A process for the reaction of an olefin with a halogenated hydrocarbon

Abstract

The application discloses a method for olefin and halogenated hydrocarbon reaction, and uses copper (I) coordination compound [Cu(dmp)(R 1 R 2 The intermolecular atom transfer radical addition reaction of the olefin and the halogenated hydrocarbon is catalyzed under visible light irradiation with the copper (I) coordination compound [Cu(dmp)(R The functionalization reaction of the aryl olefin disclosed in the application has the characteristics of high conversion efficiency (the yield of the structure simple aryl olefin can reach 80% or even more than 90%, and the yield of the heterocyclic olefin can also reach about 80%), wide application range (not only suitable for the addition of carbon tetrabromide, but also suitable for the addition of other alkyl halides, realizing different halogenated addition of the olefin), and mild reaction condition (inert atmosphere at room temperature).

Description

Technical Field

[0001] This invention belongs to the field of catalytic chemistry technology and relates to a method for the reaction of olefins with haloalkanes, specifically the photocatalytic atomic radical transfer (ATRA) reaction of four copper (I) coordination compounds with alkyl halides. Background Technology

[0002] Existing visible light catalysts suffer from scarcity, high cost, and high toxicity, while organic dye catalysts still exhibit drawbacks such as weak fluorescence in solution and instability. To overcome these shortcomings, increasing research has revealed the potential of using copper, an inexpensive metal, to prepare copper complexes as photosensitizers for catalyzing organic reactions. To date, the bis(diimide) copper(I) complex [Cu(N^N)2] has been developed... + and [Cu(N^N)(N^N) ' ] + Diimine-diphosphine copper(I) complex [Cu(N^N)(P^P)] + It also exhibits suitable excited-state lifetime and redox potential. To improve its excited-state lifetime and emission quantum yield, and to enhance its stability in solution, its photoelectric and photocatalytic properties are usually modulated by introducing substituents onto the N^N and P^P ligands. However, the double-chelated mononuclear copper(I) complex [Cu(N^N)(N^P)]... + There are few reports of compounds containing one imine-phosphine ligand and one diimine ligand. Summary of the Invention

[0003] In view of the above, the purpose of this invention is to provide a method for the reaction of olefins with haloalkanes. Using a copper (I) coordination compound as a photocatalyst, the ATRA reaction of aryl olefins with alkyl halides can be catalyzed under visible light irradiation in an acetonitrile solvent.

[0004] To achieve the above objectives, the present invention adopts the following technical solution:

[0005] A method for reacting olefins with haloalkanes, using [Cu(dmp)(R 1 R 2 Using C3HN2PPh3)]BF4 as a catalyst, an olefin and a haloalkanes are reacted. Preferably, the reaction is carried out under an inert gas atmosphere, under visible light irradiation, and in an organic solvent; the reaction temperature is room temperature, and the reaction time is 10–30 hours. Specifically, the catalyst, olefin, haloalkanes, and organic solvent are mixed and reacted at room temperature for 10–30 hours under an inert gas atmosphere and visible light irradiation to complete the reaction between the olefin and the haloalkanes; the reaction is an atom radical transfer (ATRA) reaction. After the reaction is completed, the mixture is purified to obtain the product.

[0006] In this invention, the molar ratio of olefin, haloalkane, and copper(I) coordination compound is (1-3):1:(0.005-0.02). Preferably, the molar ratio of olefin, haloalkane, and copper(I) coordination compound is 2:1:0.01.

[0007] In this invention, the olefin is an aryl olefin; the haloalkane is an alkyl halide. Specifically, the aryl olefin is selected from styrene, p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-trifluoromethylstyrene, p-acetoxystyrene, m-fluorostyrene, and 2-pyridinestyrene; the alkyl halide is selected from carbon tetrabromide, iodoform, and bromotrichloromethane.

[0008] This invention uses [Cu(dmp)(R 1 R 2 C3HN2PPh3)]BF4 is the catalyst, in which dmp is 2,9-dimethyl-1,10-phenanthroline, R 1 R 2 The catalyst is independently selected from hydrogen, alkyl, or aryl. Preferably, the alkyl group is a C1-C6 alkyl group; the aryl group is a phenyl group. Specifically, the catalyst is selected from any one of 2a, 2b, 2c, and 2d; R 1 = R 2 = H(2a); R 1 = H, R 2 = Me (2b); R 1 =H, R 2 = Ph (2c); R 1 = R 2 = Me (2d).

[0009] Compared with the prior art, the present invention, which adopts the above technical solution, has the following advantages:

[0010] This invention discloses for the first time a dual-chelate mononuclear copper(I) complex [Cu(N^N)(N^P)] as a photocatalyst. + It can catalyze the ATRA reaction of aryl olefins with alkyl halides under visible light irradiation. The functionalization reaction of aryl olefins described in this invention has the characteristics of high conversion efficiency (the yield of structurally simple aryl olefins can reach 80% or even more than 90%, and the yield of heterocyclic olefins can also reach about 80%), wide applicability (not only applicable to the addition of carbon tetrabromide, but also suitable for the addition of other alkyl halides, realizing different halogenation additions of olefins), and mild reaction conditions (inert atmosphere at room temperature is sufficient). Attached Figure Description

[0011] Figure 1 This is the chemical structural formula of the catalyst of the present invention.

[0012] Figure 2 The reactions shown in Examples 2 to 7 are illustrated. Implementation

[0013] The method for preparing the copper(I) coordination compound used as a catalyst in this invention comprises the following steps:

[0014] (1) o-fluoroiodobenzene, diphenylphosphine, and palladium chloride were added to a thick-walled pressure-resistant bottle in a molar ratio of o-fluoroiodobenzene: diphenylphosphine: palladium chloride = 1:1: (0.001~0.005). Under an inert gas atmosphere, alkali and solvent were added, the reaction vessel was sealed, and the mixture was heated to 85°C and reacted for 24 hours. After the reaction was completed, the temperature of the reaction system was lowered to room temperature, and the mixture was extracted with ethyl acetate. The organic phases were combined, dried, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain a pure product (2-fluorophenyl) diphenylphosphine as a white solid.

[0015] (2) Pyrazole, (2-fluorophenyl)diphenylphosphine, and cesium carbonate were added to a thick-walled, pressure-resistant flask according to a molar ratio of pyrazole:(2-fluorophenyl)diphenylphosphine:cesium carbonate = 3:1:(1-5). Solvent was added under an inert gas atmosphere, the reaction vessel was sealed, and the mixture was heated to 180°C and reacted for three days. The mixture was stirred at 180°C for 3 days. After the reaction was complete, the temperature of the reaction system was lowered to room temperature, and the mixture was extracted with ethyl acetate. The organic phases were combined, dried, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain a pure product, bidentate phosphine pyrazole ligand, as a white solid.

[0016] (3) According to the molar ratio of tetrafluoroborate tetraacetonitrile copper: bidentate phosphine pyrazole ligand: 2,9-dimethyl-1,10-phenanthroline = 1:1:1, first add tetrafluoroborate tetraacetonitrile copper, bidentate phosphine pyrazole ligand and 2,9-dimethyl-1,10-phenanthroline to the reaction vessel respectively, and add solvent under an inert gas atmosphere to prepare a solution. First, add the phosphine ligand solution dropwise to the copper solution, stir at room temperature for 1 hour, and then add the 2,9-dimethyl-1,10-phenanthroline solution, and stir at room temperature for 1 hour. After the reaction is completed, concentrate the reaction mixture, add a poor solvent to precipitate it, and wash and dry to obtain the copper(I) coordination compound. Preferably, in the above preparation method, the inert gas is selected from nitrogen and argon.

[0017] In the above preparation method, the solvents are ultra-dry dichloromethane and ultra-dry acetonitrile, respectively; the undesirable solvent is diethyl ether.

[0018] This invention discloses the application of the above-mentioned copper (I) coordination compound in the photocatalytic reaction of olefins and halogenated hydrocarbons, specifically in the photocatalytic construction of C-C and C-C bonds between aryl olefins and alkyl halides, wherein the aryl olefin is selected from any one of styrene, p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-trifluoromethylstyrene, p-acetoxystyrene, m-fluorostyrene, and 2-pyridinestyrene; and the alkyl halide is selected from one of carbon tetrabromide, iodoform, and bromotrichloromethane.

[0019] Specifically, the method for photocatalytic reaction of aryl olefins with alkyl halides using the aforementioned copper(I) coordination compounds includes the following steps:

[0020] Aryl olefin: alkyl halide: copper (I) coordination compound = 2:1:0.01 was added to a reaction vessel equipped with a stirrer. Solvent was added under an inert gas atmosphere, and the reaction vessel was sealed. The reaction was carried out at room temperature for 24 hours under visible light irradiation. After the reaction was complete, the mixture was extracted with ethyl acetate, and the organic phases were combined, dried, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain the target product.

[0021] In the above preparation method, the copper(I) coordination compound is selected from any one of 2a, 2b, 2c, and 2d; the solvent is ultra-dry acetonitrile; the stirring device is a magnetic stirrer; the visible light source is a 45 W fluorescent lamp; and the reaction time is 24 hours. The present invention will be further described below with reference to the accompanying drawings and specific embodiments. Unless otherwise stated, the reagents, materials, instruments, etc. used in the following embodiments are all commercially available. Chemical structural formulas and reaction diagrams of the bidentate phosphinepyrazole ligands (1a, 1b, 1c, 1d) and copper(I) coordination compounds (2a, 2b, 2c, 2d) of the present invention are provided. Figure 1 In 2a-2d, dmp and R 1 R 2 C3HN2PPh3 acts as a five-membered chelating ligand. Each copper (I) center is associated with a dmp and an R. 1 R 2 In C3HN2PPh, the three N atoms and one P atom are coordinated to form a highly distorted tetrahedron. The copper(I) coordination polymer of this invention has a triclinic crystal system and a space group of [missing information]. P ī. The cell parameters are 2a: a = 10.6131(17) Å, b = 13.336(2)Å, c = 13.515(2) Å, α = 102.248(4)°, β= 94.419(5)°, γ = 107.571(4)°, V = 1761.5(5) nm 3 , Z = 2.2b: a = 10.8101(14) Å, b = 12.1918(17) Å, c = 16.312(2) Å, α = 98.412(4)°, β = 108.062(4)°, γ = 100.700(4)°, V = 1960.0(5) nm 3 , Z = 2.2c: a = 12.0193(3)Å, b = 18.5661(6) Å, c = 18.5678(8) Å, α = 89.141(3)°, β = 72.401(3)°, γ = 75.892(3)°, V = 3822.6(2) nm 3 , Z = 4.2d: a = 9.5309(5) Å, b = 12.5267(7) Å, c = 16.7613(9)Å, α = 77.384(2)°, β = 74.714(2)°, γ = 79.755(2)°, V = 1868.30(18) nm 3 , Z = 2.

[0022] Preparation of copper(I) coordination compounds 2a, 2b, 2c, and 2d.

[0023] Pyrazole (0.41 g, 6 mmol), (2-fluorophenyl)diphenylphosphine (0.56 g, 2 mmol), and Cs₂CO₃ (1.95 g, 6 mmol) were added to a 35 mL thick-walled pressure flask. Under a nitrogen atmosphere, degassed anhydrous N,N-dimethylacetamide (DMA, 5 mL) was added. The mixture was stirred in an oil bath at 180ºC for 3 days. After the reaction was complete, it was cooled to room temperature, and the reaction mixture was extracted with CH₂Cl₂ (2 × 10 mL). The combined organic layer was backwashed with water (2 × 10 mL), filtered, and evaporated. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents (yield: 0.05 g; yield: 77%). The NMR data of product 1a are as follows: 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.59 (d, 1H), 7.50–7.40 (m, 3H), 7.35–7.25 (m, 11H), 7.02 (dd, J = 7.3, 3.1 Hz, 1H), 6.25 (t, 1H); 13 C NMR (101MHz, CDCl3, ppm): δ = 144.6 (d, J = 21.2 Hz), 140.4, 136.6 (d, J = 11.2 Hz), 134.8, 133.9 (d, J = 20.5 Hz), 131.2 (d, J = 5.3 Hz), 129.7, 128.9, 128.8, 128.6(d, J = 7.2 Hz), 128.2, 126.3 (d, J = 2.6 Hz), 106.3; 31 P NMR (162 MHz, CDCl3, ppm): δ = –14.5.

[0024] To a 5 mL solution of acetonitrile containing [Cu(CH3CN)4]BF4 (0.0315 g, 0.10 mmol), a 5 mL solution of CH2Cl2 containing 1a (0.0328 g, 0.10 mmol) was added. After stirring at room temperature for 1 hour, a 5 mL solution of CH2Cl2 containing dmp (2,9-dimethyl-1,10-phenanthroline) (0.0208 g, 0.10 mmol) was added. After stirring for another hour, a clear yellow solution was obtained. After the reaction was complete, the reaction solution was concentrated to approximately 5 mL. Then, 20 mL of the unsuitable solvent Et2O was added to the solution, and orange crystals of 2a precipitated. After filtration and separation, the crystals were washed with Et2O and dried under vacuum (yield: 0.02 g; yield: 36%, calculated as Cu). Melting point: 226–228 °C. Mass spectrometry: Theoretical value: 599.1426; Measured value: 599.1426. The NMR data of the obtained product are as follows: 1 H NMR (400 MHz, d 6 -DMSO, ppm): 8.79 (t, J = 8.1 Hz, 2H),8.65 (s, 1H), 8.24 (d, J = 16.6 Hz, 2H), 8.00 (t, J = 7.2 Hz, 2H), 7.84 (d, J =23.3 Hz, 2H), 7.57 (m, 4H), 7.46 (s, 4H), 7.29 (s, 4H), 6.98 (d, J = 29.1 Hz, 1H), 6.55 (d, J = 54.3 Hz, 1H), 2.44 (s, 6H); 3 C NMR (101 MHz, d 6 -DMSO, ppm): δ =157.7, 156.6, 142.2, 141.7, 141.4, 141.1, 137.1, 136.3, 132.6, 132.3 (t, J =15.2 Hz), 131.3 (d, J = 38.8 Hz), 130.5, 129.7 (t, J = 36.3 Hz), 128.2 (d, J = 8.9Hz), 126.1 (d, J= 6.2 Hz), 125.5, 124.8, 124.6, 106.9, 24.9, 24.1; 31 P NMR (162MHz, d 6 -DMSO, ppm): δ = –8.3.

[0025] The obtained product was subjected to single-crystal X-ray diffraction experiments, and its crystallographic parameters are shown in Table 1.

[0026]

[0027] 3-Methylpyrazole (0.49 g, 6 mmol), (2-fluorophenyl)diphenylphosphine (0.56 g, 2 mmol), and Cs₂CO₃ (1.95 g, 6 mmol) were added to a 35 mL thick-walled pressure flask. Under a nitrogen atmosphere, degassed anhydrous N,N-dimethylacetamide (DMA, 5 mL) was added. The mixture was stirred in an oil bath at 180ºC for 3 days. After the reaction was complete, it was cooled to room temperature, and the reaction mixture was extracted with CH₂Cl₂ (2 × 10 mL). The combined organic layer was backwashed with water (2 × 10 mL), filtered, and evaporated. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents (yield: 0.04 g; yield: 63%). The NMR data of product 1b are as follows: 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.48 (dd, J = 7.3, 3.6 Hz, 1H), 7.41 (t, J = 7.0 Hz, 1H), 7.35 (t, J = 2.0 Hz, 1H), 7.33–7.21 (m, 11H), 7.01(dd, J = 6.8, 3.7 Hz, 1H), 6.03 (d, J = 2.2 Hz, 1H), 2.24 (s, 3H); 13 C NMR (101MHz, CDCl3, ppm): δ = 149.7, 144.7 (d, J = 21.2 Hz), 136.8 (d, J = 10.7 Hz), 134.8, 134.0 (d, J = 20.5 Hz), 133.2 (d, J = 19.9 Hz), 131.8 (d, J= 5.6 Hz),129.6, 128.8, 128.5 (d, J = 7.0 Hz), 127.8, 126.0 (d, J = 2.5 Hz), 106.2, 13.6; 31 PNMR (162 MHz, CDCl3, ppm): δ = –14.4.

[0028] To a 5 mL solution of acetonitrile containing [Cu(CH3CN)4]BF4 (0.0315 g, 0.10 mmol), a 5 mL solution of CH2Cl2 containing 1b (0.0342 g, 0.10 mmol) was added. After stirring at room temperature for 1 hour, a 5 mL solution of CH2Cl2 containing dmp (2,9-dimethyl-1,10-phenanthroline) (0.0208 g, 0.10 mmol) was added. After stirring for another hour, a clear yellow solution was obtained. After the reaction was complete, the reaction solution was concentrated to approximately 5 mL. Then, 20 mL of the unsuitable solvent Et2O was added to the solution, and orange crystals of 2b precipitated. After filtration and separation, the crystals were washed with Et2O and dried under vacuum (yield: 0.02 g; yield: 33%, based on Cu). Melting point: 158–163 °C. Mass spectrometry: Theoretical value: 613.1582; ​​Measured value: 613.1582. The NMR data of the obtained product are as follows: 1 H NMR (400 MHz, d 6 -DMSO, ppm): δ = 8.80 (d, J = 8.1 Hz,2H), 8.59 (s, 1H), 8.26 (d, J = 8.6 Hz, 2H), 8.02 (m, 2H), 7.85 (t, J = 7.2 Hz,1H), 7.73 (s, 1H), 7.62 (t, J = 7.2 Hz, 1H), 7.52 (s, 2H), 7.44 (s, 4H), 7.33–7.11 (m, 4H), 7.00 (t, J = 7.8 Hz, 1H), 6.51 (s, 1H), 2.45 (s, 6H); 13 C NMR (101MHz, d 6 -DMSO, ppm): δ = 159.3, 158.2, 153.3, 142.7 (d,J = 4.4 Hz), 138.8,138.0, 136.1, 133.6 (d, J = 16.1 Hz), 132.9 (d, J = 32.4 Hz), 131.5 (d, J = 7.2Hz), 131.2 (d, J = 5.5 Hz), 129.8 (d, J = 9.5 Hz), 128.2 (d, J = 4.6 Hz), 127.8 (d, J = 16.5 Hz), 126.6, 126.5, 126.4, 126.2, 108.9, 26.2, 25.7, 13.5; 31 P NMR (162MHz, d 6 -DMSO, ppm): δ = –11.9.

[0029] The obtained product was subjected to single-crystal X-ray diffraction experiments, and its crystallographic parameters are shown in Table 2.

[0030]

[0031] 3-Phenylopyrazole (0.86 g, 6 mmol), (2-fluorophenyl)diphenylphosphine (0.56 g, 2 mmol), and Cs₂CO₃ (1.95 g, 6 mmol) were added to a 35 mL thick-walled pressure flask. Under a nitrogen atmosphere, degassed anhydrous N,N-dimethylacetamide (DMA, 5 mL) was added. The mixture was stirred in an oil bath at 180ºC for 3 days. After the reaction was complete, it was cooled to room temperature, and the reaction mixture was extracted with CH₂Cl₂ (2 × 10 mL). The combined organic layer was backwashed with water (2 × 10 mL), filtered, and evaporated. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents (yield: 0.05 g; yield: 61%). The NMR data of the obtained product at 1c are as follows: 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.60 (dd, J = 2.4, 1.0 Hz,1H), 7.57–7.54 (m, 2H), 7.52 (ddd, J = 7.8, 4.0, 1.2 Hz, 1H), 7.43 (td, J=7.7, 1.4 Hz, 1H), 7.32–7.23 (m, 14H), 7.06 (ddd, J = 7.7, 3.6, 1.3 Hz, 1H),6.62 (d, J = 2.4 Hz, 1H); 13 C NMR (101 MHz, CDCl3, ppm): δ = 152.3, 144.7 (d, J =21.3 Hz), 137.4 (d, J = 10.7 Hz), 135.5, 134.0 (d, J = 20.3 Hz), 133.2, 133.1,133.0, 131.8 (d, J = 3.7 Hz), 129.7, 128.7, 128.5, 128.4 (d, J = 5.9 Hz), 127.8 (d, J = 26.3 Hz), 125.8, 125.0 (d, J = 2.8 Hz), 104.0; 31 P NMR (162 MHz, CDCl3, ppm): δ = –13.7.

[0032] To a 5 mL solution of acetonitrile containing [Cu(CH3CN)4]BF4 (0.0315 g, 0.10 mmol), 1 c (0.0404 g, 0.10 mmol) of CH2Cl2 (5 mL) solution was added. After stirring at room temperature for 1 hour, a 5 mL solution of CH2Cl2 containing dmp (2,9-dimethyl-1,10-phenanthroline) (0.0208 g, 0.10 mmol) was added. After stirring for another hour, a clear yellow solution was obtained. After the reaction was complete, the reaction solution was concentrated to approximately 5 mL. Then, 20 mL of the unsuitable solvent Et2O was added to the solution, precipitating 2 c of yellow crystals. After filtration and separation, the crystals were washed with Et2O and dried under vacuum (yield: 0.04 g; yield: 59%, based on Cu). Melting point: 233–236 °C. Mass spectrometry: Theoretical value: 675.1739; Measured value: 675.1739. The NMR data of the obtained product are as follows: 1 H NMR (400 MHz, d 6-DMSO, ppm): δ = 8.62 (s, 1H), 8.59(d, J = 8.3 Hz, 2H), 8.10 (s, 2H), 7.86 (t, J = 7.5 Hz, 1H), 7.74 (d, J = 8.3Hz, 3H), 7.67 (t, J = 7.5 Hz, 1H), 7.49 (t, J = 7.1 Hz, 2H), 7.42 (t, J = 6.9Hz, 4H), 7.23 (m, 4H), 7.07 (t, J = 7.7 Hz, 1H), 6.88 (d, J = 2.3 Hz, 1H), 6.85 (d, J = 7.3 Hz, 2H), 6.54 (t, J = 6.7 Hz, 1H), 6.22 (s, 2H), 2.30 (s, 6H); 13 C NMR (101 MHz, d 6 -DMSO, ppm): δ = 158.74, 158.20, 156.33, 142.93 (d, J= 11.8 Hz), 142.70, 138.39, 137.95, 136.75, 133.75 (d, J = 16.0 Hz), 133.16,132.77, 131.74, 131.42, 131.20 (d, J = 6.9 Hz), 130.47, 129.76 (d, J = 9.6Hz), 128.70, 128.27, 127.63, 127.16, 126.66, 126.44, 126.22, 125.91, 107.06, 26.33, 25.72; 31 P NMR (162 MHz, d6-DMSO, ppm): δ = –11.3.

[0033] The obtained product was subjected to single-crystal X-ray diffraction experiments, and its crystallographic parameters are shown in Table 3.

[0034]

[0035] 3,5-Dimethylpyrazole (0.58 g, 6 mmol), (2-fluorophenyl)diphenylphosphine (0.56 g, 2 mmol), and Cs₂CO₃ (1.95 g, 6 mmol) were added to a 35 mL thick-walled pressure flask. Under a nitrogen atmosphere, degassed anhydrous N,N-dimethylacetamide (DMA, 5 mL) was added. The mixture was stirred in an oil bath at 180ºC for 3 days. After the reaction was complete, it was cooled to room temperature, and the reaction mixture was extracted with CH₂Cl₂ (2 × 10 mL). The combined organic layer was backwashed with water (2 × 10 mL), filtered, and evaporated. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents (yield: 0.02 g; yield: 26%). The NMR data of the product after 1 day are as follows: 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.38 (dd, J = 7.6, 1.3 Hz,1H), 7.32–7.24 (m, 12H), 7.10 (ddd, J = 7.6, 3.4, 1.2 Hz, 1H), 5.81 (s, 1H), 2.13 (s, 3H), 1.97 (s, 3H); 13 C NMR (101 MHz, CDCl3, ppm): δ = 148.2, 143.5 (d, J = 22.3 Hz), 140.3, 138.0 (d, J = 18.1 Hz), 136.5 (d, J = 11.4 Hz), 134.3, 134.0 (d, J = 20.8 Hz), 129.4, 128.8, 128.7, 128.3 (d, J = 7.2 Hz), 128.1 (d, J = 2.5 Hz), 105.4, 13.5, 11.7 (d, J = 4.5 Hz); 31 P NMR (162 MHz, CDCl3, ppm): δ =–14.2.

[0036] To a 5 mL solution of acetonitrile containing [Cu(CH3CN)4]BF4 (0.0315 g, 0.10 mmol), 5 mL solution of CH2Cl2 containing 1d (0.0356 g, 0.10 mmol) was added. After stirring at room temperature for 1 hour, a 5 mL solution of CH2Cl2 containing dmp (2,9-dimethyl-1,10-phenanthroline) (0.0208 g, 0.10 mmol) was added. After stirring for another hour, a clear yellow solution was obtained. After the reaction was complete, the reaction solution was concentrated to approximately 5 mL. Then, 20 mL of the unsuitable solvent Et2O was added to the solution, and 2d orange crystals precipitated. After filtration and separation, the crystals were washed with Et2O and dried under vacuum (yield: 0.03 g; yield: 48%, based on Cu). Melting point: 220–234 °C. Mass spectrometry: Theoretical value: 627.1739; Measured value: 627.1740. The NMR data of the obtained product are as follows: 1 H NMR (400 MHz, d 6 -DMSO, ppm): δ = 8.78 (d, J = 8.2 Hz, 2H), 8.24 (d, J = 9.0 Hz, 2H), 8.14–7.90 (m, 3H), 7.81 (t, J = 7.4 Hz, 1H), 7.74–7.58 (m, 2H), 7.58–7.47 (m, 2H), 7.45 (m, 4H), 7.33–7.08 (m, 3H), 6.95 (t, J =7.7 Hz, 1H), 6.25 (s, 1H), 2.42 (s, 4H), 2.40 (s, 2H); 13 C NMR (101 MHz, d 6 -DMSO, ppm): δ = 159.3, 158.2, 152.5, 144.5, 142.7 (d, J = 7.1 Hz), 138.8,138.0, 133.7 (d, J = 16.4 Hz), 132.9, 132.3, 131.4 (t, J = 21.5 Hz), 130.7 (d, J = 33.7 Hz), 129.8 (d, J = 9.5 Hz), 127.8 (d, J= 15.2 Hz), 126.6, 126.5, 126.4,126.2, 108.9, 26.2, 25.7, 13.5, 12.9; 31 P NMR (162 MHz, d 6 -DMSO, ppm): δ = –12.2.

[0037] The obtained product was subjected to single-crystal X-ray diffraction experiments, and its crystallographic parameters are shown in Table 4.

[0038]

[0039] Example 1: Catalytic ATRA reaction of styrene and carbon tetrabromide under visible light irradiation.

[0040]

[0041] A mixture of carbon tetrabromide (0.2 mmol), styrene (2 equiv, 0.4 mmol), and 2c (1 mol%) was added to a 10 mL reaction tube. Under a nitrogen atmosphere, ultra-dry MeCN (1 mL) was added. The mixture was stirred at room temperature and irradiated with a 45 W household energy-saving lamp for 24 hours, then cooled with a fan. The reaction mixture was extracted three times with ethyl acetate (3 × 5 mL), backwashed with 3 × 5 mL of water and brine, dried over anhydrous Na₂SO₄, and concentrated to dryness under reduced pressure. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents. Yields: 93% (HPLC), 91% (separation).

[0042] The NMR data of the obtained product are as follows: 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.49 (d, J =7.0 Hz, 2H), 7.37 (t, J = 7.3 Hz, 2H), 7.31 (t, J = 7.2 Hz, 1H), 5.33 (dd, J =7.7, 4.1 Hz, 1H), 4.09 (qd, J = 15.6, 5.9 Hz, 2H); 13 C NMR (101 MHz, CDCl3, ppm): δ = 140.8, 129.0, 128.9, 128.2, 66.5, 50.1, 35.0.

[0043] By changing the reaction conditions, the product yields in Table 5 were obtained. Except for the changed reaction conditions, the other reaction conditions for each group were the same as above.

[0044] Table 5 Results under different reaction conditions

[0045]

[0046]

[0047] a Standard reaction conditions, HPLC yield. b The molar ratio of 3a / 4a is 3:1. c The molar ratio of 3a / 4a is 1:1. d The dosage of 2c is 2 mol%. e The dosage of 2c is 0.5 mol%. f Store in a dark place at room temperature. g Store in the dark at 80°C. h Cu(MeCN)4BF4 and 2C are mixed in a 1:2 molar ratio. (Oxygen environment)

[0048] Example 2: Catalytic ATRA reaction of p-fluorostyrene and carbon tetrabromide under visible light irradiation.

[0049] A mixture of carbon tetrabromide (0.2 mmol), p-fluorostyrene (2 equiv, 0.4 mmol), and 2c (1 mol%) was added to a 10 mL reaction tube. Under a nitrogen atmosphere, ultra-dry MeCN (1 mL) was added. The mixture was stirred at room temperature and irradiated with a 45 W household energy-saving lamp for 24 hours, then cooled with a fan. The reaction mixture was extracted three times with ethyl acetate (3 × 5 mL), backwashed with 3 × 5 mL of water and brine, dried over anhydrous Na₂SO₄, and concentrated under reduced pressure to dryness. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents, yield: 77%.

[0050] The NMR data of the obtained product are as follows: 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.48 (dd, J =8.7, 5.2 Hz, 2H), 7.06 (t, J = 8.6 Hz, 2H), 5.34 (dd, J = 8.4, 3.8 Hz, 1H), 4.10 (dd, J = 15.5, 3.8 Hz, 1H), 4.01 (dd, J = 15.5, 8.4 Hz, 1H);13 C NMR (101MHz, CDCl3, ppm): δ = 162.8 (d, J = 248.9 Hz), 136.6, 130.1 (d, J = 8.6 Hz), 115.9 (d, J = 21.9 Hz), 66.5, 49.1, 34.7. 19 F NMR (377 MHz, CDCl3, ppm): δ = –112.0.

[0051] Example 3: Catalytic ATRA reaction of p-chlorostyrene and carbon tetrabromide under visible light irradiation.

[0052] A mixture of carbon tetrabromide (0.2 mmol), p-chlorostyrene (2 equiv, 0.4 mmol), and 2c (1 mol%) was added to a 10 mL reaction tube. Under a nitrogen atmosphere, ultra-dry MeCN (1 mL) was added. The mixture was stirred at room temperature and irradiated with a 45 W household energy-saving lamp for 24 hours, then cooled with a fan. The reaction mixture was extracted three times with ethyl acetate (3 × 5 mL), backwashed with 3 × 5 mL of water and brine, dried over anhydrous Na₂SO₄, and concentrated to dryness under reduced pressure. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents, yield: 91%.

[0053] The NMR data of the obtained product are as follows: 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.43 (d, J =8.5 Hz, 2H), 7.34 (d, J = 8.5 Hz, 2H), 5.31 (dd, J = 8.3, 3.8 Hz, 1H), 4.10(dd, J = 15.5, 3.8 Hz, 1H), 4.01 (dd, J = 15.5, 8.3 Hz, 1H); 13 C NMR (101 MHz, CDCl3, ppm): δ = 139.2, 134.8, 129.6, 129.1, 66.3, 48.9, 34.6.

[0054] Example 4: Catalytic ATRA reaction of trifluoromethylstyrene and carbon tetrabromide under visible light irradiation.

[0055] A mixture of carbon tetrabromide (0.2 mmol), p-trifluoromethylstyrene (2 equiv, 0.4 mmol), and 2c (1 mol%) was added to a 10 mL reaction tube. Under a nitrogen atmosphere, ultra-dry MeCN (1 mL) was added. The mixture was stirred at room temperature and irradiated with a 45 W household energy-saving lamp for 24 hours, then cooled with a fan. The reaction mixture was extracted three times with ethyl acetate (3 × 5 mL), backwashed with 3 × 5 mL of water and brine, dried over anhydrous Na₂SO₄, and concentrated under reduced pressure to dryness. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents, yield: 86%.

[0056] The NMR data of the obtained product are as follows: 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.70–7.56 (m,4H), 5.34 (dd, J = 8.1, 3.9 Hz, 1H), 4.13 (dd, J = 15.6, 3.9 Hz, 1H), 4.04 (dd, J =15.6, 8.1 Hz, 1H); 13 C NMR (101 MHz, CDCl3, ppm): δ = 144.6, 131.0 (q, J = 32.7Hz), 128.6, 125.9 (q, J = 3.7 Hz), 123.8 (q, J = 272.3 Hz), 66.2, 48.3, 34.4; 19 FNMR (377 MHz, CDCl3, ppm) δ = –62.7.

[0057] Example 5: Catalytic ATRA reaction of p-acetoxystyrene and carbon tetrabromide under visible light irradiation.

[0058] A mixture of carbon tetrabromide (0.2 mmol), p-acetoxystyrene (2 equiv, 0.4 mmol), and 2c (1 mol%) was added to a 10 mL reaction tube. Under a nitrogen atmosphere, ultra-dry MeCN (1 mL) was added. The mixture was stirred at room temperature and irradiated with a 45 W household energy-saving lamp for 24 hours, then cooled with a fan. The reaction mixture was extracted three times with ethyl acetate (3 × 5 mL), backwashed with 3 × 5 mL of water and brine, dried over anhydrous Na₂SO₄, and concentrated to dryness under reduced pressure. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents, yield: 87%.

[0059] The NMR data of the obtained product are as follows: 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.50 (d, J =8.6 Hz, 2H), 7.10 (d, J = 8.6 Hz, 2H), 5.32 (dd, J = 7.8, 4.0 Hz, 1H), 4.11 (dd, J = 15.6, 4.0 Hz, 1H), 4.01 (dd, J = 15.6, 7.8 Hz, 1H); 13 C NMR (101 MHz, CDCl3, ppm): δ = 169.1, 150.8, 138.2, 129.3, 122.0, 66.5, 49.1, 34.8, 21.1.

[0060] Example 6: Catalytic ATRA reaction of m-fluorostyrene and carbon tetrabromide under visible light irradiation.

[0061] A mixture of carbon tetrabromide (0.2 mmol), m-fluorostyrene (2 equiv, 0.4 mmol), and 2c (1 mol%) was added to a 10 mL reaction tube. Under a nitrogen atmosphere, ultra-dry MeCN (1 mL) was added. The mixture was stirred at room temperature and irradiated with a 45 W household energy-saving lamp for 24 hours, then cooled with a fan. The reaction mixture was extracted three times with ethyl acetate (3 × 5 mL), backwashed with 3 × 5 mL of water and brine, dried over anhydrous Na₂SO₄, and concentrated to dryness under reduced pressure. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents, yield: 83%.

[0062] The NMR data of the obtained product are as follows: 1H NMR (400 MHz, CDCl3, ppm): δ = 7.32 (td, J =7.9, 5.7 Hz, 1H), 7.28–7.24 (m, 1H), 7.23–7.18 (m, 1H), 7.00 (tdd, J = 8.3,2.5, 1.1 Hz, 1H), 5.28 (dd, J = 7.9, 3.9 Hz, 1H), 4.05 (ddd, J = 23.5, 15.6, 6.0Hz, 2H); 13 C NMR (101 MHz, CDCl3, ppm): δ = 162.7 (d, J = 247.6 Hz, 1H), 143.1 (d, J = 7.3 Hz, 1H), 130.5 (d, J = 8.3 Hz, 3H), 123.9, 116.1 (d, J = 21.1 Hz, 3H), 115.3 (d, J = 22.5 Hz, 3H), 66.3, 48.8 (d, J = 2.0 Hz, 3H), 34.7; 19 F NMR (377 MHz, CDCl3, ppm) δ = –111.6.

[0063] Example 7: Catalytic ATRA reaction of 2-vinylpyridine and carbon tetrabromide under visible light irradiation.

[0064] A mixture of carbon tetrabromide (0.2 mmol), 2-vinylpyridine (2 equiv, 0.4 mmol), and 2c (1 mol%) was added to a 10 mL reaction tube. Under a nitrogen atmosphere, ultra-dry MeCN (1 mL) was added. The mixture was stirred at room temperature and irradiated with a 45 W household energy-saving lamp for 24 hours, then cooled with a fan. The reaction mixture was extracted three times with ethyl acetate (3 × 5 mL), backwashed with 3 × 5 mL of water and brine, dried over anhydrous Na₂SO₄, and concentrated to dryness under reduced pressure. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as eluents. Yield: 83%.

[0065] The NMR data of the obtained product are as follows: 1 H NMR (400 MHz, CDCl3, ppm): δ = 8.66 (d,J =4.7 Hz, 1H), 7.69 (td, J = 7.7, 1.6 Hz, 1H), 7.42 (d, J = 7.8 Hz, 1H), 7.23 (dd, J = 7.5, 4.8 Hz, 1H), 5.37 (dd, J = 8.4, 2.8 Hz, 1H), 4.67 (dd, J = 15.5, 8.4 Hz, 1H), 4.03 (dd, J = 15.5, 2.8 Hz, 1H); 13 C NMR (101 MHz, CDCl3, ppm): δ = 158.4,150.0, 137.1, 123.5 (d, J = 7.5 Hz), 64.1, 49.2, 35.4, 29.7.

[0066] Figure 2 The above embodiment illustrates the reaction. The functionalization reaction of aryl olefins described in this invention has the characteristics of high conversion efficiency (the yield of structurally simple aryl olefins can reach 80% or even more than 90%, and the yield of heterocyclic olefins can also reach about 80%), wide applicability (not only applicable to the addition of carbon tetrabromide, but also suitable for the addition of other alkyl halides, realizing different halogenation additions of olefins), and mild reaction conditions (an inert atmosphere at room temperature is sufficient).

Claims

1. A method for reacting an olefin with a haloalkanes, characterized in that, Using [Cu(dmp)(R1R2C3HN2PPh3)]BF4 as a catalyst, and olefins and haloalkanes as raw materials, the reaction is carried out; the catalyst is as follows: ； The reaction is carried out under an inert gas atmosphere and visible light irradiation; the olefin is an aryl olefin; the haloalkane is an alkyl halide; the aryl olefin is selected from styrene, p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-trifluoromethylstyrene, p-acetoxystyrene, m-fluorostyrene, and 2-pyridinestyrene; the alkyl halide is selected from carbon tetrabromide, iodoform, and bromotrichloromethane.

2. The method for reacting olefins with haloalkanes according to claim 1, characterized in that, The molar ratio of olefins, haloalkanes, and copper(I) coordination compounds is (1-3):1:(0.005-0.02).

3. The method for reacting olefins with haloalkanes according to claim 1, characterized in that, The reaction was carried out at room temperature for 10–30 hours.

4. The method for reacting olefins with haloalkanes according to claim 1, characterized in that, The reaction takes place in an organic solvent.

5. The method for reacting olefins with haloalkanes according to claim 1, characterized in that, The reaction is an atomic free radical transfer reaction.

6. The method for reacting olefins with haloalkanes according to claim 1, characterized in that, The catalyst, olefin, haloalkanes, and organic solvent are mixed and reacted at room temperature for 10–30 hours under an inert gas atmosphere and visible light irradiation to complete the reaction between the olefin and the haloalkanes.

7. The method for reacting olefins with haloalkanes according to claim 1, characterized in that, After the reaction was completed, the product was purified to obtain the final product.

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