A method for synthesizing aryl sulfonamides by reacting halogenated aromatic hydrocarbons with sulfonamides using a nickel / ketone dual catalyst

Abstract

This invention discloses a method for synthesizing arylsulfonamides by reacting nickel / ketone dual-catalyzed halogenated aromatic hydrocarbons with sulfonamides. The method comprises the following steps: under inert gas protection, halogenated aromatic hydrocarbons, sulfonamides, TXO, NiBr2×3H2O, 4,4¢-di(tert-butyl)-2,2¢-bipyridine, and TMG are added to a reaction vessel equipped with a stirrer. Then, dimethyl sulfoxide (DMSO) is added, and the reaction is carried out under CFL irradiation with stirring at room temperature to obtain arylsulfonamide compounds. Furthermore, the entire process of this invention is green, efficient, and easy to operate, making it a good method for synthesizing arylsulfonamide compounds.

Description

Technical Field

[0001] This invention belongs to the field of catalytic chemistry technology, specifically relating to a method for synthesizing arylsulfonamides by reacting nickel / ketone dual-catalyzed haloaromatic hydrocarbons with sulfonamides. Background Technology

[0002] Sulfonamides are commonly found in bioactive molecules, agrochemicals, pharmaceuticals, and advanced materials [J. Med. Chem., 2019, 62, 4265–4311; J. Med. Chem., 2004, 47, 1303–1314; ACS Catal., 2025, 15, 2292–2304]. Traditionally, arylsulfonamides are obtained by condensation of amine nucleophiles with toxic and unstable sulfonyl chlorides [J. Am. Chem. Soc., 2013, 135, 10638−10641]. In addition, palladium, copper, or nickel-catalyzed cross-coupling reactions of sulfonamides with halogenated aromatics [Org. Lett., 2019, 21, 8981−8986; Angew. Chem., Int. Ed., 2022, 61, e202210483; Organometallics, 2024, 43,1706–1712] are alternative strategies for constructing arylsulfonamides, but these reactions typically require high temperatures, which significantly reduce the functional group tolerance of the substrate. Summary of the Invention

[0003] To overcome the aforementioned technical problems, this invention provides a novel synergistic catalytic system utilizing a photocatalyst and a metal catalyst to synthesize arylsulfonamide compounds. Specifically, using 9-thioxanthone (TXO) as a photosensitizer, NiBr2×3H2O as a metal catalyst, 4,4¢-di(tert-butyl)-2,2¢-bipyridine as a ligand, and tetramethylguanidine as a base, a series of cross-coupling reactions between halogenated aromatic hydrocarbons and sulfonamides were achieved under 45 W CFL irradiation. Furthermore, this invention yields arylsulfonamide compounds in high yields. The entire catalytic process of this invention is green, efficient, and easy to operate, making it a good method for synthesizing arylsulfonamide compounds.

[0004] Specifically, the present invention adopts the following technical solution: A method for synthesizing arylsulfonamides by reacting nickel / ketone dual-catalyzed halogenated aromatic hydrocarbons with sulfonamides, wherein nickel is a nickel compound and ketone is a ketone photosensitizer.

[0005] In this invention, the ketone photosensitizer is 9-thioxanone; the nickel compound is an inorganic nickel compound.

[0006] In this invention, the reaction is carried out under inert gas protection, in the presence of a pyridine compound and a base, and in a solvent.

[0007] In this invention, the molar ratio of halogenated aromatic hydrocarbons, sulfonamides, ketone photosensitizers, nickel compounds, pyridine compounds, and bases is 1:(1.8-2.2):(0.1-0.3):(0.05-0.15):(0.1-0.15):(1.5-2.5).

[0008] Preferably, the molar ratio of halogenated aromatic hydrocarbons, sulfonamides, ketone photosensitizers, nickel compounds, pyridine compounds, and bases is 1:2:0.2:0.1:0.12:2.0.

[0009] In this invention, the inert gas is selected from any one of nitrogen, helium, neon, and argon, with nitrogen being preferred.

[0010] In this invention, 9-thioxanone (TXO) has the structural formula shown in formula (A):

[0011] In this invention, the haloaromatic compounds have a general structural formula as shown in any one of formulas (B) to (E):

[0012] Where: R 1 X can be selected from ester, trifluoromethyl, cyano, phenyl, methoxy, and methyl groups; X can be selected from iodine and bromine.

[0013] In this invention, the sulfonamide compounds have a general structural formula as shown in any one of formula (F):

[0014] Where: R 2 It can be selected from ethyl, methoxy, and tert-butyl.

[0015] In this invention, the base is selected from one or more of tetramethylguanidine (TMG), diethylamine (Et2NH), 1,8-diazabicycloundec-7-ene (DBU), cesium carbonate (Cs2CO3), and potassium fluoride (KF).

[0016] In this invention, the solvent is selected from any one or more of dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), acetonitrile (MeCN), N,N-dimethylacetamide (DME), chloroform (CHCl3), and methanol (MeOH).

[0017] In this invention, the pyridine compound is 4,4¢-bis(tert-butyl)-2,2¢-bipyridine.

[0018] In this invention, the nickel compound is NiBr2×3H2O.

[0019] Preferably, in the above-mentioned method for synthesizing aryl sulfonamide compounds, the molar ratio between the haloaromatic hydrocarbon, sulfonamide, TXO, NiBr2×3H2O, 4,4¢-bis(tert-butyl)-2,2¢-bipyridine, and the base is 1:2:0.2:0.1:0.12:2.0.

[0020] In this invention, the reaction is carried out under visible light irradiation, such as under irradiation with 45 W CFL, and stirred at room temperature.

[0021] Preferably, in the above-mentioned method for synthesizing arylsulfonamide compounds, the reaction time is 10 to 30 hours.

[0022] Compared with existing technologies, the present invention employing the above-described technical solution has the following advantages: For the first time, the present invention uses 9-thioxanone (TXO) as a photosensitizer, NiBr2×3H2O as a metal catalyst, 4,4¢-di(tert-butyl)-2,2¢-bipyridine as a ligand, and TMG as a base, under 45 W CFL irradiation, to achieve the synthesis of a series of arylsulfonamide compounds. Furthermore, the present invention obtains arylsulfonamide compounds in high yields. The entire process is green, efficient, and easy to operate, making it a good method for synthesizing arylsulfonamide compounds. Detailed Implementation

[0023] This invention discloses a nickel / ketone dual-catalyzed method for synthesizing arylsulfonamides by reacting halogenated aromatic hydrocarbons with sulfonamides. The sulfonation reaction of the halogenated aromatic hydrocarbons is carried out in a solvent under inert gas protection, with TXO as a photosensitizer, NiBr2×3H2O as a metal catalyst, 4,4¢-bis(tert-butyl)-2,2¢-bipyridine as a ligand, and a base as an additive, under the irradiation of a 45 W compact fluorescent lamp (45 W CFL) for 24 hours.

[0024] The method for synthesizing arylsulfonamides by reacting nickel / ketone dual-catalyzed haloaromatic hydrocarbons with sulfonamides according to the present invention is illustrated below:

[0025] Furthermore, Having a general structural formula as shown in any of equations (B) to (E):

[0026] Where: R 1 X can be selected from ester, trifluoromethyl, cyano, phenyl, methoxy, and methyl groups; X can be selected from iodine and bromine.

[0027] Furthermore, Having a general structural formula as shown in any of the formulas (F):

[0028] Where: R 2 It can be selected from ethyl, methoxy, and tert-butyl.

[0029] Specifically, this invention discloses a method for synthesizing arylsulfonamides by reacting nickel / ketone dual-catalyzed haloaromatic hydrocarbons with sulfonamides, comprising the following steps: under inert gas protection, the above reactants are added to a reaction vessel equipped with a stirring device according to the molar ratio of haloaromatic hydrocarbons, sulfonamides, TXO, NiBr2×3H2O, 4,4¢-di(tert-butyl)-2,2¢-bipyridine (dtbbpy), and TMG of 1:2:0.2:0.1:0.12:2.0, and then 1 mL of dimethyl sulfoxide (DMSO) is added. The reaction is carried out under 45 W CFL irradiation at room temperature with stirring for 24 hours to obtain arylsulfonamide compounds.

[0030] The present invention will be further described below with reference to specific embodiments. Unless otherwise stated, the reagents, materials, instruments, etc. used in the following embodiments are all commercially available. The stirring device is a magnetic stirrer, and the reaction vessel is a sealed reaction tube, at room temperature.

[0031] Example 1: TXO was used as a photosensitizer, and nickel catalyzed the reaction of methyl p-bromobenzoate and 4-methylbenzenesulfonamide.

[0032] Methyl p-bromobenzoate (0.2 mmol), 4-methylbenzenesulfonamide (0.4 mmol), TXO (20 mol %), NiBr2×3H2O (10 mol %), 4,4¢-di(tert-butyl)-2,2¢-bipyridine (12 mol %), TMG (0.4 mmol), and DMSO (1 mL) were added to a dry reaction tube equipped with a magnetic stirrer. The reaction tube was then purged with N2 three times and stirred for 24 hours under 45 WCFL irradiation. After the reaction was completed, 5 mL of water was added, followed by extraction with 3×5 mL of ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then separated by silica gel column chromatography to obtain the target product (yield 90%).

[0033] The obtained NMR data are as follows: 1 H NMR (400 MHz, CDCl3, ppm) δ = 7.91 (d, J = 8.7 Hz, 2H), 7.73 (d, J= 8.3 Hz, 2H), 7.29 (s, 1H), 7.25 (d, J = 8.2 Hz, 2H), 7.14(d, J = 8.7 Hz, 2H), 3.87 (s, 3H), 2.38 (s, 3H). 13 C10 NMR (101 MHz, CDCl3, ppm) δ = 166.6, 144.6, 141.2, 135.9, 131.3, 130.1, 127.5, 126.4, 119.2, 52.3, 21.8. High-resolution mass spectrometry data are as follows: C10 NMR (101 MHz, CDCl3, ppm) δ = 166.6, 144.6, 141.2, 135.9, 131.3, 130.1, 127.5, 126.4, 119.2, 52.3, 21.8. 15 H 16 NO4S + [M + H] + Theoretical value: 306.0795; Tested value: 306.0770.

[0034] Extended Implementation Examples Referring to Example 1, by changing the reaction conditions using a single factor, the following results were obtained:

[0035] a Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), [Ni] (10 mol %), ligand (12mol %), TMG (2.0 equiv), TXO (20 mol %), DMSO (1 mL), N2, 24 h, diobpy = 4,4¢-di-methoxy-2,2¢-bipyridine; dimbpy = 4,4¢-di-methyl-2,2¢-bipyridine; bpy = 2,2¢-bipyridine.

[0036] b NiBr2∙3H2O (5 mol %), dtbbpy (6 mol %).

[0037] c NiBr2∙3H2O (12 mol %), dtbbpy (15 mol %).

[0038] d TMG (1.5 equiv).

[0039] e TMG (2.5 equiv).

[0040] f 10 mol % TXO.

[0041] g No TXO.

[0042] h Keep away from light.

[0043] Example 2: TXO as a photosensitizer, nickel-catalyzed reaction of p-trifluoromethylbromobenzene and 4-methylbenzenesulfonamide.

[0044] The target product was isolated and obtained (yield 89%) according to the preparation method of Example 1.

[0045] The obtained NMR data are as follows: 1 H NMR (400 MHz, CDCl3, ppm) δ = 7.76 (d, J = 8.0 Hz, 3H), 7.47 (d, J = 8.5 Hz, 2H), 7.28 – 7.24 (m, 2H), 7.20 (d, J = 8.4 Hz, 2H), 2.38 (s, 3H). 13 C NMR (101 MHz, CDCl3, ppm) δ = 144.8, 140.2, 135.8, 130.2,127.5, 126.8 (q, J = 3.7 Hz), 126.7 (q, J = 32.9 Hz), 124.1 (q, J = 271.7Hz). 119.7, 21.8. 19 F NMR (376 MHz, CDCl3, ppm) δ = -62.22. High-resolution mass spectrometry data are as follows: C 14 H 13 F3NO2S + [M + H] + Theoretical value: 316.0614; Tested value: 316.0633.

[0046] Example 3: TXO as a photosensitizer, nickel-catalyzed reaction of ethyl p-bromobenzoate and 4-methylbenzenesulfonamide.

[0047] The target product was isolated using the preparation method described in Example 1 (yield 92%).

[0048] The obtained NMR data are as follows:1 H NMR (400 MHz, CDCl3, ppm) δ = 7.92 (d, J = 8.6 Hz, 2H), 7.71 (d, J = 8.2 Hz, 2H), 7.23 (s, 2H), 7.12 (d, J = 8.6 Hz, 2H), 6.97(s, 1H), 4.33 (q, J = 7.1 Hz, 2H), 2.38 (s, 3H), 1.36 (t, J = 7.1 Hz, 3H). 13 CNMR (101 MHz, CDCl3, ppm) δ = 166.1, 144.6, 141.0, 136.0, 131.3, 130.1, 127.5, 126.8, 119.3, 61.2, 21.8, 14.5. High-resolution mass spectrometry data are as follows: C 16 H 18 NO4S + [M + H] + Theoretical value: 320.0951; Tested value: 320.0946.

[0049] Example 4: TXO as a photosensitizer, nickel-catalyzed reaction of p-bromobenzonitrile and 4-methylbenzenesulfonamide.

[0050] The target product was isolated and obtained (yield 89%) according to the preparation method of Example 1.

[0051] The obtained NMR data are as follows: 1 H NMR (400 MHz, CDCl3, ppm) δ = 7.75 (d, J = 8.1 Hz,2H), 7.58 (s, 1H), 7.51 (d, J = 8.6 Hz, 2H), 7.28 (d, J = 8.2 Hz, 2H), 7.17(d, J = 8.5 Hz, 2H), 2.40 (s, 3H). 13 C10 NMR (101 MHz, CDCl3, ppm) δ = 145.1, 141.2, 135.8, 133.8, 130.3, 127.5, 119.5, 118.7, 107.9, 21.8. High-resolution mass spectrometry data are as follows: C10 NMR (101 MHz, CDCl3, ppm) δ = 145.1, 141.2, 135.8, 133.8, 130.3, 127.5, 119.5, 118.7, 107.9, 21.8.14 H 13 N2O2S + [M + H] + Theoretical value: 273.0692; Test value: 273.0699.

[0052] Example 5: TXO as a photosensitizer, nickel-catalyzed reaction of 4-bromobiphenyl and 4-methylbenzenesulfonamide.

[0053] The target product was isolated using the preparation method described in Example 1 (yield 64%).

[0054] The obtained NMR data are as follows: 1 ¹H NMR (400 MHz, CDCl₃, ppm) δ = 7.74 (d, J = 8.3 Hz,2H), 7.55 – 7.49 (m, 2H), 7.47 (d, J = 8.5 Hz, 2H), 7.41 (t, J = 7.6 Hz, 2H), 7.32 (t, J = 7.3 Hz, 1H), 7.24 (d, J = 8.2 Hz, 2H), 7.22 (s, 1H), 7.17 (d, J = 8.5 Hz, 2H), 2.38 (s, 3H). 13 C10 NMR (101 MHz, CDCl3, ppm) δ = 144.2, 140.2, 138.3, 136.2, 136.0, 129.9, 129.0, 128.1, 127.5, 127.0, 121.9, 21.8. High-resolution mass spectrometry data are as follows: C10 NMR (101 MHz, CDCl3, ppm) δ = 144.2, 140.2, 138.3, 136.2, 136.0, 129.9, 129.0, 128.1, 127.5, 127.0, 121.9, 21.8. 19 H 18 NO2S + [M + H] + Theoretical value: 324.1053; Tested value: 324.1062.

[0055] Example 6: TXO as a photosensitizer, nickel-catalyzed reaction of 4-methoxyiodobenzene and 4-methylbenzenesulfonamide.

[0056] The target product was isolated and obtained (yield 74%) according to the preparation method of Example 1.

[0057] The obtained NMR data are as follows: 1¹H NMR (400 MHz, CDCl₃, ppm) δ = 7.61 (d, J = 8.3 Hz, 2H), 7.20 (d, J = 8.1 Hz, 2H), 7.03 – 6.97 (m, 2H), 6.96 (s, 1H), 6.78 – 6.70 (m, 2H), 3.74 (s, 3H), 2.37 (s, 3H). 13 C10 NMR (101 MHz, CDCl3, ppm) δ = 158.0, 143.8, 136.1, 129.7, 129.2, 127.5, 125.4, 114.6, 55.6, 21.7. High-resolution mass spectrometry data are as follows: C10 NMR (101 MHz, CDCl3, ppm) δ = 158.0, 143.8, 136.1, 129.7, 129.2, 127.5, 125.4, 114.6, 55.6, 21.7. 14 H 16 NO3S + [M + H] + Theoretical value: 278.0845; Tested value: 278.0823.

[0058] Example 7: TXO as a photosensitizer, nickel-catalyzed reaction of 4-methyliodobenzene and 4-methylbenzenesulfonamide.

[0059] The target product was isolated using the preparation method described in Example 1 (yield 76%).

[0060] The obtained NMR data are as follows: 1 ¹H NMR (400 MHz, CDCl₃, ppm) δ = 7.67 (d, J = 8.1 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 7.14 (s, 1H), 6.99 (q, J = 8.4 Hz, 4H), 2.36(s, 3H), 2.25 (s, 3H). 13 C10 NMR (101 MHz, CDCl3, ppm) δ = 143.9, 136.3, 135.4, 134.0, 130.0, 129.8, 127.5, 122.3, 21.7, 21.0. High-resolution mass spectrometry data are as follows: C10 NMR (101 MHz, CDCl3, ppm) δ = 143.9, 136.3, 135.4, 134.0, 130.0, 129.8, 127.5, 122.3, 21.7, 21.0. 14 H 16 NO2S + [M + H] +Theoretical value: 262.0896; Tested value: 262.0915.

[0061] Example 8: TXO as a photosensitizer, nickel-catalyzed reaction of 3-bromo-5-trifluoromethylbenzonitrile and 4-methylbenzenesulfonamide.

[0062] The target product was isolated and obtained (yield 80%) according to the preparation method of Example 1.

[0063] The obtained NMR data are as follows: 1 H NMR (400 MHz, CDCl3, ppm) δ = 7.73 (d, J = 8.3 Hz,2H), 7.60 (s, 1H), 7.56 (s, 2H), 7.39 (s, 1H), 7.32 (d, J = 8.2 Hz, 2H), 2.42 (s, 3H). 13 C NMR (101 MHz, CDCl3, ppm) δ = 145.5, 139.0, 135.3, 133.5 (q, J =34.1 Hz), 130.5, 127.4, 125.8, 124.8 (q, J = 3.8 Hz), 122.56 (q, J = 273.3Hz), 120.87 (q, J = 3.7 Hz), 116.9, 114.8, 21.9. 19 F NMR (376 MHz, CDCl3, ppm) δ = -63.33. High-resolution mass spectrometry data are as follows: C 15 H 12 F3N2O2S + [M + H] + Theoretical value: 341.0566; Tested value: 341.0576.

[0064] Example 9: TXO as a photosensitizer, nickel-catalyzed reaction of 3-bromobenzonitrile and 4-methylbenzenesulfonamide.

[0065] The target product was isolated using the preparation method described in Example 1 (yield 77%).

[0066] The obtained NMR data are as follows: 1 ¹H NMR (400 MHz, CDCl₃, ppm) δ = 7.72 (d, J = 8.3 Hz,2H), 7.63 (s, 1H), 7.37 (dd, J = 6.5, 3.7 Hz, 4H), 7.28 (d, J = 7.6 Hz, 2H), 2.40 (s, 3H). 13 C10 NMR (101 MHz, CDCl3, ppm) δ = 144.9, 138.0, 135.6, 130.5, 130.2, 128.6, 127.4, 125.2, 123.7, 118.3, 113.5, 21.8. High-resolution mass spectrometry data are as follows: C10 NMR (101 MHz, CDCl3, ppm) δ = 144.9, 138.0, 135.6, 130.5, 130.2, 128.6, 127.4, 125.2, 123.7, 118.3, 113.5, 21.8. 14 H 13 N2O2S + [M + H] + Theoretical value: 273.0692; Test value: 273.0703.

[0067] Example 10: TXO as a photosensitizer, nickel-catalyzed reaction of 4-bromo-2-fluoroacetophenone and 4-methylbenzenesulfonamide.

[0068] The target product was isolated and obtained (yield 82%) according to the preparation method of Example 1.

[0069] The obtained NMR data are as follows: 1 H NMR (400 MHz, CDCl3, ppm) δ = 7.77 (dd, J = 13.3, 8.2 Hz, 3H), 7.29 (d, J = 8.1 Hz, 2H), 7.13 (s, 1H), 6.98 (d, J = 12.7 Hz, 1H), 6.83 (d, J = 8.6 Hz, 1H), 2.57 (d, J = 5.0 Hz, 3H), 2.40 (s, 3H). 13 C NMR (101 MHz, CDCl3, ppm) δ = 194.7 (d, J = 3.9 Hz), 163.2 (d, J = 255.8 Hz), 145.0, 142.8 (d, J = 11.5 Hz), 135.8, 132.3 (d,J = 3.9 Hz), 130.3, 127.5,121.6 (d, J = 13.1 Hz), 114.8 (d, J = 2.9 Hz), 106.7 (d, J = 29.1 Hz), 31.5(d, J = 7.6 Hz), 21.8. 19 F NMR (376 MHz, CDCl3, ppm) δ = -105.73. High-resolution mass spectrometry data are as follows: C 15 H 15 FNO3S + [M + H] + Theoretical value: 308.0751; Tested value: 308.0737.

[0070] Example 11: TXO as a photosensitizer, nickel-catalyzed reaction of methyl p-bromobenzoate and 4-ethylbenzenesulfonamide.

[0071] The target product was isolated and obtained (yield 90%) according to the preparation method of Example 1.

[0072] The obtained NMR data are as follows: 1 ¹H NMR (400 MHz, CDCl₃, ppm) δ = 7.95 – 7.88 (m, 2H),7.74 (d, J = 8.4 Hz, 2H), 7.28 (s, 2H), 7.17 – 7.09 (m, 2H), 7.02 (s, 1H), 3.87 (s, 3H), 2.67 (q, J = 7.6 Hz, 2H), 1.22 (t, J = 7.6 Hz, 3H). 13 C NMR (101MHz, CDCl3, ppm) δ = 166.4, 150.5, 140.9, 136.0, 131.1, 128.7, 127.3, 126.2, 119.0, 52.1, 28.8, 14.9. High-resolution mass spectrometry data are as follows: C 16 H 18 NO4S + [M + H] + Theoretical value: 320.0951; Tested value: 320.0966.

[0073] Example 12: TXO as a photosensitizer, nickel-catalyzed reaction of methyl p-bromobenzoate and 4-methoxybenzenesulfonamide.

[0074] The target product was isolated using the preparation method described in Example 1 (yield 91%).

[0075] The obtained NMR data are as follows: 1 ¹H NMR (400 MHz, CDCl₃, ppm) δ = 7.91 (d, J = 8.6 Hz, 2H), 7.78 (d, J = 8.9 Hz, 2H), 7.26 – 7.23 (m, 1H), 7.13 (d, J = 8.6 Hz, 2H), 6.90 (d, J = 8.9 Hz, 2H), 3.87 (s, 3H), 3.82 (s, 3H). 13 C10 NMR (101 MHz, CDCl3, ppm) δ = 166.6, 163.7, 141.3, 131.3, 130.4, 129.7, 126.3, 119.2, 114.6, 55.8, 52.3. High-resolution mass spectrometry data are as follows: C10 NMR (101 MHz, CDCl3, ppm) δ = 166.6, 163.7, 141.3, 131.3, 130.4, 129.7, 126.3, 119.2, 114.6, 55.8, 52.3. 15 H 16 NO5S + [M + H] + Theoretical value: 322.0744; Tested value: 322.0724.

[0076] Example 13: TXO as a photosensitizer, nickel-catalyzed reaction of methyl p-bromobenzoate and 4-tert-butylbenzenesulfonamide.

[0077] The target product was isolated and obtained (yield 87%) according to the preparation method of Example 1.

[0078] The obtained NMR data are as follows: 1 ¹H NMR (400 MHz, CDCl₃, ppm) δ = 7.91 (d, J = 8.5 Hz, 2H), 7.80 (d, J = 9.1 Hz, 3H), 7.46 (d, J = 8.4 Hz, 2H), 7.18 (d,J = 8.5 Hz, 2H), 3.86 (s, 3H), 1.28 (s, 9H). 13 C10 NMR (101 MHz, CDCl3, ppm) δ = 166.7, 157.5, 141.4, 135.9, 131.3, 127.3, 126.5, 126.1, 118.9, 52.3, 35.4, 31.2. High-resolution mass spectrometry data are as follows: C10 NMR (101 MHz, CDCl3, ppm) δ = 166.7, 157.5, 141.4, 135.9, 131.3, 127.3, 126.5, 126.1, 118.9, 52.3, 35.4, 31.2. 18 H 22 NO4S + [M + H] + Theoretical value: 348.1264; Tested value: 348.1257. This invention discloses a novel nickel / ketone dual-catalyzed method for synthesizing arylsulfonamides by reacting halogenated aromatic hydrocarbons with sulfonamides. The method comprises the following steps: Under an inert gas atmosphere, the reactants are added to a reaction vessel equipped with a stirrer in a molar ratio of halogenated aromatic hydrocarbon, sulfonamide, TXO, NiBr2×3H2O, 4,4¢-di(tert-butyl)-2,2¢-bipyridine, and TMG of 1:2:0.2:0.1:0.12:2.0. Then, 1 mL of dimethyl sulfoxide (DMSO) is added, and the reaction is carried out under 45 W CFL irradiation at room temperature with stirring for 24 hours to obtain arylsulfonamide compounds. Furthermore, this invention is a green, efficient, and easy-to-operate method for synthesizing arylsulfonamide compounds.

Claims

1. A method for synthesizing arylsulfonamides by reacting nickel / ketone dual-catalyzed haloaromatic hydrocarbons with sulfonamides, characterized in that, In nickel / ketone dual catalysis, nickel is a nickel compound and ketone is a ketone photosensitizer.

2. The method according to claim 1, characterized in that, The ketone photosensitizer is 9-thioxanone; the nickel compound is an inorganic nickel compound.

3. The method according to claim 1, characterized in that, The reaction is carried out under inert gas protection, in the presence of pyridine compounds and bases, and in a solvent.

4. The method according to claim 3, characterized in that, The molar ratio of halogenated aromatic hydrocarbons, sulfonamides, ketone photosensitizers, nickel compounds, pyridine compounds, and bases is 1:(1.8–2.2):(0.1–0.3):(0.05–0.15):(0.1–0.15):(1.5–2.5).

5. The method according to claim 4, characterized in that, The molar ratio of halogenated aromatic hydrocarbons, sulfonamides, ketone photosensitizers, nickel compounds, pyridine compounds, and bases is 1:2:0.2:0.1:0.12:2.

0.

6. The method according to claim 3, characterized in that, The inert gas is selected from any one of nitrogen, helium, neon, and argon; the base is selected from one or more of tetramethylguanidine, diethylamine, 1,8-diazabicycloundec-7-ene, cesium carbonate, and potassium fluoride; the solvent is selected from any one or more of dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, N,N-dimethylacetamide, chloroform, and methanol.

7. The method according to claim 1, characterized in that, The reaction takes place at room temperature under light.

8. The method according to claim 1, characterized in that, Halogenated aromatic compounds have a general structural formula as shown in any one of formulas (B) to (E): ； Where: R 1 X can be selected from ester group, trifluoromethyl group, cyano group, phenyl group, methoxy group, and methyl group; X can be selected from iodine and bromine. The sulfonamide compounds have a general structural formula as shown in any of formula (F): ； Where: R 2 It can be selected from ethyl, methoxy, and tert-butyl.

9. The application of nickel / ketone dual catalysis in the synthesis of arylsulfonamides from the reaction of haloaromatic hydrocarbons and sulfonamides, characterized in that, Nickel is a nickel compound, and ketone is a ketone photosensitizer.

10. The method according to claim 1 to prepare arylsulfonamides.

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