A photochemical manganese-catalyzed synthesis of arylamines

Abstract

The application discloses a photochemical inexpensive manganese catalytic synthesis method of arylamine compounds, uses bipyridine as a ligand, uses manganese salt as a catalyst, uses inexpensive and abundant aryl bromide and amine compounds as reactants, adds 1,8-diazabicyclo[5,4,0]undec-7 and the like as an organic base, and realizes synthesis of arylamine compounds by photo-promotion manganese catalytic C-N coupling reaction of aryl bromide and amine compounds in an argon atmosphere. The reaction system is simple, the operation is simple and convenient, the reaction condition is mild, post-treatment is simple, the target compound is good in selectivity and high in yield, problems such as complicated catalytic system reaction and poor functional group compatibility caused by use of traditional expensive metal catalysts and inorganic bases 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 manganese catalysis. Background Technology

[0002] Amination of aryl halides is one of the methods for synthesizing organic compounds containing N-aryl groups, and it has been widely used in synthetic chemistry (Nature 2008, 455, 314; Org. Process Res. Dev. 2019, 23, 1529). After more than 20 years of development, by designing specific ligand strategies, the cross-coupling reaction of aryl halides with N-nucleophiles catalyzed by Pd (Chem.Soc.Rev.2013,42,9283; Chem.Rev.2016,116,12564; 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.ProcessRes.Dev.2022,26,2281; Org.Chem.Front.2023,10,548) has provided an important route for the synthesis of aryl amines. Therefore, the development of efficient methods for the synthesis of aromatic amines is of great significance in medicinal chemistry and synthetic chemistry, and has attracted widespread attention from synthetic chemists. With the advancements in photochemistry (Chem. Rev. 2016, 116, 10075; Angew. Chem. Int. Ed. 2019, 58, 6152; Chem. Rev. 2013, 113, 5322) and electrochemistry (Angew. Chem. Int. Ed. 2017, 56, 13088; J. Am. Chem. Soc. 2019, 141, 6392; JACS Au 2021, 1, 1057), new solutions have been proposed for the scientific problems existing in CN coupling reactions, and some reactions that are difficult to complete in a single catalytic system have been realized. However, there is still a need to develop new strategies using inexpensive and sustainable metal catalysis.

[0003] Manganese (Mn) is the third most abundant transition metal after iron and titanium. With an abundance of approximately 1000 ppm in the Earth's crust, this low-toxicity metal is less studied than other 3d metal catalysis methods (Pd, Ni, Cu) for carbon-heteroatom bond formation. Mn-catalyzed cross-coupling reactions are still in their early stages of development, with limited research on their application in transition metal catalysis (Eur. J. Org. Chem. 2016, 3912). In 2009, Teo (Chem. Commun. 2009, 6258-6260) reported a CN cross-coupling reaction between an N-nucleophile and an aryl iodide, using MnCl2·4H2O as a catalyst, trans-1,2-diaminocyclohexane as a ligand, K3PO4 as a base, and water as a solvent. However, the yield of the ortho-substituted aryl iodide product was poor. Next, to expand the range of N-nucleophiles, the group (Tetrahedron Lett. 2010, 51, 3910–3912) proposed a catalytic system based on MnCl2·4H2O with L-proline as a ligand for the N-arylation of aliphatic amines using aryl halides. This method provided good to moderate yields for a range of aliphatic amines (e.g., morpholines and several primary and secondary amines). In 2012, Teo and Yong (Synlett 2012, 23, 2106–2110) reported extending the nucleophile range to the coupling of indole, 7-azaindole, and indazole derivatives with pyridine and thiophene iodides in an aqueous phase using MnF2 and Cs2CO3. To reduce the high temperatures required in previous reactions and further broaden the substrate range, the research group subsequently developed the bimetallic system MnF2 / CuI (Eur. J. Org. Chem. 2013, 3, 515–524), under which many CN coupling reactions can proceed at 60 °C. Furthermore, this catalytic system can also achieve the coupling of benzamide and sulfonamide derivatives with various aryl halides. However, in 2017, Madsen and colleagues discovered that the manganese-catalyzed CN coupling in aqueous phase, as observed by Teo et al., was likely a metal contamination-induced catalytic reaction, where the active component was possibly a copper salt (Eur. J. Org. Chem. 2017, 5269). Since then, manganese-catalyzed CN coupling reactions have almost stagnated. Compared to Pd or Ni-catalyzed processes, Mn-catalyzed reactions are less clearly understood mechanistically, and their scope has not been fully utilized. Existing manganese catalytic systems are limited to substrates, confined to aryl iodides. Therefore, developing universal manganese-catalyzed coupling reactions under mild conditions remains of paramount importance. Summary of the Invention

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

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: the (hetero)aryl bromide shown in Formula I, the amine compound shown in Formula II, bipyridine, manganese catalyst, and organic base are added to an organic solvent, heated and irradiated in an argon atmosphere, and after the reaction is complete, the product is separated and purified to obtain the aromatic amine compound shown in Formula III.

[0006]

[0007] In the formula, Ar represents any one of phenyl, thienyl, thiazolyl, pyridyl, pyrazolyl, pyrimidinyl, piperidinyl, pyrazinyl, quinolinyl, phenylpropiophenyl, benzofuranyl, dibenzothiophenyl, quinoxalinyl, or phenyl or pyridinyl containing at least one substituent from C1-C6 alkyl, C6-cycloalkyl, tert-butyldimethylsiloxy, sulfonyl, phenoxy, tetrahydronaphthyl, acridineyl, piperidinyl, trimethylsilyl, halogen, trifluoromethoxy, trifluoromethyl, cyano, ester, acyl, carbonyl, borosilicate; HNNu represents any one of aromatic amine, substituted aromatic amine, heterocyclic aromatic amine, pyrazole, amide, sulfonamide, aliphatic amine.

[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 manganese catalyst is any one of manganese bromide, manganese carbonate, manganese acetate, manganese chloride, manganese 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 manganese salt and bipyridine catalytic system to achieve the CN coupling reaction of aryl bromides and amines under light irradiation to synthesize aromatic amines. The reaction system of this invention is simple, economically efficient, environmentally friendly, and the post-reaction processing is straightforward. The aromatic amines synthesized using this method exhibit advantages such as high yield and excellent functional group compatibility. This is a simple and efficient method for synthesizing aromatic amines, aligning with the current pursuit of environmentally friendly, economical, and green chemistry, and possesses significant application prospects. 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, 2.6 mg (0.01 mmol) manganese acetate, 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 then 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 at 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 NMR spectral data of the obtained products are as follows: ¹H NMR (400MHz, CDCl₃) δ 7.17 (t, J = 7.6Hz, 2H), 6.69 (t, J = 7.3Hz, 1H), 6.61 (d, J = 8.4Hz, 2H), 3.12 (t, J = 7.1Hz, 2H), 1.66–1.57 (m, 2H), 1.52–1.37 (m, 2H), 0.96 (t, J = 7.3Hz, 3H); ¹³C NMR (100MHz, CDCl₃) δ 148.7, 129.4, 117.2, 112.9, 43.9, 31.9, 20.5, 14.0; HRMS (ESI) m / z calc. C10H16N[M+H]+: Theoretical value 150.1277, measured value 150.1279.

[0021] Example 2

[0022] In this embodiment, 4-methylbromobenzene 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 oily substance with the following structural formula, in a yield of 88%.

[0023]

[0024] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.04(d,J=8.5Hz,2H),6.58(d,J=8.3Hz,2H),3.38(br,1H),3.13(t ,J=7.1Hz,2H),2.29(s,3H),1.69-1.69(m,2H),1.54-1.42(m,2H),1.01(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ146.4,129.8,126.4,113.0,44.2,31.8,20.5,20.4,14.0; HRMS(ESI)m / z C 11 H 18 N[M+H] + Theoretical value: 164.1434, measured value: 164.1435.

[0025] Example 3

[0026] In this embodiment, ethyl 3-(4-bromophenyl)propionate benzene 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 oily substance with the following structural formula, in a yield of 93%.

[0027]

[0028] 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,2H),6.54(d,J=8.4Hz,2H),4.13(q,J=7.1Hz,2H),3.09(t,J=7.1Hz,2H),2.89 -2.78(m,2H),2.62-2.52(m,2H),1.65-1.54(m,2H),1.50-1.37(m,2H),1.24(t,J=7.1Hz,3H),0.96(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ173.3,147.1,129.2,113.0,60.4,44.0,36.6,31.9,30.3,20.4,14.3,14.0; HRMS(ESI)m / z C15 H 24 NO2[M+H] + Theoretical value 250.1802, measured value 250.1803.

[0029] Example 4

[0030] In this embodiment, 4-bromodiphenyl ether 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 88%.

[0031]

[0032] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.35-7.18(m,2H),6.98(t,J=7.3Hz,1H),6.99-6.84(m,4H),6.57(d,J=8.8Hz,2 H),3.35(br,1H),3.08(t,J=7.1Hz,2H),1.66-1.52(m,2H),1.51-1.35(m,2H),0.96(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ159.3,147.4,145.3,129.5,121.9,121.3,117.1,113.7,44.2,31.8,20.4,14.0; HRMS(ESI)m / z C 16 H 20 NO[M+H] + Theoretical value: 242.1539, measured value: 242.1535.

[0033] Example 5

[0034] In this embodiment, 4-chlorobromobenzene 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 oily substance with the following structural formula, with 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) δ7.11(d,J=8.7Hz,2H),6.51(d,J=8.7Hz,2H),3.60(br,1H),3 .08(t,J=7.1Hz,2H),1.64-1.55(m,2H),1.48-1.37(m,2H),0.96(t,J=7.3Hz,3H); 13C NMR(100MHz, CDCl3)δ147.2,129.1,121.7,113.8,43.9,31.7,20.4,14.0; HRMS(ESI)m / z C 10 H 15 ClN[M+H] + Theoretical value: 184.0888, measured value: 184.0886.

[0037] Example 6

[0038] In this embodiment, equimolar 4-fluorobromobenzene 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 84%.

[0039]

[0040] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ6.88 (t, J = 8.7Hz, 2H), 6.59-6.49 (m, 2H), 3.47 (br, 1H), 3. 07(t,J=7.1Hz,2H),1.64-1.55(m,2H),1.48-1.38(m,2H),0.96(t,J=7.3Hz,3H); 13 C NMR (100MHz, CDCl3) δ155.7 (d, J = 233.0Hz), 144.9, 115.6 (d, J = 22.0Hz), 113.5 (d, J = 7.5Hz), 44.4, 31.7, 20.3, 13.9; 19 F NMR (376MHz, CDCl3) δ-128.59 (s, F); HRMS (ESI) m / z C 10 H 15 FN[M+H] + Theoretical value: 168.1183, measured value: 168.1185.

[0041] Example 7

[0042] In this embodiment, 6-bromo-1,1,4-4-tetramethyl-1,2,3,4-tetrahydronaphthalene was replaced with an equimolar amount of 6-bromo-1,1,4-4-tetramethyl-1,2,3,4-tetrahydronaphthalene, 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 82%.

[0043]

[0044] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.13(t,J=7.5Hz,1H),6.55(t,J=3.2Hz,1H),6.50-6.43(m,1H),3.11(t,J=7.0Hz, 2H),1.73-1.76(m,4H),1.64-1.57(m,2H),1.52-1.39(m,2H),1.36-1.00(m,12H),0.98(t,J=7.3Hz,3H); 13 C NMR (100MHz, CDCl3) δ146.3,145.8,134.0,127.4,111.2,110.5,44.1,35.5,35.4,34.4,33.6,32.2,32.0,32.0,20.5,14.1; HRMS (ESI) m / z C 18 H 30 N[M+H] + Theoretical value: 260.2373, measured value: 260.2374.

[0045] Example 8

[0046] In this embodiment, 2,4,5-trimethylbromobenzene 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, in a yield of 80%.

[0047]

[0048] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ6.84 (s, 1H), 6.46 (s, 1H), 3.16 (t, J = 7.0Hz, 2H), 2.24 (s, 3H), 2 .17(s,3H),2.10(s,3H),1.72-1.62(m,2H),1.54-1.41(m,2H),0.99(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ144.6,134.8,131.6,124.4,119.3,111.9,44.2,32.0,20.5,20.0,18.7,17.0,14.1; HRMS(ESI)m / z C 13 H 22 N[M+H] + Theoretical value: 192.1747, measured value: 192.1750.

[0049] Example 9

[0050] In this embodiment, 2-oxotrifluoromethylbromobenzene 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 84%.

[0051]

[0052] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.10-7.01(m,2H),6.65(d,J=8.0Hz,1H),6.61-6.48(m,1H),3.98(b r,1H),3.08(t,J=7.1Hz,2H),1.61-1.50(m,2H),1.47-1.30(m,2H),0.89(t,J=7.3Hz,3H); 13 C NMR (100MHz, CDCl3) δ 140.8, 136.1), 127.7, 122.2, 121.0 (q, J = 126.3Hz), 120.8 116.0, 112.0, 43.2, 31.4, 20.2, 13.8; HRMS (ESI) m / zC 11 H 15 F3NO[M+H] + Theoretical value: 234.1100, measured value: 234.1098.

[0053] Example 10

[0054] In this embodiment, 2-trifluoromethyl-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, with a yield of 86%.

[0055]

[0056] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ8.17(d,J=5.2Hz,1H),6.74(s,1H),6.48(d,J=5.6Hz,1H),4.91(b r,1H),3.18-3.10(m,2H),1.64-1.49(m,2H),1.43-1.30(m,2H),0.91(t,J=7.3Hz,3H); 13C NMR (150MHz, CDCl3) δ154.6, 149.9, 148.6 (q, J = 33.0Hz), 122.1 (q, J = 115.5Hz), 108.9, 104.2, 42.5, 30.9, 20.1, 13.7; HRMS (ESI) m / zC 10 H 14 F3N2[M+H] + Theoretical value: 219.1104, measured value: 219.1106.

[0057] Example 11

[0058] In this embodiment, 2,6-dimethyl-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 89%.

[0059]

[0060] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (600MHz, CDCl3) δ6.14(s,2H),4.16(br,1H),3.11(m,2H),2.37(s,6H),1.62-1.54(m,2H),1.45-1.36(m,2H),0.95(t,J=7.4Hz,3H); 13 CNMR(150MHz, CDCl3)δ157.5,154.6,104.1,42.4,31.3,24.2,20.2,13.8; HRMS(ESI)m / zC 11 H 19 N2[M+H] + Theoretical value: 179.1543, measured value: 179.1545.

[0061] Example 12

[0062] In this embodiment, 2-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 80%.

[0063]

[0064] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR(400MHz, CDCl3)δ8.05(d,J=4.3Hz,1H),7.41(t,J=7.7Hz,1H),6.60-6.48(m,1H),6.37(d,J=8.4Hz ,1H),4.63(br,1H),3.24(t,J=6.9Hz,2H),1.67-1.54(m,2H),1.49-1.37(m,2H),0.95(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ158.9,148.0,137.5,112.5,106.3,42.0,31.6,20.2,13.8; HRMS(ESI)m / z C9H 15 N2[M+H] + Theoretical value 151.1230, measured value 151.1233.

[0065] Example 13

[0066] In this embodiment, 2-bromo-6-methoxypyridine 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 83%.

[0067]

[0068] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.34(t,J=7.9Hz,1H),6.00(d,J=7.9Hz,1H),5.92(d,J=7.9Hz,1H),4.36( br,1H),3.84(s,3H),3.23(m,2H),1.65-1.55(m,2H),1.49-1.37(m,2H),0.95(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ164.8,159.1,141.1,98.4,98.2,54.5,43.2,32.9,21.4,15.0; HRMS(ESI)m / z C 10 H 17 N₂O[M+H] + Theoretical value: 181.1335, measured value: 181.1338.

[0069] Example 14

[0070] In this embodiment, 2-bromopyrimidine 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%.

[0071]

[0072] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) 1 H NMR (400MHz, CDCl3) δ8.18(d,J=4.4Hz,2H),6.41(t,J=4.6Hz,1H),5.54(br,1H),3.36-3.27(m,2H),1.62-1.43(m,2H),1.39 -1.27(m,2H),0.86(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ162.5,157.9,110.1,41.2,31.7,20.1,13.8; HRMS(ESI)m / z calc.for C8H 14 N3[M+H] + Theoretical value: 152.1182, measured value: 152.1185.

[0073] Example 15

[0074] In this embodiment, 2-methyl-4-bromo-pyridine 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 85%.

[0075]

[0076] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.97(s,2H),3.67(br,1H),3.05(t,J=7.1Hz,2H),2.52(s,3H),1.59-1.50(m,2H),1.41-1.34(m,2H),0.89(t,J=7.3Hz,3H); 13 C NMR(100MHz, CDCl3)δ156.6,141.1,139.6,43.1,31.3,24.5,20.1,13.8; HRMS(ESI)m / z C 10 H 20 N3[M+H] + Theoretical value: 182.1652, measured value: 182.1654.

[0077] Example 16

[0078] In this embodiment, bromobenzene in Example 1 was replaced with an equimolar amount of bromoestrolone, 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 76%.

[0079]

[0080] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz, CDCl3) δ7.09(d,J=8.4Hz,1H),6.44(dd,J=8.4,2.4Hz,1H),6.36(d,J=2.2Hz,1H),3.44(br,1H) ,3.09(t,J=7.1Hz,2H),2.92-2.84(m,2H),2.59-2.42(m,1H),2.42-2.32(m,1H),2.22(t,J=10.2Hz,1H),2.11 -2.06(m,2H),2.01-1.91(m,2H),1.75-1.54(m,11H),0.95(t,J=7.3Hz,3H),0.90(s,3H); 13 CNMR (100MHz, CDCl3) δ221.1,146.6,137.2,128.6,126.1,112.75,110.9,50.4,48.1,44. 0,43.9,38.6,35.9,31.9,31.8,29.7,26.7,26.0,21.6,20.3,14.0,13.9; HRMS(ESI)m / zC 22 H 32 N₂O[M+H] + Theoretical value: 326.2478, measured value: 326.2480.

[0081] Example 17

[0082] In this embodiment, bromobenzene in Example 1 was replaced with an equimolar amount of gemfibrozil methyl ester, 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 73%.

[0083]

[0084] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ6.59(s,1H),6.44(s,1H),3.84(d,J=4.5Hz,2H),3.65(s,3H),3.09(t,J=7.1Hz,2H),2.91-2.86(m,1 H),2.19(s,3H),2.09(s,3H),1.75-1.65(m,4H),1.67-1.55(m,2H),1.52-1.36(m,2H),1.21(s,6H),0.96(t,J=7.3Hz,3H); 13 C NMR (100MHz, CDCl3) δ178.4,148.8,140.5,125.3,120.0,115.8,113.3,69.6,5 1.7,44.6,42.1,37.2,32.0,25.5,25.2,20.4,17.4,16.1,14.0; HRMS(ESI)m / z C 20 H 34 NO3[M+H] + Theoretical value: 336.2533, measured value: 336.2535.

[0085] Example 18

[0086] In this embodiment, 4-tert-butylbromobenzene in Example 1 was replaced with 4-tert-butylbromobenzene, and n-butylamine in Example 1 was replaced with 4-tert-butylbromobenzene. 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 92%.

[0087]

[0088] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.22 (d, J = 8.5 Hz, 2H), 6.58 (d, J = 8.6 Hz, 2H), 2.81 (s, 3H), 1.28 (s, 9H); 13 C NMR (100MHz, CDCl3) δ147.2, 140.2, 126.1, 112.4, 34.0, 31.7, 31.1; HRMS (ESI) m / z C 11 H 18 N[M+H] + Theoretical value: 164.1434, measured value: 164.1435.

[0089] Example 19

[0090] In this embodiment, 4-tert-butylbromobenzene was used to replace bromobenzene in Example 1, and 2-methylprop-2-en-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 93%.

[0091]

[0092] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.20 (d, J = 8.6 Hz, 2H), 6.57 (d, J = 8.6 Hz, 2H), 4.50-4.86 (m, 2H), 3.67 (s, 2H), 1.79 (s, 3H), 1.28 (s, 9H); 13 C NMR(100MHz, CDCl3)δ146.0,143.1,140.1,125.9,112.54,110.8,50.3,33.8,31.6,20.5; HRMS(ESI)m / z C 14 H 22 N[M+H] + Theoretical value: 204.1747, measured value: 204.1750.

[0093] Example 20

[0094] In this embodiment, 4-tert-butylbromobenzene was replaced with an equimolar amount of bromobenzene in Example 1, and 2-(1,3-dioxolane-4-yl)ethane-1-amine was replaced with an equimolar amount of 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%.

[0095]

[0096] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.20(d,J=8.5Hz,2H),6.58(d,J=8.5Hz,2H),4.98(t,J=4.4Hz,1H),3.9 8(t,J=6.9Hz,2H),3.91-3.83(m,2H),3.25(t,J=6.5Hz,2H),2.03-1.97(m,2H),1.27(s,9H); 13 C NMR(100MHz, CDCl3)δ146.2,140.2,126.1,112.7,103.9,65.0,39.6,34.0,33.7,33.2,31.7; HRMS(ESI)m / z C 15 H24 NO2[M+H] + Theoretical value 250.1802, measured value 250.1805.

[0097] Example 21

[0098] In this embodiment, 4-tert-butylbromobenzene was replaced with an equimolar amount of bromobenzene in Example 1, and tert-butyl 3-aminopropionate was replaced with an equimolar amount of 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 91%.

[0099]

[0100] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.21(d,J=8.3Hz,2H),6.59(d,J=8.3Hz,2H),3.39(t,J=6.3Hz,2H),2.52(t,J=6.3Hz,2H),1.46(s,9H),1.28(s,9H); 13 C NMR(100MHz, CDCl3)δ171.8,145.4,140.5,126.6,112.9,80.8,40.0,35.3,33.9,31.9,28.1; HRMS(ESI)m / z C 17 H 28 NO2[M+H] + Theoretical value: 278.2115, measured value: 278.2110.

[0101] Example 22

[0102] In this embodiment, 4-tert-butylbromobenzene was replaced with an equimolar amount of bromobenzene in Example 1, and 4-aminobutyrone was replaced with an equimolar amount of 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 93%.

[0103]

[0104] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.51(d,J=8.8Hz,2H),7.38(d,J=8.8Hz,2H),3.85(t,J=7.0Hz,2H),2.60(t,J=8.1Hz,2H),2.22-2.09(m,2H),1.31(s,9H); 13C NMR (100MHz, CDCl3) δ174.1,147.5,136.8,125.7,119.9,48.9,34.4,32.7,31.3,18.1; HRMS (ESI) m / z C 14 H 21 N2[M+H] + Theoretical value: 217.1699, measured value: 217.1696.

[0105] Example 23

[0106] In this embodiment, 4-tert-butylbromobenzene was replaced with an equimolar amount of bromobenzene in Example 1, and 2,2,2-trifluoroethane-1-amine was replaced with an equimolar amount of 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 85%.

[0107]

[0108] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.16 (d, J = 8.7Hz, 2H), 6.56 (d, J = 8.6Hz, 2H), 3.65 (q, J = 9.0Hz, 2H), 1.20 (s, 9H); 13 C NMR (100MHz, CDCl3) δ143.9, 142.0, 126.9, 125.1 (q, J = 278.6Hz), 112.9, 46.3 (q, J = 33.4Hz), 33.9, 31.5; HRMS (ESI) m / z C 12 H 17 F3N[M+H] + Theoretical value: 232.1308, measured value: 232.1305.

[0109] Example 24

[0110] In this embodiment, 4-tert-butylbromobenzene was used to replace the bromobenzene in Example 1, and dehydrorosin 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 82%.

[0111]

[0112] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.21(d,J=8.6Hz,3H),7.04(s,1H),6.92(s,1H),6.60(d,J=8.5Hz,2H),3.55(br,1H),3.12-3.06(m,1H),2.95-2 .81(m,4H),2.39-2.42(m,1H),1.85-1.75(m,3H),1.74-1.61(m,2H),1.55-1.44(m,3H),1.30(s,9H),1.32-1.21(m,9H),1.04(s,3H); 13 C NMR (100MHz, CDCl3) δ147.4,146.6,145.7,139.8,134.8,126.9,126.0,124.3,123.9,112.5,55.3 ,45.3,38.5,37.5,37.4,36.3,33.8,33.5,31.6,30.1,25.3,24.0,19.4,18.9,18.8; HRMS(ESI)m / z C 30 H 44 N[M+H] + Theoretical value: 418.3468, measured value: 418.3471.

[0113] Example 25

[0114] In this embodiment, 4-tert-butylbromobenzene was replaced with an equimolar amount of bromobenzene in Example 1, and 3,3-difluorocyclobutylamine was replaced with an equimolar amount of 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 82%.

[0115]

[0116] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.31 (d, J = 8.6 Hz, 2H), 6.49 (d, J = 8.6 Hz, 2H), 4.21 (t, J = 11.9 Hz, 4H), 1.31 (s, 9H); 13 C NMR (100MHz, CDCl3) δ147.6, 141.8, 126.0, 116.1 (q, J = 273Hz), 112.2, 63.5 (q, J = 25Hz), 34.0, 31.5; 19 F NMR (376MHz, CDCl3) δ-99.21 (p, J = 11.8Hz); HRMS (ESI) m / z C 14 H 20F2N[M+H] + Theoretical value: 240.1558, measured value: 240.1555.

[0117] Example 26

[0118] In this embodiment, 4-tert-butylbromobenzene was used instead of bromobenzene in Example 1, and 3-fluoroazacyclobutane was used instead of 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%.

[0119]

[0120] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.18 (d, J = 8.6 Hz, 2H), 6.36 (d, J = 8.6 Hz, 2H), 5.44-5.12 (m, 1H), 4.16-3.93 (m, 2H), 3.91-3.75 (m, 2H), 1.21 (s, 9H); 13 CNMR(100MHz, CDCl3)δ149.0,141.0,125.9,111.7,82.9(d,J=204.3Hz),59.8(d,J=23.2Hz),34.0,31.6; HRMS(ESI)m / z C 13 H 19 FN[M+H] + Theoretical value: 208.1496, measured value: 208.1493.

[0121] Example 27

[0122] In this embodiment, 4-tert-butylbromobenzene 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 oily substance with the following structural formula was obtained with a yield of 88%.

[0123]

[0124] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ8.06 (br, 1H), 7.49 (d, J = 8.2Hz, 2H), 7.40 (d, J = 8.3Hz, 2H), 1.32 (s, 9H); 13C NMR (100MHz, CDCl3) δ155.0, (q, J = 40Hz), 132.6, 126.3, 120.5, 120.3, 116.0 (q, J = 286.9Hz), 34.7, 31.4; HRMS (ESI) m / zC 12 H 15 F3NO[M+H] + Theoretical value: 246.1100, measured value: 246.1103.

[0125] Example 28

[0126] In this embodiment, equimolar 4-tert-butylbromobenzene was used to replace the bromobenzene in Example 1, and equimolar pyrazole 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 91%.

[0127]

[0128] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR (400MHz, CDCl3) δ7.89 (d, J = 2.4Hz, 1H), 7.71 (d, J = 1.1Hz, 1H), 7.61 (d, J = 8.7Hz, 2H), 7.46 (d, J = 8.7Hz, 2H), 6.44 (t, J = 2.0Hz, 1H); 1.34 (s, 9H); 13 C NMR (100MHz, CDCl3) δ149.6,140.8,137.9,126.7,126.3,118.9,107.3,34.5,31.4; HRMS (ESI) m / z C 13 H 17 N2[M+H] + Theoretical value: 201.1386, measured value: 201.1389.

[0129] Example 29

[0130] In this embodiment, equimolar 4-tert-butylbromobenzene was used to replace the bromobenzene in Example 1, and equimolar p-methylaniline 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%.

[0131]

[0132] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1H NMR (400MHz, CDCl3) δ7.31 (d, J = 3.0Hz, 2H), 7.11 (d, J = 6.2Hz, 2H), 7.06-6.98 (m, 4H), 2.34 (s, 3H), 1.36 (s, 9H); 13 C NMR (100MHz, CDCl3) δ143.5, 141.2, 141.0, 130.3, 129.8, 126.1, 118.2, 117.2, 34.2, 31.5, 20.7; HRMS (ESI) m / zC 17 H 22 N[M+H] + Theoretical value: 240.1747, measured value: 240.1749.

[0133] Example 30

[0134] In this embodiment, equimolar 4-tert-butylbromobenzene was used to replace the bromobenzene in Example 1, and equimolar benzidine 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 88%.

[0135]

[0136] The nuclear magnetic resonance (NMR) spectral data of the obtained product are as follows: 1 H NMR(400MHz, CDCl3) δ7.56(d,J=7.3Hz,2H),7.48(d,J=8.5Hz,2H),7.44-7.37 (m,2H),7.36-7.24(m,3H),7.07(t,J=8.7Hz,4H),5.70(br,1H),1.32(s,9H); 13 C NMR(100MHz,iCDCl3)δ144.5,143.2,141.0,140.1,133.2,128.8,128.0,126.5,126.2,118.5,117.2,34.2,31.5; HRMS(ESI)m / zC 22 H 24 N[M+H] + Theoretical value: 302.1903, measured value: 302.1907.

Claims

1. A method for photochemical manganese-catalyzed synthesis of aromatic amine compounds, characterized in that: The aryl bromide shown in Formula I, the amine compound shown in Formula II, bipyridine, manganese catalyst, and organic base were added to an organic solvent, heated in an argon atmosphere, and reacted under ultraviolet light with a wavelength of 360–430 nm. After the reaction was completed, the product was separated and purified to obtain the aryl amine compound shown in Formula III. In the formula, Ar represents any one of phenyl, thienyl, thiazolyl, pyridyl, pyrazolyl, pyrimidinyl, pyrazinyl, quinolinyl, and quinoxalinyl, or phenyl or pyridyl containing at least one substituent from C1 to C6 alkyl, C6 cycloalkyl, phenoxy, halogen, trifluoromethoxy, trifluoromethyl, and cyano; HNNu represents any one of n-butylamine, methylamine, 2-methylprop-2-en-1-amine, 2-(1,3-dioxolane-4-yl)ethane-1-amine, tert-butyl 3-aminopropionate, 4-aminobutyronitrile, 2,2,2-trifluoroethane-1-amine, trifluoromethylacetamide, pyrazole, p-methylaniline, and benzidine. The manganese catalyst is manganese acetate; The organic base is 1,8-diazabicycloundec-7-ene.

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

5. The method for photochemical manganese-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 manganese-catalyzed synthesis of aromatic amine compounds according to claim 1, characterized in that: The organic solvent is dimethyl sulfoxide, toluene, isopropanol, N,N -Dimethylformamide, N,N - Any one or two of dimethylacetamides.

7. The method for photochemical manganese-catalyzed synthesis of aromatic amine compounds according to claim 1, characterized in that: The photoreaction is carried out under ultraviolet light with a wavelength of 360–430 nm at 80–90°C for 24–36 hours.

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