Halogen exchange method from light-mediated brominated aromatic hydrocarbon to chlorinated aromatic hydrocarbon

Abstract

The invention belongs to the technical field of organic synthesis and photocatalysis, and relates to a light-mediated halogen exchange method from brominated aromatic hydrocarbon to chlorinated aromatic hydrocarbon by taking hydrochloric acid as a chlorine source. According to the method, hydrochloric acid (HCl) is used as a safe and cheap chlorine source, and under ultraviolet irradiation, efficient conversion from aryl bromide to aryl chloride is realized in an acetonitrile solvent by using vanadyl acetylacetonate [VO (acac) 2] as a catalyst and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline as a ligand. The reaction is carried out under a mild condition (0-30 DEG C), dangerous chlorinating agents such as chlorine, SOCl2 and the like are not needed, the operation is simple and convenient, and the method is safe and environment-friendly. According to the method, active chlorine species (Cl <. > or [VO]-Cl < + >) are generated through light-induced metal-halogen bond activation, C-Br bond breakage and chlorine substitution reaction are promoted, and high-selectivity conversion from Br to Cl is achieved. The reaction has the advantages of wide substrate applicability, high selectivity, few side reactions, recyclable catalytic system and the like, and is especially suitable for later modification and green synthesis of fine chemicals and drug intermediates. The invention provides a new halogen exchange strategy which is high in atom economy, environment-friendly and capable of being popularized on a large scale, and provides a new technical path and an industrial application prospect for efficient chlorination of aryl halide.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis and photocatalysis technology, specifically relating to a method for efficiently converting aryl bromides to corresponding aryl chlorides by using hydrochloric acid as a chlorine source and through photoinduced catalysis, which is particularly suitable for the synthesis and modification of fine chemicals and pharmaceutical intermediates. Background Technology

[0002] Aryl halides are important building blocks in organic synthesis, especially in metal-catalyzed cross-coupling, drug molecule modification, and the synthesis of functional materials. For certain molecular designs and later modifications, it is often necessary to convert bromine substituents to chlorine to improve stability or adjust physicochemical properties. Traditional methods for converting bromine to chlorine often rely on high-temperature halogen exchange, or use toxic / inconvenient halogen reagents (Cl2, SOCl2, etc.), or require expensive / complex catalytic systems, resulting in poor selectivity, harsh conditions, or safety hazards.

[0003] In recent years, photocatalysis, especially photochemical strategies based on ligand-to-metal charge transfer (LMCT), has shown unique advantages in the generation of halogen radicals and the mild introduction of halogens. Photoinduced metal-halogen bonds can generate halogen radicals at room temperature, thereby achieving mild halogen exchange reactions. Based on this idea, this invention proposes a method for the highly selective conversion of brominated aromatics to chloroaromatics using HCl hydrochloride as the chlorine source, combined with photoinduced LMCT or related photochemical pathways, through a metal catalytic system. Summary of the Invention

[0004] The purpose of this invention is to provide a simple, safe, mild Br→Cl halogen exchange method with broad substrate applicability. It uses hydrochloric acid as the chlorine source and completes the reaction through photo-induced metal catalysis, avoiding the direct use of chlorine gas or other hazardous chlorination reagents, while achieving high yield and high selectivity.

[0005] This invention uses hydrochloric acid (HCl) as the chlorine source and, under ultraviolet or visible light irradiation, achieves a highly efficient halogen exchange reaction from brominated aromatics to chlorinated aromatics through the synergistic effect of inexpensive metal catalysts such as acetylacetone vanadium oxide [VO(acac)2]. This method activates the metal-halogen bond in the photo-induced catalytic system, generating active chlorine species (such as Cl· or [VO]-Cl) in situ. + This facilitates the precise breaking of the C-Br bond and chlorine substitution in aryl bromides, achieving a highly selective Br→Cl conversion. Compared with existing halogen exchange methods, this invention has the following advantages:

[0006] 1) Safe and economical chlorine source: It uses cheap and readily available hydrochloric acid to replace dangerous chlorination reagents such as chlorine gas and SO2Cl2, making the operation safe and the cost low;

[0007] 2) Mild and green conditions: The reaction is carried out at room temperature and under light conditions, without the need for high temperature and high pressure, and avoids the use of strong oxidants and toxic solvents;

[0008] 3) High efficiency and good selectivity: It can achieve high yields of monosubstituted aryl bromides to aryl chlorides in the presence of multiple substituents, with few side reactions;

[0009] 4) The catalytic system is recyclable: the catalyst has high utilization rate, the system is stable, and it can maintain its activity in multiple cycles;

[0010] 5) Environmentally friendly: No additional halogen source or corrosive chlorinating agent is required, reducing halogen wastewater discharge and conforming to the concepts of green chemistry and sustainable development.

[0011] Therefore, this invention not only provides a simple, safe, and efficient new method for halogen exchange of aryl bromides, but also offers new ideas and technical approaches for the green synthesis of halogenated aromatic hydrocarbons and the later modification of pharmaceutical intermediates, with broad prospects for industrial application and environmental benefits.

[0012] The technical solution adopted in this invention is: a photo-mediated halogen exchange method for brominated aromatic hydrocarbons to chlorinated aromatic hydrocarbons.

[0013]

[0014] R can be one or more of the following: chlorine (-Cl), fluorine (-F), hydrogen (-H), phenyl (-Ph), trifluoromethyl (-CF3), methoxy (-OMe), tert-butyl (-t-Bu), methyl (-Me), or an aromatic ring replaced by one or more other aromatic heterocycles.

[0015] The organic solvent is acetonitrile;

[0016] The chlorine source is hydrochloric acid;

[0017] The metal salt catalyst is selected from vanadium acetylacetonate [VO(acac)2];

[0018] The ligand is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline;

[0019] Based on the technical solution of the present invention, the following beneficial effects are achieved:

[0020] Based on the method of this invention, chlorination of bromoaromatic hydrocarbons is achieved by using brominated aromatic hydrocarbons and hydrochloric acid as the main raw materials through photoinitiation and metal salt catalysis. The reaction requires few raw materials and reagents, has simple reaction conditions, and is economical in terms of steps and atom. In addition, it has a wide substrate range, which facilitates the further derivatization of the conversion products to prepare complex functional molecules.

[0021] Based on the above solution, the present invention can be further improved as follows:

[0022] Furthermore, the substituents of the substituted aromatic group or heteroaromatic group are selected from halogen, cyano, nitro, alkyl, alkoxy, aryloxy, ester, thiophene, thiazolyl, phenyl, or one or more of these groups.

[0023] Furthermore, the metal salt catalyst is vanadium acetylacetonate [VO(acac)2].

[0024] Furthermore, the ligand is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.

[0025] Furthermore, the reaction temperature is 0–30°C.

[0026] Furthermore, the molar ratio of the brominated aromatic compound to the metal catalyst, ligand, and hydrochloric acid is 1:(0.1-0.3):(0.1-0.3):10.

[0027] Furthermore, the bromoaromatic hydrocarbon is selected from one of the following structures:

[0028]

[0029] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Detailed Implementation

[0030] Step 1: At room temperature, add brominated aromatic compound 1, acetylacetonate vanadyl[VO(acac)2], and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline sequentially to a 10 mL quartz reaction flask (bromoaromatic compound 1: acetylacetonate vanadyl[VO(acac)2]: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline = 0.1 mmol: 0.01 mmol: 0.01 mmol), add 1 mL of acetonitrile, and then add 83 μL of concentrated hydrochloric acid (HCl) (1.0 mmol). Stir the reaction under a 365 nm ultraviolet light source for about 36-48 hours.

[0031] Step 2: After the reaction is complete, add 10 mL of water and a small amount of ethyl acetate to the reaction system for extraction. The aqueous phase is extracted three times with 10 mL of ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, filter, concentrate the organic phase, and separate and purify by rapid column chromatography to obtain the target chlorinated aromatic ring product b.

[0032] In step 1 of this invention, the molar ratio of the brominated aromatic compound to the metal catalyst, ligand, and chlorine source is 1:0.1:0.1:10, and the amount of solvent acetonitrile has little effect on the reaction yield.

[0033] In step 1 of this invention, the chlorination reaction is completed within 36 to 48 hours, and extending the reaction time does not significantly reduce or increase the yield.

[0034] The embodiments of the present invention are described in detail below. These embodiments are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0035] Example 1

[0036]

[0037] 1) At room temperature, 1a (23.2 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 12.6 mg of the target product as a colorless liquid, with a yield of 93%. The product structure was confirmed by NMR spectroscopy.

[0038] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, CDCl3) δ7.57 (ddd, J=7.4, 2.2, 1.1Hz, 2H), 7.54-7.50 (m, 2H), 7.48-7.40 (m, 4H), 7.40-7.35 (m, 1H). 13 C NMR (101MHz, CDCl3) δ140.0, 139.7, 133.4, 128.9, 128.9, 128.4, 127.6, 127.0.

[0039] Example 2

[0040]

[0041] 1) At room temperature, 2a (19.0 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 13.9 mg of the target product, with a yield of 95%. The product structure was confirmed by NMR spectroscopy.

[0042] 2) The characterization data of the obtained products are as follows: ¹H NMR (400MHz, Chloroform-d) δ 7.47-7.41 (m, 2H), 7.20 (dd, J = 6.0, 3.6Hz, 2H). ¹³C NMR (101MHz, CDCl₃) δ 132.5, 130.5, 127.7.

[0043] Example 3

[0044]

[0045] 1) At room temperature, 3a (17.4 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)2 (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 9.7 mg of the target product as a colorless liquid, with a yield of 75%. The product structure was confirmed by NMR spectroscopy.

[0046] 2) The characterization data of the obtained products are as follows: 1 H NMR (400MHz, CDCl3) δ7.41-7.17(m, 2H), 7.10-6.90(m, 2H). 13 C NMR (101MHz, CDCl3) δ162.5, 160.1, 130.0, 129.9, 129.1, 129.1, 116.8, 116.6. 19F NMR (376MHz, CDCl3) δ-115.9.

[0047] Example 4

[0048]

[0049] 1) At room temperature, 4a (20.8 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 14.3 mg of the target product as a colorless liquid, with a yield of 87%. The product structure was confirmed by NMR spectroscopy.

[0050] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.31 (dd, J=8.9, 5.4Hz, 1H), 7.11 (dd, J=8.2, 2.9Hz, 1H), 6.85 (ddd, J=8.9, 7.6, 2.9Hz, 1H). 13 C NMR (151MHz, CDCl3) δ161.7, 160.0, 133.4, 133.29, 131.1, 128.0, 117.8, 115.2, 115.1. 19 F NMR (565MHz, CDCl3) δ-113.3.

[0051] Example 5

[0052]

[0053] 1) At room temperature, 5a (20.4 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 13.6 mg of the target product as a colorless liquid, with a yield of 85%. The product structure was confirmed by NMR spectroscopy.

[0054] 2) The characterization data of the obtained products are as follows: 1 H NMR (400MHz, Chloroform-d) δ7.40-7.34 (m, 1H), 7.16 (d, J=1.7Hz, 2H), 2.36 (s, 3H). 13 C NMR (101MHz, CDCl3) δ134.9, 134.6, 131.9, 131.6, 128.8, 126.8, 19.5.

[0055] Example 6

[0056]

[0057] 1) At room temperature, 6a (20.4 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After the reaction was confirmed by TLC, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 14.4 mg of the target product as a colorless liquid, with a yield of 90%. The product structure was confirmed by NMR spectroscopy.

[0058] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.32-7.21 (m, 2H), 7.13 (dd, J=2.5, 0.7Hz, 1H), 2.37 (s, 3H). 13C NMR (151MHz, CDCl3) δ137.7, 132.6, 132.1, 130.7, 130.0, 127.1, 20.0.

[0059] Example 7

[0060]

[0061] 1) At room temperature, 7a (20.4 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 14.6 mg of the target product as a colorless liquid, with a yield of 91%. The product structure was confirmed by NMR spectroscopy.

[0062] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.14-7.05 (m, 2H), 6.90 (t, J=8.8Hz, 1H), 3.89 (d, J=0.9Hz, 3H). 13 C NMR (151MHz, CDCl3) δ153.0, 151.3, 125.2, 124.2, 116.9, 116.8, 114.1, 56.41. 19 F NMR (565MHz, CDCl3) δ-132.2.

[0063] Example 8

[0064]

[0065] 1) At room temperature, 8a (17.0 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 11.0 mg of the target product as a colorless liquid, with a yield of 87%. The product structure was confirmed by NMR spectroscopy.

[0066] 2) The characterization data of the obtained products are as follows: 1 H NMR (400MHz, Chloroform-d) δ7.29-7.23 (m, 2H), 7.13 (d, J=8.1Hz, 2H), 2.36 (s, 3H). 13 C NMR (101MHz, CDCl3) δ136.2, 131.1, 130.3, 128.3, 20.8.

[0067] Example 9

[0068]

[0069] 1) At room temperature, 9a (21.2 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 14.3 mg of the target product as a colorless liquid, with a yield of 85%. The product structure was confirmed by NMR spectroscopy.

[0070] 2) The characterization data of the obtained products are as follows: 11 H NMR (600MHz, Chloroform-d) δ7.35 (d, J = 8.7Hz, 2H), 7.30 (d, J = 8.6Hz, 2H), 1.35 (s, 9H). 13C NMR (151MHz, CDCl3) δ149.6, 131.1, 128.1, 126.7, 34.5, 31.3.

[0071] Example 10

[0072]

[0073] 1) At room temperature, 10a (22.6 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added to a 10 mL quartz reaction flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The reaction was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After the reaction was confirmed to be complete by TLC monitoring, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 14.6 mg of the target product as a colorless liquid, with a yield of 80%.

[0074] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.17-7.13 (m, 2H), 7.04-7.00 (m, 2H), 2.51-2. 46 (m, 2H), 1.54-1.47 (m, 2H), 1.27-1.19 (m, 4H), 0.81 (tt, J=7.1, 0.8Hz, 3H). 13 C NMR (151MHz, CDCl3) δ141.3, 131.2, 129.7, 128.3, 35.3, 31.4, 31.1, 22.5, 14.0.

[0075] Example 11

[0076]

[0077] 1) At room temperature, 11a (18.6 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 11.9 mg of the target product as a colorless liquid, with a yield of 84%. The product structure was confirmed by NMR spectroscopy.

[0078] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.39 (dt, J=7.8, 1.3Hz, 1H), 7.25 (ddd, J=8.2, 7.4, 1.6Hz, 1H), 6.99-6.88 (m, 2H), 3.92 (d, J=1.0Hz, 3H). 13 C NMR (151MHz, CDCl3) δ155.0, 130.2, 127.7, 122.4, 121.2, 112.1, 112.0, 56.0.

[0079] Example 12

[0080]

[0081] 1) At room temperature, 12a (18.4 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 11.5 mg of the target product as a colorless liquid, with a yield of 82%. The product structure was confirmed by NMR spectroscopy.

[0082] 2) The characterization data of the obtained products are as follows: 1H NMR (600MHz, Chloroform-d) δ7.31-7.21 (m, 1H), 7.07 (d, J=2.3Hz, 1H), 7.00-6.92 (m, 1H), 2.37 (s, 3H), 2.32 (s, 3H). 13 C NMR (151MHz, CDCl3) δ136.3, 135.6, 131.7, 131.2, 128.7, 127.7, 20.7, 19.9.

[0083] Example 13

[0084]

[0085] 1) At room temperature, 13a (17.0 mg, 0.1 mmol), 2,9-didimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 10.5 mg of the target product as a colorless liquid, with a yield of 83%. The product structure was confirmed by NMR spectroscopy.

[0086] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.39 (dt, J=7.7, 1.7Hz, 1H), 7.30-7.25 (m, 1H), 7.24-7.13 (m, 2H), 2.44 (d, J=1.9Hz, 3H). 13 C NMR (151MHz, CDCl3) δ136.0, 134.3, 130.9, 129.0, 127.1, 126.5, 20.0.

[0087] Example 14

[0088]

[0089] 1) At room temperature, 14a (19.8 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 12.3 mg of the target product as a colorless liquid, with a yield of 80%. The product structure was confirmed by NMR spectroscopy.

[0090] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.39 (ddt, J=7.9, 3.4, 1.5Hz, 1H), 7.35 (dq, J=6.2, 2.0Hz, 1 H), 7.30-7.26 (m, 1H), 7.16 (tt, J=7.5, 1.9Hz, 1H), 3.52-3.43 (m, 1H), 1.34-1.28 (m, 6H). 13 C NMR (151MHz, CDCl3) δ145.7, 133.4, 129.4, 126.9, 126.8, 126.6, 30.1, 22.6.

[0091] Example 15

[0092]

[0093] 1) At room temperature, 15a (21.2 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 13.8 mg of the target product as a colorless liquid, with a yield of 82%. The product structure was confirmed by NMR spectroscopy.

[0094] 2) The characterization data of the obtained products are as follows: 1H NMR (600MHz, Chloroform-d) δ7.31 (dt, J=7.9, 1.7Hz, 1H), 7.23 (dt, J=7.9, 1.6Hz, 1H), 7.12-7.05 (m, 1H), 7.05-6.97 (m, 1H), 1.38 (d, J=2.8Hz, 9H). 13 C NMR (151MHz, CDCl3) δ146.4, 133.7, 131.9, 127.7, 127.1, 126.6, 36.0, 29.6.

[0095] Example 16

[0096]

[0097] 1) At room temperature, 16a (18.4 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 12.0 mg of the target product as a colorless liquid, with a yield of 86%. The product structure was confirmed by NMR spectroscopy.

[0098] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.15-7.05 (m, 3H), 2.43 (d, J=1.0Hz, 6H). 13 C NMR (151MHz, CDCl3) δ134.6, 128.4, 125.9, 20.7.

[0099] Example 17

[0100]

[0101] 1) At room temperature, 17a (19.8 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 11.9 mg of the target product as a colorless liquid, with a yield of 77%. The product structure was confirmed by NMR spectroscopy.

[0102] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ6.94 (s, 2H), 2.39 (s, 6H), 2.30 (s, 3H). 13 C NMR (151MHz, CDCl3) δ135.8, 135.5, 131.5, 129.1, 20.6, 20.5.

[0103] Example 18

[0104]

[0105] 1) At room temperature, 18a (20.6 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 14.1 mg of the target product as a colorless liquid, with a yield of 87%. The product structure was confirmed by NMR spectroscopy.

[0106] 2) The characterization data of the obtained products are as follows: 1H NMR (600MHz, Chloroform-d) δ8.34 (dq, J=8.4, 0.9Hz, 1H), 7.92-7.85 (m, 1H), 7.81 (dd, J=8.1, 1.2Hz, 1H), 7.67-7.52 (m, 3H), 7.43 (dd, J=8.2, 7.4Hz, 1H). 13 C NMR (151MHz, CDCl3) δ134.5, 131.9, 130.8, 128.2, 127.1, 127.0, 126.6, 126.1, 125.7, 124.7.

[0107] Example 19

[0108]

[0109] 1) At room temperature, 19a (20.6 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 13.0 mg of the target product as a colorless liquid, with a yield of 80%. The product structure was confirmed by NMR spectroscopy.

[0110] 2) The characterization data of the obtained products are as follows: 1 H NMR (400MHz, Chloroform-d) δ7.85-7.72 (m, 4H), 7.53-7.38 (m, 3H). 13 C NMR (101MHz, CDCl3) δ134.0, 131.6, 131.5, 129.5, 127.8, 127.0, 126.9, 126.75, 126.6, 126.1.

[0111] Example 20

[0112]

[0113] 1) At room temperature, 20a (23.2 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 g / L, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 16.9 mg of the target product as a colorless liquid, with a yield of 90%. The product structure was confirmed by NMR spectroscopy.

[0114] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chl) o roform-d) δ7.51 (dd, J=7.8, 1.5Hz, 1H), 7.50-7.46 (m, 4H), 7.44-7.41 (m, 1H), 7.39 (dd, J=7.5, 2.0Hz, 1H), 7.37-7.30 (m, 2H). 13 C NMR (151 MHz, CDCl3) δ140.5, 139.4, 132.5, 131.4, 129.9, 129.4, 128.5, 128.0, 127.6, 126.8.

[0115] Example 21

[0116]

[0117] 1) At room temperature, 21a (30.8 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 24.0 mg of the target product as a colorless liquid, with a yield of 91%. The product structure was confirmed by NMR spectroscopy.

[0118] 2) The characterization data of the obtained products are as follows: 1H NMR (600MHz, Chloroform-d) δ7.62-7.59 (m, 2H), 7.58-7.54 (m, 4H), 7.51-7.47 (m, 2H), 7.39 (dd, J=8.4, 7.0Hz, 2H), 7.36-7.33 (m, 2H), 7.30 (d, J=7.4Hz, 1H). 13 C NMR (151MHz, CDCl3) δ140.5, 139.1, 138.8, 133.4, 129.0, 128.8, 128.3, 127.6, 127.5, 127.3, 127.0.

[0119] Example 22

[0120]

[0121] 1) At room temperature, 22a (25.6 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 18.9 mg of the target product as a colorless liquid, with a yield of 89%. The product structure was confirmed by NMR spectroscopy.

[0122] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ 8.75-8.64 (m, 2H), 8.46-8.41 (m, 1H), 7.90 (s, 1H), 7.83 (dq, J=7.8, 1.6Hz, 1H), 7.77-7.71 (m, 2H), 7.71-7.61 (m, 2H). 13 C NMR (151MHz, CDCl3) δ131.7, 131.3, 130.5, 129.4, 129.4, 127.8, 127.4, 127.3, 127.2, 126.8, 126.4, 125.2, 122.8, 122.7.

[0123] Example 23

[0124]

[0125] 1) At room temperature, 23a (31.0 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 18.4 mg of the target product as a colorless liquid, with a yield of 83%. The product structure was confirmed by NMR spectroscopy.

[0126] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.39 (d, J=8.6Hz, 4H), 7.34-7.30 (m, 4H). 13 C NMR (151MHz, CDCl3) δ138.4, 133.7, 129.0, 128.2.

[0127] Example 24

[0128]

[0129] 1) At room temperature, 24a (32.6 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 20.2 mg of a colorless liquid, with a yield of 85%. The product structure was confirmed by NMR spectroscopy.

[0130] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.33 (d, J=8.9Hz, 4H), 6.96 (d, J=8.9Hz, 4H). 13 C NMR (151MHz, CDCl3) δ155.5, 129.8, 128.6, 120.1.

[0131] Example 25

[0132]

[0133] 1) At room temperature, 25a (15.7 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 10.5 mg of the target product as a colorless liquid, with a yield of 93%. The product structure was confirmed by NMR spectroscopy.

[0134] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ8.38 (ddd, J=5.0, 2.1, 0.9Hz, 1H), 7.65 (tdd, J=7.4, 2.1, 0.9Hz, 1H), 7.35-7.19 (m, 2H). 13 C NMR (151MHz, CDCl3) δ151.4, 149.6, 138.7, 124.4, 122.2.

[0135] Example 26

[0136] 1) At room temperature, 26a (19.1 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 14.0 mg of the target product as a colorless liquid, with a yield of 95%. The product structure was confirmed by NMR spectroscopy.

[0137] 2) The characterization data of the obtained products are as follows: 1H NMR (600MHz, Chloroform-d) δ 8.31 (dd, J=4.7, 1.7Hz, 1H), 7.79 (dd, J=7.9, 1.7Hz, 1H), 7.22 (dd, J=7.9, 4.7Hz, 1H). 13 C NMR (151MHz, CDCl3) δ149.2, 147.2, 138.7, 130.6, 123.2.

[0138] Example 27

[0139]

[0140] 1) At room temperature, 27a (21.5 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 15.4 mg of the target product as a colorless liquid, with a yield of 90%. The product structure was confirmed by NMR spectroscopy.

[0141] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ8.55 (dd, J=5.1, 0.8Hz, 1H), 7.97-7.68 (m, 2H), 3.98 (s, 3H). 13 C NMR (151MHz, CDCl3) δ164.2, 152.4, 150.4, 140.2, 124.1, 121.6, 53.0.

[0142] Example 28

[0143]

[0144] 1) At room temperature, 28a (18.2 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 12.0 mg of the target product as a colorless liquid, with a yield of 87%. The product structure was confirmed by NMR spectroscopy.

[0145] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ8.61 (dd, J=5.0, 0.9Hz, 1H), 7.61 (t, J=1.0Hz, 1H), 7.49 (dd, J=5.0, 1.3Hz, 1H). 13 C NMR (151 MHz,, CDCl3) δ152.6, 150.8, 126.3, 123.7, 122.9, 115.1.

[0146] Example 29

[0147]

[0148] 1) At room temperature, 29a (20.2 mg, 0.1 mmol), 2,9-dimethyl-4,7-phenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 14.4 mg of the target product as a colorless liquid, with a yield of 91%. The product structure was confirmed by NMR spectroscopy.

[0149] 2) The characterization data of the obtained products are as follows: 1H NMR (600MHz, Chloroform-d) δ9.32-9.18 (m, 1H), 8.46 (dd, J=8.7, 2.8Hz, 1H), 7.57 (dd, J=8.7, 0.6Hz, 1H). 13 C NMR (151MHz, CDCl3) δ157.0, 145.4, 133.6, 124.8.

[0150] Example 30

[0151]

[0152] 1) At room temperature, 30a (17.5 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 11.8 mg of the target product as a colorless liquid, with a yield of 90%. The product structure was confirmed by NMR spectroscopy.

[0153] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ8.23 (dd, J=4.8, 1.7Hz, 1H), 7.50 (td, J=8.1, 1.5Hz, 1H), 7.28 (ddd, J=7.2, 4.7, 3.6Hz, 1H). 13 C NMR (151MHz, CDCl3) δ155.7, 154.0, 144.7, 144.7, 139.1, 139.0, 124.5, 124.4, 123.7. 19 F NMR (565MHz, CDCl3) δ-118.2.

[0154] Example 31

[0155]

[0156] 1) At room temperature, 31a (18.2 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 12.1 mg of the target product as a colorless liquid, with a yield of 88%. The product structure was confirmed by NMR spectroscopy.

[0157] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ 8.70 (dd, J=2.4, 0.8Hz, 1H), 7.94 (dd, J=8.3, 2.3Hz, 1H), 7.50 (dd, J=8.4, 0.8Hz, 1H). 13 C NMR (151MHz, CDCl3) δ155.5, 152.6, 141.3, 124.9, 115.6, 108.8.

[0158] Example 32

[0159]

[0160] 1) At room temperature, 32a (23.5 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 16.2 mg of the target product as a colorless liquid, with a yield of 85%. The product structure was confirmed by NMR spectroscopy.

[0161] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MH) z, Chloroform-d) δ8.47 (d, J=2.5Hz, 1H), 7.78 (dd, J=8.4, 2.5Hz, 1H), 7.34-7.15 (m, 1H). 13 C NMR (151MHz, CDCl3) δ150.7, 150.0, 141.2, 125.6, 119.1.

[0162] Example 33

[0163]

[0164] 1) At room temperature, 33a (15.8 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 10.4 mg of the target product as a colorless liquid, with a yield of 91%. The product structure was confirmed by NMR spectroscopy.

[0165] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ8.47 (d, J=2.5Hz, 1H), 7.78 (dd, J=8.4, 2.5Hz, 1H), 7.34-7.15 (m, 1H). 13 C NMR (151MHz, CDCl3) δ150.7, 150.0, 141.2, 125.6, 119.1.

[0166] Example 34

[0167]

[0168] 1) At room temperature, 34a (23.6 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 12.3 mg of the target product as a colorless liquid, with a yield of 83%. The product structure was confirmed by NMR spectroscopy.

[0169] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ8.40 (s, 2H). 13 C NMR (151MHz, CDCl3) δ147.5, 143.7.

[0170] Example 35

[0171]

[0172] 1) At room temperature, 35a (20.7 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 g / L, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 14.3 mg of the target product as a colorless liquid, with a yield of 88%. The product structure was confirmed by NMR spectroscopy.

[0173] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ 8.08-7.86 (m, 2H), 7.76-7.60 (m, 2H), 7.47 (ddd, J=8.1, 6.9, 1.2Hz, 1H), 7.34-7.10 (m, 1H). 13 C NMR (151MHz,

[0174] CDCl3) δ150.5, 147.6, 139.0, 130.6, 128.3, 127.5, 127.0, 126.7, 122.3.

[0175] Example 36

[0176]

[0177] 1) At room temperature, 36a (20.7 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 11.4 mg of the target product as a colorless liquid, with a yield of 70%. The product structure was confirmed by NMR spectroscopy.

[0178] 2) The characterization data of the obtained products are as follows: 1 H NMR (400MHz, Chloroform-d) δ8.94 (dd, J=4.2, 1.5Hz, 1H),

[0179] 8.05 (dd, J=8.3, 1.5Hz, 1H), 7.72 (d, J=7.5Hz, 1H), 7.62 (d, J=8.1Hz, 1H), 7.40-7.27 (m, 2H). 13 C NMR (101MHz, CDCl3) δ150.7, 144.0, 136.3, 133.0, 129.3, 129.3, 126.8126.22, 121.6.

[0180] Example 37

[0181]

[0182] 1) At room temperature, 37a (21.3 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 15.5 mg of the target product as a colorless liquid, with a yield of 92%. The product structure was confirmed by NMR spectroscopy.

[0183] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ 8.00-7.94 (m, 1H), 7.79 (dd, J=8.0, 1.4Hz, 1H), 7.50 (ddd, J=8.3, 7.2, 1.2Hz, 1H), 7.46-7.40 (m, 1H). 13 C NMR (151MHz, CDCl3) δ157.5, 129.2, 125.3, 115.7, 63.7, 14.7.

[0184] Example 38

[0185]

[0186] 1) At room temperature, 38a (16.3 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 10.7 mg of the target product as a colorless liquid, with a yield of 90%. The product structure was confirmed by NMR spectroscopy.

[0187] 2) The characterization data of the obtained products are as follows: 1H NMR (600MHz, Chloroform-d) δ7.58 (dd, J=3.6, 2.6Hz, 1H), 7.25 (dd, J=3.7, 1.7Hz, 1H). 13 C NMR (151MHz, CDCl3) δ152.0, 141.5, 121.1.

[0188] Example 39

[0189]

[0190] 1) At room temperature, 39a (16.2 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 11.2 mg of the target product as a colorless liquid, with a yield of 95%. The product structure was confirmed by NMR spectroscopy.

[0191] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.13 (dd, J=5.6, 1.5Hz, 1H), 6.95 (dd, J=3.7, 1.5Hz, 1H), 6.91 (dd, J=5.6, 3.7Hz, 1H). 13 C NMR (151MHz, CDCl3) δ130.0, 126.6, 126.0, 124.1.

[0192] Example 40

[0193]

[0194] 1) At room temperature, 40a (17.6 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 12.1 mg of the target product as a colorless liquid, with a yield of 92%. The product structure was confirmed by NMR spectroscopy.

[0195] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.04 (d, J=5.6Hz, 1H), 6.81 (d, J=5.6Hz, 1H), 2.23 (s, 3H). 13 C NMR (151MHz, CDCl3) δ134.2, 128.8, 121.8, 13.4.

[0196] Example 41

[0197]

[0198] 1) At room temperature, 41a (21.2 mg, 0.1 mmol), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (3.60 mg, 0.01 mmol), and VO(acac)₂ (2.65 mg, 0.01 mmol) were added sequentially to a 10 mL quartz flask. After adding 1 mL of MeCN, HCl (83 μL, 1.0 mmol) was added. The mixture was then stirred uniformly at room temperature under 365 nm UV light for approximately 48 hours. After TLC monitoring confirmed the reaction was complete, 10 mL of water was added to the reaction system, followed by extraction with 3 × 10 mL of ethyl acetate. The organic phases were combined, dried, concentrated, and purified by rapid column chromatography to obtain 15.1 mg of the target product as a colorless liquid, with a yield of 90%. The product structure was confirmed by NMR spectroscopy.

[0199] 2) The characterization data of the obtained products are as follows: 1 H NMR (600MHz, Chloroform-d) δ7.70 (ddt, J=26.9, 8.0, 0.9Hz, 2H), 7.34-7.24 (m, 2H), 7.15 (s, 1H). 13C NMR (151MHz, CDCl3) δ138.3, 136.0, 125.2, 124.8, 123.0, 122.8, 121.8, 121.1, 120.7.

[0200] Although the invention has been described by way of examples, those skilled in the art will understand that various modifications, equivalent substitutions, or improvements can be made without departing from the basic concept of the invention. All such modifications, substitutions, or improvements should fall within the scope of protection claimed by the invention.

Claims

1. A light-mediated halogen exchange method for brominated aromatic hydrocarbons to chloroaromatic hydrocarbons using hydrochloric acid as the chlorine source, characterized in that, The method involves adding a metal catalyst, a brominated aromatic compound, and a chlorine source to a solvent, and reacting them under near-visible light irradiation. After the reaction, the compound is processed to obtain a chlorinated substituted aromatic ring compound as shown in the figure. The reaction formula is as follows: Wherein R is one or more of the following, including but not limited to chlorine (-Cl), fluorine (-F), hydrogen (-H), phenyl (-Ph), trifluoromethyl (-CF3), methoxy (-OMe), tert-butyl (-t-Bu), methyl (-Me), or the aromatic ring is replaced by other aromatic heterocycles such as thiophene, thiazole, benzothiophene, benzothiazole, etc.

2. The method for photo-mediated halogen exchange of brominated aromatics to chloroaromatics using hydrochloric acid as a chlorine source according to claim 1, characterized in that, The molar ratio of the brominated aromatic compound to the metal catalyst, ligand, and chlorine source is 1:(0.1-0.3):(0.1-0.3):10 and related proportions.

3. The method for photo-mediated halogen exchange of brominated aromatics to chloroaromatics using hydrochloric acid as a chlorine source according to claim 1, characterized in that, The metal catalysts mentioned include, but are not limited to, transition metal catalysts such as vanadium acetylacetonate, vanadium sulfate, ferric chloride, copper chloride, cerium chloride, nickel chloride, and lanthanum chloride.

4. The method for photo-mediated halogen exchange of brominated aromatics to chloroaromatics using hydrochloric acid as a chlorine source according to claim 1, characterized in that, The reaction temperature includes, but is not limited to, 0-30°C, preferably 25°C, or heating.

5. The method for photo-mediated halogen exchange of brominated aromatics to chloroaromatics using hydrochloric acid as a chlorine source according to claim 1, characterized in that, The concentration of the reaction system includes, but is not limited to, 0.01 mol per liter to 100 mol per liter, preferably 0.1 mol per liter.

6. The method for photo-mediated halogen exchange of brominated aromatics to chloroaromatics using hydrochloric acid as a chlorine source according to claim 1, characterized in that, The reactive light source includes, but is not limited to, 365-765 nanometers, preferably 365-465 nanometers.

7. The method for photo-mediated halogen exchange of brominated aromatics to chloroaromatics using hydrochloric acid as a chlorine source according to claim 1, characterized in that, The substituent R of the reaction substrate, bromoaromatic compound a, includes, but is not limited to, chlorine (-Cl), fluorine (-F), hydrogen (-H), phenyl (-Ph), trifluoromethyl (-CF3), methoxy (-OMe), tert-butyl (-t-Bu), methyl (-Me), or the aromatic ring may be replaced by one or more of other aromatic heterocyclic groups such as thiophene, thiazole, benzothiophene, and benzothiazole. It may also include one or more of chlorine, fluorine, hydrogen, ketone, trifluoromethyl, trifluoromethoxy, cyano, methyl, or quinoline groups.

8. The method for photo-mediated halogen exchange of brominated aromatics to chloroaromatics using hydrochloric acid as a chlorine source according to claim 1, characterized in that, The reaction solvent includes, but is not limited to, one or more of acetonitrile, acetone, ethyl acetate, and N,N-dimethylformamide, with acetonitrile being preferred.

9. The method for photo-mediated halogen exchange of brominated aromatics to chloroaromatics using hydrochloric acid as a chlorine source according to claim 1, characterized in that, The reaction time is 36-48 hours, or other durations until the raw materials have reacted completely.

10. The photo-mediated halogen exchange method for brominated aromatic hydrocarbons to chloroaromatic hydrocarbons using hydrochloric acid as the chlorine source according to claim 1, characterized in that, The waste chlorine sources mentioned include, but are not limited to, hydrochloric acid (HCl), chloroform (CHCl3), N-chlorosuccinimide (NCS), magnesium chloride (MgCl2), or dichloroethane (DCE).

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