Preparation method and application of quinazoline compound

Abstract

The preparation method comprises the following steps: uniformly mixing a nitro aromatic compound, an alkyl aldehyde compound / aromatic aldehyde compound, an inorganic ammonium salt and an organic solvent, carrying out a reaction in an air or inert atmosphere at 50-150 DEG C under the irradiation of a light source with the wavelength of 254-580 nm, and then cooling to room temperature to obtain the quinazoline compound. And performing concentration and column chromatography purification to obtain the compound. The method realizes visible light promotion of quinazoline construction without an additional photocatalyst, metal and an additional oxidant, utilizes ingenious combination of weak photosensitivity of nitro-aromatic hydrocarbon and 2-nitrobenzyl structural design, generates a key active intermediate in situ under mild conditions, realizes high-efficiency tandem cyclization and oxidative aromatization, and improves the yield of quinazoline. The method thoroughly gets rid of dependence on precious metal or dye in a traditional method, and is green, environment-friendly and low in cost.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for preparing quinazoline compounds and their applications. Background Technology

[0002] Quinazolines, as an important class of polynitrogenous heterocyclic skeletons, have broad research value and application prospects in medicinal chemistry, materials science, and photocatalysis. These compounds can be used as epidermal growth factor receptor (EGFR) inhibitors, leucine-rich repeat kinase 2 (LRRK2) inhibitors, and phosphatidylinositol-3-kinase (PI3K) inhibitors for the treatment of various diseases, including antitumor, antibacterial, antiviral, and antimalarial applications. They can also participate in diverse transformations as organic synthesis intermediates. In recent years, quinazoline compounds have received increasing attention as hole transport layers, emissive layers, or host materials in organic light-emitting diodes (OLEDs).

[0003] Traditional quinazoline synthesis methods mainly use o-aminoacetophenone as the starting material, and construct the quinazoline ring through multiple steps with aromatic aldehydes, benzylamine or toluene under the catalysis of oxidants or transition metals (e.g., RSC Adv., 2016, 6, 36192-36197; J. Org. Chem. 2018, 83, 2395−2401; Angew. Chem. Int. Ed. 2012, 51, 8077-8081). Such methods generally suffer from the following drawbacks: First, o-aminoacetophenone requires multi-step pre-synthesis, making raw material preparation cumbersome and costly; second, the reaction often requires strong oxidants or transition metals (such as Cu, Fe, Pd, etc.) for catalysis, leading to difficulties in removing metal residues, increased synthesis costs, and environmental pollution risks; third, harsh oxidation conditions and high temperatures easily lead to side reactions, and the functional group compatibility is poor, limiting its applicability only to the introduction of simple inert substituents, thus restricting the direct construction of complex functionalized quinazolines, especially derivatives modified with large conjugated luminescent groups; finally, traditional methods are lengthy, have low atom economy, and generate a lot of waste, failing to meet the requirements of green synthesis.

[0004] In recent years, visible light photocatalysis has attracted widespread attention as a mild, green, and atom-economical synthetic strategy. Existing literature reports the use of Ir, Ru complexes, or organic dyes as photocatalysts to achieve heterocyclic construction involving nitro compounds. However, these methods still require the addition of photosensitizers, and the products are mostly quinolines or quinoxaline compounds, rather than quinazolines. Furthermore, the use of precious metals or dyes increases costs and may introduce separation and purification challenges. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing quinazoline compounds.

[0006] Another object of the present invention is to provide applications of the quinazoline compounds prepared by the above-described method.

[0007] The technical solution of the present invention is as follows:

[0008] A method for preparing a quinazoline compound, wherein the structural formula of the quinazoline compound is as follows: ,in:

[0009] R 1 It can be methyl, ester, methoxy, sulfonyl, cyano, tert-butyl, N,N-dimethyl, aromatic, or heteroaromatic.

[0010] R 2 It can be alkyl, furanyl, benzothiophene, thiophene, pyridyl, substituted pyridyl, anthraquinyl, quinolinyl, thiazinyl, phenothiazinyl, carbazole, benzophenone, pyrene, triarylamine, heterocyclic, monosubstituted aryl, polysubstituted aryl, or fused-ring group;

[0011] R 3 It can be alkyl, anthracene, quinolinyl, thiazinyl, phenothiazinyl, carbazole, benzophenone, pyrene, triarylamine, thiaanthrayl, heterocyclic, monosubstituted aryl, polysubstituted aryl, or fused-ring group;

[0012] The preparation method includes: mixing nitroaromatic compounds, alkyl aldehydes / aromatic aldehydes, inorganic ammonium salts and organic solvents evenly, reacting them in air or an inert atmosphere at 50-150 °C and under the illumination of a light source with a wavelength of 254 nm-580 nm, then cooling to room temperature, and then purifying by concentration and column chromatography to obtain the product;

[0013] The structural formulas of the above nitroaromatic compounds are as follows: ;

[0014] The structural formula of the above alkyl aldehyde compounds is as follows: ;

[0015] The structural formulas of the above aromatic aldehydes and heteroaromatic aldehydes are selected from... .

[0016] In a preferred embodiment of the present invention, the inorganic ammonium salt is selected from ammonium acetate, ammonium sulfate and ammonium chloride.

[0017] More preferably, the inorganic ammonium salt is ammonium acetate.

[0018] In a preferred embodiment of the present invention, the organic solvent is selected from methanol, ethanol, isopropanol, hexafluoroisopropanol, tetrahydrofuran, diethyl ether, DME, 1,4-dioxane, dichloroethane, carbon tetrachloride, chloroform, and toluene.

[0019] More preferably, the organic solvent is isopropanol.

[0020] In a preferred embodiment of the present invention, the inorganic ammonium salt is ammonium acetate and the organic solvent is isopropanol.

[0021] In a preferred embodiment of the present invention, the molar ratio of the nitroaromatic compound, the aromatic aldehyde compound / heteroaromatic aldehyde compound and the inorganic ammonium salt is 1:2:2.

[0022] More preferably, each 0.1 mmol of nitroaromatic compound corresponds to 2 mL of organic solvent.

[0023] The above-mentioned preparation method is used in the preparation of quinazoline compounds in the preparation of multifunctional photocatalysts (covering oxidative photocatalysts, reduced photocatalysts, energy transfer photocatalysts, and hydrogen atom transfer photocatalysts).

[0024] The use of quinazoline compounds prepared by the above method in the preparation of OLED devices.

[0025] The beneficial effects of this invention are:

[0026] 1. This invention achieves visible light-promoted construction of quinazoline without any external photocatalyst, metal, or oxidant. It cleverly combines the weak photosensitivity of nitroaromatic hydrocarbons with the 2-nitrobenzyl structure to generate key active intermediates in situ under mild conditions (50-120 °C, ordinary blue LED), achieving efficient tandem cyclization and oxidative aromatization. This completely eliminates the dependence on precious metals or dyes in traditional methods, making it green, environmentally friendly, and low-cost.

[0027] 2. The reaction raw materials of this invention are inexpensive and readily available (nitroaromatics, aldehydes, and ammonium salts are all bulk chemical products), avoiding the multi-step pre-synthesis of o-aminoacetophenone. The substrate range is extremely broad, compatible with alkynes, pinacol borate esters, all halogens, cyano groups, ester groups, trifluoromethyl groups, and many other sensitive functional groups. It introduces alkyl, aryl, heteroaryl, and anthracene, pyrene, carbazole, phenothiazine, triarylamine, and other large conjugated luminescent groups in one step, providing a new route for the efficient construction of complex functionalized quinazoline and OLED materials.

[0028] 3. The reaction conditions of this invention are mild and the operation is simple (one-pot method, air or inert atmosphere). The post-processing only requires conventional column chromatography and no waste polluting gas is generated. It is easy to scale up to the gram level and above, and fully meets the requirements of green chemistry and industrial production.

[0029] 4. The quinazoline compounds prepared by this invention have excellent photophysical properties and all-organic photocatalytic activity. They can efficiently catalyze a variety of oxidation, reduction, energy transfer, hydrogen atom transfer and free radical addition reactions, showing great potential as a new generation of metal-free photocatalysts and blue / green OLED materials. Detailed Implementation

[0030] The technical solution of the present invention will be further explained and described below through specific embodiments.

[0031] Examples 3 to 33 below relate to the synthesis of quinazoline compounds, and the reaction routes are as follows:

[0032]

[0033] Example 1

[0034] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 370 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and the target product was obtained by column chromatography.

[0035] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 25.5 mg of the target product, with a yield of 90%.

[0036] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to the reaction vessel and stirred. The mixture was then reacted at 410 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 25.5 mg of the target product, with a yield of 90%.

[0037] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1HNMR (500 MHz, CDCl3) δ 8.74 – 8.64 (m, 2H), 8.15 (dd, J = 17.6, 8.4 Hz, 2H), 7.94 – 7.85 (m, 3H), 7.60 (dd, J = 5.1, 1.9 Hz, 3H), 7.58 – 7.48 (m, 4H). 13 CNMR (126 MHz, CDCl3) δ 168.5, 160.4, 152.1, 138.3, 137.8, 133.7, 130.7,130.3, 130.1, 129.3, 128.8, 128.7, 127.2, 127.2, 121.9.

[0038] Example 2

[0039] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 4-(tert-butyl)benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 23.0 mg of the target product, with a yield of 68%.

[0040] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR(500 MHz, CDCl3) δ 8.60 (d, J = 8.5 Hz, 2H), 8.18 – 8.09 (m, 2H), 7.93 – 7.85(m, 3H), 7.60 (dd, J = 5.2, 1.9 Hz, 3H), 7.57 – 7.50 (m, 3H), 1.39 (s, 9H). 13 C NMR (126 MHz, CDCl3) δ 168.4, 160.5, 154.0, 152.2, 137.9, 135.6, 133.6,130.4, 130.0, 129.3, 128.7, 128.6, 127.2, 126.9, 125.8, 125.7, 121.7, 35.0,31.4.

[0041] Example 3

[0042] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 4-trifluoromethylbenzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 30.5 mg of the target product, with a yield of 87%.

[0043] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR (500 MHz, CDCl3) δ 8.82 (d, J = 8.1 Hz, 2H), 8.20 – 8.11 (m,2H), 7.93 – 7.86 (m, 3H), 7.78 (d, J = 8.3 Hz, 2H), 7.66 – 7.60 (m, 3H), 7.58(ddd, J = 8.2, 6.9, 1.2 Hz, 1H). 13 C NMR (126 MHz, CDCl3) δ 168.7, 158.9,152.0, 141.6, 137.5, 134.0, 132.1 (q, J = 32 Hz), 130.3, 130.3, 129.4, 129.0,128.8, 127.8, 127.2, 125.5 (q, J = 4 Hz), 122.1. 19 F NMR (471 MHz, CDCl3) δ -62.6 – -62.6 (m).

[0044] Example 4

[0045] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 4-formylphenylboronic acid pinacol ester (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 20.8 mg of the target product, with a yield of 51%.

[0046] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1H NMR (500 MHz, CDCl3) δ 8.70 (d, J = 8.2 Hz, 2H), 8.18 (d, J = 8.5Hz, 1H), 8.13 (d, J = 8.3 Hz, 1H), 7.97 (d, J = 8.1 Hz, 2H), 7.92 – 7.86 (m,3H), 7.64 – 7.57 (m, 3H), 7.55 (tt, J = 8.1, 1.2 Hz, 1H), 1.39 (s, 12H). 13 CNMR (126 MHz, CDCl3) δ 168.5, 160.3, 152.1, 140.8, 137.8, 135.1, 133.7,130.4, 130.1, 129.4, 128.7, 128.0, 127.3, 127.2, 121.9, 84.1, 25.1.

[0047] Example 5

[0048] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 4-ynylbenzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 27.3 mg of the target product, with a yield of 89%.

[0049] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR (500 MHz, CDCl3) δ 8.68 (d, J = 8.3 Hz, 2H), 8.15 (dd, J = 12.6,8.4 Hz, 2H), 7.93 – 7.86 (m, 3H), 7.66 (d, J = 8.4 Hz, 2H), 7.63 – 7.59 (m,3H), 7.57 (ddd, J = 8.2, 6.9, 1.2 Hz, 1H), 3.21 (s, 1H). 13C NMR (126 MHz, CDCl3) δ 168.6, 159.5, 152.0, 138.6, 137.7, 133.8, 132.5, 130.3, 130.2,129.3, 128.8, 128.7, 128.7, 128.7, 127.4, 127.2, 124.2, 121.9, 83.9, 78.9.

[0050] Example 6

[0051] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 2-fluoro-5-formylbenzonitrile (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 30.1 mg of the target product, with a yield of 93%.

[0052] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR (500 MHz, CDCl3) δ 9.00 (dd, J = 6.3, 2.1 Hz, 1H), 8.95 (ddd, J =8.9, 5.3, 2.2 Hz, 1H), 8.14 (t, J = 8.6 Hz, 2H), 7.93 (ddd, J = 8.4, 6.8, 1.5Hz, 1H), 7.89 – 7.81 (m, 2H), 7.65 – 7.57 (m, 4H), 7.33 (t, J = 8.6 Hz, 1H). 13 C NMR (126 MHz, CDCl3) δ 168.9, 164.5 (d, J = 258 Hz), 157.2, 151.9, 137.3,135.5 (d, J = 3 Hz), 135.3 (d, J = 9 Hz), 134.2 (d, J =3 Hz), 130.4, 130.3,129.2, 128.8, 127.9, 127.3, 122.0, 116.6 (d, J = 20 Hz), 114.1, 101.8 (d, J =16 Hz).

[0053] Example 7

[0054] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 3,4,5-trimethoxybenzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 18.0 mg of the target product, with a yield of 48%.

[0055] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR (500 MHz, CDCl3) δ 8.22 (s, 1H), 8.12 (d, J = 8.3 Hz, 1H), 8.03 (s,2H), 7.93 – 7.87 (m, 3H), 7.63 – 7.60 (m, 3H), 7.56 (ddd, J = 8.2, 6.8, 1.1Hz, 1H), 4.03 (s, 6H), 3.95 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 159.8, 153.5,137.7, 133.9, 130.4, 130.2, 128.7, 127.2, 127.2, 121.7, 106.1, 61.1, 56.5.

[0056] Example 8

[0057] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 1-naphthaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to the reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 27.0 mg of the target product, with a yield of 81%.

[0058] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1H NMR(500 MHz, CDCl3) δ 8.84 (d, J = 8.4 Hz, 1H), 8.32 – 8.25 (m, 2H), 8.22 (d, J= 7.9 Hz, 1H), 8.00 (d, J = 8.2 Hz, 1H), 7.94 (ddd, J = 15.3, 6.2, 2.8 Hz,4H), 7.67 – 7.53 (m, 7H). 13 C NMR (126 MHz, CDCl3) δ 168.6, 162.8, 151.8,137.5, 136.6, 134.3, 133.9, 131.5, 130.4, 130.2, 130.1, 129.8, 129.2, 128.7,128.5, 127.6, 127.1, 126.8, 126.2, 125.9, 125.4, 121.3.

[0059] Example 9

[0060] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 2-naphthaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to the reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 29.8 mg of the target product, with a yield of 90%.

[0061] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 HNMR (500 MHz, CDCl3) δ 9.25 (s, 1H), 8.82 (dd, J = 8.7, 1.7 Hz, 1H), 8.22 (d,J = 8.4 Hz, 1H), 8.15 (dd, J = 8.4, 1.4 Hz, 1H), 8.05 (dd, J = 6.6, 2.7 Hz,1H), 7.99 (d, J = 8.6 Hz, 1H), 7.96 – 7.87 (m, 4H), 7.68 – 7.59 (m, 3H), 7.59– 7.50 (m, 3H). 13C NMR (126 MHz, CDCl3) δ 168.6, 160.4, 152.1, 137.8, 135.7,134.9, 133.8, 133.6, 130.4, 130.1, 129.5, 129.3, 129.2, 128.8, 128.3, 127.9,127.3, 127.2, 127.2, 126.3, 125.7, 121.9.

[0062] Example 10

[0063] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), thiophene-2-carboxaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 16.2 mg of the target product, with a yield of 56%.

[0064] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 HNMR (500 MHz, CDCl3) δ 8.22 (d, J = 3.0 Hz, 1H), 8.13 – 8.05 (m, 2H), 7.86 (m, 3H), 7.64 – 7.56 (m, 3H), 7.54 – 7.47 (m, 2H), 7.19 (dd, J = 5.0, 3.7 Hz, 1H). 13 C NMR (126 MHz, CDCl3) δ 168.6, 157.3, 151.9, 144.2, 137.4, 133.9,130.3, 130.2, 130.0, 129.6, 128.8, 128.7, 128.4, 127.3, 126.9, 121.7.

[0065] Example 11

[0066] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 3-formaldehyde benzothiophene (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 27.2 mg of the target product, with a yield of 80%.

[0067] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 HNMR (500 MHz, CDCl3) δ 9.48 (d, J = 8.1 Hz, 1H), 8.86 (s, 1H), 8.21 (d, J =8.2 Hz, 1H), 8.11 (dd, J = 8.4, 1.4 Hz, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.91(dd, J = 6.6, 2.9 Hz, 2H), 7.90 – 7.85 (m, 1H), 7.65 – 7.57 (m, 4H), 7.55 –7.50 (m, 1H), 7.49 – 7.44 (m, 1H). 13 C NMR (126 MHz, CDCl3) δ 168.1, 151.7,141.2, 137.6, 137.4, 135.2, 133.6, 132.8, 130.2, 130.0, 129.1, 128.6, 127.1,126.9, 126.2, 124.9, 124.6, 122.7, 121.4.

[0068] Example 12

[0069] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 6-methoxy-3-pyridinecarboxaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 14.8 mg of the target product, with a yield of 47%.

[0070] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1H NMR (500 MHz, CDCl3) δ 9.49 (d, J = 2.3 Hz, 1H), 8.82 (dd, J = 8.7, 2.3 Hz, 1H), 8.12 (dd, J = 8.4, 4.7 Hz, 2H), 7.92 – 7.80 (m, 3H), 7.59 (t, J = 3.3 Hz,3H), 7.54 (ddd, J = 8.2, 6.9, 1.2 Hz, 1H), 6.87 (d, J = 8.7 Hz, 1H), 4.04 (s,3H). 13 C NMR (126 MHz, CDCl3) δ 168.5, 165.8, 158.8, 152.1, 148.7, 138.9,137.7, 133.8, 130.3, 130.2, 129.1, 128.7, 127.7, 127.2, 127.1, 121.7, 110.6,53.9.

[0071] Example 13

[0072] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 1-methyl-1H-pyrazole-3-carboxaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 15.7 mg of the target product, with a yield of 55%.

[0073] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 HNMR (500 MHz, CDCl3) δ 8.23 ​​(d, J = 8.4 Hz, 1H), 8.08 (d, J = 8.8 Hz, 1H), 7.89 – 7.82 (m, 3H), 7.56 (dd, J = 5.0, 1.9 Hz, 3H), 7.54 – 7.50 (m, 1H), 7.46 (d, J = 2.3 Hz, 1H), 7.22 (d, J = 2.2 Hz, 1H), 4.07 (s, 3H). 13C NMR (126MHz, CDCl3) δ 168.9, 156.5, 151.9, 151.4, 137.6, 133.7, 131.5, 130.3, 130.0,129.4, 128.6, 127.1, 127.0, 122.0, 108.0, 39.7.

[0074] Example 14

[0075] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 4-(2-pyridyl)benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 20.2 mg of the target product, with a yield of 56%.

[0076] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR (500 MHz, CDCl3) δ 8.83 (d, J = 8.5 Hz, 2H), 8.78 – 8.69 (m,1H), 8.14 – 8.07 (m, 3H), 8.11 (d, J = 8.1 Hz, 1H), 7.93 – 7.84 (m, 3H), 7.82(d, J = 7.9 Hz, 1H), 7.75 (td, J = 7.7, 1.7 Hz, 1H), 7.64 – 7.57 (m, 3H), 7.55 – 7.50 (m, 1H), 7.29 – 7.21 (m, 1H). 13 C NMR (126 MHz, CDCl3) δ 168.4,159.9, 157.1, 152.1, 149.8, 141.2, 138.8, 137.7, 136.9, 133.7, 130.3, 130.0,129.3, 129.2, 128.6, 127.2, 127.1, 122.4, 121.8, 120.9.

[0077] Example 15

[0078] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), N-(4-benzaldehyde)-carbazole (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 29.2 mg of the target product, with a yield of 65%.

[0079] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR (500 MHz, CDCl3) δ 9.05 – 8.92 (m, 2H), 8.26 – 8.16 (m, 4H), 7.98 – 7.89 (m, 3H), 7.79 (dd, J = 8.6, 1.8 Hz, 2H), 7.68 – 7.62 (m, 3H), 7.62 – 7.55 (m, 3H), 7.47 (t, J = 7.7 Hz, 2H), 7.34 (t, J = 7.4 Hz, 2H). 13 CNMR (126 MHz, CDCl3) δ 168.6, 159.6, 152.1, 140.7, 139.8, 137.7, 137.3,133.8, 130.4, 130.3, 130.1, 129.3, 128.7, 127.3, 127.2, 126.9, 126.1, 123.7,121.8, 120.4, 120.2, 110.1.

[0080] Example 16

[0081] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 4-(10H-phenyloxazin-10-yl)benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 26.0 mg of the target product, with a yield of 56%.

[0082] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1H NMR (500 MHz, CDCl3) δ 8.89 (d, J = 8.1 Hz, 2H), 8.26 – 8.14 (m,2H), 7.98 – 7.89 (m, 3H), 7.71 – 7.58 (m, 4H), 7.55 – 7.49 (m, 2H), 6.75 –6.56 (m, 6H), 6.05 (d, J = 7.9 Hz, 2H). 13 C NMR (126 MHz, CDCl3) δ 168.8,159.6, 152.1, 138.6, 137.6, 134.0, 131.6, 130.3, 130.2, 129.3, 128.8, 127.5,127.3, 123.4, 121.9, 113.5.

[0083] Example 17

[0084] Under an argon atmosphere, 1-benzylnitrobenzene (0.1 mmol), 4-(10H-phenthiazin-10-yl)benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 22.8 mg of the target product, with a yield of 48%.

[0085] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR (500 MHz, CDCl3) δ 8.89 (d, J = 1.9 Hz, 2H), 8.27 – 8.14(m, 2H), 7.99 – 7.86 (m, 3H), 7.65 – 7.48 (m, 6H), 7.08 (dd, J = 7.4, 1.8 Hz,2H), 6.95 – 6.80 (m, 4H), 6.43 (dd, J = 8.1, 1.5 Hz, 2H). 13 C NMR (126 MHz, CDCl3) δ 168.6, 159.6, 152.0, 144.0, 143.5, 137.7, 137.6, 133.8, 131.2,130.3, 130.1, 129.8, 129.2, 128.7, 127.4, 127.2, 127.0, 122.9, 121.8, 121.4,117.1.

[0086] Example 18

[0087] Under an argon atmosphere, methyl 4-(2-nitrobenzene)benzoate (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 23.2 mg of the target product, with a yield of 68%.

[0088] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 HNMR (500 MHz, CDCl3) δ 8.68 (d, J = 7.7 Hz, 2H), 8.27 (d, J = 8.4 Hz, 2H), 8.17 (d, J = 8.5 Hz, 1H), 8.04 (d, J = 8.4 Hz, 1H), 7.95 (d, J = 8.4 Hz, 2H),7.89 (ddd, J = 8.5, 6.9, 1.5 Hz, 1H), 7.58 – 7.47 (m, 4H), 4.00 (s, 3H). 13 CNMR (126 MHz, CDCl3) δ 167.4, 166.8, 160.3, 152.1, 142.0, 138.1, 133.9,131.4, 130.8, 130.3, 130.0, 129.9, 129.4, 129.0, 128.8, 128.7, 127.4, 126.6,121.6, 52.5.

[0089] Example 19

[0090] Under an argon atmosphere, 1-(4-(methylthio-1)phenyl)-2-nitrobenzene (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 22.5 mg of the target product, with a yield of 62%.

[0091] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1H NMR (500 MHz, CDCl3) δ 8.71 – 8.64 (m, 2H), 8.25 – 8.17 (m, 3H), 8.09 (d, J= 8.1 Hz, 2H), 8.01 (d, J = 8.4 Hz, 1H), 7.99 – 7.92 (m, 1H), 7.63 – 7.58 (m,1H), 7.58 – 7.50 (m, 3H), 3.17 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 166.5,160.4, 152.2, 143.1, 141.8, 137.9, 134.2, 131.3, 131.0, 129.7, 128.8, 127.8,127.8, 126.3, 121.5, 44.7.

[0092] Example 20

[0093] Under an argon atmosphere, 1-fluoro-2-(2-nitrobenzene)benzene (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 18.9 mg of the target product, with a yield of 63%.

[0094] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 HNMR (500 MHz, CDCl3) δ 8.75 – 8.58 (m, 2H), 8.17 (d, J = 8.3 Hz, 1H), 7.90 (ddd, J = 8.4, 6.8, 1.4 Hz, 1H), 7.82 (ddd, J = 8.6, 3.3, 1.0 Hz, 1H), 7.71(td, J = 7.3, 1.8 Hz, 1H), 7.61 – 7.48 (m, 5H), 7.39 (td, J = 7.6, 1.1 Hz,1H), 7.29 (ddd, J = 9.6, 8.4, 1.1 Hz, 1H). 13C NMR (126 MHz, CDCl3) δ 164.7,160.6, 159.8 (d, J = 248 Hz), 151.5, 138.2, 134.0, 132.1 (d, J =3 Hz), 131.8 (d, J = 8 Hz), 130.7, 129.1, 128.8, 128.7, 127.3, 127.0 (d, J = 3 Hz), 125.8 (d, J = 12 Hz), 124.8 (d, J = 3 Hz), 122.6, 116.3 (d, J = 21 Hz). 19 F NMR (471MHz, CDCl3) δ -110.7 – -110.8 (m).

[0095] Example 21

[0096] Under an argon atmosphere, 0.1 mmol of 2,4-dimethyl-1-(2-nitrophenyl)benzene, 0.2 mmol of benzaldehyde, 0.2 mmol of ammonium acetate, and 2 mL of isopropanol were added to a reaction vessel and stirred. The mixture was then reacted at 120 °C under 390 nm light source irradiation for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 15.9 mg of the target product, with a yield of 46%.

[0097] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 HNMR (500 MHz, CDCl3) δ 8.65 (d, J = 7.6 Hz, 2H), 8.12 (d, J = 8.4 Hz, 1H), 7.84 (t, J = 7.6 Hz, 1H), 7.75 (d, J = 7.8 Hz, 1H), 7.54 – 7.44 (m, 5H), 6.71(dd, J = 8.4, 2.3 Hz, 1H), 6.65 (d, J = 2.3 Hz, 1H), 3.92 (s, 3H), 3.72 (s,3H). 13 C NMR (126 MHz, CDCl3) δ 167.6, 162.4, 160.7, 158.5, 151.1, 138.6,133.5, 132.4, 130.4, 128.9, 128.8, 128.6, 127.9, 126.6, 123.2, 120.2, 105.3,99.0, 55.7, 55.6.

[0098] Example 22

[0099] Under an argon atmosphere, 1,3,5-trimethyl-2-(2-nitrophenyl)benzene (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 19.9 mg of the target product, with a yield of 53%.

[0100] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR (500 MHz, CDCl3) δ 8.65 – 8.59 (m, 2H), 8.12 (d, J = 8.4 Hz, 1H), 7.83 (ddd, J = 8.4, 6.8, 1.5 Hz, 1H), 7.63 (dd, J = 8.3, 1.4 Hz, 1H), 7.52 – 7.42(m, 4H), 6.30 (s, 2H), 3.91 (s, 3H), 3.65 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ166.1, 162.5, 161.0, 159.3, 151.1, 138.9, 133.4, 130.2, 129.0, 128.8, 128.5,127.2, 126.7, 124.4, 108.6, 91.3, 56.1, 55.6.

[0101] Example 23

[0102] Under an argon atmosphere, (4-(2-nitrophenyl)phenyl)(phenyl)methane (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 17.5 mg of the target product, with a yield of 45%.

[0103] The structural formula of the target product in this embodiment is = Its NMR characterization is as follows: 1H NMR (500 MHz, CDCl3) δ 8.70 (dd, J = 8.0, 1.7 Hz, 2H), 8.19 (d, J = 8.5Hz, 1H), 8.11 (dd, J = 8.4, 1.5 Hz, 1H), 8.06 – 7.98 (m, 4H), 7.95 – 7.87 (m,3H), 7.67 – 7.62 (m, 1H), 7.61 – 7.57 (m, 1H), 7.57 – 7.49 (m, 5H). 13 C NMR(126 MHz, CDCl3) δ 196.3, 167.4, 160.4, 152.2, 141.5, 138.8, 138.1, 137.4,134.0, 132.9, 130.8, 130.3, 130.3, 129.5, 128.8, 128.7, 128.6, 127.5, 126.7,121.7.

[0104] Example 24

[0105] Under an argon atmosphere, 8-(2-nitrobenzyl)quinoline (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 22.0 mg of the target product, with a yield of 66%.

[0106] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1HNMR (500 MHz, CDCl3) δ 8.78 (dd, J = 4.1, 1.8 Hz, 1H), 8.65 (dd, J = 8.0, 1.7Hz, 2H), 8.29 (dd, J = 8.3, 1.8 Hz, 1H), 8.18 (d, J = 8.5 Hz, 1H), 8.05 (dd,J = 8.2, 1.5 Hz, 1H), 7.94 (dd, J = 7.0, 1.5 Hz, 1H), 7.84 (ddd, J = 8.4,6.7, 1.5 Hz, 1H), 7.76 (dd, J = 8.2, 7.0 Hz, 1H), 7.53 – 7.46 (m, 3H), 7.45 –7.40 (m, 2H), 7.36 (ddd, J = 8.2, 6.7, 1.2 Hz, 1H). 13 C NMR (126 MHz, CDCl3) δ169.1, 160.8, 151.1, 150.8, 146.7, 138.6, 137.5, 136.3, 133.6, 131.2, 130.4,129.7, 129.0, 129.0, 128.6, 128.4, 128.0, 126.8, 126.5, 123.9, 121.6.

[0107] Example 25

[0108] Under an argon atmosphere, 1-benzyl-4-methyl-2-nitrobenzene (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 15.5 mg of the target product, with a yield of 52%.

[0109] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1H NMR (600 MHz, CDCl3) δ 8.76 – 8.69 (m, 2H), 8.01 (d, J = 8.5 Hz, 1H), 7.95 (s, 1H), 7.91 – 7.87 (m, 2H), 7.63 – 7.57 (m, 3H), 7.57 – 7.50 (m, 3H), 7.36 (dd, J = 8.5, 1.7 Hz, 1H), 2.59 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ 167.8,160.4, 152.4, 144.5, 138.5, 137.9, 130.5, 130.2, 129.9, 129.3, 128.7, 128.6,128.2, 126.7, 119.9, 22.2.

[0110] Example 26

[0111] Under an argon atmosphere, 1-benzyl-4-methoxy-2-nitrobenzene (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 21.4 mg of the target product, with a yield of 69%.

[0112] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR (500 MHz, CDCl3) δ 8.68 (d, J = 6.3 Hz, 2H), 8.00 (d, J = 9.1Hz, 1H), 7.86 (dd, J = 6.4, 1.9 Hz, 2H), 7.58 (dd, J = 5.4, 1.7 Hz, 3H), 7.56– 7.48 (m, 3H), 7.45 (d, J = 2.3 Hz, 1H), 7.15 (dt, J = 9.2, 2.0 Hz, 1H), 4.01 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 167.3, 163.9, 161.0, 154.6, 138.5,138.0, 130.5, 130.2, 129.9, 128.7, 128.6, 128.5, 120.3, 117.2, 106.8, 55.9.

[0113] Example 27

[0114] Under an argon atmosphere, 5-(4-(tert-butyl)-2-nitrobenzyl)-1,2,3-trifluorobenzene (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 32.8 mg of the target product, with a yield of 84%.

[0115] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR (500 MHz, CDCl3) δ 8.65 (dd, J = 8.0, 1.7 Hz, 2H), 8.14 (d, J = 2.0Hz, 1H), 8.00 (d, J = 8.8 Hz, 1H), 7.70 (dd, J = 8.9, 2.0 Hz, 1H), 7.59 –7.52 (m, 5H), 1.47 (s, 9H). 13 C NMR (126 MHz, CDCl3) δ 164.2, 160.4, 158.2,152.7, 151.4 (ddd, J = 251, 8, 4 Hz), 141.0 (dt, J = 247, 22 Hz), 138.0,133.8 (ddd, J = 12, 4, 2 Hz), 130.9, 128.8, 128.7, 126.9, 125.5, 124.9,119.2, 114.7 (dd, J = 16, 6 Hz), 35.7, 31.0. 19 F NMR (471 MHz, CDCl3) δ -133.2(d, J = 20 Hz), -134.4 (d, J = 21 Hz), -158.0 (t, J = 20 Hz), -163.4 (t, J =20 Hz).

[0116] Example 28

[0117] Under an argon atmosphere, 9-(4-(2-nitrobenzyl)phenyl)anthracene (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 21.8 mg of the target product, with a yield of 48%.

[0118] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR (500 MHz, CDCl3) δ 8.79 (d, J = 7.0 Hz, 2H), 8.56 (s, 1H), 8.39 (d, J =8.3 Hz, 1H), 8.25 (d, J = 8.4 Hz, 1H), 8.16 (d, J = 7.9 Hz, 2H), 8.10 (d, J =8.4 Hz, 2H), 7.96 (ddd, J = 8.3, 6.8, 1.3 Hz, 1H), 7.83 (d, J = 8.8 Hz, 2H),7.72 – 7.64 (m, 3H), 7.59 (t, J = 7.2 Hz, 2H), 7.56 – 7.49 (m, 3H), 7.43(ddd, J = 8.0, 6.5, 1.2 Hz, 2H). 13 C NMR (126 MHz, CDCl3) δ 168.2, 160.5,152.2, 141.0, 138.3, 137.0, 136.2, 134.2, 133.8, 131.7, 131.5, 130.7, 130.5,130.3, 129.4, 128.9, 128.8, 128.6, 127.4, 127.3, 127.2, 127.1, 126.8, 125.8,125.4, 121.9.

[0119] Example 29

[0120] Under an argon atmosphere, 1-(4-(2-nitrobenzyl)phenyl)pyrene (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 23.1 mg of the target product, with a yield of 48%.

[0121] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 HNMR (500 MHz, CDCl3) δ 8.78 (d, J = 6.7 Hz, 2H), 8.37 – 8.30 (m, 2H), 8.28 (d, J = 7.8 Hz, 1H), 8.22 (dd, J = 12.4, 7.7 Hz, 3H), 8.14 – 8.07 (m, 6H), 8.04 (t, J = 7.6 Hz, 1H), 7.94 (ddd, J = 8.3, 6.8, 1.3 Hz, 1H), 7.88 (d, J =7.9 Hz, 2H), 7.63 (ddd, J = 8.2, 6.8, 1.2 Hz, 1H), 7.61 – 7.53 (m, 3H).

[0122] 13 C NMR (126 MHz, CDCl3) δ 168.2, 160.5, 152.2, 143.2, 138.3, 136.9,136.7, 133.8, 131.6, 131.1, 131.1, 131.0, 130.7, 130.5, 129.4, 128.9, 128.7,128.7, 127.9, 127.8, 127.7, 127.5, 127.3, 127.2, 126.3, 125.5, 125.2, 125.2,125.0, 124.9, 121.9.

[0123] Example 30

[0124] Under an argon atmosphere, 9,9-dimethyl-10-(4-(2-nitrobenzyl)phenyl)-9,10-dihydroacridine (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 34.1 mg of the target product, with a yield of 70%.

[0125] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 H NMR (500 MHz, CDCl3) δ 8.81 – 8.72 (m, 2H), 8.29 (d, J = 8.3 Hz, 1H), 8.22 (dd, J = 15.5, 8.3 Hz, 3H), 7.96 (ddd, J = 8.3, 6.8, 1.3 Hz, 1H), 7.65(ddd, J = 8.3, 6.8, 1.2 Hz, 1H), 7.63 – 7.57 (m, 4H), 7.57 – 7.51 (m, 3H), 7.07 (t, J = 7.4, 2H), 7.00 (t, J = 7.5, 2H), 6.48 (dd, J = 8.1, 1.3 Hz, 2H), 1.76 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ 167.5, 160.5, 152.3, 143.2, 140.9,138.2, 137.6, 133.9, 133.0, 131.6, 130.8, 130.4, 129.5, 128.8, 128.8, 127.4,126.9, 126.6, 125.5, 121.7, 121.0, 114.4, 36.2, 31.4.

[0126] Example 31

[0127] Under an argon atmosphere, 10-(4-(2-nitrobenzyl)phenyl)-10H-phenthiazide (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 19.6 mg of the target product, with a yield of 41%.

[0128] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1 HNMR (500 MHz, CDCl3) δ 8.72 (d, J = 7.1 Hz, 2H), 8.21 (dd, J = 15.2, 8.4 Hz,2H), 8.08 (d, J = 8.1 Hz, 2H), 7.94 (t, J = 7.3 Hz, 1H), 7.65 – 7.49 (m, 6H), 7.17 (d, J = 7.5 Hz, 2H), 7.04 (t, J = 7.7 Hz, 2H), 6.95 (t, J = 7.4 Hz, 2H), 6.66 (d, J = 8.1 Hz, 2H). 13 C NMR (126 MHz, CDCl3) δ 167.5, 160.4, 152.2,144.1, 143.6, 138.2, 135.9, 133.9, 132.6, 130.8, 129.4, 128.8, 128.7, 127.5,127.3, 127.2, 127.0, 123.9, 123.7, 121.7, 119.0.

[0129] Example 32

[0130] Under an argon atmosphere, 0.1 mmol of 4'-(2-nitrobenzyl)-N,N-diphenyl-[1,1'-biphenyl]-4-amine, 0.2 mmol of benzaldehyde, 0.2 mmol of ammonium acetate, and 2 mL of isopropanol were added to a reaction vessel and stirred. The mixture was then reacted at 120 °C under 390 nm light source irradiation for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 31.3 mg of the target product, with a yield of 61%.

[0131] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1H NMR (500 MHz, CDCl3) δ 8.72 (d, J = 8.1 Hz, 2H), 8.20 (dd, J = 18.6, 8.4Hz, 2H), 7.98 (d, J = 8.2 Hz, 2H), 7.90 (t, J = 7.6 Hz, 1H), 7.80 (d, J = 8.2Hz, 2H), 7.61 – 7.50 (m, 6H), 7.30 (t, J = 7.8 Hz, 4H), 7.19 (t, J = 7.8 Hz, 6H), 7.07 (t, J = 7.5 Hz, 2H). 13 C NMR (126 MHz, CDCl3) δ 168.1, 160.4, 152.2,147.9, 147.7, 142.5, 138.4, 136.1, 134.0, 133.7, 130.9, 130.7, 129.5, 129.3,128.8, 128.7, 128.0, 127.2, 127.2, 126.8, 124.8, 123.7, 123.3, 121.9.

[0132] Example 33

[0133] Under an argon atmosphere, 1-(4-(2-nitrobenzyl)phenyl)thiophene (0.1 mmol), benzaldehyde (0.2 mmol), ammonium acetate (0.2 mmol), and isopropanol (2 mL) were added to a reaction vessel and stirred. The mixture was then reacted at 390 nm light source and 120 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 24.9 mg of the target product, with a yield of 50%.

[0134] The structural formula of the target product in this embodiment is: Its NMR characterization is as follows: 1HNMR (500 MHz, CDCl3) δ 8.86 – 8.74 (m, 2H), 8.35 (d, J = 8.3 Hz, 1H), 8.27(d, J = 8.4 Hz, 1H), 8.09 (d, J = 7.9 Hz, 2H), 7.99 (t, J = 7.5 Hz, 1H), 7.75– 7.66 (m, 3H), 7.64 – 7.57 (m, 4H), 7.50 (d, J = 7.3 Hz, 1H), 7.45 – 7.38(m, 2H), 7.36 – 7.26 (m, 3H). 13 C NMR (126 MHz, CDCl3) δ 168.1, 160.5, 152.2,142.1, 141.9, 138.3, 137.2, 136.5, 136.0, 136.0, 135.2, 133.8, 130.7, 130.3,129.9, 129.5, 129.4, 129.1, 128.9, 128.8, 128.7, 128.0, 127.8, 127.4, 127.3,127.2, 121.8.

[0135] Table 1 below shows the fluorescence spectral data of the target products, quinazoline compounds, prepared in Examples 1 to 32.

[0136] Table 1. Fluorescence spectral data of quinazoline compounds prepared in Examples 1 to 32

[0137]

[0138] Examples 34-40 below relate to the catalytic performance testing of quinazoline compounds.

[0139] Example 34

[0140]

[0141] Under an oxygen atmosphere, 0.005 mmol of quinazoline, 0.1 mmol of 2-phenoxy-1-phenylethane-1-ol, and 1 mL of DCE, prepared in Examples 10, 9, 2, 18, or 3 above, were added to a photoreaction tube and stirred. The mixture was then irradiated with a 410 nm light source at room temperature for 24 h. After the reaction was completed, the mixture was concentrated under reduced pressure and separated by column chromatography to obtain the target product. The NMR data are as follows: 1H NMR (500 MHz, CDCl3) δ 8.21 – 8.03 (m, 2H), 7.62 (t, J = 7.4Hz, 1H), 7.55 – 7.41 (m, 2H). 13 The C NMR (126 MHz, CDCl3) values ​​of δ 171.9, 133.9, 130.4, 129.4, and 128.6 are consistent with the reported NMR data of the compound. The screening conditions are shown in Table 2 below.

[0142] Table 2 Optimization of photocatalytic conditions for quinazoline [a]

[0143]

[0144] Example 35

[0145]

[0146] Under an argon atmosphere, 0.01 mmol of quinazoline, 0.1 mmol of 1,1-stilbene, 0.01 mmol of 2,3,4,5,6-pentafluorobenzenethiol, and MeCN:H2O (9:1 = 1 mL) prepared in Examples (9, 2) were added to a photoreaction tube and stirred. The mixture was then irradiated with a 410 nm light source at room temperature for 24 h. After the reaction was completed, the mixture was concentrated under reduced pressure and the target product was obtained by column chromatography. The NMR data are as follows: 1 H NMR (500 MHz, CDCl3) δ 7.39 – 7.34 (m,4H), 7.33 – 7.26 (m, 6H), 4.26 (dd, J = 8.5, 5.7 Hz, 1H), 4.22 (d, J = 7.5Hz, 2H), 1.53 (s, 1H). 13 The C NMR (126 MHz, CDCl3) values ​​were 141.5, 128.9, 128.5, 127.0, 66.3, and 53.8, consistent with the reported NMR data of the compound. The selection criteria are shown in Table 3 below.

[0147] Table 3 Optimization of photocatalytic conditions for quinazoline [a]

[0148]

[0149] Example 36

[0150]

[0151] Under an argon atmosphere, 0.005 mmol of quinazoline, 0.1 mmol of 1-ethyl-4-methoxybenzene, 0.2 mmol of 4-bromo-1H-pyrazole, 0.1 mmol of potassium persulfate, and DCE:HFIP (7:3 = 1 mL) prepared in Examples 10, 9, 2, 18, or 3 were added to a photoreaction tube and stirred. The mixture was then irradiated with a 410 nm light source at room temperature for 24 h. After the reaction was complete, the mixture was concentrated under reduced pressure and separated by column chromatography to obtain the target product. The NMR data are as follows: 1 H NMR (500 MHz, CDCl3) δ7.48 (s, 1H), 7.33 (s, 1H), 7.20 – 7.15 (m, 2H), 6.90 – 6.85 (m, 2H), 5.43(q, J = 7.0 Hz, 1H), 3.79 (s, 3H), 1.85 (d, J = 7.1 Hz, 3H). 13 C NMR (126 MHz, CDCl3) δ 159.5, 139.6, 133.0, 128.0, 127.9, 114.3, 93.0, 61.4, 55.4, 21.3, the selection criteria are shown in Table 4 below.

[0152] Table 4 Optimization of photocatalytic conditions for quinazoline [a]

[0153]

[0154] Example 37

[0155]

[0156] Under an argon atmosphere, 0.005 mmol of quinazoline, 0.3 mmol of anisole, 0.1 mmol of N-phenylmaleimide, 0.2 mmol of potassium persulfate, and 2 mL of CHCl3 were added to a photoreaction tube and stirred. The mixture was then irradiated with a 410-525 nm light source at room temperature for 24-48 h. After the reaction, the mixture was concentrated under reduced pressure and separated by column chromatography to obtain the target product. The NMR data are as follows: 1H NMR (500 MHz, CDCl3) δ7.53 – 7.45 (m, 3H), 7.43 – 7.39 (m, 1H), 7.37 (dd, J = 7.1, 2.0 Hz, 1H), 7.35 – 7.25 (m, 4H), 4.28 (d, J = 9.4 Hz, 1H), 3.83 (ddd, J = 9.4, 4.8, 2.4Hz, 1H), 3.46 (dd, J = 13.4, 2.5 Hz, 1H), 2.96 (dd, J = 13.3, 4.8 Hz, 1H). 13 CNMR (126 MHz, CDCl3) δ 177.3, 175.1, 134.9, 132.1, 132.0, 130.6, 129.8, 129.2, 128.9, 128.2, 127.1, 126.6, 45.7, 44.7, 30.5 are consistent with the reported NMR data of the compound. The screening conditions are shown in Table 5.

[0157] Table 5 Optimization of photocatalytic conditions for quinazoline [a]

[0158]

[0159] Example 38

[0160]

[0161] Under an argon atmosphere, 0.005 mmol of quinazoline, 0.2 mmol of benzaldehyde, 0.1 mmol of terephthalonitrile, 0.3 mmol of DIPEA, and 1 mL of DMSO, prepared in Examples 30, 28, 32, 16, 17, or 31, were added to a photoreaction tube and stirred. The mixture was then irradiated with a 427 nm light source at room temperature for 24 h. After the reaction was complete, the mixture was concentrated under reduced pressure and separated by column chromatography to obtain the target product. The NMR data are as follows: 1 H NMR (500 MHz, CDCl3) δ 7.65 – 7.57 (m,2H), 7.51 (d, J = 8.1 Hz, 2H), 7.39 – 7.28 (m, 5H), 5.86 (s, 1H), 2.76 – 2.50(s, 1H). 13C NMR (126 MHz, CDCl3) δ 149.0, 142.9, 132.4, 129.0, 128.4, 127.1, 126.8, 118.9, 111.3, 75.8 are consistent with the NMR data of the reported compound. The screening conditions are shown in Table 6.

[0162] Table 6 Optimization of photocatalytic conditions for quinazoline [a]

[0163]

[0164] Example 39

[0165]

[0166] Under an argon atmosphere, 0.005 mmol of quinazoline, 0.2 mmol of biphenyltoluene, 0.1 mmol of 2-benzylmalonium (2-Benzylmalonium), and 1 mL of DCE, prepared in Examples 10, 2, 18, 23, or 3, were added to a photoreaction tube and stirred. The mixture was then irradiated with a 440 nm light source at room temperature for 32 h. After the reaction was complete, the mixture was concentrated under reduced pressure and separated by column chromatography to obtain the target product. The NMR data are as follows: 1 H NMR (500 MHz, CDCl3) δ 7.61 – 7.52 (m, 4H), 7.50 – 7.37 (m,7H), 7.37 – 7.33 (m, 1H), 7.27 – 7.23 (m, 2H), 3.90 (d, J = 5.1 Hz, 1H), 3.49(td, J = 8.5, 7.2 Hz, 1H), 3.40 – 3.19 (m, 2H). 13 C NMR (126 MHz, CDCl3) δ 140.7, 140.5, 136.5, 135.7, 129.5, 129.4, 129.2, 129.0, 128.2, 127.9, 127.7, 127.1, 112.2, 111.6, 48.4, 38.3, 28.7. These values ​​are consistent with the reported NMR data of the compound. The screening conditions are shown in Table 7.

[0167] Table 7 Optimization of photocatalytic conditions for quinazoline [a]

[0168]

[0169] Example 40

[0170]

[0171] Under an argon atmosphere, 0.01 mmol of quinazoline, 0.1 mmol of 1,2-diphenylacetylene, 0.4 mmol of N-cyclohexylmaleamide, and 2.0 mL of DCM (prepared in Examples 29, 30, 32, 16, 17, or 31) were added to a photoreaction tube and stirred. The mixture was then irradiated with a 390 nm light source at room temperature for 48 h. After the reaction was complete, the mixture was concentrated under reduced pressure and separated by column chromatography to obtain the target product. The NMR data are as follows: 1 H NMR (500 MHz, CDCl3) δ 7.80 – 7.69 (m, 4H),7.41 – 7.31 (m, 6H), 4.00 (s, 2H), 3.95 – 3.89 (m, 1H), 2.11 (dd, J = 12.5,3.7 Hz, 2H), 1.78 (dt, J = 12.9, 2.9 Hz, 2H), 1.61 – 1.54 (m, 4H), 1.29 –1.23 (m, 2H). 13 C NMR (126 MHz, CDCl3) δ 175.3, 139.8, 133.2, 129.3, 128.8, 127.1, 51.7, 44.7, 28.7, 26.0, 25.2, and the selection criteria are shown in Table 8 below.

[0172] Table 8 Optimization of photocatalytic conditions for quinazoline [a]

[0173]

[0174] The above description is merely a preferred embodiment of the present invention, and therefore should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made in accordance with the scope of the patent and the contents of the specification should still fall within the scope of the present invention.

Claims

1. A process for the preparation of a quinazoline compound, characterized by: The quinazoline compound has a structural formula wherein: R 1 is methyl, ester, methoxy, sulfonyl, cyano, tert-butyl, N,N-dimethyl, aryl ring or heteroaromatic ring, R 2 is alkyl, furanyl, benzothienyl, thienyl, pyridyl, substituted pyridyl, anthryl, quinolinyl, thiazinyl, phenothiazinyl, carbazolyl, benzophenonyl, pyrenyl, triarylaminyl, heterocyclyl, mono-substituted aryl, poly-substituted aryl, or fused ring group; R 3 is alkyl, anthryl, quinolinyl, thiazinyl, phenothiazinyl, carbazolyl, benzophenonyl, pyrenyl, triarylaminyl, thianthrenyl, heterocyclyl, mono-substituted aryl, poly-substituted aryl, or fused ring group; The preparation method comprises: uniformly mixing a nitroarene compound, an alkyl aldehyde compound / aromatic aldehyde compound, an inorganic ammonium salt, and an organic solvent, performing a reaction under irradiation of a light source with a wavelength of 254 nm-580 nm at 50-150 ℃ in air or an inert atmosphere, then cooling to room temperature, and then performing concentration and column chromatography purification to obtain the quinazoline compound. The structural formula of the above nitroaromatic compound is ; The structural formula of the above-mentioned alkyl aldehyde compound is ; The structural formula of the above-mentioned aromatic aldehyde and heteroaromatic aldehyde compound is selected from .

2. The production method according to claim 1, characterized by: The inorganic ammonium salt is selected from ammonium acetate, ammonium sulfate, and ammonium chloride inorganic ammonium salt, and alcohol or ether.

3. The production method according to claim 2, characterized by: The inorganic ammonium salt is ammonium acetate.

4. The production method according to claim 1, wherein: The organic solvent is selected from methanol, ethanol, isopropanol, hexafluoroisopropanol, tetrahydrofuran, diethyl ether, DME, 1,4-dioxane, dichloroethane, carbon tetrachloride, chloroform, and toluene.

5. The production method according to claim 4, characterized by: The organic solvent is isopropanol.

6. The production method according to claim 1, wherein: The inorganic ammonium salt is ammonium acetate, and the organic solvent is isopropanol.

7. The production method according to any one of claims 1 to 6, characterized by: The molar ratio of the nitroarene compound, the aromatic aldehyde compound / heteroaromatic aldehyde compound, and the inorganic ammonium salt is 1:2:

2.

8. The production method according to claim 7, characterized by: 2 mL of the organic solvent corresponds to 0.1 mmol of the nitroarene compound.

9. Use of the quinazoline compound prepared by the preparation method in any one of claims 1 to 8 in preparation of a multifunctional photocatalyst.

10. Use of the quinazoline compound prepared by the preparation method in any one of claims 1 to 8 in preparation of an OLED device.

Images