1,3-diarylformylbenzene compound, preparation method and application thereof

Abstract

The application belongs to the technical field of organic photoelectric materials, and particularly relates to a 1,3-di-aromatic formyl benzene compound, a preparation method and application. The structural formula of the 1,3-di-aromatic formyl benzene compound is shown as formula (I). 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 photosensitive materials, photoelectric materials, fluorescent probes, photocatalysis, photocuring and the like, and has a wide market application prospect. Meanwhile, the preparation method provided by the application is simple in operation, mild in conditions, green and environment-friendly, reagents and substrates are simple, economical, inexpensive and easy to obtain, the reaction is efficient, the substrate has wide applicability, and the application has a wide industrial application prospect.

Description

Technical Field

[0001] This invention belongs to the field of organic optoelectronic materials technology, specifically relating to a 1,3-diaromatic formylbenzene compound, its preparation method, and its application. Background Technology

[0002] Diaryl ketones are among 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 transformation 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. For example, in photocatalytic CH bond activation reactions, research over the past decade has shown that diaryl ketones can completely replace noble metal photosensitizers and other organic photosensitizers to achieve CH bond dehydrogenation functionalization and coupling reactions. Diaryl ketones are also commonly used photoinitiators, widely applied in the field of photocuring. Photocuring is a technology that utilizes photoinitiators to absorb ultraviolet or visible light energy to initiate a chemical reaction, thereby instantly curing coatings or adhesives. Existing diaryl ketone photoinitiators have slow photocuring rates and poor light source compatibility, while this invention can significantly improve the curing rate. Summary of the Invention

[0003] The purpose of this invention is to solve the above-mentioned technical problems and provide a 1,3-diaromatic formylbenzene compound, its preparation method, and its applications. The 1,3-diaromatic formylbenzene compound of this invention maintains good competitiveness in photocatalytic CH activation, and at the same time, exhibits stronger advantages and wider applicability in the fields of photocatalytic oxidation and photocuring.

[0004] The technical solution adopted by this invention to solve its technical problem is:

[0005] One objective of this invention is to provide a 1,3-diaromatic formylbenzene compound, the structural formula of which is shown in formula (I):

[0006]

[0007]

[0008] In formula (I), X is at least one of fluorine and chlorine, D is one of C1-C6 alkoxy and C1-C6 alkylthio, 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-C6 alkyl, C1-C6 alkoxy, hydroxyl, or halogen group (including fluorine, chlorine, bromine, and iodine).

[0009] Preferably, the 1,3-diaromatic formylbenzene compound is most preferably a m-(2,4,6-trialkylphenyl)formyldifluorodimethoxybenzene compound, the structure of which is shown in formula (II):

[0010]

[0011] In formula (II), R1 is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0012] A second objective of this invention is to provide a method for preparing the aforementioned 1,3-diaromatic formylbenzene compounds. The method comprises: reacting a meta-diaromatic formyl tetrahalobenzene compound with an alcohol under inorganic alkaline conditions and heating with Williamson ether to synthesize the target 1,3-diaromatic formylbenzene compound.

[0013] Preferably, the reaction formula of the method is as follows:

[0014]

[0015] In the formula, X is at least one of fluorine and chlorine, D is one of C1-C6 alkoxy and C1-C6 alkylthio, and Ar is a substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted thiophene group. The substituent is selected from at least one of C1-C6 alkyl, C1-C6 alkoxy, hydroxyl, and halogen group. The halogen group includes at least one of fluorine, chlorine, bromine, and iodine.

[0016] Preferably, the alcohol used in the Williamson ether synthesis reaction is one of C1-C6 alkyl alcohols or C1-C6 alkyl thiols.

[0017] Preferably, the inorganic base used in the Williamson ether synthesis reaction is at least one selected from sodium hydroxide, potassium hydroxide, potassium tert-butoxide, and sodium methoxide. Sodium methoxide is the most preferred choice.

[0018] Preferably, the molar ratio of the intermediate diaromatic formyl tetrahalobenzene, alcohol and inorganic base in the Williamson ether synthesis reaction is 1:1 to 100:1 to 10, and the most preferred ratio is 1:80 to 110:2 to 3.

[0019] Preferably, the optimal temperature for the Williamson ether synthesis reaction is 65–85°C, and the optimal reaction time is 10–15 h.

[0020] Preferably, the post-processing of the Williamson ether synthesis reaction includes conventional purification steps such as extraction, drying to remove moisture, solvent removal, washing, and column chromatography.

[0021] Preferably, the preparation method includes: acyl chlorination of tetrahaloisophthalic acid with a chlorinating reagent to obtain a tetrahaloisophthaloyl chloride intermediate; under inert gas protection, dissolving an aromatic compound Ar-H in an organic solvent, then adding the tetrahaloisophthaloyl chloride intermediate dropwise to the reaction system, and performing a Friedel-Crafts acylation reaction in the presence of a catalyst to obtain a m-diaromaticformyltetrahalobenzene compound; and reacting the m-diaromaticformyltetrahalobenzene with an alcohol under inorganic base conditions with Williamson ether to synthesize the target 1,3-diaromaticformylbenzene compound. This preparation route uses simple and economical raw materials, facilitates the design of functional groups for reactants or intermediates, and operates under mild and easy-to-operate reaction conditions.

[0022] Preferably, the reaction formula for the preparation method of the 1,3-diaromatic formylbenzene compound is shown below:

[0023]

[0024] Wherein, Ar-H is an aromatic compound, X is at least one of fluorine and chlorine, D is one of C1-C6 alkoxy and C1-C6 alkylthio, 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-C6 alkyl, C1-C6 alkoxy, hydroxyl, or halogen group, and the halogen group includes at least one of fluorine, chlorine, bromine, or iodine.

[0025] Preferably, the molar ratio of the tetrahalophthalic acid to the chlorinating reagent is 1:1 to 200, and most preferably 1:20 to 35.

[0026] Preferably, the chlorinating agent is one or a mixture of two or more of thionyl chloride, oxaloyl chloride, phosgene, and triphosgene in any proportion. Most preferably, it is thionyl chloride.

[0027] Preferably, the catalyst is one of aluminum trichloride, ferric trichloride, zinc dichloride, titanium tetrachloride, and tin tetrachloride. Most preferably, it is aluminum trichloride.

[0028] Preferably, the organic solvent is one or a mixture of two or more of the following: dichloromethane, dichloroethane, nitrobenzene, chloroform, tetrahydrofuran, 1,4-dioxane, diethyl ether, methyl tert-butyl ether, and C4-C8 alkanes in any proportion. Dichloroethane is most preferred. More preferably, the volumetric amount of the organic solvent used is 1-1000 mL / g based on the mass of the tetrahalophthaloyl chloride intermediate.

[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 molar ratio of the tetrahaloisophthaloyl chloride intermediate, the aromatic compound Ar-H, and the catalyst is 1:1 to 100:0.1 to 10, and the most preferred ratio is 1:2 to 3:3 to 4.

[0031] Preferably, the dropping rate of the tetrahaloisophthaloyl chloride intermediate is 5 mL / min.

[0032] The third objective of this invention is to provide an application of the aforementioned 1,3-diaromatic formylbenzene compounds, which are applied in fields such as photosensitive materials, optoelectronic materials, photocatalysis, photocuring, and fluorescent probes.

[0033] Preferably, the 1,3-diaromatic formylbenzene compound is used for photocatalytic oxidation, comprising: under light source irradiation, the 1,3-diaromatic formylbenzene compound acts as a photosensitizer to photocatalyze the oxidation of toluene compounds under oxygen conditions to generate benzoic acid compounds.

[0034] The preferred reaction formula is shown below:

[0035]

[0036] Wherein R is at least one of the ortho, meta, and para positions of the benzene ring methyl group, and R can be at least one of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, hydroxyl, halogen group, tert-butyl, nitro, cyano, and trifluoromethyl; PS is a 1,3-diaromatic formylbenzene compound as described in this invention.

[0037] Preferably, the 1,3-diaromatic formylbenzene compound is used for photocatalytic hydrocarbon activation reaction, comprising: using the 1,3-diaromatic formylbenzene compound as a photosensitizer to photocatalyze the C(sp3)-H activation of toluene compounds under light source irradiation, and coupling with haloalkanes via C-C bonds to obtain diarylmethane compounds.

[0038] The preferred reaction formula is shown below:

[0039]

[0040] Where R1 is hydrogen, ortho, meta and para methyl groups, etc., and R2 is para hydrogen, cyano group, etc.;

[0041] PS is a 1,3-diaromatic formylbenzene compound as described in this invention.

[0042] Preferably, the application of the 1,3-diaromatic formylbenzene compound in the field of photocuring includes: adding the 1,3-diaromatic formylbenzene compound and additives, and under the irradiation of a light source, the C-C bond of trimethylolpropane triacrylate breaks to generate free radicals, thereby causing the monomer of the compound to polymerize and thus cure it.

[0043] The chemical formula of trimethylolpropane triacrylate is:

[0044] More preferably, the light source can be an ultraviolet light source with a wavelength of 254-365nm; most preferably, it is a 254nm ultraviolet light source.

[0045] More preferably, the additive may be one of ethyl 4-dimethylaminobenzoate and bis(4-tert-butylphenyl)iodonium hexafluorophosphate, with bis(4-tert-butylphenyl)iodonium hexafluorophosphate being the most preferred.

[0046] This invention relates to a novel 1,3-diaromaticformylbenzene compound obtained by further substituting and modifying the halogen in a diaromaticformyltetrahalobenzene compound. Compared with the original structure, this compound not only maintains good competitiveness in photocatalytic CH activation but also exhibits stronger and more unexpected advantages and wider applicability in photocatalytic oxidation and photocuring. This novel compound can effectively promote photogenerated charge separation, facilitating the efficient transfer of excited-state electrons or hydrogen, thus improving quantum efficiency and catalytic efficiency. It can be applied in photosensitive materials, optoelectronic materials, fluorescent probes, photocatalysis, and photocuring, for example, in photocatalytic carbon-carbon coupling reactions and photocatalytic oxidation reactions. It can also be widely used in photocuring as a photoinitiator, absorbing ultraviolet or visible light energy to initiate chemical reactions, thereby enabling coatings or adhesives to cure instantaneously, showing broad market application prospects. Furthermore, the preparation method provided by this invention is simple to operate, operates under mild conditions, is environmentally friendly, and uses simple, economical, and readily available reagents and substrates. The reaction is highly efficient, and the substrates have wide applicability, showing broad prospects for industrial application.

[0047] Compared with the prior art, the beneficial effects of the present invention are:

[0048] (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 are more green and environmentally friendly, with broad prospects for industrial application.

[0049] (2) This invention synthesizes a series of novel 1,3-diaromatic formylbenzene compounds, which can be applied to fields such as luminescent materials, photocatalytic oxidation, photocatalytic hydrocarbon activation, photocuring, fluorescent probes, etc., and have broad market application prospects. Attached Figure Description

[0050] Figure 1 This is a graph showing the ultraviolet absorption wavelength data of the product from Example 1;

[0051] Figure 2 The image shows the cyclic voltammetry data of the product from Example 1. Detailed Implementation

[0052] 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.

[0053] 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℃. The substituents and conditions described in the inventive summary section of this invention can all be achieved with comparable results. Due to space limitations, this specification specifically presents the following examples. For the preparation method of the meta-diaromatic formyl tetrahalobenzene compounds described in this invention, please further refer to the relevant content of patent CN202310254098.2, "A Diaromatic Formyl Tetrahalobenzene Compound and its Preparation Method and Application".

[0054] Example 1

[0055]

[0056] Add a (2.21 g) and thionyl chloride (18 mL) to a 50 mL round-bottom flask. Heat under reflux at 80 °C for 12 h, then cool to 25 °C and remove thionyl chloride by vacuum distillation. After no liquid distills out, heat to 140 °C and distill under vacuum to obtain acyl chloride intermediate b (2.15 g), with a yield of 84.0%. Under nitrogen protection, place mesitylene (1.88 g), anhydrous dichloroethane (30 mL), and anhydrous aluminum chloride (3.12 g) in a 100 mL round-bottom flask. Gradually add the obtained b (2.15 g) at room temperature and react for 18 h at room temperature. After the reaction is complete, add 20 mL of water to the reaction solution and extract with 3 x 15 mL dichloromethane. Combine the organic layers and dry with anhydrous sodium sulfate to remove water. After solvent removal and washing with n-hexane, obtain white solid product c (3.11 g), with a yield of 90.1%. The obtained c (3.11 g) was placed in a 50 mL round-bottom flask, and 20 mL of methanol and 0.76 g of sodium methoxide were added. The mixture was heated to reflux at 70 °C for 12 h. After column purification, the target product d (2.54 g) was obtained, with a yield of 77.3%. The HPLC purity was 99.1%.

[0057] The obtained product NMR data are characterized as follows: 1 HNMR (400MHz, CDCl3) δ6.85 (s, 4H), 3.41 (d, J = 2.4Hz, 6H), 2.30 (s, 6H), 2.20 (s, 12H)

[0058] 13 C NMR (101MHz, CDCl3) δ194.59,155.01,152.44,149.84,149.73,149.65,147.24,144 .73,139.91,138.59,135.49,129.30,120.70,120.54,62.14,62.07,21.46,20.05.

[0059] The high-resolution molecular weight of the obtained product was: (M+H) + = 467.20154, molecular formula is C 28 H 28 F2O4.

[0060] The UV absorption wavelength data and cyclic voltammetry data of the obtained products are attached. Figure 1 and attached Figure 2From the ultraviolet absorption wavelength diagram, the main absorption wavelength range is in the 220-270nm ultraviolet region. Compared with m-(2,4,6-trimethylphenyl)formyltetrafluorobenzene (the absorption intensity measured at the same concentration is 1.8A), it has a higher absorbance, which makes its photocatalytic effect better at specific wavelengths. From the product cyclic voltammetry diagram, we can see that there is a reduction site at about 1.5V, and the reduction potential is relatively large (the reduction potential of most halobenzophenones is -2.09V), which makes the application of this photosensitizer in electrocatalytic chemical reactions promising.

[0061] Following the operating procedures of Example 1, the products of Examples 2-5 were synthesized by changing the relevant conditions. The conditions and product yields are shown in the table below:

[0062]

[0063] In Example 2, the molar ratio of tetrahalophthalic acid to chlorinating reagent was 1:20, the temperature in the Williamson ether synthesis reaction was 65°C, and the reaction time was 10 h. In Example 3, the molar ratio of acyl chloride intermediate, aromatic compound, and catalyst was 1:2:3, the temperature in the Williamson ether synthesis reaction was 85°C, and the reaction time was 15 h. In Example 4, the molar ratio of tetrahalophthalic acid to chlorinating reagent was 1:25, and the molar ratio of m-diaromaticformyltetrahalobenzene, alcohol, and inorganic base was 1:90:2. In Example 5, the molar ratio of acyl chloride intermediate, aromatic compound, and catalyst was 1:3:4, and the molar ratio of m-diaromaticformyltetrahalobenzene, alcohol, and inorganic base was 1:100:3.

[0064] Example 2

[0065]

[0066] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR (400MHz, CDCl3) δ7.87(d,J=7.36Hz,4H),7.60(t,J=7.4Hz,2H),7.48(t,J=7.6Hz,4H).3.93(d,J=2.4Hz,6H).

[0067] 13 C NMR (101MHz, CDCl3) δ189.81, 189.80, 152.53-143.92 (m, 3C) 137.00, 134.30, 129.69, 128.88, 117.28, 117.06, 62.46, 62.40.

[0068] The high-resolution molecular weight of the obtained product was: (M+H) + =383.14309, molecular formula is C 22 H 16 F2O4.

[0069] Example 3

[0070]

[0071] The obtained product NMR data are characterized as follows: 1 HNMR (400MHz, CDCl3) δ7.79-7.74(m,4H),7.30-7.27(m,4H),3.96(s,3H),2.42(s,6H).

[0072] 13 C NMR (101MHz, CDCl3) δ188.67,186.40,145.97,145.81,134.24,134.21,130.00,129.85,129.74,129.72,62.29,62.22,21.96.

[0073] The high-resolution molecular weight of the obtained product was: (M+H) + =398.34617, molecular formula is C 23 H 17 F3O3

[0074] Example 4

[0075]

[0076] The obtained product NMR data are characterized as follows: 1 HNMR (400MHz, CDCl3) δ7.00 (s, 4H), 2.98 (d, J = 4Hz, 6H), 2.32 (s, 12H), 2.20 (s, 6H)

[0077] 13 C NMR (101MHz, CDCl3) δ197.19,152.91,151.47,148.24,147.73,147.05,14684,144 .83,140.91,139.19,134.19,127.37,120.70,120.04,61.17,61.07,20.96,20.15.

[0078] The high-resolution molecular weight of the obtained product was: (M+H) + = 498.52148, molecular formula is C 28 H28 F2O4S2.

[0079] Example 5

[0080]

[0081] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR(400MHz, CDCl3) δ7.87(d,J=7.5Hz,4H),7.50(d,J=7.4Hz,4H),3.93(d,J=2.4Hz,6H).

[0082] 13 C NMR (101MHz, CDCl3) δ188.74,188.71,157.50,157.46,155.47,155.43,152.09,138 .15,138.12,131.60,127.97,116.01,115.97,115.90,61.91,61.88,61.84,61.71.

[0083] The high-resolution molecular weight of the obtained product was: (M+H) + =540.1925, molecular formula is C 22 H 14 Br2F2O4.

[0084] Application Example 1

[0085] UV curing experiment: Three identical curing reagents were prepared by mixing equimolar amounts of benzophenone, 2-isopropylthionone, the novel 1,3-diaromatic formylbenzene compound from Example 1, and m-(2,4,6-trimethylphenyl)formyltetrafluorobenzene with equal amounts of acrylate monomers (monomers) and iodonium salts (additives). The three reagents were dropped onto a prepared mold (50mm x 50mm x 0.5mm) and irradiated under the same UV lamp. The final film formation on the sample was observed as the reaction endpoint, and the reaction time was calculated. Details are shown in the table below:

[0086]

[0087] The data above show that, under the same environmental conditions, when photopolymerization was carried out using equal amounts of photocuring reagents, the novel 1,3-diaromatic formylbenzene compound of Example 1 exhibited excellent photocuring effect.

[0088] Application Example 2

[0089]

[0090] The photosensitizer synthesized in Example 2 (51 mg), toluene (138 mg), potassium carbonate (10 mg), or 0.1 molar equivalent of trifluoroacetic acid was placed in a Shrek bottle and sealed. Ethyl acetate (5 mL) was added under 1 bar O2. The mixture was then stirred at 35°C for 38 h under a 30 W blue LED lamp. After solvent removal, white solid benzoic acid was obtained by column chromatography with a yield of 85%.

[0091] Meanwhile, compared with existing photosensitizers such as m-diaromatic formyltetrafluorobenzene, in the same molar amounts, it was placed in a Shrek flask with toluene (138 mg), potassium carbonate (10 mg), or 0.1 molar equivalent of trifluoroacetic acid, sealed, and ethyl acetate (5 mL) was added under 1 bar O2. The mixture was then stirred at 35°C for 38 h under a 30 W blue LED lamp, followed by solvent removal. The resulting white solid benzoic acid was obtained by column chromatography, with a yield of only 35%. Therefore, the 1,3-diaromatic formylbenzene compounds modified in this invention can exhibit superior and unpredictable photocatalytic effects.

[0092] The obtained product NMR data are characterized as follows: 1 HNMR (400MHz, CDCl3) δ11.47 (s, 1H), 8.15 (d, J = 7.3Hz, 2H), 7.88 (t, J = 7.2Hz, 1H) 7.98 (t, J = 7.6Hz, 2H).

[0093] Application Example 3

[0094]

[0095] The photosensitizer synthesized in Example 3 (65 mg), p-tert-butyltoluene (222 mg), potassium carbonate (10 mg), or 0.1 molar equivalent of trifluoroacetic acid was placed in a Shrek flask and sealed. Ethyl acetate (5 mL) was added under 1 bar O2. The mixture was then stirred at 35°C for 38 h under a 30 W blue LED lamp. After solvent removal, the white solid p-tert-butylbenzoic acid was obtained by column chromatography with a yield of 88%. Furthermore, replacing the substituents of the reactants with C1-C6 alkyl, C1-C6 alkoxy, hydroxyl, halogen groups, nitro, cyano, and trifluoromethyl substituents, or replacing the photocatalyst with other 1,3-diaromatic formylbenzene compounds of this invention, all exhibited a catalytic effect of not less than 70%.

[0096] Meanwhile, using m-(4-methylphenyl)formyltetrafluorobenzene as a photosensitizer, and in the same amount of molar amounts, p-tert-butyltoluene (222 mg), potassium carbonate (10 mg), or 0.1 molar equivalent of trifluoroacetic acid were placed in a Shrek bottle and sealed. Ethyl acetate (5 mL) was added under 1 bar O2. The mixture was then stirred at 35°C for 38 h under a 30 W blue LED lamp. After solvent removal, the white solid p-tert-butylbenzoic acid was obtained by column chromatography with a yield of 38%.

[0097] The obtained product NMR data are characterized as follows: 1 HNMR (400MHz, CDCl3) δ8.06 (d, J = 8.7Hz, 2H), 7.49 (d, J = 8.7Hz, 2H), 1.35 (s, 9H);

[0098] 13 CNMR (101MHz, CDCl3) δ172.6,157.7,130.2,126.7,125.6,35.3,31.2.

[0099] Application Example 4

[0100]

[0101] The photosensitizer synthesized in Example 1 (48 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%.

[0102] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR (400MHz, CDCl3) δ7.28 (t, J = 7.1Hz, 10H), 4.21 (s, 2H).

[0103] Application Example 5

[0104]

[0105] The photosensitizer (62 mg) synthesized in Example 4, along with 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 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 95% yield.

[0106] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR (400MHz, CDCl3) δ7.28 (t, J = 7.1Hz, 10H), 4.13 (s, 2H).

[0107] Application Example 6

[0108]

[0109] The photosensitizer (54 mg) synthesized in Example 5, along with 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 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 97% yield.

[0110] Products obtained 1 The HNMR data characterization is as follows: 1 HNMR (400MHz, CDCl3) δ7.28 (t, J = 7.5 Hz, 6H), 7.01 (t, J = 7 Hz, 2H), 4.27 (s, 2H), 2.08 (s, 6H).

[0111] 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 1,3-diaromatic formylbenzene compound, characterized in that, The structural formula of the 1,3-diaromatic formylbenzene compounds is shown in formula (I): ， （I） In formula (I), X is one of fluorine and chlorine, D is one of C1-C6 alkoxy and C1-C6 alkylthio, 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-C6 alkyl, C1-C6 alkoxy, hydroxyl, or halogen group.

2. The 1,3-diaromatic formylbenzene compound according to claim 1, characterized in that, Its structure is shown in equation (II): ， （Ⅱ） In formula (II), R1 is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

3. A method for preparing the 1,3-diaromatic formylbenzene compound according to claim 1 or 2, characterized in that, The reaction formula for the preparation method is shown below: ， (III) (I) In the formula, X is one of fluorine and chlorine, D is one of C1-C6 alkoxy and C1-C6 alkylthio, 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-C6 alkyl, C1-C6 alkoxy, hydroxyl, and halogen group, and the halogen group is selected from fluorine, chlorine, bromine, and iodine; The alcohol used in the reaction is one of C1-C6 alkyl alcohols or C1-C6 alkyl thiols.

4. The method for preparing a 1,3-diaromatic formylbenzene compound according to claim 3, characterized in that, The inorganic base used in the reaction is at least one of sodium hydroxide and potassium hydroxide.

5. The method for preparing a 1,3-diaromatic formylbenzene compound according to claim 3, characterized in that, In the reaction, the molar ratio of formula (III), alcohol and inorganic base is 1:1~100:1~10.

6. The method for preparing a 1,3-diaromatic formylbenzene compound according to claim 5, characterized in that, The reaction temperature is 65~85℃, and the reaction time is 10~15h.

7. The application of the 1,3-diaromatic formylbenzene compound of claim 1 or 2 in the field of photocuring.

8. The application of the 1,3-diaromatic formylbenzene compound of claim 1 or 2 in the field of photocatalytic oxidation, wherein the photocatalytic oxidation reaction formula is as follows: ， Wherein R is at least one of the ortho, meta, and para positions of the benzene ring methyl group, and R is selected from at least one of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, hydroxyl, halogen group, tert-butyl, nitro, cyano, and trifluoromethyl; PS is the 1,3-diaromatic formylbenzene compound as described in claim 1 or 2.

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