A diaromatic formyl tetrahalobenzene compound, a preparation method and application thereof

Abstract

The application belongs to the field of organic photoelectric materials, and particularly relates to a kind of diary aromatic formyl tetrahalogen benzene compound and preparation method and application.The diary aromatic formyl tetrahalogen benzene compound is tetrahalogen benzene dimethyl acid, which is synthesized by acyl chlorination and Friedel-Crafts acylation, and the novel compound can effectively separate photo-generated charges, promote efficient transmission of excited state electrons or hydrogen, improve photo quantum efficiency and catalytic efficiency, and can be applied to the fields of luminescent materials, photocatalysis, photocuring, fluorescent probes and the like as photosensitive material, photoelectric material, fluorescent probe and the like, for example, applied to photocatalytic carbon-hydrogen bond activation reaction, and has wide market application prospect.Meanwhile, the preparation method provided by the application is simple in operation, mild in condition, simple in reagent and substrate, economical and inexpensive, easy to obtain, efficient in reaction, wide in substrate applicability, and has wide industrial application prospect.

Description

Technical Field

[0001] This invention belongs to the field of organic optoelectronic materials, specifically relating to a diaromatic formyl tetrahalobenzene compound, its preparation method, and its application. Background Technology

[0002] Diaryl ketones are the simplest and cheapest organic optoelectronic materials. Their key characteristic is that after absorbing light energy, the carbonyl group can be directly excited, undergoing an intersystem crossing process to reach a triplet excited state. Photoexcited ketone catalysts possess relatively high oxidation potentials and triplet excited-state energies, along with low bond dissociation energies. Therefore, they can facilitate the smooth conversion of many organic reactions through hydrogen atom transfer (HAT), energy transfer (ET), or single electron transfer (SET) pathways, playing a crucial role in organic photochemistry, particularly in photopolymerization where they have achieved large-scale industrial applications. In the area of ​​photocatalytic CH bond activation reactions, research over the past decade has revealed that diaryl ketones can completely replace noble metal photosensitizers and other organic photosensitizers to achieve CH bond dehydrogenation functionalization and coupling reactions, demonstrating very broad application prospects.

[0003] However, existing diaryl ketone photosensitizers for CH bond activation reactions generally suffer from the following problems: 1. A large excess of CH bond substrate is required, sometimes even requiring the substrate as the solvent for the reaction to proceed; 2. The amount of photocatalyst added is usually more than 20% of the substrate, and sometimes even as high as 1.5 times. These data indicate that current diaryl ketone photosensitizers have low quantum efficiency, and only by increasing the concentration of substrate and photosensitizer can the utilization rate of light energy be improved. This severely limits the universality of photocatalytic CH activation and also results in photocatalyst waste. Therefore, the research and development of efficient and inexpensive diaryl ketone photosensitive dyes remains a key research topic in photocatalysis. Effectively separating photogenerated charges and promoting the efficient transfer of excited-state electrons or hydrogen through the structural design and optimization of photocatalysts is crucial to improving the quantum efficiency of photocatalytic reactions. Summary of the Invention

[0004] The purpose of this invention is to solve the problems of the prior art and provide a high-efficiency and low-cost diaryl ketone photosensitive dye that can effectively perform photogenerated charge separation to promote the efficient transfer of excited-state electrons or hydrogen, improve the quantum efficiency of photocatalytic reactions, and be applied to photocatalytic carbon-hydrogen bond activation reactions.

[0005] The technical solution adopted by this invention to solve its technical problem is:

[0006] One objective of this invention is to provide a diaromatic formyl tetrahalobenzene compound, the structural formula of which is shown in formula (I):

[0007]

[0008] In formula (I), X is at least one of fluorine and chlorine, R is an aromatic formyl group, and Ar is a substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted thiophene group, wherein the substituent is selected from at least one of C1-C12 alkyl, C1-C6 alkoxy, hydroxyl, or halogen group (including fluorine, chlorine, bromine, and iodine); R is positioned ortho, meta, or para on the benzene ring of the compound and exists alone, constituting a tetrahalobenzene compound of ortho, meta, or para-diaromatic formyl group.

[0009] Preferably, the diaromatic formyl tetrahalobenzene compound is a meta-diaromatic formyl tetrafluorobenzene compound, the structure of which is shown in formula (II):

[0010]

[0011] In formula (II), Ar is phenyl, C1-C12 alkyl-substituted phenyl, or naphthyl.

[0012] Preferably, the diaromatic formyl tetrahalobenzene compound is a m-(2,4,6-trialkylphenyl)formyl tetrafluorobenzene compound, the structure of which is shown in formula (III):

[0013]

[0014] In formula (III), R1 is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0015] A second objective of this invention is to provide a method for preparing the above-mentioned diaromatic formyl tetrahalobenzene compound, the method comprising: reacting tetrahalophthalic acid with a chlorinating reagent to obtain a tetrahalophthaloyl chloride intermediate; dissolving an aromatic compound Ar-H in an organic solvent under an inert gas atmosphere, then adding the tetrahalophthaloyl chloride intermediate dropwise to the reaction system, and performing a Friedel-Crafts acylation reaction in the presence of a catalyst to obtain the target product;

[0016] Preferably, the acyl chloride reaction conditions are: stirring at 0℃ to 150℃ for 1 to 120 h;

[0017] Preferably, the Friedel-Crafts acylation reaction conditions are -20℃ to 100℃ for 1 to 120 h.

[0018] Preferably, the reaction formula for the preparation method of the diaromatic formyl tetrahalobenzene compound is shown below:

[0019]

[0020] Wherein, formula (a) is a tetrahalophthalic acid, in which the benzene ring includes four halogen groups X and two carboxyl groups, and the two carboxyl groups are in the ortho, meta or para position; formula (b) is a tetrahalophthaloyl chloride intermediate; formula (c) is an aromatic compound Ar-H; formula (I) is the target product diaromaticformyl tetrahalobenzene compound, in which the benzene ring includes four halogen groups X and two aromaticformyl groups;

[0021] Wherein, X is at least one of fluorine and chlorine.

[0022] Ar represents phenyl (substituted or unsubstituted), naphthyl (substituted or unsubstituted), or thiophene (substituted or unsubstituted).

[0023] The substituent is selected from at least one of C1-C12 alkyl, C1-C6 alkoxy, hydroxyl, and halogen groups; the halogen group includes at least one of fluorine, chlorine, bromine, and iodine.

[0024] R is an aromatic formyl group, and R is positioned ortho, meta, or para on the benzene ring of the compound and exists alone, forming a tetrahalobenzene compound with ortho, meta, or para-diaromatic formyl groups.

[0025] Preferably, the preparation method specifically includes: reacting tetrahalophthalic acid with a chlorinating agent at 0℃~150℃ for 1~120h with stirring; removing the chlorinating agent by distillation; and then distilling off the tetrahalophthaloyl chloride intermediate under reduced pressure; dissolving the aromatic compound Ar-H in an organic solvent under inert gas protection; gradually adding the tetrahalophthaloyl chloride intermediate; adding a catalyst; and reacting at -20℃~100℃ for 1~120h; and then post-processing the reaction solution to obtain the target product.

[0026] Preferably, the temperature for distilling off the greening reagent is 50℃-150℃; the temperature for distilling off the tetrahalophthaloyl chloride intermediate under reduced pressure is 50-150℃, and the pressure is 50-500pa.

[0027] Preferably, the molar ratio of the tetrahalophthalic acid to the chlorinating reagent is 1:1 to 200.

[0028] Preferably, the chlorinating agent is one or a mixture of two or more of thionyl chloride, oxaloyl chloride, phosgene, and triphosgene in any proportion.

[0029] Preferably, the inert gas is one or a mixture of two or more of nitrogen, helium, and argon in any proportion.

[0030] Preferably, the organic solvent is one or a mixture of two or more of the following: dichloromethane, dichloroethane, chloroform, tetrahydrofuran, 1,4-dioxane, diethyl ether, methyl tert-butyl ether, and C4-C8 alkanes in any proportion. More preferably, the volumetric amount of the organic solvent used is 1-1000 mL / g based on the mass of the tetrahalophthaloyl chloride intermediate.

[0031] Preferably, the catalyst is one or a mixture of two or more of anhydrous aluminum trichloride, anhydrous ferric trichloride, anhydrous zinc dichloride, anhydrous titanium tetrachloride, and anhydrous tin tetrachloride in any proportion.

[0032] Preferably, the molar ratio of the tetrahalophthaloyl chloride intermediate, the aromatic compound, and the catalyst is 1:1 to 100:0.1 to 10.

[0033] Preferably, the dropping rate of the tetrahalophthaloyl chloride intermediate is 5 mL / min.

[0034] Preferably, the post-processing includes conventional purification steps such as extraction, drying to remove moisture, solvent removal, and washing.

[0035] Preferably, the stirring speed is 50-300 r / min, more preferably 60 r / min.

[0036] The third objective of this invention is to provide an application of the aforementioned diaromatic formyl tetrahalobenzene compound, which is used as a photosensitive material, optoelectronic material, fluorescent probe, etc., in the fields of luminescent materials, photocatalysis, photocuring, and fluorescent probes.

[0037] Preferably, the photocatalytic application of the diaromatic formyl tetrahalobenzene compound is used for photocatalytic activation of carbon-hydrogen bonds.

[0038] Preferably, the photocatalytic application of the diarylformyltetrahalobenzene compound includes: using the diarylformyltetrahalobenzene compound as a photosensitizer to photocatalyze the C(sp3)-H activation of toluene compounds under blue LED irradiation and C / C bond coupling with haloalkanes to obtain diarylmethane compound products; and using the diarylformyltetrahalobenzene compound as a photosensitizer to photocatalyze the C(sp3)-H activation of toluene compounds under blue LED irradiation and C / C bond coupling with carbon dioxide to obtain arylacetic acid compound products.

[0039] Preferably, the photocatalytic application of the diaromatic formyl tetrahalobenzene compound includes its use as a photosensitizer in the following photocatalytic reactions:

[0040]

[0041] Wherein R1 is at least one of hydrogen group, methyl group, etc., and is in at least one of the ortho, meta, or para positions with the methyl group in formula (d); R2 is at least one of cyano group, fluoro group, methyl group, trifluoromethyl group, etc., and is in at least one of the ortho or para positions with the bromo group in formula (e); X is one of C or N.

[0042] PS is a diaromatic formyl tetrahalobenzene compound as described in this invention.

[0043] This invention synthesizes diaromatic tetrahalobenzene compounds from tetrahalophthalic acid via acyl chloride and Friedel-Crafts acylation reactions. These compounds can effectively perform photogenerated charge separation to promote the efficient transfer of excited-state electrons or hydrogen, thereby improving quantum efficiency and catalytic efficiency. They can be applied to photocatalytic carbon-hydrogen bond activation reactions.

[0044] Compared with the prior art, the beneficial effects of the present invention are:

[0045] (1) The reagents and substrates of the present invention are simple, economical and inexpensive and readily available. The preparation method is simple, the reaction operation is mild and the reaction is highly efficient. The substrates have wide applicability and have broad prospects for industrial application.

[0046] (2) This invention synthesizes a series of novel diaromatic formyl tetrahalobenzene compounds, which can be applied to fields such as luminescent materials, photocatalysis, photocuring, and fluorescent probes, and have broad market application prospects. Detailed Implementation

[0047] The technical solution of the present invention will be further clearly and completely described below through specific embodiments. It should be understood that the embodiments described in this invention are implemented under the premise of the technical solution of the present invention, and detailed implementation methods and specific operation processes are given, but they are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0048] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, and the materials and reagents used in the examples are commercially available unless otherwise specified. In the following examples, the room temperature is 15℃-40℃, more preferably 25℃-30℃.

[0049] Example 1

[0050]

[0051] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. Once no liquid distilled off, the mixture was heated to 150 °C and distilled under reduced pressure to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3a (1.72 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was complete, 20 mL of water was added to the reaction mixture, followed by extraction with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. After solvent removal and washing with methanol, the target product 4a was obtained. The target product was a white solid with a yield of 94% and an HPLC purity of 99.2%. The post-processing steps in this embodiment are applicable to other embodiments.

[0052] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.90(d,J=7.7Hz,4H),7.70(t,J=7.6Hz,2H),7.56(d,J=7.4Hz,4H).

[0053] The high-resolution molecular weight of the obtained product was: (M+H) + =359.0612, molecular formula is C 20 H8F4O2.

[0054] Example 2

[0055]

[0056] 1b (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. Once no liquid distilled off, the mixture was heated to 150 °C and distilled under reduced pressure to obtain intermediate 2b (2.21 g), with a yield of 40.3%. Under nitrogen protection, 3a (1.72 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2b (2.72 g) was then gradually added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was complete, 20 mL of water was added to the reaction mixture, followed by extraction with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. After solvent removal and washing with methanol, the target product 4b was obtained. The target product was a white solid with a yield of 92% and an HPLC purity of 97.0%.

[0057] The obtained product was characterized by 1H NMR data as follows: 1H NMR (400MHz, Chloroform-d) δ 7.88 (d, J = 7.7Hz, 4H), 7.74 (t, J = 7.6Hz, 2H), 7.57 (d, J = 7.4Hz, 4H).

[0058] The high-resolution molecular weight of the obtained product was: (M+H) + =359.0612, molecular formula is C 20 H8F4O2.

[0059] Example 3

[0060]

[0061] 1c (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 100 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. Once no liquid distilled off, the mixture was heated to 150 °C and distilled under reduced pressure to obtain intermediate 2c (4.286 g), with a yield of 88.7%. Under nitrogen protection, 3a (1.72 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2c (2.72 g) was then gradually added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was complete, 20 mL of water was added to the reaction solution, followed by extraction with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. After solvent removal and washing with methanol, the target product 4c was obtained. The target product was a white solid with a yield of 93% and an HPLC purity of 94.6%.

[0062] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.94(d,J=7.0Hz,4H),7.72(d,J=7.5Hz,2H),7.59(t,J=7.8Hz,4H).

[0063] The high-resolution molecular weight of the obtained product was: (M+H) + =359.0612, molecular formula is C 20 H8F4O2.

[0064] Example 4

[0065]

[0066] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. After no liquid distilled off, the mixture was heated to 150 °C and distilled under vacuum to obtain 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3b (2.22 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The mixture was reacted at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. The solvent was removed, and the product was separated by column chromatography (EA:PE = 1:4) to obtain the target product 4d. The target product was a white solid with a yield of 90%.

[0067] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.93(t,J=6.9Hz,4H),7.25(dd,J=18.9,10.5Hz,4H).

[0068] The high-resolution molecular weight of the obtained product was: (M+H) + =395.0505, molecular formula is C 20 H8F6O2.

[0069] Example 5

[0070]

[0071] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. After no liquid distilled off, the mixture was heated to 150 °C and distilled under reduced pressure to obtain 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3c (2.52 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The mixture was reacted at 50 °C for 18 h. After the reaction was complete, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. The solvent was removed, and the product was separated by column chromatography (EA:PE = 1:4) to obtain the target product 4e. The target product was a white solid with a yield of 88%.

[0072] Products obtained 1 The HNMR data characterization is as follows: 1HNMR(400MHz,Chloroform-d)δ7.93(t,J=6.9Hz,4H),7.23(t,J=8.3Hz,4H).

[0073] Example 6

[0074]

[0075] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. After no liquid distilled off, the mixture was heated to 150 °C and distilled under vacuum to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3d (3.62 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The mixture was reacted at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. The solvent was removed, and the product was separated by column chromatography (EA:PE = 1:4) to obtain the target product 4f. The target product was a white solid with a yield of 76%.

[0076] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.93(t,J=6.9Hz,4H),7.23(t,J=8.3Hz,4H).

[0077] Example 7

[0078]

[0079] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated under reflux for 12 h, then cooled to room temperature. The thionyl chloride was removed by vacuum distillation. After no liquid distilled off, the mixture was heated to 150 °C and distilled under vacuum to obtain 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3e (2.15 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The mixture was reacted at room temperature for 18 h. After the reaction was complete, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. The solvent was removed, and the product was separated by column chromatography (EA:PE = 1:4) to obtain 4 g of the target product. The target product was a white solid with a yield of 98%.

[0080] Products obtained1 The HNMR data characterization is as follows: 1 HNMR (400MHz, Chloroform-d) δ7.52(d,J=7.5Hz,2H),7.46(d,J=7.9Hz,2H),7.39(d,J=7.5Hz,2H),7.35–7.26(m,2H),2.69(s,6H).

[0081] Example 8

[0082]

[0083] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to room temperature. The thionyl chloride was removed by vacuum distillation. After no liquid distilled off, the mixture was heated to 150 °C and distilled under reduced pressure to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3f (2.23 g), anhydrous dichloromethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The mixture was reacted at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. The solvent was removed, and the product was separated by column chromatography (EA:PE = 1:4) to obtain the target product. The target product was a white solid with a yield of 36%.

[0084] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.93(t,J=6.9Hz,4H),7.23(t,J=8.3Hz,4H).

[0085] Example 9

[0086]

[0087] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. After no liquid distilled off, the mixture was heated to 150 °C and distilled under reduced pressure to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3 g (2.32 g), anhydrous dichloromethane (30 mL), and anhydrous ferric chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The mixture was reacted at room temperature for 18 h. After the reaction was complete, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. The solvent was removed, and the product was separated by column chromatography (EA:PE = 1:4) to obtain the target product. The target product was a white solid with a yield of 88%.

[0088] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR (400MHz, Chloroform-d) δ7.73 (t, J = 6.9 Hz, 4H), 7.01 (t, J = 8.3 Hz, 4H), 3.81 (s, 6H).

[0089] Example 10

[0090]

[0091] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. After no liquid distilled off, the mixture was heated to 150 °C and distilled under reduced pressure to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3h (2.46 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The mixture was reacted at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. The solvent was removed, and the product was separated by column chromatography (EA:PE = 1:4) to obtain the target product. The target product was a white solid with a yield of 76%.

[0092] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.73(t,J=6.9Hz,4H),7.01(t,J=8.3Hz,4H),2.72(t,J=8.3Hz,4H)1.18(s,6H).

[0093] Example 11

[0094]

[0095] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. Once no liquid distilled off, the mixture was heated to 150 °C and distilled under reduced pressure to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3i (2.73 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was complete, 20 mL of water was added to the reaction mixture, followed by extraction with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. After solvent removal and washing with petroleum ether, the target product 4k was obtained. The target product was a white solid with a yield of 94%.

[0096] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ6.89(s,4H),2.32(s,6H),2.21(s,12H).

[0097] Example 12

[0098]

[0099] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. After no liquid distilled off, the mixture was heated to 150 °C and distilled under vacuum to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3j (2.72 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The mixture was reacted at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. The solvent was removed, and the product was separated by column chromatography (EA:PE = 1:10) to obtain the target product 4l. The target product was a white solid with a yield of 67%.

[0100] Products obtained 1 The HNMR data characterization is as follows: 1HNMR(400MHz,Chloroform-d)δ7.42(t,J=6.9Hz,4H),6.98(t,J=8.3Hz,4H),1.33(s,9H).

[0101] Example 13

[0102]

[0103] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. After no liquid distilled off, the mixture was heated to 150 °C and distilled under reduced pressure to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3k (4.52 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The mixture was reacted at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. The solvent was removed, and the product was separated by column chromatography (EA:PE = 1:4) to obtain the target product 4m. The target product was a white solid with a yield of 66%.

[0104] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.87(t,J=6.9Hz,4H),7.44(t,J=8.3Hz,4H).

[0105] Example 14

[0106]

[0107] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. After no liquid distilled off, the mixture was heated to 150 °C and distilled under vacuum to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3l (2.52 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The mixture was reacted at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. After solvent removal and washing with petroleum ether, the target product 4n was obtained. The target product was a white solid with a yield of 93%.

[0108] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.52(t,J=6.9Hz,4H),7.23(t,J=8.3Hz,4H),5.02(dd,J=18.2Hz,2H),1.20(s,12H).

[0109] Example 15

[0110]

[0111] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. Once no liquid distilled off, the mixture was heated to 150 °C and distilled under reduced pressure to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3m (2.78 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was complete, 20 mL of water was added to the reaction mixture, followed by extraction with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. After solvent removal and washing with petroleum ether, the target product 4o was obtained. The target product was a white solid with a yield of 92%.

[0112] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.93(t,J=6.9Hz,4H),7.23(t,J=8.3Hz,4H),4.05(t,J=8.3Hz,4H)1.34(s,6H).

[0113] Example 16

[0114]

[0115] 1d (6.06 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask, and two drops of DMF were added dropwise. The mixture was heated to reflux at 90 °C for 18 h, then cooled to 25 °C. Thionyl chloride was removed by vacuum distillation. When no liquid distilled out, toluene (10 mL) was added, and the mixture was heated to 50-80 °C and vacuum distilled out. When no liquid distilled out, the vacuum was broken under nitrogen purging to obtain a white solid 2d (6.52 g), with a yield of 95.8%. 3a ( 1.72 g of anhydrous dichloromethane, 25 mL of anhydrous dichloromethane, and 3.99 g of anhydrous aluminum chloride were placed in a 100 mL round-bottom flask. The obtained 2d was then dissolved in 10 mL of dichloromethane and added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL of dichloromethane. The organic layers were combined and dried with anhydrous sodium sulfate to remove water. The solvent was removed to obtain the target product 4p, which was a white solid with a yield of 93%.

[0116] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.90(d,J=7.7Hz,4H),7.70(t,J=7.6Hz,2H),7.56(d,J=7.4Hz,4H).

[0117] Example 17

[0118]

[0119] 1d (6.06 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask, and two drops of DMF were added dropwise. The mixture was heated to reflux at 90 °C for 18 h, then cooled to 25 °C. Thionyl chloride was removed by vacuum distillation. After no liquid distilled off, toluene (10 mL) was added, and the mixture was heated to 50-80 °C and vacuum distilled off. After no liquid distilled off, the vacuum was broken under nitrogen purging to obtain a white solid 2d (6.52 g), with a yield of 95.8%. 3e (2.12 g) was then added under nitrogen protection. 25 mL of anhydrous dichloromethane and 3.99 g of anhydrous aluminum chloride were placed in a 100 mL round-bottom flask. The obtained 2d (3.37 g) was then dissolved in 10 mL of dichloromethane and added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL of dichloromethane. The organic layers were combined and dried with anhydrous sodium sulfate to remove water. The solvent was removed to obtain the target product 4q, which was a white solid with a yield of 77%.

[0120] Products obtained 1 The HNMR data characterization is as follows: 1HNMR(400MHz,Chloroform-d)δ7.83(d,J=7.7Hz,4H),7.55(d,J=7.4Hz,4H).2.41(s,6H).

[0121] Example 18

[0122]

[0123] 1d (6.06 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask, and two drops of DMF were added dropwise. The mixture was heated to reflux at 90 °C for 18 h, then cooled to 25 °C. Thionyl chloride was removed by vacuum distillation. After no liquid distilled off, toluene (10 mL) was added, and the mixture was heated to 50-80 °C and distilled under vacuum. After no liquid distilled off, the vacuum was broken under nitrogen purging to obtain a white solid 2d (6.52 g), with a yield of 95.8%. 3c (2.52 g) was then added under nitrogen protection. 25 mL of anhydrous dichloromethane and 3.99 g of anhydrous aluminum chloride were placed in a 100 mL round-bottom flask. The obtained 2d (3.37 g) was then dissolved in 10 mL of dichloromethane and added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL of dichloromethane. The organic layers were combined and dried with anhydrous sodium sulfate to remove water. The solvent was removed to obtain the target product 4r, which was a white solid with a yield of 86%.

[0124] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.83(d,J=7.7Hz,4H),7.55(d,J=7.4Hz,4H).

[0125] Example 19

[0126]

[0127] 1d (6.06 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask, and two drops of DMF were added dropwise. The mixture was heated to reflux at 90 °C for 18 h, then cooled to 25 °C. Thionyl chloride was removed by vacuum distillation. After no liquid distilled off, toluene (10 mL) was added, and the mixture was heated to 50-80 °C and distilled under vacuum. After no liquid distilled off, the vacuum was broken under nitrogen purging to obtain a white solid 2d (6.52 g), with a yield of 95.8%. 3d (3.52 g) was then added under nitrogen protection. 25 mL of anhydrous dichloromethane and 3.99 g of anhydrous aluminum chloride were placed in a 100 mL round-bottom flask. The obtained 2d (3.37 g) was then dissolved in 10 mL of dichloromethane and added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried with anhydrous sodium sulfate to remove water. The solvent was removed to obtain the target product 4p, which was a white solid with a yield of 93%.

[0128] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.83(d,J=7.7Hz,4H),7.55(d,J=7.4Hz,4H).

[0129] Example 20

[0130]

[0131] 1d (6.06 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask, and two drops of DMF were added dropwise. The mixture was heated to reflux at 90 °C for 18 h, then cooled to 25 °C. Thionyl chloride was removed by vacuum distillation. After no liquid distilled off, toluene (10 mL) was added, and the mixture was heated to 50-80 °C and distilled under vacuum. After no liquid distilled off, the vacuum was broken under nitrogen purging to obtain a white solid 2d (6.52 g), with a yield of 95.8%. 3f (2.43 g) was then added under nitrogen protection. 25 mL of anhydrous dichloromethane and 3.99 g of anhydrous aluminum chloride were placed in a 100 mL round-bottom flask. The obtained 2d (3.37 g) was then dissolved in 10 mL of dichloromethane and added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried with anhydrous sodium sulfate to remove water. The solvent was removed to obtain the target product 4p, which was a white solid with a yield of 93%.

[0132] Products obtained 1 The HNMR data characterization is as follows: 1HNMR (400MHz, Chloroform-d) δ9.68 (s, 2H), 7.83 (d, J = 7.7Hz, 4H), 7.55 (d, J = 7.4Hz, 4H).

[0133] Example 21

[0134]

[0135] 1 d (6.06 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask, and two drops of DMF were added dropwise. The mixture was heated to reflux at 90 °C for 18 h, then cooled to 25 °C. Thionyl chloride was removed by vacuum distillation. After no liquid distilled off, toluene (10 mL) was added, and the mixture was heated to 50-80 °C and vacuum distilled off. After no liquid distilled off, the vacuum was broken under nitrogen purging to obtain a white solid 2 d (6.52 g), with a yield of 95.8%. 3 g (2.33 g) was then added under nitrogen protection. 25 mL of anhydrous dichloromethane and 3.99 g of anhydrous aluminum chloride were placed in a 100 mL round-bottom flask. The obtained 2d (3.37 g) was then dissolved in 10 mL of dichloromethane and added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried with anhydrous sodium sulfate to remove water. The solvent was removed to obtain the target product 4u, which was a white solid with a yield of 93%.

[0136] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.83(d,J=7.7Hz,4H),7.55(d,J=7.4Hz,4H),3.81(s,6H).

[0137] Example 22

[0138]

[0139] 1d (6.06 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask, and two drops of DMF were added dropwise. The mixture was heated to reflux at 90 °C for 18 h, then cooled to 25 °C. Thionyl chloride was removed by vacuum distillation. After no liquid distilled off, toluene (10 mL) was added, and the mixture was heated to 50-80 °C and distilled under vacuum. After no liquid distilled off, the vacuum was broken under nitrogen purging to obtain a white solid 2d (6.52 g), with a yield of 95.8%. 3b (2.32 g) was then added under nitrogen protection. 25 mL of anhydrous dichloromethane and 3.99 g of anhydrous aluminum chloride were placed in a 100 mL round-bottom flask. The obtained 2d (3.37 g) was then dissolved in 10 mL of dichloromethane and added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL of dichloromethane. The organic layers were combined and dried with anhydrous sodium sulfate to remove water. The solvent was removed to obtain the target product 4v, which was a white solid with a yield of 93%.

[0140] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.83(d,J=7.7Hz,4H),7.55(d,J=7.4Hz,4H).

[0141] Example 23

[0142]

[0143] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. Once no liquid distilled off, the mixture was heated to 150 °C and distilled under reduced pressure to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3n (2.43 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was complete, 20 mL of water was added to the reaction mixture, followed by extraction with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. After solvent removal and washing with petroleum ether, the target product 4w was obtained. The target product was a pale yellow solid with a yield of 68%.

[0144] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR (400MHz, Chloroform-d) δ8.04(t,J=7.2Hz,2H),7.83(t,J=6.9Hz,2H),7.22(t,J=6.9Hz,2H).

[0145] Example 24

[0146]

[0147] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. Once no liquid distilled off, the mixture was heated to 150 °C and distilled under reduced pressure to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3o (4.25 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was complete, 20 mL of water was added to the reaction mixture, followed by extraction with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. After solvent removal and washing with petroleum ether, the target product 4x was obtained. The target product was a pale yellow solid with a yield of 52%.

[0148] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR (400MHz, Chloroform-d) δ8.38(t,J=7.2Hz,2H), 8.16(t,J=6.9Hz,2H), 8.10(t,J=7.84Hz,4H), 7.72(t,J=7.38Hz,2H), 7.65(t,J=7.48Hz,2H).

[0149] Example 25

[0150]

[0151] 1a (4.76 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask. The mixture was heated to reflux at 90 °C for 12 h, then cooled to 25 °C. The thionyl chloride was removed by vacuum distillation. After no liquid distilled off, the mixture was heated to 150 °C and vacuum distilled to obtain intermediate 2a (4.42 g), with a yield of 80.6%. Under nitrogen protection, 3p (7.23 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.99 g) were placed in a 100 mL round-bottom flask. The obtained 2a (2.72 g) was then gradually added dropwise. The mixture was reacted at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried over anhydrous sodium sulfate to remove water. After solvent removal and washing with petroleum ether, the target product 4y was obtained. The target product was a white solid with a yield of 47%.

[0152] Products obtained 1 The HNMR data characterization is as follows:1 HNMR(400MHz,Chloroform-d)δ7.39(t,J=7.2Hz,4H),2.88(t,J=1.50Hz,6H).1.18(d,J=0.80Hz,36H)

[0153] Example 26

[0154]

[0155] 1e (5.90 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask, and two drops of DMF were added dropwise. The mixture was heated to reflux at 90 °C for 18 h, then cooled to 25 °C. Thionyl chloride was removed by vacuum distillation. When no liquid distilled off, toluene (10 mL) was added, and the mixture was heated to 50-80 °C and vacuum distilled off. When no liquid distilled off, the vacuum was broken under nitrogen purging to obtain a white solid 2e (6.33 g), with a yield of 94%. 3b (2.32 g) was then added under nitrogen protection. 25 mL of anhydrous dichloromethane and 3.99 g of anhydrous aluminum chloride were placed in a 100 mL round-bottom flask. The obtained 2f (2.95 g) was then dissolved in 10 mL of dichloromethane and added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL of dichloromethane. The organic layers were combined and dried with anhydrous sodium sulfate to remove water. The solvent was removed to obtain the target product 5a, which was a white solid with a yield of 92%.

[0156] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.72(d,J=7.7Hz,4H),7.39(d,J=7.4Hz,4H).

[0157] Example 27

[0158]

[0159] 1f (5.90 g) and thionyl chloride (30 mL) were added to a 100 mL round-bottom flask, and two drops of DMF were added dropwise. The mixture was heated to reflux at 90 °C for 18 h, then cooled to 25 °C. Thionyl chloride was removed by vacuum distillation. When no liquid distilled off, toluene (10 mL) was added, and the mixture was heated to 50-80 °C and distilled under vacuum. When no liquid distilled off, the vacuum was broken under nitrogen purging to obtain a white solid 2f (6.37 g), with a yield of 94%. 3b (2.32 g) was then added under nitrogen protection. 25 mL of anhydrous dichloromethane and 3.99 g of anhydrous aluminum chloride were placed in a 100 mL round-bottom flask. The obtained 2f (2.95 g) was then dissolved in 10 mL of dichloromethane and added dropwise. The reaction was carried out at room temperature for 18 h. After the reaction was completed, 20 mL of water was added to the reaction solution, and the mixture was extracted with 3 x 15 mL dichloromethane. The organic layers were combined and dried with anhydrous sodium sulfate to remove water. The solvent was removed to obtain the target product 5b, which was a white solid with a yield of 88%.

[0160] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz,Chloroform-d)δ7.72(d,J=7.7Hz,4H),7.39(d,J=7.4Hz,4H).

[0161] Example 28

[0162]

[0163] Photosensitizer 4a (27 mg), bromobenzene (32 mg), nickel chloride hexahydrate (2.4 mg), 4,4'-di-tert-butylbipyridine (2.7 mg), and sodium bicarbonate (40 mg) were placed in a Shrek flask, sealed, protected with nitrogen, and toluene (5 mL) was injected. The mixture was then stirred at 35°C under a 20W blue LED lamp for 10 h. After solvent removal, the solution was separated by column chromatography using petroleum ether:diethyl ether = 95:5 as the developing solvent to obtain colorless liquid diphenylmethane with a yield of 98%.

[0164] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR (400MHz, Chloroform-d) δ7.26 (t, J = 7.2Hz, 10H), 4.09 (s, 2H).

[0165] Example 29

[0166]

[0167] Photosensitizer 4b (27 mg), bromobenzene (32 mg), nickel chloride hexahydrate (2.4 mg), 4,4'-di-tert-butylbipyridine (2.7 mg), and sodium bicarbonate (40 mg) were placed in a Shrek flask, sealed, protected with nitrogen, and toluene (5 mL) was injected. The mixture was then stirred at 35°C under a 20 W blue LED lamp for 14 h. After solvent removal, the solution was separated by column chromatography using petroleum ether:diethyl ether = 95:5 as the developing solvent to obtain colorless liquid diphenylmethane with a yield of 96%.

[0168] Example 30

[0169]

[0170] Photosensitizer 4C (27 mg), bromobenzene (32 mg), nickel chloride hexahydrate (2.4 mg), 4,4'-di-tert-butylbipyridine (2.7 mg), and sodium bicarbonate (40 mg) were placed in a Shrek flask, sealed, protected with nitrogen, and toluene (5 mL) was injected. The mixture was then stirred at 35°C under a 20 W blue LED lamp for 10 h. After solvent removal, the solution was separated by column chromatography using petroleum ether:diethyl ether = 95:5 as the developing solvent to obtain colorless liquid diphenylmethane with a yield of 97%.

[0171] Example 31

[0172]

[0173] Photosensitizer 4e (30 mg), bromobenzene (32 mg), nickel chloride hexahydrate (2.4 mg), 4,4'-di-tert-butylbipyridine (2.7 mg), and sodium bicarbonate (40 mg) were placed in a Shrek flask, sealed, protected with nitrogen, and toluene (5 mL) was injected. The mixture was then stirred at 35°C under a 20 W blue LED lamp for 10 h. After solvent removal, the solution was separated by column chromatography using petroleum ether:diethyl ether = 95:5 as the developing solvent to obtain colorless liquid diphenylmethane with a yield of 98%.

[0174] Example 32

[0175]

[0176] 4 g (29 mg) of photosensitizer, 32 mg of bromobenzene, 2.4 mg of nickel chloride hexahydrate, 2.7 mg of 4,4'-di-tert-butylbipyridine, and 40 mg of sodium bicarbonate were placed in a Shrek flask, sealed, protected with nitrogen, and toluene (5 mL) was injected. The mixture was then stirred at 35 °C under a 20 W blue LED lamp for 10 h. After solvent removal, the solution was separated by column chromatography using petroleum ether:diethyl ether = 95:5 as the developing solvent to obtain colorless liquid diphenylmethane with a yield of 98%.

[0177] Example 33

[0178]

[0179] Photosensitizer 4h (29 mg), bromobenzene (32 mg), nickel chloride hexahydrate (2.4 mg), 4,4'-di-tert-butylbipyridine (2.7 mg), and sodium bicarbonate (40 mg) were placed in a Shrek flask, sealed, protected with nitrogen, and toluene (5 mL) was injected. The mixture was then stirred at 35°C under a 20W blue LED lamp for 10 h. After solvent removal, the solution was separated by column chromatography using petroleum ether:diethyl ether = 95:5 as the developing solvent to obtain colorless liquid diphenylmethane with a yield of 98%.

[0180] Example 34

[0181]

[0182] Photosensitizer 4p (42 mg), bromobenzene (32 mg), nickel chloride hexahydrate (2.4 mg), 4,4'-di-tert-butylbipyridine (2.7 mg), and sodium bicarbonate (40 mg) were placed in a Shrek flask, sealed, protected with nitrogen, and toluene (5 mL) was injected. The mixture was then stirred at 35°C under a 20 W blue LED lamp for 10 h. After solvent removal, the solution was separated by column chromatography using petroleum ether:diethyl ether = 95:5 as the developing solvent to obtain colorless liquid diphenylmethane with a yield of 98%.

[0183] Example 35

[0184]

[0185] Photosensitizer 4p (36 mg), p-cyanobromobenzene (36 mg), nickel chloride hexahydrate (2.4 mg), 4,4'-di-tert-butylbipyridine (2.7 mg), and sodium bicarbonate (40 mg) were placed in a Shrek flask, sealed, protected with nitrogen, and toluene (5 mL) was injected. The mixture was then stirred at 35°C under a 20 W blue LED lamp for 10 h. After solvent removal, the solution was separated by column chromatography using petroleum ether:diethyl ether = 95:5 as the developing solvent to obtain colorless liquid diphenylmethane with a yield of 99%.

[0186] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR (400MHz, Chloroform-d) δ7.26 (t, J = 7.2Hz, 10H), 4.09 (s, 2H).

[0187] Example 36

[0188]

[0189] Photosensitizer 4K (36 mg), p-bromofluorobenzene (34 mg), nickel chloride hexahydrate (2.4 mg), 4,4'-di-tert-butylbipyridine (2.7 mg), and sodium bicarbonate (40 mg) were placed in a Shrek flask, sealed, protected with nitrogen, and toluene (5 mL) was injected. The mixture was then stirred at 35°C under a 20W blue LED lamp for 10 h. After solvent removal, the solution was separated by column chromatography using petroleum ether:diethyl ether = 95:5 as the developing solvent to obtain colorless liquid diphenylmethane in 89% yield.

[0190] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR (400MHz, Chloroform-d) δ7.26 (t, J = 7.2 Hz, 5H), 7.18 (t, J = 6.8 Hz, 4H), 4.09 (s, 2H).

[0191] Example 37

[0192]

[0193] Photosensitizer 4a (27 mg), bromobenzene (32 mg), nickel chloride hexahydrate (2.4 mg), 4,4'-di-tert-butylbipyridine (2.7 mg), and sodium bicarbonate (40 mg) were placed in a Shrek flask, sealed, protected with nitrogen, and 5 mL of mesitylene was injected. The mixture was then stirred at 35 °C for 10 h under a 20 W blue LED lamp. After solvent removal, the solution was separated by column chromatography using petroleum ether:diethyl ether = 95:5 as the developing solvent to obtain colorless liquid diphenylmethane in 78% yield.

[0194] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR (400MHz, Chloroform-d) δ7.26 (t, J = 7.8 Hz, 6H), 6.99 (t, J = 7.2 Hz, 2H), 4.07 (s, 2H), 2.18 (s, 6H).

[0195] Example 38

[0196]

[0197] Photosensitizer 5a (28 mg), bromobenzene (32 mg), nickel chloride hexahydrate (2.4 mg), 4,4'-di-tert-butylbipyridine (2.7 mg), and sodium bicarbonate (40 mg) were placed in a Shrek flask, sealed, protected with nitrogen, and 5 mL of mesitylene was injected. The mixture was then stirred at 35°C under a 20 W blue LED lamp for 10 h. After solvent removal, the solution was separated by column chromatography using petroleum ether:diethyl ether = 95:5 as the developing solvent to obtain colorless liquid diphenylmethane in 78% yield.

[0198] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR (400MHz, Chloroform-d) δ7.26 (t, J = 7.8 Hz, 6H), 6.99 (t, J = 7.2 Hz, 2H), 4.07 (s, 2H), 2.18 (s, 6H).

[0199] Example 39

[0200]

[0201] Photosensitizer 5b (28 mg), bromobenzene (32 mg), nickel chloride hexahydrate (2.4 mg), 4,4'-di-tert-butylbipyridine (2.7 mg), and sodium bicarbonate (40 mg) were placed in a Shrek flask, sealed, protected with nitrogen, and toluene (5 mL) was injected. The mixture was then stirred at 35°C under a 20 W blue LED lamp for 10 h. After solvent removal, the solution was separated by column chromatography using petroleum ether:diethyl ether = 95:5 as the developing solvent to obtain colorless liquid diphenylmethane with a yield of 98%.

[0202] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the present invention in any way. Other variations and modifications may be made without departing from the technical solutions described in the claims.

Claims

1. A diaromatic formyl tetrahalobenzene compound, characterized in that, The structural formula of the diaromatic formyl tetrahalobenzene compound is shown in formula (I): ， In formula (I), X is at least one of fluorine and chlorine, and Ar is a substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted thiophene group, wherein the substituent is selected from at least one of C1-C12 alkyl, C1-C6 alkoxy, hydroxyl, or halogen group.

2. The diaromatic formyl tetrahalobenzene compound according to claim 1, characterized in that, The diaromatic formyl tetrahalobenzene compound is a meta-diaromatic formyl tetrafluorobenzene compound, and its structure is shown in formula (II): ， In formula (II), Ar is phenyl, C1-C12 alkyl-substituted phenyl, or naphthyl.

3. The diaromatic formyl tetrahalobenzene compound according to claim 1, characterized in that, The diaromatic formyl tetrahalobenzene compound is a m-(2,4,6-trialkylphenyl)formyl tetrafluorobenzene compound, the structure of which is shown in formula (III): ， In formula (III), R1 is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

4. A method for preparing a diaromatic formyl tetrahalobenzene compound as described in any one of claims 1-3, characterized in that, include: Tetrahalophthalic acid is reacted with a chlorinating reagent to give a tetrahalophthaloyl chloride intermediate; under inert gas protection, an aromatic compound Ar-H is dissolved in an organic solvent, and then the tetrahalophthaloyl chloride intermediate is added to the reaction system. In the presence of a catalyst, a Friedel-Crafts acylation reaction is carried out to give the target product.

5. The method for preparing a diaromatic formyl tetrahalobenzene compound according to claim 4, characterized in that, The molar ratio of the tetrahalophthalic acid to the chlorinating reagent is 1:1 to 200.

6. The method for preparing a diaromatic formyl tetrahalobenzene compound according to claim 4, characterized in that, The organic solvent is one or a mixture of two or more of dichloromethane, dichloroethane, chloroform, tetrahydrofuran, 1,4-dioxane, diethyl ether, methyl tert-butyl ether, and C4-C8 alkanes in any proportion; the catalyst is one or a mixture of two or more of aluminum trichloride, ferric trichloride, zinc dichloride, titanium tetrachloride, and tin tetrachloride in any proportion.

7. The method for preparing a diaromatic formyl tetrahalobenzene compound according to claim 4, characterized in that, The molar ratio of the tetrahalophthaloyl chloride intermediate, the aromatic compound shown in formula (I), and the catalyst is 1:1 to 100:0.1 to 10.

8. The application of a diaromatic formyl tetrahalobenzene compound in the field of photocatalysis, characterized in that, The photocatalysis is a reaction used to photocatalytically activate carbon-hydrogen bonds for C / C bond coupling; the structural formula of the diaromatic formyl tetrahalobenzene compound is shown below. ， In the formula, X is at least one of fluorine and chlorine, R is at least one, and R is an aromatic formyl group, Ar is a substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted thiophene group, wherein the substituent is selected from at least one of C1-C12 alkyl, C1-C6 alkoxy, hydroxyl, or halogen group. Alternatively, the structural formula of the diaromatic formyl tetrahalobenzene compound is shown in any one of claims 1-3.

9. The application of photocatalysis according to claim 8, characterized in that, include: Under light irradiation, diarylformyltetrahalobenzene compounds were used as photosensitizers to photocatalyze the C(sp3)-H activation of toluene compounds, which then underwent C-C bond coupling with haloalkanes to yield diarylmethane compounds. Under light irradiation, diarylformyltetrahalobenzene compounds were used as photosensitizers to photocatalyze the C(sp3)-H activation of toluene compounds, which then underwent C-C bond coupling with carbon dioxide to yield arylacetic acid compounds.

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