,129.4,126.0,118.3,110.9,58.9; HRMS (ESI) m / z C 12 H 15 N2O + [M+H] + Theoretical value: 203.1179, measured value: 203.1182.

[0161] Example 37

[0162] In this embodiment, equimolar benzoinazole was used to replace n-butylamine in Example 1, and the other steps were the same as in Example 1, resulting in a pale yellow solid with the following structural formula, with a yield of 78%.

[0163]

[0164] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ8.20 (s, 1H), 7.79 (d, J = 8.1Hz, 1H), 7.74 (t, J = 7.6Hz, 3H), 7.5 3(t,J=7.9Hz,2H),7.42(t,J=7.7Hz,1H),7.35(t,J=7.4Hz,1H),7.26-7.18(m,1H); 13 C NMR (100MHz, CDCl3) δ140.2,138.8,135.4,129.5,127.2,126.7,125.4,122.8,121.4,121.3,110.5; HRMS (ESI) m / zC 15 H 15 N2 + [M+H] + Theoretical value: 223.1230, measured value: 223.1233.

[0165] Example 38

[0166] In this embodiment, equimolar ethyl 4-bromobenzoate is used to replace bromobenzene in Example 1, and equimolar... 15 The n-butylamine in Example 1 was replaced with N-labeled ammonium chloride, and the other steps were the same as in Example 1, to obtain a pale yellow solid with the following structural formula in a yield of 82%.

[0167]

[0168] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ6.73 (d, J = 8.8 Hz, 1H), 6.61 (d, J = 8.8, 1H), 3.94 (d, J = 7.0 Hz, 1H), 3.36 (s, 1H), 1.36 (t, J = 7.0 Hz, 2H); 13 C NMR (100MHz, CDCl3) δ152.1, 140.0 (d, J = 10.2Hz), 116.4 (d, J = 2.9Hz), 115.7, 64.1, 15.0; HRMS (ESI) m / z C9H 12 15 NO2 + [M+H] + Theoretical value: 167.0833, measured value: 167.0838.

[0169] Example 39

[0170] In this embodiment, equimolar bromoestrone was used to replace bromobenzene in Example 1, and equimolar... 15 The n-butylamine in Example 1 was replaced with N-labeled ammonium chloride, and the other steps were the same as in Example 1, to obtain a pale yellow solid with the following structural formula in a yield of 70%.

[0171]

[0172] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.01(d,J=8.3Hz,1H),6.45(d,J=8.3Hz,1H),6.38(s,1H),2.82-2.72(m,2H),2.48 -2.40(m,2H),2.33-2.26(m,1H),2.19-2.07(m,2H),1.94-1.85(m,2H),1.49-1.40(m,6H),0.83(s,3H); 13 C NMR (100MHz, CDCl3) δ221.0,144.2,137.4,130.1,126.2,115.4,113.1,50. 4,48.0,44.0,38.5,35.9,31.6,29.5,26.6,25.9,21.6,13.9; HRMS(ESI)m / z C 18 H 24 15 NO + [M+H] + Theoretical value: 271.1823, measured value: 271.1829.

Claims

1. A method for photochemical cobalt-catalyzed synthesis of aromatic amine compounds, characterized in that: The aryl bromide shown in Formula I, the amine compound shown in Formula II, bipyridine, cobalt catalyst, and organic base were added to an organic solvent and reacted at 80–90 °C for 24–36 hours under an argon atmosphere and irradiated with light of wavelength 360–430 nm. After the reaction was completed, the product was separated and purified to obtain the aryl amine compound shown in Formula III. The aromatic amine compounds shown in Formula III are selected from , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Any one of them; The cobalt catalyst is any one of cobalt bromide, cobalt carbonate, cobalt acetate, cobalt chloride, and cobalt perchlorate. The organic base is any one of 1,8-diazabicycloundec-7-ene, tetramethylguanidine, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine.

2. The method for photochemical cobalt-catalyzed synthesis of aromatic amine compounds according to claim 1, characterized in that: The amount of the amine compound used is 1.1 to 2 times the molar amount of the aryl bromide.

3. The method for photochemical cobalt-catalyzed synthesis of aromatic amine compounds according to claim 1, characterized in that: The amount of bipyridine used is 5% to 15% of the molar amount of aryl bromide.

4. The method for photochemical cobalt-catalyzed synthesis of aromatic amine compounds according to claim 1, characterized in that: The amount of cobalt catalyst used is 5% to 15% of the molar amount of aryl bromide.

5. The method for photochemical cobalt-catalyzed synthesis of aromatic amine compounds according to claim 1, characterized in that: The amount of the organic base used is 2 to 3 times the molar amount of the aryl bromide.

6. The method for photochemical cobalt-catalyzed synthesis of aromatic amine compounds according to claim 1, characterized in that: The organic solvent is any one or two of dimethyl sulfoxide, toluene, isopropanol, N,N-dimethylformamide, and N,N-dimethylacetamide.

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