Process for the selective preparation of quinolin-2-ones or 3,4-dihydroquinolin-2-ones by photocatalyst regulation

Abstract

The application discloses a method for selectively preparing quinolin-2-ketone or 3,4-dihydroquinolin-2-ketone compounds by regulating a photocatalyst, and the method is characterized in that quinolin-2-ketone or 3,4-dihydroquinolin-2-ketone compounds are prepared by intramolecular cyclization of 1,7-alkenyl alkynes under a photocatalytic condition; the selectivity of the product is controlled by the photocatalyst; when a Cu(I) photocatalyst with strong reducing capacity is used, 3,4-dihydroquinolin-2-ketone compounds are obtained; when a Cu(I) photocatalyst with weak reducing capacity is used, quinolin-2-ketone compounds are obtained; the raw material is simple and easy to obtain, the reaction condition is mild, the substrate has good universality, and the method is suitable for industrial production.

Description

Technical Field

[0001] This invention relates to a method for synthesizing quinoline-2-one compounds, specifically a method for selectively preparing quinoline-2-one or 3,4-dihydroquinoline-2-one compounds under photocatalyst regulation. Background Technology

[0002] Quinoline-2-ones and 3,4-dihydroquinoline-2-ones are important structural units in many drug molecules and natural products, and possess good biological activity. For example, Zavzpret (an acute migraine medication for adults), Brexpiprazaole (an antipsychotic), and Rebamipide (an anti-ulcer drug) all contain quinoline-2-one structural units. Aripiprazole (an antipsychotic), Carteolol (a non-selective beta-blocker), Vesnarinone (a cardiotonic), and Cilostazo1 (a phosphodiesterase-3 inhibitor) also contain the quinoline-2-one skeleton. Furthermore, as important synthetic intermediates, they can be further converted into other common heterocyclic compounds, such as tetrahydroquinolines and octahydroquinolineones.

[0003]

[0004] Given the significant scientific value and broad application prospects of quinoline-2-one compounds, synthetic chemists have developed many different strategies to construct quinoline-2-one skeletons. Among these, the base-promoted Knoevenagel condensation / nucleophilic substitution tandem reaction between anthranilic aminoacyl aromatics and dialkyl malonate is a key strategy. The most classic method for synthesizing 3-carbonyl-substituted quinolin-2-ones is the reaction (see Eur. J. Med. Chem., 2018, 157, 1-13.) or the nucleophilic substitution / Knoevenagel condensation tandem reaction (see Org. Lett., 2021, 23, 3593-3598.). Acid-catalyzed Friedel-Craft intramolecular cyclization of β-carbonyl amides provides an efficient route for synthesizing 4-substituted quinolin-2-ones (see Tetrahedron Lett., 2020, 61, 152-535.). Furthermore, transition metal-catalyzed cyclization reactions are also an efficient method for constructing the quinolin-2-one skeleton (see Org. Lett., 2015, 17, 222-225., Org. Lett., 2014, 16, 3568-3571.). Free radical-mediated cyclization reactions are also an efficient route for synthesizing quinoline-2-one compounds (Synlett, 2020, 31, 1517-1522).

[0005] Similarly, 3,4-dihydroquinoline-2-one, as an important drug molecule backbone, has always been a hot topic in synthetic chemistry and medicinal chemistry research. Lewis acid-catalyzed Friedel-Crafts is the most classic method for synthesizing 3,4-dihydroquinoline-2-one (see J. Heterocyclic Chem., 2014, 51, 1811-1813.), however, the harsh reaction conditions and limited substrate universality restrict its application. Transition metal-catalyzed intermolecular hydrogen arylation / cyclization and intramolecular cyclization have overcome this limitation to some extent (see Org. Lett., 2013, 15, 2128-2131. Chem. Commun., 2018, 54, 34-37.). Palladium-catalyzed intramolecular CH activation / cyclization is more atom-economical (see Angew. Chem. Int. Ed., 2014, 53, 4945-4949.). Radical-mediated tandem cyclization provides a reliable route for constructing multi-substituted 3,4-dihydroquinoline-2-ones (see J. Org. Chem., 2018, 83, 1525-1531.). Furthermore, asymmetric hydrogenation of quinoline-2-ones is one of the most efficient methods for the rapid synthesis of chiral 3,4-dihydroquinoline-2-ones (see Org. Lett., 2021, 23, 3593-3598.).

[0006] While the aforementioned methods for constructing quinoline-2-ones and 3,4-dihydroquinoline-2-ones possess certain advantages, they still face numerous limitations, such as lengthy starting material preparation processes, expensive noble metal catalysts, stoichiometric oxidants, high reaction temperatures, limited substrate universality, and functional group tolerance. Therefore, continuing to explore mild and efficient methods for the synthesis of quinoline-2-ones and 3,4-dihydroquinoline-2-ones to meet the needs of drug development remains extremely urgent. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a method for the selective preparation of quinoline-2-one or 3,4-dihydroquinoline-2-one compounds controlled by a photocatalyst.

[0008] This invention relates to the preparation of quinoline-2-ones or 3,4-dihydroquinoline-2-ones from 1,7-enyne compounds under photocatalytic conditions via intramolecular cyclization. This process is suitable for industrial production. Notably, the selectivity of the products in this invention is controlled by the photocatalyst. When a Cu(I) photocatalyst with strong reducing power is used, 3,4-dihydroquinoline-2-ones are obtained; when a Cu(I) photocatalyst with weak reducing power is used, quinoline-2-ones are obtained.

[0009] The technical solution of the present invention is as follows:

[0010] A method for the selective preparation of quinoline-2-one or 3,4-dihydroquinoline-2-one compounds regulated by a photocatalyst, comprising:

[0011] Under inert gas protection, the raw material 1,7-enyne compound (I), photocatalyst (PC), electron donor triethylamine and solvent are mixed and reacted under visible light irradiation and at 15-45°C (preferably 35°C). The reaction is monitored by TLC until the reaction is complete, and then the reaction solution is post-treated to obtain the product.

[0012] The visible light source is a blue LED, preferably a 15W blue LED, and the reaction solution can be placed 3 cm away from the light source to carry out the photocatalytic reaction.

[0013] When selectively preparing quinoline-2-one compounds:

[0014] Photocatalysts are selected from one of the following:

[0015]

[0016] PC3 is particularly preferred;

[0017] The solvent is selected from 1,4-dioxane, toluene, N,N-dimethylformamide, methanol, ethanol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide or ethyl acetate, with toluene being particularly preferred;

[0018] The reaction time is 6 to 48 hours, with 36 hours being particularly preferred;

[0019] The preferred molar ratio of photocatalyst to raw material 1,7-enyne compound (I) is 0.025–0.1:1;

[0020] The preferred volume ratio of the electron donor triethylamine to the solvent is 1.2:1.8;

[0021] The specific post-processing method of the reaction solution is as follows: After the reaction is completed, 100-200 mesh silica gel for column chromatography is added to the reaction solution and stirred. The solvent is removed by vacuum distillation. The sample is loaded dry and separated by silica gel column chromatography with n-hexane / ethyl acetate as the eluent. The elution process is tracked by TLC. The eluent containing the target product is collected, the solvent is removed by evaporation and dried to obtain the product quinoline-2-one compound (II).

[0022] The reaction formula is as follows:

[0023]

[0024] In formula (I) or (II),

[0025] R 1The derivative is H, methyl, ethyl, methoxy, methylthio, aryl, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy, methoxycarbonyl, cyano, or amino; preferably R. 1 It can be H, methoxy, fluorine, chlorine, or cyano;

[0026] R 2 It is alkyl, thiophene, pyridinyl, naphthyl or Wherein R is H, methyl, ethyl, methoxy, methylthio, aryl, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy, methoxycarbonyl, cyano, or amino; preferably R 2 It is butyl, cyclopropyl, cyclohexenyl, thiophene, naphthyl or Where R is H, methyl, methoxy, methylthio, fluorine, bromine, or methoxycarbonyl;

[0027] R 3 It is H, methyl, ethyl, phenyl, benzyl, 4-methoxybenzyl, 2,4-dimethoxybenzyl, benzoyl, tert-butoxycarbonyl, or benzyloxycarbonyl; preferably R. 3 It can be methyl or ethyl.

[0028] When selectively preparing 3,4-dihydroquinoline-2-one compounds:

[0029] Photocatalysts are selected from one of the following:

[0030]

[0031] PC5 is the preferred choice;

[0032] The solvent is a mixture of an organic solvent and water, wherein the organic solvent is selected from 1,4-dioxane, toluene, N,N-dimethylformamide, methanol, ethanol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide or ethyl acetate, with methanol being particularly preferred;

[0033] The reaction time is 6 to 24 hours, preferably 9 hours;

[0034] The preferred molar ratio of photocatalyst to raw material 1,7-enyne compound (I) is 0.025–0.1:1;

[0035] The preferred volume ratio of the electron donor triethylamine to the organic solvent and water is 1.2:1.6:0.2.

[0036] The specific post-processing method of the reaction solution is as follows: After the reaction is completed, 100-200 mesh silica gel for column chromatography is added to the reaction solution and stirred. The solvent is removed by vacuum distillation. The sample is loaded dry and separated by silica gel column chromatography with n-hexane / ethyl acetate as the eluent. The elution process is tracked by TLC. The eluent containing the target product is collected, the solvent is evaporated and dried to obtain the product 3,4-dihydroquinoline-2-one compound (III).

[0037] The reaction formula is as follows:

[0038]

[0039] In formula (I) or (III),

[0040] R 4 The derivative is H, methyl, ethyl, methoxy, methylthio, aryl, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy, methoxycarbonyl, cyano, or amino; preferably R. 4 It can be H, methyl, trifluoromethyl, chlorine, or bromine;

[0041] R 5 It is alkyl, thiophene, pyridinyl or Wherein R is H, methyl, methoxy, fluorine, chlorine, bromine, tert-butyl formate amino, trifluoromethyl, methylthio, methoxycarbonyl, cyano, or amino; preferably R 5 It is butyl, cyclohexenyl, thiophene, pyridyl or Where R is H, methyl, methoxy, fluorine, chlorine, bromine, tert-butyl formate amino, trifluoromethyl, methylthio, or methoxycarbonyl;

[0042] R 6 The derivative is H, methyl, ethyl, phenyl, benzyl, 4-methoxybenzyl, 2,4-dimethoxybenzyl, benzoyl, tert-butoxycarbonyl, or benzyloxycarbonyl, preferably R. 6 It can be methyl, ethyl, or benzyl.

[0043] It is worth noting that the selectivity of the product in this invention is controlled by the photocatalyst. The preferred photocatalyst for preparing quinoline-2-one compounds is PC3, whose corresponding reduced state has relatively weak reducing power [E]. 1 / 2 (Cu Ⅰ / Cu 0 = -1.48V vs SCEin MeCN]. The preferred photocatalyst for preparing 3,4-dihydroquinoline-2-one compounds is PC5, whose corresponding reduced state exhibits strong reducing power [E]. 1 / 2 (Cu Ⅰ / Cu 0 = -1.66V vs SCE in MeCN], according to the reaction mechanism ( Figure 1 Quinoline-2-one compounds (2a) can be further reduced by PC5, which has a strong reducing power, to obtain 3,4-dihydroquinoline-2-one compounds (3a).

[0044] To facilitate understanding of the technical solution of this invention by those skilled in the art, the reaction mechanism can be found in the appendix. Figure 1 .

[0045] The 1,7-enyne compounds used in this invention can be prepared by those skilled in the art based on methods disclosed in existing literature.

[0046] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0047] 1) The 1,7-enyne raw material used in this invention can be obtained by combining various inexpensive and variable fragments through simple chemical reactions, thus making the raw material simple and readily available with variable functional groups.

[0048] 2) The present invention obtains the target product through photo-oxidation-reduction reaction. The reaction conditions are mild, the substrate is universal, and the functional group tolerance is high.

[0049] 3) This invention uses inexpensive copper complexes as photocatalytic groups, and can selectively obtain quinoline-2-one or 3,4-dihydroquinoline-2-one through the regulation of visible light catalysts. Attached Figure Description

[0050] Figure 1 The reaction mechanism involved in the photocatalytic reaction of this invention. Detailed Implementation

[0051] The present invention is further described below through specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0052] The 1,7-enyne raw material of this invention can be prepared according to literature, and the typical steps are as follows:

[0053]

[0054] To a dry three-necked flask equipped with a magnetic buoy, add o-iodoaniline compound S1 (10 mmol, 1.0 equiv.), Pd(PPh3)2Cl2 (0.1 mmol, 1 mol%), and CuI (0.2 mmol, 2 mmol%), and evacuate to nitrogen. Then add degassed triethylamine (25 mL) and alkyne (12 mmol, 1.2 equiv.) to the flask and react at room temperature for 2 hours. After the reaction is complete, remove the solvent using a rotary evaporator, and separate the product S2 by column chromatography.

[0055] Product S2 (5 mmol) was then added to a dry three-necked flask equipped with a magnetic stir bar and placed under nitrogen protection. Dry THF (20 mL) was then injected into the flask. Next, n-BuLi (5.5 mmol, 1.1 equiv.) was slowly injected into the dry three-necked flask at -78 °C, and the reaction was maintained at -78 °C for 1 hour. After one hour, Mel (5.5 mmol, 1.1 equiv.) was added dropwise. After the addition was complete, the reaction was allowed to return to room temperature and continued overnight. After the reaction was complete, 10 mL of saturated ammonium chloride aqueous solution was added to quench the reaction. After quenching, the solvent was removed by rotary evaporation, and product S3 was obtained by column chromatography.

[0056] Product S3 (5 mmol) was added to a dry three-necked flask, and the mixture was then protected with nitrogen. Dry DCM (15 mL) was then injected into the flask, followed by Et3N (10 mmol, 2 equiv.). Acryloyl chloride (6 mmol, 1.2 equiv.) was slowly added to the flask under an ice-water bath at 0 °C. After removing the ice-water bath and reacting at room temperature for 12 hours, the reaction was quenched with a saturated sodium bicarbonate aqueous solution (10 mL). After quenching, the organic phase was extracted with dichloromethane (3 × 30 mL). The solvent was then removed by rotary evaporation, and product S4 was obtained by column chromatography.

[0057] All 1,7-enyne compounds (I) are known compounds. 1 The H NMR characterization results are consistent with those reported in the literature.

[0058] The synthesis methods of photocatalysts PC3 and PC5 used in the following examples are as follows:

[0059] Synthesis of photocatalyst PC3:

[0060]

[0061] First, cyclopropyl malonate B (10.06 g, 70 mmol) was added to a 250 mL three-necked flask equipped with a condenser. Nitrogen gas was purged three times. Then, trimethyl orthoformate (130 mL) was added, and the mixture was stirred and refluxed at 105 °C for 1 hour. The temperature was then lowered to 75 °C, and o-phenylenediamine A (3.24 g, 30 mmol) was added. The mixture was stirred and refluxed at 105 °C for another 4 hours. Finally, the mixture was moved to room temperature and stirred for 24 hours. After the reaction was complete, the mixture was filtered and washed three times with diethyl ether to obtain intermediate C, a white solid, with a yield of 9.15 g, representing a yield of 73%.

[0062] In the second step, intermediate C (4.16 g, 10 mmol) was added to a 250 mL three-necked flask, nitrogen gas was purged three times, diphenyl ether (125 mL) was added, the reaction was then heated to 250 °C, stirred for 1 hour, cooled to 70 °C and filtered, and washed successively with acetone, n-hexane and diethyl ether to obtain intermediate D, a brown solid, with a yield of 1.70 g and a yield of 80%.

[0063] In the third step, intermediate D (0.85 g, 4 mmol) and phosphorus tribromooxy (30.20 g, 100 mmol) were added to a three-necked flask. Nitrogen gas was purged three times, and 34 mL of anhydrous chloroform was added. The reaction was moved to 85 °C and stirred for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was slowly poured into 100 mL of ice water. The mixture was stirred for another hour at room temperature. Then, 50 mL of chloroform was added, and the pH was adjusted to 13-14 with 50% sodium hydroxide aqueous solution. The mixture was stirred for another hour. Finally, the mixture was extracted with ethyl acetate, and the organic phase was collected. The solvent was removed under vacuum, and the mixture was separated by column chromatography using a methanol / dichloromethane mixture with a volume ratio of 1:30 as the eluent. The eluent containing the target product was collected and evaporated to dryness to obtain intermediate E, a white solid with a yield of 1.00 g and a yield of 37.5%.

[0064] Step 4: Intermediate E (1.99 g, 3 mmol), sodium carbonate (6.36 g, 60 mmol), tetrakis(triphenylphosphine)palladium (0.34 g, 0.3 mmol), and 3,5-bis(trifluoromethyl)phenylboronic acid (3.10 g, 12 mmol) were added sequentially to a 250 mL three-necked flask. Nitrogen gas was purged three times. 150 mL of 1,4-dioxane and 60 mL of water were added. The mixture was stirred and refluxed at 130 °C for 24 hours. The reaction temperature was then lowered to room temperature. The solvent was removed under vacuum, followed by extraction with dichloromethane. The organic phases were combined and collected. The solvent was removed under vacuum, and the mixture was separated by column chromatography using a methanol / ethyl acetate mixture (v / v) of 1:30 as the eluent. The eluent containing the target product was collected and evaporated to dryness to obtain intermediate F, a white solid with a yield of 0.80 g (40%).

[0065] Step 5: Add intermediate F (0.66 g, 1 mmol) to a 50 mL three-necked flask, purge with nitrogen three times, add 20 mL of anhydrous toluene, lower the solution temperature to 0 °C, add 4 mL (4.0 mmol) of sec-butyllithium (1.0 M n-hexane solution) dropwise, and continue stirring in an ice bath for 2 hours after the addition is complete. Then raise the reaction temperature to room temperature and stir for 16 hours, quench the reaction with saturated ammonium chloride solution, extract with dichloromethane, collect the organic phase, remove the organic solvent under vacuum, add activated manganese dioxide (10.74 g, 20 mmol) and 20 mL of dichloromethane, continue stirring at 30 °C for 2 hours, cool to room temperature, filter, wash with dichloromethane, combine the organic phases, remove the organic solvent under vacuum, use a 1:20 volume ratio of ethyl acetate / petroleum ether mixture as the eluent, collect the eluent containing the target product, evaporate to dryness to obtain ligand G, yield 0.36 g, yield 50%.

[0066] In step six, Cu(MeCN)4PF6 (0.37 g, 1 mmol) and Xantphos (0.58 g, 1 mmol) were added to a 50 mL three-necked flask. The mixture was evacuated to nitrogen three times, and then 20 mL of anhydrous dichloromethane was added. The reaction mixture was stirred and refluxed at 35 °C for 4 hours. The temperature was then lowered to room temperature, and ligand G (0.72 g, 1 mmol) was dissolved in 10 mL of anhydrous dichloromethane and added dropwise to the reaction mixture. After the addition was complete, the mixture was stirred at 35 °C for another 3 hours. After the reaction was complete, the mixture was cooled to room temperature, and n-hexane was added to precipitate the crude product. The precipitate was filtered and washed with n-hexane. The crude product was recrystallized from dichloromethane and n-hexane to give catalyst PC3, with a yield of 1.50 g, representing a 100% yield.

[0067] Synthesis of photocatalyst PC5:

[0068]

[0069] First, phenanthroline H (0.33 g, 1 mmol) was added to a 50 mL three-necked flask, and the flask was purged with nitrogen three times. Then, 20 mL of anhydrous toluene was added, and the solution temperature was lowered to 0 °C. Isopropyllithium (1.0 M n-hexane solution) (4 mL, 4.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred in an ice bath for 2 hours. Then, the reaction temperature was raised to room temperature and stirred for 16 hours. The reaction was quenched with saturated ammonium chloride solution, extracted with dichloromethane, and the organic phase was collected. The organic solvent was removed under vacuum. Then, 20 mmol of activated manganese dioxide and 20 mL of dichloromethane were added, and the mixture was stirred at 30 °C for 2 hours. The mixture was then cooled to room temperature, filtered, washed with dichloromethane, and the organic phases were combined. The organic solvent was removed under vacuum. An ethyl acetate / petroleum ether mixture (1:20 v / v) was used as the eluent, and the eluent containing the target product was collected. The eluent was evaporated to dryness to obtain ligand I, with a yield of 0.29 g, or 70%.

[0070] In the second step, Cu(MeCN)4PF6 (0.37 g, 1 mmol) and Xantphos (0.58 g, 1 mmol) were added to a 50 mL three-necked flask. The mixture was evacuated to nitrogen three times, and then 20 mL of anhydrous dichloromethane was added. The reaction mixture was stirred and refluxed at 35 °C for 4 hours. The temperature was then lowered to room temperature, and ligand I (0.42 g, 1 mmol) was dissolved in 10 mL of anhydrous dichloromethane and added dropwise to the reaction mixture. After the addition was complete, the mixture was stirred at 35 °C for another 3 hours. After the reaction was complete, the mixture was cooled to room temperature, and n-hexane was added to precipitate the crude product. The precipitate was filtered and washed with n-hexane. The crude product was recrystallized from dichloromethane and n-hexane to give catalyst PC5, with a yield of 1.20 g, representing a 100% yield.

[0071] Examples of synthesis of quinoline-2-one compounds:

[0072] Example 1

[0073]

[0074] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-2-(phenylethynyl)phenyl)acrylamide (0.2 mmol, 52.3 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-benzyl-1-methyl-quinoline-2(1H)-one. This substance was a yellow solid, with a yield of 38.8 mg and a yield of 78%.

[0075] Characterization data: 1 HNMR (500M, CDC13): δ7.76 (dd, J1=8.0Hz, J2=1.2Hz, 1H), 7.58-7.54 (m, 1H), 7.40 (d, J=8 .4Hz,1H),7.34-7.31(m,2H),7.27-7.20(m,4H),6.53(s,1H),4.18(s,2H),3.73(s,3H). 13 CNMR (125MHz, CDC13): δ162.14,148.57,140.08,137.47,130.44,128.90 ,128.77,126.80,125.35,121.98,121.87,120.60,114.56,38.40,29.31.

[0076] Example 2

[0077]

[0078] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-((4-fluorophenyl)ethynyl)phenyl)acrylamide (0.2 mmol, 55.9 mg, 1.0 equⅳ.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-(4-fluorobenzyl)-1-methyl-quinoline-2(1H)-one. This substance was a yellow solid, with a yield of 34.7 mg and a yield of 65%.

[0079] Characterization data:1 H NMR (500M, CDC13): δ7.73-7.71(m,1H),7.58-7.55(m,1H),7.40(d,J=8.4Hz,1H ),7.23-7.18(m,3H),7.03-6.98(m,2H),6.48(s,1H),4.15(s,2H),3.72(s,3H). 13 C NMR (125MHz, CDCl3) δ162.06, 161.78 (d, J = 243.75Hz), 148.37, 140.14, 133.14 (d, J = 2.5Hz), 130.56, 130.38(d,J=7.5Hz),125.21,122.02,121.83,120.43,115.66(d,J=21.25Hz),114.63,37.57,29.31.

[0080] Example 3

[0081]

[0082] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-((4-bromophenyl)ethynyl)phenyl)acrylamide (0.2 mmol, 68.0 mg, 1.0 equⅳ.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction mixture was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-(4-bromobenzyl)-1-methyl-quinoline-2(1H)-one. This substance was a yellow solid, with a yield of 50.5 mg and a yield of 77%.

[0083] Characterization data: 1 H NMR (500M, CDC13): δ7.69 (d, J=8.0Hz, 1H), 7.59-7.55 (m, 1H), 7.44-7.39 (m, 3H), 7.21(t,J=7.6Hz,1H),7.12-7.10(m,2H),6.50(s,1H),4.13(s,2H),3.73(s,3H). 13C NMR (125MHz, CDCl3) δ162.01,147.90,140.16,136.54,131.90,130.61,130.57,125.23,122.06,121.99,120.75,120.35,114.66,37.84,29.35.

[0084] Example 4

[0085]

[0086] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-((4-methoxyphenyl)ethynyl)phenyl)-acrylamide (0.2 mmol, 58.3 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-(4-methoxybenzyl)-1-methyl-quinoline-2(1H)-one. This substance was a yellow solid, with a yield of 41.8 mg and a yield of 75%.

[0087] Characterization data: 1 HNMR (500M, CDC13): δ7.77-7.75(m,1H),7.57-7.54(m,1H),7.38(d,J=8.0Hz,1H),7.22-7.19(m ,1H),7.16-7.13(m,2H),6.87-6.84(m,2H),6.50(s,1H),4.11(s,2H),3.79(s,3H),3.72(s,3H). 13 C NMR (125MHz, CDC13) δ162.20,158.48,149.02,140.10,130.41,129.92,129 .43,125.33,121.96,121.64,120.64,114.55,114.24,55.28,37.55,29.30.

[0088] Example 5

[0089]

[0090] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-((4-methylthiophenyl)ethynyl)phenyl)-acrylamide (0.2 mmol, 61.5 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction mixture. The reaction mixture was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-(4-methylthiobenzyl)-1-methyl-quinoline-2(1H)-one. This substance was a yellow solid, with a yield of 23.6 mg, or 40%.

[0091] Characterization data: 1 H NMR (500M, CDCl3): δ7.74-7.73(m,1H),7.58-7.55(m,1H),7.40(d,J=7.9Hz,1H),7.28 -7.15(m,3H),7.17-7.15(m,2H),6.51(s,1H),4.14(s,2H),3.73(s,3H),2.48(s,3H). 13 C NMR (125MHz, CDCl3) δ162.12,148.43,140.41,136.87,134.40,134.48,129 .38,127.22,125.31,121.99,121.87,120.54,114.58,37.89,29.32,16.02.

[0092] Example 6

[0093]

[0094] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), methyl 4-((2-N-methacrylamido)phenyl)ethynyl)benzoate (0.2 mmol, 63.9 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to obtain the corresponding methyl 4-((1-methyl-2-oxo-1,2-dihydroquinoline-4-yl)methyl)benzoate. This substance was a white solid, with a yield of 39.9 mg and a yield of 65%.

[0095] Characterization data: 1 H NMR (500M, CDCl3): δ7.99 (d, J = 8.3Hz, 1H), 7.67-7.66 (m, 1H), 7.59-7.53 (m, 1H), 7.40(d,J=8.4Hz,1H),7.21-7.18(m,1H),6.53(s,1H),4.23(s,2H),3.91(s,3H). 13 C NMR (125MHz, CDCl3) δ166.6,161.69,147.58,142.95,140.20,130.61,130.09, 128.88,128.85,125.26,122.19,122.04,120.35,114 / 65,52.04,38.44,29.33.

[0096] Example 7

[0097]

[0098] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-((4-methylphenyl)ethynyl)phenyl)acrylamide (0.2 mmol, 55.1 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-(4-methylbenzyl)-1-methylquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 44.2 mg, representing a yield of 84%.

[0099] Characterization data: 1 H NMR (500M, CDCl3): δ7.77-7.76(m,1H),7.57-7.54(m,1H),7.38(d,J=8.3Hz,1H),7 .22-7.19(m,1H),7.13(s,4H),6.52(s,1H),4.14(s,2H),3.72(s,3H),2.33(s,3H). 13C NMR (125MHz, CDCl3) δ162.19,148.85,140.11,136.38,134.39,130.40,129.46,128.78,125.38,121.96,120.67,114.53,38.02,29.29,21.01.

[0100] Example 8

[0101]

[0102] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-(5-chloro-2-(phenylethynyl)phenyl)-N-methylacrylamide (0.2 mmol, 59.2 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-benzyl-7-chloro-1-methylquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 36.2 mg, representing a yield of 64%.

[0103] Characterization data: 1 H NMR (500M, CDCl3): δ7.65(d,J=8.6Hz,1H),7.38(d,J=1.9Hz,1H),7.34-7.31(m,2 H),7.28-7.24(m,3H),7.17-7.15(m,1H),6.51(s,1H),4.15(s,2H),3.69(s,3H). 13 C NMR (125MHz, CDCl3) δ161.97,148.10,141.05,137.13,136.59,128.87,128.82,126.60,122.31,121.95,119.11,114.59,38.46,29.44.

[0104] Example 9

[0105]

[0106] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-(5-fluoro-2-(phenylethynyl)phenyl)-N-methacrylamide (0.2 mmol, 59.2 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-benzyl-7-fluoro-1-methylquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 37.4 mg, representing a yield of 70%.

[0107] Characterization data: 1 H NMR(500M, CDCl3): δ7.73-7.70(m,1H),7.34-7.31(m,2H),7.28-7.20(m,3H), 7.07-7.05(m,1H),6.94-6.90(m,1H),6.47(s,1H),4.15(s,2H),3.68(s,3H). 13 CNMR (125MHz, CDCl3) δ163.85 (d, J = 250Hz), 162.86, 148.22, 141.87 (d, J = 2.5Hz), 127.44 (d, J = 10Hz), 12 6.93.120.88(d,J=2.5Hz),117.22,117.21,109.83(d,J=22.5Hz),101.48(d,J=26.25Hz),38.60,29.53.

[0108] Example 10

[0109]

[0110] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-(5-bromo-2-(phenylethynyl)phenyl)-N-methacrylamide (0.2 mmol, 68.0 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-benzyl-7-bromo-1-methylquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 44.6 mg and a yield of 68%.

[0111] Characterization data: 1 H NMR (500M, CDCl3): δ7.88 (d, J = 2.2Hz, 1H), 7.65-7.63 (m, 1H), 7.36-7.33 (m, 2H), 7.30-7 .28(m,1H),7.27-7.26(m,1H),7.24-7.23(m,2H),6.48(s,1H),4.13(s,2H),3.70(s,3H). 13 C NMR (125MHz, CDCl3) δ161.72,147.66,139.06,136.77,133.17,129.01,128.93,127.77,127.06,122.81,122.28,116.24,115.10,38.17,29.43.

[0112] Example 11

[0113]

[0114] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-(5-methoxy-2-(phenylethynyl)phenyl)-N-methacrylamide (0.2 mmol, 58.3 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-benzyl-7-methoxy-1-methyl-quinoline-2(1H)-one. This substance was a yellow solid, with a yield of 44.6 mg, or 80%.

[0115] Characterization data: 1 H NMR (500M, CDCl3): δ7.34-7.30(m,3H),7.26-7.23(m,3H),7.17-7.14(m,2H),6.55(s,1H),4.14(s,2H),3.78(s,3H),3.71(s,3H). 13 C NMR (125MHz, CDCl3) δ161.69,154.51,147.87,137.51,134.68,128.87,128 .81,126.84,122.48,121.37,118.39,115.72,108.21,55.59,38.73,29.41.

[0116] Example 12

[0117]

[0118] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-(5-acrylonitrile-2-(phenylethynyl)phenyl)-N-methacrylamide (0.2 mmol, 57.3 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-benzyl-1-methyl-2-oxo-1,2-dihydroquinoline-7-onitrile. This substance was a yellow solid, with a yield of 38.4 mg, representing a yield of 70%.

[0119] Characterization data: 1 H NMR (500M, CDCl3): δ8.05 (d, J = 1.8Hz, 1H), 7.79-7.77 (m, 1H), 7.46-7.45 (m, 1H), 7.37-7 .33(m,2H),7.30-7.27(m,1H),7.23-7.22(m,2H),6.57(s,1H),4.17(s,2H),3.73(s,3H). 13 C NMR (125MHz, CDCl3) δ161.68,147.83,142.77,136.33,132.99,130.03,129. 07,128.84,127.28,123.48,120.86,118.49,115.45,105.52,38.20,29.58.

[0120] Example 13

[0121]

[0122] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-ethyl-N-(2-(phenylethynyl)phenyl)acrylamide (0.2 mmol, 55.1 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction mixture was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-benzyl-1-ethyl-quinoline-2(1H)-one. This substance was a yellow solid, with a yield of 37.9 mg, representing a yield of 72%.

[0123] Characterization data: 1 H NMR (500M, CDCl3): δ7.79-7.77(m,1H), 7.57-7.54(m,1H)7.43-7.41(d,J=8.5Hz,1H),7.34-7.31(m,2H),7. 26-7.23(m,3H),7.22-7.18(m,1H),6.51(s,1H),4.38(q,J=7.1Hz,2H),4.17(s,2H),1.38(t,J=7.2Hz,3H). 13 C NMR (125MHz, CDCl3) δ161.69,148.51,139.06,137.51,130.40,128.96,128 .78,126.81,125.56,121.96,121.78,120.90,114.46,38.46,37.13,12.82.

[0124] Example 14

[0125]

[0126] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-(thiophene-3-ylethynyl)phenyl)acrylamide (0.2 mmol, 53.5 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 1-methyl-4-(thiophene-3-ylmethyl)quinoline-2(1H)-one. This substance was a yellow solid, with a yield of 35.7 mg, representing a yield of 70%.

[0127] Characterization data: 1 H NMR(500M, CDCl3): δ7.77-7.75(m,1H),7.58-7.55(m,1H),7.40-7.39(m,1H),7.30-7.27(m,1H), 7.24-7.21(m,1H),7.02-7.01(m,1H),6.97-6.95(m,1H),6.56(s,1H),4.18(s,2H).3.72(s,3H). 13 C NMR (125MHz, CDCl3) δ162.19,148.29,140.13,137.67,130.50,128.21,126.15,125.23,122.32,122.00,121.36,120.49,114.59,33.15,29.32.

[0128] Example 15

[0129]

[0130] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-(2-(hex-1-yn-1-yl)phenyl)-N-methacrylamide (0.2 mmol, 48.3 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 1-methyl-4-pentyl-quinoline-2(1H)-one. This substance was a yellow solid, with a yield of 20.6 mg, or 45%.

[0131] Characterization data: 1 H NMR (500M, CDCl3): δ7.76-7.75(m,1H),7.58-7.55(m,1H),7.39(d,J=8.0Hz,1H),7.28-7.24(m,1H),6. 60(s,1H),3.72(s,3H),2.83-2.79(m,2H),1.74-1.68(m,2H),1.45-1.34(m,4H).0.92(t,J=7.1Hz,3H). 13 C NMR (125MHz, CDCl3) δ161.97,148.10,141.05,137.13,136.59,128.87,128.82,126.97,126.60,122.31,121.95,119.11,114.59,38.46,29.44.

[0132] Example 16

[0133]

[0134] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-(2-(cyclopropylethynyl)phenyl)-N-methacrylamide (0.2 mmol, 45.1 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction mixture was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-(cyclopropylmethyl)-1-methylquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 21.7 mg, representing a yield of 51%.

[0135] Characterization data: 1 H NMR (500M, CDCl3): δ7.76-7.74(m,1H),7.58-7.55(m,1H),7.39(d,J=8.4Hz,1H),7.27-7.24(m,1H),6.84(s ,1H),3.73(s,3H),2.75(d,J=6.8Hz,2H),1.13-1.05(m,1H),0.67-0.63(m,2H).0.27-0.23(q,J=4.8Hz,2H). 13C NMR (125MHz, CDCl3) δ162.38,149.69,139.89,130.27,124.68,121.84,120.95,119.88,114.52,36.31,29.24,9.11,5.13.

[0136] Example 17

[0137]

[0138] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-(2-(cyclohexyl-1-en-1-ylethynyl)phenyl)-N-methacrylamide (0.2 mmol, 53.1 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 4-(cyclohexyl-1-en-1-ylmethyl)-1-methylquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 31.4 mg, representing a yield of 62%.

[0139] Characterization data: 1 H NMR (500M, CDCl3): δ7.79-7.77(m,1H),7.57-7.54(m,1H),7.39-7.38(m,1H),7.25-7.22(m,1H),6.60(s,1H),5. 53(s,1H),3.73(s,3H),3.45(s,2H),2.03-2.00(m,2H).1.96-1.95(m,2H).1.67-1.61(m,2H).1.59-1.54(m,2H). 13 C NMR (125MHz, CDCl3) δ162.23,148.14,140.01,134.05,130.25,125.35,125.2 4,121.77,121.24,121.13,114.42,40.57,29.25,28.54,25.32,22.81,22.16.

[0140] Example 18

[0141]

[0142] Under nitrogen protection, photocatalyst PC3 (0.01 mmol, 5 mol%, 15 mg), N-methyl-(2-(naphthyl-2-ylethynyl)phenyl)acrylamide (0.2 mmol, 62.2 mg, 1.0 equiv.), and a prepared solution (MePh / Et3N = 1.8 / 1.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 36 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-2 / 1) to give the corresponding 1-methyl-4-(naphthyl-2-ylmethyl)quinoline-2(1H)-one. This substance was a yellow solid, with a yield of 40.0 mg and a yield of 67%.

[0143] Characterization data: 1 H NMR (500M, CDCl3): δ7.84-7.76(m,4H),7.68(m,1H),7.57-7.54(m,1H),7.50-7.44( m,2H),7.42-7.36(s,2H),7.21-7.16(m,1H),6.59(s,1H),4.35(s,2H),3.75(s,3H). 13 C NMR (125MHz, CDCl3) δ162.16,148.40,140.19,135.07,133.60,132.37,130.47,128.50,127.66, 127.57,127.43,127.05,126.23,125.75,125.45,122.13,122.01,120.63,114.58,38.65,29.34.

[0144] Examples of synthesis of 3,4-dihydroquinoline-2-one compounds:

[0145] Example 19

[0146]

[0147] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-(phenylethynyl)phenyl)acrylamide (0.2 mmol, 52.3 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 4-benzyl-1-methyl-3,4-dihydroquinoline-2(1H)-one. This substance was a colorless liquid, with a yield of 37.6 mg and a yield of 75%.

[0148] Characterization data: 1 H NMR (500M, CDCl3): δ7.30 -7.20(m,3H),7.24-7.20(m,1H),7.10-7.07(m,2H),7.04-6.99(m,3H),3.66(s, 3H),3.16-3.11(m,1H),2.94-2.90(m,1H),2.77-2.67(m,2H),2.64-2.60(m,1H). 13 C NMR (125MHz, CDCl3) δ169.30,139.84,138.69,129.34,129.00,128.36,128 .82,127.72,127.69,126.44,122.80,114.85,40.55,38.23,35.93,29.32.

[0149] Example 20

[0150]

[0151] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-(2-((4-methoxyphenyl)ethynyl)phenyl)-N-methacrylamide (0.2 mmol, 58.3 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 4-(4-methoxybenzyl)-1-methyl-3,4-dihydroquinoline-2(1H)-one. This substance was a white solid, with a yield of 36.5 mg and a yield of 65%.

[0152] Characterization data: 1 H NMR (500M, CDCl3): δ7.30-7.26(m,1H),7.04-6.97(m,5H),6.83-6.80(m,2H),3.80(s,3H) ,3.66(s,3H),3.10-3.05(m,1H),2.87-2.83(m,1H),2.70-2.66(m,2H),2.63-2.59(m,1H). 13 C NMR (125MHz, CDCl3) δ169.34,158.23,139.82,130.75,120.28,129.08,128.82,127.77,1 27.62,122.77,114.81,113.77,77.28,77.03,76.78,55.26,39.69,38.41,35.87,29.31.

[0153] Example 21

[0154]

[0155] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-(2-((4-bromophenyl)ethynyl)phenyl)-N-methylacrylamide (0.2 mmol, 68.0 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 4-(4-bromobenzyl)-1-methyl-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 35.6 mg, representing a yield of 54%.

[0156] Characterization data: 1 H NMR (500M, CDCl3): δ7.40-7.37(m,2H),7.30-7.27(m,1H),7.02-6.97(m,3H),6.92-6. 90(m,2H),3.34(s,3H),3.12-3.07(m,1H),2.87-2.82(m,1H),2.73-2.68(m,2H),2.62 -2.58(m,1H). 13 C NMR (125MHz, CDCl3) δ169.03,139.78,137.60,131.39,131.06,128.43,127.86,127.81,122.85,120.36,114.92,40.02,38.11,36.03,29.30.

[0157] Example 22

[0158]

[0159] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-(2-((4-chlorophenyl)ethynyl)phenyl)-N-methacrylamide (0.2 mmol, 59.2 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 4-(4-chlorobenzyl)-1-methyl-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 38.8 mg and a yield of 68%.

[0160] Characterization data: 1 H NMR (500M, CDCl3): δ7.30-7.27(m,1H),7.24-7.21(m,2H),7.01-6.95(m,5H),3.34( s,3H),3.12-3.06(m,1H),2.87-2.83(m,1H),2.74-2.67(m,2H),2.62-2.58(m,1H). 13 C NMR (125MHz, CDCl3) δ169.04,139.78,137.10,132.28,130.68,128.45,128.43,127.85,127.81,122.84,114.92,39.94,38.16,36.02,29.30.

[0161] Example 23

[0162]

[0163] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-(2-((4-fluorophenyl)ethynyl)phenyl)-N-methylacrylamide (0.2 mmol, 55.9 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 4-(4-fluorobenzyl)-1-methyl-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 30.1 mg and a yield of 56%. Characterization data:1 H NMR (500M, CDCl3): δ7.30-7.26(m,1H),7.02-6.93(m,7H),3.34(s,3H),3. 11-3.06(m,1H),2.88-2.85(m,1H),2.74-2.67(m,2H),2.62-2.59(m,1H). 13 C NMR (125MHz, CDCl3) δ 169.11, 161.63 (d, J = 242.5Hz), 139.80, 134.31 (d, J = 2.5Hz), 130.75 (d, J = 7. 5Hz),128.59,127.81,127.80,122.81,115.19,114.95(d,J=16.25Hz),39.77,38.30,35.97,29.29.

[0164] Example 24

[0165]

[0166] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), methyl 4-((2-(N-methylpropamido)phenyl)ethynyl)benzoate (0.2 mmol, 63.9 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to obtain the corresponding methyl 4-((1-methyl-2-oxo-1,2,3,4-tetrahydroquinoline-4-yl)methyl)benzoate. This substance was a yellow solid, with a yield of 37.1 mg, or 60%.

[0167] Characterization data: 1 H NMR (500M, CDCl3): δ7.94 (d, J = 8.3Hz, 2H), 7.30-7.26 (m, 1H),

[0168] 7.11(d,J=8.2Hz,2H),7.02-6.93(m,3H),3.91(s,3H),3.34(s,3H),3.16-3.13(m ,1H),2.95-2.91(m,1H),2.83-2.79(m,1H),2.73-2.69(m,1H),2.63-2.60(m,1H). 13C NMR (125MHz, CDCl3) δ168.98,166.99,144.12,139.76,129.65,129.39,128.44 ,128.30,127.89,127.80,122.84,114.94,52.03,40.56,38.07,36.16,29.31.

[0169] Example 25

[0170]

[0171] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), tert-butyl (4-((2-(N-methylpropamido)phenyl)ethynyl)phenyl)aminocarbamate (0.2 mmol, 75.5 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to obtain the corresponding tert-butyl (4-((1-methyl-2-oxo-1,2,3,4-tetrahydroquinoline-4-yl)methyl)aminocarbamate). This substance was a white solid, with a yield of 40.9 mg, representing a yield of 56%.

[0172] Characterization data: 1 H NMR (500M, CDCl3): δ7.28-7.25(m,3H),7.02-6.96(m,5H),6.63(s,1H),3.35(s,3H),3. 09-3.05(m,1H),2.85-2.81(m,1H),2.70-2.55(m,2H),2.62-2.58(m,1H),1.52(s,9H). 13 C NMR (125MHz, CDCl3) δ169.32,152.84,139.75,136.86,133.24,129.81,128.95,12 7.83,127.65,122.81,118.54,114.84,80.35,39.89,38.32,35.92,29.32,28.36.

[0173] Example 26

[0174]

[0175] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-((4-(trifluoromethyl)phenyl)ethynyl)phenyl)acrylamide (0.2 mmol, 65.9 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 1-methyl-4-(4-(trifluoromethyl)benzyl)-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 42.1 mg and a yield of 66%.

[0176] Characterization data: 1 H NMR (500M, CDCl3): δ7.53-7.51(d,J=8.0Hz,1H),7.31-7.27(m,1H),7.16-7.15(m,2H),7.02-6.98(m,3H),3 .33(s,3H),3.17-3.13(m,1H),2.97-2.93(m,1H),2.84-2.79(m,1H),2.74-2.69(m,1H),2.62-2.59(m,1H). 13 C NMR(125MHz, CDCl3)δ168.91,142.72,139.80,129.67,128.84(q,J=32.5Hz),128.21,127.97,1 27.75,125.22(q,J=3.75Hz),124.24(q,J=270Hz),122.90,114.98,40.42,38.02,36.05,29.28.

[0177] Example 27

[0178]

[0179] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-((4-methylphenyl)ethynyl)phenyl)acrylamide (0.2 mmol, 55.1 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 1-methyl-4-(4-methylphenyl)-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 31.8 mg, or 60%.

[0180] Characterization data: 1 H NMR (500M, CDCl3): δ7.32-7.22(m,3H),7.11-7.09(m,3H),6.93-6.89(m,2H),3.35(s,3H),3.12-3. 05(m,1H),2.95-2.91(m,1H),2.75-2.67(m,1H),2.64-2.63(m,1H),2.62-2.57(m,1H),2.31(s,3H). 13 C NMR (125MHz, CDCl3) δ169.39,139.83,135.91,135.58,129.21,129.18,12 9.04,127.71,127.63,122.80,114.83,40.10,38.28,35.86,29.32,21.02.

[0181] Example 28

[0182]

[0183] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-methyl-(N-2-((4-methylthiophenyl)ethynyl)phenyl)acrylamide (0.2 mmol, 61.4 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 1-methyl-4-(4-methylthiobenzyl)-3,4-dihydroquinoline-2(H)-one. This substance was a yellow solid, with a yield of 32.7 mg and a yield of 55%.

[0184] Characterization data: 1 H NMR (500M, CDCl3): δ7.30-7.26(m,1H),7.19-7.17(m,2H),7.04-6.97(m,5H),3.35(s,3H) ,3.12-3.07(m,1H),2.89-2.85(m,1H),2.73-2.66(m,2H),2.63-2.59(m,1H),2.48(s,3H). 13 C NMR (125MHz, CDCl3) δ169.20,139.78,136.24,135.66,129.83,128.84,12 7.75,127.72,126.93,122.81,114.86,40.05,38.21,35.94,29.30,16.15.

[0185] Example 29

[0186]

[0187] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-(3-methoxyphenyl)ethynyl)phenyl)acrylamide (0.2 mmol, 58.3 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 1-methyl-4-(3-methoxybenzyl)-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 32.6 mg and a yield of 58%.

[0188] Characterization data: 1 H NMR (500M, CDCl3): δ7.30-7.27(m,1H),7.20(t,J=7.9Hz,1H),7.06-6.99(m,3HD,6.78-6.76(m,1H),6.69-6.67(m,1H),6 .60-6.59(m,1H),3.77(s,3H),3.36(s,3H),3.16-3.11(m,1H),2.92-2.88(m,1H),2.74-2.67(m,2H),2.64-2.60(m,1H). 13 C NMR (125MHz, CDCl3): δ169.28,159.58,140.23,139.87,129.33,128.98,12 7.69,122.78,121.74,114.83,112.04,55.15,40.59,38.10,36.00,29.31.

[0189] Example 30

[0190]

[0191] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-((3-chlorophenyl)ethynyl)phenyl)acrylamide (0.2 mmol, 59.2 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 1-methyl-4-(3-chlorobenzyl)-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 34.2 mg, or 60%.

[0192] Characterization data: 1 H NMR(500M, CDCl3]): δ7.31-7.27(m,1H),7.22-7.19(m,2H),7.04-6.98(m,4H),6.95-6.93(m, 1H),3.36(s,3H),3.15-3.10(m,1H),2.90-2.86(m,1H),2.75-2.68(m,2H),2.62-2.58(m,1H). 13 C NMR (125MHz, CDCl3) δ169.04,140.70,139.79,134.12,129.58,129.24,128.41 ,127.89,127.72,127.65,126.68,122.85,114.93,40.16,38.03,36.01,29.32.

[0193] Example 31

[0194]

[0195] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-((2-methoxyphenyl)ethynyl)phenyl)acrylamide (0.2 mmol, 58.3 mg, 1.0 equiv.), and a prepared mixture (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 1-yl-4-(2-methoxybenzyl)-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 32.6 mg and a yield of 58%.

[0196] Characterization data: 1 H NMR (500M, CDCl3): δ7.29-7.19(m,1H),7.06-6.92(m,2H),6.88-6.83(m,1H),3.79(s,1H),3.3 8(s,1H),3.26-3.17(m,1H),3.00(d,J=13.1,6.3Hz,1H),2.74-2.65(m,1H),2.64-2.57(m,1H). 13 C NMR (125MHz, CDCl3) δ169.68,157.60,139.91,131.22,129.71,127.76,127.63,12 7.40,127.21,122.63,120.29,114.60,110.21,55.15,36.28,36.01,34.86,29.32.

[0197] Example 32

[0198]

[0199] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-((2-chlorophenyl)ethynyl)phenyl)acrylamide (0.2 mmol, 59.2 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 1-methyl-4-(2-chlorobenzyl)-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 36.5 mg and a yield of 64%. Characterization data: 1 H NMR (500M, CDCl3): δ7.37-7.35(m,1H),7.30-7.27(m,1H),7.20-7.14(m,2H),7.04-6.96(m,4H),3.42( s,3H),3.30-3.25(m,1H),3.10-3.06(m,1H),2.84-2.79(m,1H),2.72-2.67(m,1H),2.64-2.60(m,1H). 13 C NMR (125MHz, CDCl3) δ169.29,139.79,136.48,134.21,131.90,129.61,128 .78,128.03,127.75,126.70,122.83,114.83,37.83,36.05,35.88,29.38.

[0200] Example 33

[0201]

[0202] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-(5-chloro-2-(phenylethynyl)phenyl)-N-methylacrylamide (0.2 mmol, 59.2 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 4-benzyl-7-chloro-1-methyl-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 34.2 mg, representing a yield of 60%.

[0203] Characterization data: 1 H NMR (500M, CDCl3): δ7.29-7.21(m,3H),7.04-7.03(m,2H),7.00-6.99(m,1H),6.96-6.94(m,1H),6.90-6. 88(m,1H),3.32(s,3H),3.14-3.08(m,1H),2.88-2.84(m,1H),2.76-2.71(dd,J=m,1H),2.70-2.60(m,2H). 13 C NMR (125MHz, CDCl3) δ169.00,141.01,138.28,133.33,129.29,128.80,128.42,127.21,126.58,122.47,115.19,40.51,37.80,35.90,29.35.

[0204] Example 34

[0205]

[0206] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-(phenylethynyl)-5-(trifluoromethyl)phenyl)acrylamide (0.2 mmol, 65.9 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 4-benzyl-1-methyl-7-(trifluoromethyl)-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 38.3 mg, or 60%.

[0207] Characterization data: 1 H NMR (500M, CDCl3): δ7.55-7.53(m,1H),7.30-7.26(m,2H),7.25 -7.21(m,2H),7.08(d,J=8.5Hz,1H),7.04-7.02(m,2H),3.37(s,3H),3.2 1-3.16(m,1H),2.92-2.88(m,1H),2.79-2.74(m,1H),2.73-2.65(m,2H). 13 C NMR (125MHz, CDCl3) δ169.07,142.67,137.94,129.25,128.46,126.72,124.96(q,J=3.75Hz),1 24.89,124.86,124.71(q,J=32.5Hz),124.06(q,J=270Hz),114.73,40.41,38.19,35.58,29.42.

[0208] Example 35

[0209]

[0210] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(5-methyl-2-(phenylethynyl)phenyl)acrylamide (0.2 mmol, 55.1 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 4-benzyl-1,7-dimethyl-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 32.9 mg and a yield of 62%.

[0211] Characterization data: 1 H NMR (500M, CDCl3): δ7.32-7.22(m,3H),7.11-7.09(m,3H),6.92 -6.89(m,2H),3.35(s,3H),3.12-3.05(m,1H),2.95-2.90(m,1H),2.75-2.68(m,1H),2.64-2.63(m,1H),2.62-2.57(m,1H),2.31(s,3H). 13 C NMR (100MHz, CDCl3) δ169.20,138.76,137.43,132.36,129.38,128.95,12 8.40,128.36,128.06,126.43,114.77,40.61,38.27,35.79,29.34,20.61.

[0212] Example 36

[0213]

[0214] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-ethyl-N-(2-(phenylethynyl)phenyl)acrylamide (0.2 mmol, 55.1 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction was completed, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 4-benzyl-1-ethyl-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 35.5 mg and a yield of 67%.

[0215] Characterization data: 1 H NMR (500M, CDCl3): δ7.29-7.20(m,4H),7.07-7.06(m,3H),7.01 -6.96(m,2H),4.02(d,J=7.1Hz,2H),3.13-3.07(m,1H),2.90-2.86(m,1H),2.76 -2.70(m,2H),2.61-2.59(m,1H),1.28(t,J=7.1Hz,3H). 13 C NMR (125MHz, CDCl3) δ168.68,138.75,138.62,129.37,128.36,128.11,127.69.126.41,122.63,114.86,40.45,38.44,36.99,36.06,12.74.

[0216] Example 37

[0217]

[0218] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-benzyl-N-(2-(phenylethynyl)phenyl)acrylamide (0.2 mmol, 55.1 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 1,4-dibenzyl-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow liquid, with a yield of 39.2 mg, or 60%.

[0219] Characterization data: 1 H NMR (500M, CDCl3): δ7.35-7.26(m,6H),7.27-7.23(m,2H),7.17-7.12(m,1H),7.08-7.06(m,2H),6.99-6.93(m,3H),5.3 2(d,J=16.1Hz,1H),5.08(d,J=16.1Hz,1H),3.22-3.16(m,1H),2.96-2.92(m,1H),2.88-2.78(m,2H),2.77-2.74(m,1H). 13 CNMR (125MHz, CDCl3) δ169.42,139.00,138.69,137.15,129.38,129.10,128.72,128.39 ,127.97,127.64,127.15,126.70,126.47,122.86,115.80,45.94,40.57,38.54,36.19.

[0220] Example 38

[0221]

[0222] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-(4-bromo-2-(phenylethynyl)phenyl)-N-methacrylamide (0.2 mmol, 68.0 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 4-benzyl-6-bromo-1-methyl-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 42.8 mg and a yield of 65%.

[0223] Characterization data: 1 HNMR (500M, CDCl3): δ7.40-7.38(m,1H),7.31-7.27(m,2H),7.25-7.22(m,1H),7.16(d,J=2.2Hz,1H),7.06-7.05(m, 2H),6.87(d,J=8.6Hz,1H),3.31(s,3H),3.12-3.06(m,1H),2.93-2.88(m,1H),2.74-2.69(m,1H),2.67-2.58(m,2H). 13 CNMR (125MHz, CDCl3) δ168.86,139.02,138.08,131.09,130.51,130.48,129.28,128.46,126.67,116.45,115.52,40.39,38.03,35.51,29.37.

[0224] Example 39

[0225]

[0226] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-(thiophene-3-ylethynyl)phenyl)acrylamide (0.2 mmol, 53.5 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 1-methyl-4-(thiophene-3-ylmethyl)-3,4-dihydroquinoline-2(1H)one. This substance was a yellow liquid, with a yield of 27.2 mg and a yield of 53%.

[0227] Characterization data: 1 H NMR (500M, CDCl3): δ7.30-7.24(m,2H),7.08-7.06(m,1H),7.03-7.00(m,2H),6.89-6.88(m,1H),6.84-6.83(m,1H),3. 35(s,3H),3.35(m,3H),3.16-3.11(m,1H),2.95-2.91(m,1H),2.84-2.79(m,1H),2.74-2.69(m,1H),2.65-2.61(m,1H). 13 C NMR (125MHz, CDCl3) δ169.08,139.86,138.86,128.87,128.50,127.73,127.69,125.50,122.81,122.23,114.84,36.11,34.89,29.31.

[0228] Example 40

[0229]

[0230] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-methyl-N-(2-(pyridin-3-ylethynyl)phenyl)acrylamide (0.2 mmol, 52.5 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 1-methyl-4-(pyridin-3-ylmethyl)-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow solid, with a yield of 32.8 mg and a yield of 65%.

[0231] Characterization data: 1 HNMR (500M, CDCl3): δ8.45-8.44(m,1H),8.26(s,1H),7.34-7.26(m,2H),7.19-7.17(m,1H),7.02-6. 90(m,3H),3.32(s,3H),3.14-3.09(m,1H),2.89-2.85(m,1H),2.79-2.71(m,2H),2.64-2.60(m,1H). 13 C NMR (125MHz, CDCl3) δ168.84,150.43,147.94,139.71,136.92,134.04,128 .04,127.89,127.86,123.15,122.89,115.02,37.99,37.69,36.21,29.30.

[0232] Example 41

[0233]

[0234] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-(2-(hex-1-yn-1-yl)phenyl)-N-methylacrylamide (0.2 mmol, 48.3 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 1-methyl-4-pentyl-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow liquid, with a yield of 22.2 mg, representing a yield of 48%.

[0235] Characterization data: 1 HNMR (500M, CDCl3): δ7.28-7.25(m,1H),7.16-7.14(m,1H),7.05-6.99(m,2H),3.37(s,3H),2.84(m,1H),2.77- 2.73(m,1H),2.62-2.59(m,1H),1.61-1.45(m,2H),1.45-1.34(m,1H),1.34-1.21(m,5H),0.87(t,J=7.0Hz,3H). 13 CNMR (125MHz, CDCl3) δ169.79,139.71,130.09,127.60,127.35,122.71,114.88,36.87,36.02,33.57,31.70,29.30,26.60,22.60,14.00.

[0236] Example 42

[0237]

[0238] Under nitrogen protection, photocatalyst PC5 (0.01 mmol, 5 mol%, 15 mg), N-(2-(cyclohexyl-1-en-1-ylethynyl)phenyl)-N-methacrylamide (0.2 mmol, 53.1 mg, 1.0 equiv.), and a prepared solution (MeOH / Et3N / H2O = 1.8 / 0.6 / 0.2 mL) were added to a dry Schlenk reaction tube. The reaction solution was placed 3 cm away from a 15 W blue LED light source and reacted at 35 °C for 9 hours. After the reaction, the solvent was removed under vacuum, and the mixture was further purified by column chromatography (eluent PE / EA = 10 / 1-5 / 1) to give the corresponding 4-(cyclohexyl-1-en-1-1-ylmethyl)-1-methyl-3,4-dihydroquinoline-2(1H)-one. This substance was a yellow liquid, with a yield of 25.5 mg, representing a yield of 50%.

[0239] Characterization data: 1 HNMR (500M, CDCl3): δ7.27-7.24(m,1H),7.15(dJ=7.4Hz.1H),7.04-6.98(m,2H),5.38(s,1H),5.37(s,3H),3.04-2.99(m,1H),2.70-2.56( m,1H)2.60-2.57(m,1H),2.24-2.20(m,1H),2.10-2.05(m,1H),2.01- 1.97(m,1H),1.92-1.89(m,3H),1.65-1.62(m,2H),1.58-1.53(m,2H). 13 CNMR (125MHz, CDCl3) δ168.86,139.02,138.08,131.09,130.51,130.48,129.28,128.46,126.67,116.45,115.52,40.39,38.03,35.51,29.37.

Claims

1. A method for the selective preparation of quinoline-2-one or 3,4-dihydroquinoline-2-one compounds regulated by a photocatalyst, characterized in that, The method includes: Under inert gas protection, the raw material 1,7-enyne compound (I), photocatalyst, electron donor triethylamine and solvent were mixed and reacted under visible light irradiation and at 15-45°C. The reaction was monitored by TLC until it was completed. The reaction solution was then post-treated to obtain the product. When selectively preparing quinoline-2-one compounds: The photocatalyst is PC3: The solvent is toluene; The reaction formula is as follows: In formula (I) or (II), R 1 It can be H, methyl, ethyl, methoxy, methylthio, aryl, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy, methoxycarbonyl, cyano, or amino; R 2 It is alkyl, thiophene, pyridinyl, naphthyl or Where R is H, methyl, ethyl, methoxy, methylthio, aryl, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy, methoxycarbonyl, cyano, or amino; R 3 It can be H, methyl, ethyl, phenyl, benzyl, 4-methoxybenzyl, 2,4-dimethoxybenzyl, benzoyl, tert-butoxycarbonyl, or benzyloxycarbonyl; When selectively preparing 3,4-dihydroquinoline-2-one compounds: The photocatalyst is PC5: The solvent is a mixture of methanol and water; The reaction formula is as follows: In formula (I) or (III), R 4 It can be H, methyl, ethyl, methoxy, methylthio, aryl, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy, methoxycarbonyl, cyano, or amino; R 5 It is alkyl, thiophene, pyridinyl or Where R is H, methyl, methoxy, fluorine, chlorine, bromine, tert-butyl formate, amino, trifluoromethyl, methylthio, methoxycarbonyl, cyano, or amino; R 6 It can be H, methyl, ethyl, phenyl, benzyl, 4-methoxybenzyl, 2,4-dimethoxybenzyl, benzoyl, tert-butoxycarbonyl or benzyloxycarbonyl.

2. The method for selectively preparing quinoline-2-one or 3,4-dihydroquinoline-2-one compounds by photocatalyst regulation as described in claim 1, characterized in that, When selectively preparing quinoline-2-one compounds, the reaction temperature is 35℃ and the reaction time is 36h.

3. The method for selectively preparing quinoline-2-one or 3,4-dihydroquinoline-2-one compounds by photocatalyst regulation as described in claim 1, characterized in that, When selectively preparing quinoline-2-one compounds, the molar ratio of photocatalyst to raw material 1,7-enyne compound (I) is 0.025–0.1:1; the volume ratio of electron donor triethylamine to solvent toluene is 1.2:1.

8.

4. The method for selectively preparing quinoline-2-one or 3,4-dihydroquinoline-2-one compounds by photocatalyst regulation as described in claim 1, characterized in that, When selectively preparing the product 3,4-dihydroquinoline-2-one, the reaction temperature is 35℃ and the reaction time is 9h.

5. The method for selectively preparing quinoline-2-one or 3,4-dihydroquinoline-2-one compounds by photocatalyst regulation as described in claim 1, characterized in that, When selectively preparing the product 3,4-dihydroquinoline-2-one, the molar ratio of the photocatalyst to the raw material 1,7-enyne compound (I) is 0.025–0.1:1; the volume ratio of the electron donor triethylamine to methanol and water is 1.2:1.6:0.2.

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