A method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives

Abstract

This invention discloses a photocatalytic method for synthesizing 3-sulfonyl-substituted chromone derivatives. The method involves adding o-hydroxyphenylenamine ketone (Formula I), arylsulfonyl chloride (Formula II), a photocatalyst, and additives to a solvent, stirring the mixture under light irradiation, and then post-processing to obtain the 3-sulfonyl-substituted chromone derivative as shown in Formula III. The reaction formula is as follows: This invention has advantages such as simple operation, readily available and inexpensive raw materials, mild reaction conditions, and high reaction yield. Compared with traditional processes, it avoids high-temperature conditions and the use of oxidants, making it environmentally friendly.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method and application of using phenothiazine derivatives as small molecule photocatalysts to achieve visible light-induced 3-position sulfonyl-substituted chromone derivatives. Background Technology

[0002] Phenothiazine (PTH), as a heterocyclic compound, has gradually attracted attention in the field of photoinitiators due to its unique photoelectric properties and multifunctionality. Because its structure contains both S and N atoms, it can serve as a strong electron-donating group to construct materials with intramolecular electron transfer (ICT) properties. Modification of different sites in the phenothiazine structure will have different effects on the properties of the final compound. Currently, the number of photocatalysts derived from its structural modification is limited, and their applications are relatively small. Therefore, further research is needed to broaden the structural modification and related applications of its derivatives.

[0003]

[0004] Chromones (benzo-γ-pyranones) are high-quality heterocyclic lead compound skeletons abundant in natural products and drug synthesis. Due to their anti-inflammatory, antioxidant, antibacterial, and antitumor biological activities, many chromone derivatives have been applied in clinical treatment. Therefore, the development of simple and efficient synthetic methods for chromone lead structures with potential pharmacological activity has attracted widespread attention.

[0005]

[0006] On the other hand, sulfonyl groups possess numerous biological activities, such as anti-inflammatory and antiviral activities. Notably, sulfonyl groups are structurally and electronically similar to carbonyl groups, making them potentially valuable as bioisosteres in drug design. Therefore, introducing sulfonyl groups into heterocyclic compounds has been a hot research topic in organic chemistry synthesis. Furthermore, 3-substituted sulfonyl chromones can serve as reaction intermediates for synthetic applications, reacting with o-diphenylamine to generate benzimidazole compounds, which can then be further synthesized into fluorescent probes for bioimaging (J.Org.Chem.2018,83,2361-2368, CN202210901189).

[0007]

[0008] Current strategies involve using sulfonyl hydrazides as functionalizing agents to provide sulfonyl radicals and construct sulfonyl-substituted heterocycles. For example, in 2017, Wan et al. reported a cascade cyclization reaction using iodine at equivalent levels as catalysis, with o-hydroxyphenylenamine ketone as the substrate and benzenesulfonyl hydrazide participating, to construct 3-sulfonyl-substituted chromones (Eur. J. Org. Chem. 2017, 30, 4401–4404). Compared to this work, inducing cyclization with visible light while avoiding traditional thermodynamic conditions and the use of transition metal photocatalysts remains challenging and has been studied relatively little. Summary of the Invention

[0009] To address the aforementioned technical problems in the existing technology, the purpose of this invention is to provide a simple, mild, high-purity, green, and efficient method for synthesizing a class of phenothiazine derivatives, using them as photocatalysts under visible light induction for the synthesis of 3-substituted sulfonyl chromone derivatives.

[0010] The technical solution of the present invention is as follows:

[0011] The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives includes the following steps: adding o-hydroxyphenylenamine ketone of formula I, arylsulfonyl chloride of formula II, a photocatalyst, and an additive to a solvent, stirring the reaction under light source irradiation, and after the reaction is completed, post-treatment is performed to obtain the 3-sulfonyl-substituted chromone derivative as shown in formula III, the reaction formula of which is as follows:

[0012]

[0013] Wherein: R1 is hydrogen, C1-C4 alkyl, halogen or C1-C4 alkoxy, R2 is hydrogen, C1-C4 alkyl, halogen, C1-C4 alkoxy, trifluoromethyl or aryl, and the substituents R1 and R2 are each independently monosubstituted or polysubstituted.

[0014] Further, the photocatalyst is Ir[dF(CF3)ppy]2(dtbbpy)PF6, Ir(ppy)3, 4CzIPN, or a PTH phenothiazine derivative, wherein the PTH phenothiazine derivative is selected from PTH 1-9; the structural formula of the photocatalyst is as follows:

[0015]

[0016] Furthermore, the photocatalyst is selected from PTH 5 or PTH 6.

[0017] Furthermore, the solvent may be selected from one or any combination of the following: THF, acetone, C1-C4 alkyl alcohol, acetonitrile, DMF, DMA, DMSO, preferably acetone or acetonitrile; the concentration of compound I in the solvent is 0.01-0.5 mol / L, preferably 0.05-0.2 mol / L.

[0018] Furthermore, the light source is blue light, white light, or violet light, preferably blue light or white light; the illuminance of the light source is 10-100W, preferably 20-50W.

[0019] Further, the additive is at least one selected from Na2HPO4, K3PO4, NaOH, K2CO3, Na2CO3, NaHCO3, NaOAc, Et3N, DBU, DIPEA, TMEDA, and TMDETA, preferably K2CO3, NaOAc, or Et3N; the molar ratio of the additive to compound I is 1-5:1, preferably 1.5-3:1.

[0020] Furthermore, the molar ratio of compound I to compound II is 1.0:1.0 to 3.0, preferably 1.0:1.5 to 2.0; the molar ratio of compound I to photocatalyst is 1.0:0.01 to 0.02.

[0021] Furthermore, the reaction temperature is 10–40°C, the reaction time is 8–24 hours, the preferred reaction temperature is room temperature, and the preferred reaction time is 10–15 hours.

[0022] Further, the post-processing procedure was as follows: the reaction was quenched with water, extracted with ethyl acetate, the combined organic layers were dried with anhydrous Na2SO4 and concentrated under reduced pressure, and then separated by column chromatography to obtain the product. The solvent used for column chromatography was a petroleum ether / ethyl acetate mixture with a volume ratio of 20-30:1.

[0023] By employing the above-described technology, compared with the prior art, the present invention has the following significant advantages:

[0024] 1) The present invention has a simple operation process, inexpensive and readily available raw materials, mild reaction conditions, high product yield, and a wide range of substrates;

[0025] 2) This invention utilizes a photocatalytic method to synthesize 3-sulfonyl substituted chromone derivatives in one step by using aryl sulfonyl chloride to perform a tandem sulfonylation cyclization reaction on enamine ketone compounds. It exhibits good regioselectivity and avoids the use of oxidants and additives compared to traditional processes. The reaction yield is high, it is environmentally friendly, and it is conducive to large-scale production.

[0026] Based on our previous work on visible light-catalyzed radical cyclization, we synthesized a series of phenothiazine derivatives by modifying their structures, such as by increasing or decreasing the electronic and steric effects of substituents on heteroatoms through the conjugated structure of benzo[a]heterocyclic rings. Using these derivatives as small-molecule photocatalysts, we constructed a series of 3-substituted sulfonyl chromone compounds using substituted arylsulfonyl chlorides as sulfonyl sources and o-hydroxyphenylenamine ketones as substrates. Detailed Implementation

[0027] The present invention will be further described below with reference to embodiments, which will enable those skilled in the art to have a more comprehensive understanding of the present invention, but will not limit the scope of the present invention in any way. It is well known to those skilled in the art that due to objective factors such as sample preparation, sample purity, instrument conditions, and other experimental conditions, the obtained experimental results will have certain errors.

[0028] Example 1 7-Toluenesulfonyl-4H-benzopyran-4-one

[0029]

[0030] Compound (I) 3-(dimethylamino)-1-(2-hydroxyphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-toluenesulfonyl chloride (0.4 mmol), PTH 1 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The reaction was stirred at room temperature for 12 hours under 25 W blue light irradiation. 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid in 48% yield.

[0031] 1 H NMR (600MHz, CDCl3) δ8.13(d,J=8.6Hz,1H),7.84(s,1H),7.25(d,J=1.7Hz,2H) ,7.23(s,1H),7.21(s,1H),7.17–7.15(m,1H),7.12–7.10(m,1H),2.49(s,6H).

[0032] 13C NMR (151MHz, CDCl3) δ174.98,156.51,155.52,145.39,138.69,132.47,130.61, 130.02,127.46,127.18,126.79,126.14,121.19,120.09,117.80,21.83,20.37.

[0033] Example 2 7-Methyl-3-((2-fluorophenyl)sulfonyl)-4H-benzopyran-4-one

[0034]

[0035] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) 2-fluorobenzenesulfonyl chloride (0.4 mmol), PTH 2 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 51%.

[0036] 1 H NMR (400MHz, CDCl3) δ8.18(s,1H),8.11(d,J=8.1Hz,1H),7.39(td,J=7.5,1.5Hz,1H),7.26–7.18(m,3H),7.08–7.03(m,2H),2.49(s,3H).

[0037] 13 C NMR (101MHz, CDCl3) δ174.93,161.20(d,J=246.5Hz),159.98,157.58,156.51,145.59,132.59,129.28(d,J=7.7 Hz), 127.35, 126.16, 124.67 (d, J = 4.0Hz), 121.44, 121.12 (d, J = 17.2Hz), 117.89, 115.90 (d, J = 22.0Hz), 21.86.

[0038] 19 F NMR (376MHz, CDCl3) δ -109.86

[0039] Example 3 7-Methyl-3-((2-trifluoromethylphenyl)sulfonyl)-4H-benzopyran-4-one

[0040]

[0041] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) 2-trifluoromethylbenzenesulfonyl chloride (0.4 mmol), PTH 3 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 36%.

[0042] 1 H NMR (400MHz, CDCl3) δ8.23(s,1H),8.12(d,J=8.0Hz,1H),7.66(d,J=7.6Hz,1H) ,7.40(d,J=7.5Hz,1H),7.36(t,J=7.1Hz,1H),7.30–7.27(m,3H),2.50(s,3H).

[0043] 13 C NMR (101MHz, CDCl3) δ174.84,158.96,156.53,145.83,134.58,132.09,131.10,129.12(d,J=3 1.2Hz), 127.54, 126.89 (q, J = 5.7Hz), 126.50, 126.25, 125.20, 122.48, 121.59, 117.95, 21.88.

[0044] 19 FNMR (376MHz, CDCl3) δ -60.56.

[0045] Example 4 7-Methyl-3-((2-thienyl)sulfonyl)-4H-benzopyran-4-one

[0046]

[0047] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) 2-thiophene sulfonyl chloride (0.4 mmol), PTH 4 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give a yellow oily liquid with a yield of 45%.

[0048] 1 H NMR (600MHz, CDCl3) δ8.17(d,J=8.2Hz,1H),7.89(s,1H),7.46(d,J=5.3Hz,1H),7.41(d,J=3.6 Hz,1H),7.32(d,J=7.4Hz,1H),7.27(d,J=8.4Hz,1H),7.07(dd,J=5.3,3.6Hz,1H),2.52(s,3H).

[0049] 13 C NMR (151MHz, CDCl3) δ174.67,156.41,154.38,145.39,135.65,130.91,130.31,127.87,127.15,125.99,122.91,121.14,117.77,21.82.

[0050] Example 5 7-Methyl-3-((3,5-difluorophenyl)sulfonyl-4H-benzopyran-4-one

[0051]

[0052] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) 3,5-difluorobenzenesulfonyl chloride (0.4 mmol), PTH 5 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 72%.

[0053] 1 H NMR (400MHz, CDCl3) δ8.19(s,1H),8.08(d,J=8.1Hz,1H),7.57–7.51(m,1H),7.23(d,J=9.0Hz,2H),6.85–6.80(m,2H),2.48(s,3H).

[0054] 13 C NMR (101MHz, CDCl3) δ175.36,164.17(dd,J=99.8,11.8Hz),161.68(dd,J=98.9,12.1Hz),157.74,156.91,146.07,135.63(dd,J=9.5,2 .3Hz),127.81,126.50,121.89,118.85,118.32,116.53(dd,J=17.5,4.0Hz),112.48(dd,J=21.5,3.9Hz),105.06(t,J=26.0Hz),22.30.

[0055] 19 F NMR (376MHz, CDCl3) δ-104.01,-109.49.

[0056] Example 6 3-((4-chlorophenyl)sulfonyl)-6-methyl-4H-benzopyran-4-one

[0057]

[0058] Compound (I) 3-dimethylamino-1-(2-hydroxy-3-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-chlorobenzenesulfonyl chloride (0.4 mmol), PTH 6 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 75%.

[0059] 1 H NMR (600MHz, CDCl3) δ8.21(s,1H),8.02(s,1H),7.51(dd,J=8.6,2.5Hz,1H),7.38(d,J=8.5Hz,1H),7.32–7.29(m,2H),7.24–7.21(m,2H),2.46(s,3H). 13 C NMR (151MHz, CDCl3) δ175.06,157.99,154.68,136.06,135.39,133.08,132.99,130.72,129.24,125.75,123.45,118.86,117.95,20.97.

[0060] Example 7 7-Methoxy-3-((4-tert-butyl)phenyl)sulfonyl)-4H-benzopyran-4-one

[0061]

[0062] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methoxyphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-tert-butylbenzenesulfonyl chloride (0.4 mmol), PTH 7 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 52%.

[0063] 1 H NMR(600MHz, CDCl3)δ8.15(d,J=8.9Hz,1H),7.99(s,1H),7.37–7.35(m,2H),7.31(d,J=8 .5Hz,2H),6.98(dd,J=8.9,2.4Hz,1H),6.82(d,J=2.4Hz,1H),3.90(s,3H),1.28(s,9H).

[0064] 13 C NMR (151MHz, CDCl3) δ174.46,164.25,158.14,156.19,150.53,130.32,130 .29,127.86,126.31,120.65,117.57,114.88,100.31,55.88,34.53,31.24.

[0065] Example 8 7-Methoxy-3-((4-bromophenyl)sulfonyl)-4H-benzopyran-4-one

[0066]

[0067] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methoxyphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-bromobenzenesulfonyl chloride (0.4 mmol), PTH 8 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 41%.

[0068] 1 H NMR (600MHz, CDCl3) δ8.16 (s, 1H), 8.14 (d, J = 8.9Hz, 1H), 7.39–7.37 (m, 2H), 7.2 5–7.23(m,2H),7.00(dd,J=8.9,2.4Hz,1H),6.86(d,J=2.3Hz,1H),3.92(s,3H).

[0069] 13C NMR (151MHz, CDCl3) δ174.19,164.45,158.19,157.57,133.84,132.15,130.93,127.92,120.91,118.96,117.66,115.11,100.44,55.93.

[0070] Example 9 3-((4-bromophenyl)sulfonyl)-5,7-dimethoxy-4H-benzopyran-4-one

[0071]

[0072] Compound (I) 3-dimethylamino-1-(2-hydroxy-4,6-dimethylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-bromobenzenesulfonyl chloride (0.4 mmol), PTH 9 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 38%.

[0073] 1 H NMR (600MHz, CDCl3) δ8.01(s,1H),7.39(d,J=2.0Hz,1H),7.38(d,J=2.0Hz,1H),7.28(d,J=2.0Hz, 1H),7.27(d,J=1.9Hz,1H),6.45(d,J=2.3Hz,1H),6.40(d,J=2.3Hz,1H),3.93(s,3H),3.91(s,3H).

[0074] 13 C NMR (151MHz, CDCl3) δ173.17,164.34,161.35,160.04,155.41,134.03,132.07,131.25,120.81,120.27,109.25,96.64,92.79,56.42,55.81.

[0075] Example 10 6-Methyl-3-toluenesulfonyl-4H-benzopyran-4-one

[0076]

[0077] Compound (I) 3-dimethylamino-1-(2-hydroxy-3-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-toluenesulfonyl chloride (0.4 mmol), 4CzIPN (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 16%.

[0078] 1 H NMR (600MHz, CDCl3) δ8.04(s,1H),8.02(s,1H),7.48(dd,J=8.5,2.4Hz,1H),7.34(t,J=8.1Hz,3H),7.10(d,J=7.9Hz,2H),2.45(s,3H),2.31(s,3H).

[0079] 13 C NMR (151MHz, CDCl3) δ175.19,156.43,154.63,137.45,135.70,135.13,130.81,130.02,125.69,123.30,120.69,117.86,21.08,20.96.

[0080] Example 11 3-((3-(trifluoromethyl)phenyl)sulfonyl)-4H-benzopyran-4-one

[0081]

[0082] Compound (I) 3-dimethylamino-1-(2-hydroxyphenyl)prop-2-en-1-one (0.2 mmol), compound (II) 3-trifluoromethylbenzenesulfonyl chloride (0.4 mmol), Ir(ppy)3 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 22%.

[0083] 1 H NMR (600MHz, CDCl3) δ8.32(s,1H),8.25(d,J=8.0Hz,1H),7.73(t,J=7.8Hz,1H),7.60(s,1H),7. 52(d,J=3.7Hz,1H),7.51(d,J=4.2Hz,1H),7.46(dd,J=15.9,8.6Hz,2H),7.38(t,J=7.8Hz,1H).

[0084] 13 C NMR (151MHz, CDCl3) δ174.84,158.75,156.42,136.19,134.28,131.98,131.59,131.37,12 9.46,126.53,126.05,125.46(q,J=3.7Hz),123.81,123.53(q,J=4.1Hz),118.26,118.12.

[0085] 19 F NMR (376MHz, CDCl3) δ -62.76.

[0086] Example 12 7-Methoxy-3-((3-(trifluoromethoxy)phenyl)sulfonyl)-4H-benzopyran-4-one

[0087]

[0088] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methoxyphenyl)prop-2-en-1-one (0.2 mmol), compound (II) 3-(trifluoromethoxy)benzenesulfonyl chloride (0.4 mmol), Ir[dF(CF3)ppy]2(dtbbpy)PF6 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The reaction was stirred at room temperature for 12 hours under 25 W blue light irradiation. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 29%.

[0089] 1H NMR (600MHz, CDCl3) δ8.32(s,1H),8.25(d,J=8.9Hz,1H),7.37(d,J=7.2Hz,1H),7.35–7. 33(m,1H),7.26(t,J=2.2Hz,1H),7.14–7.10(m,2H),6.97(d,J=2.4Hz,1H),4.02(s,3H).

[0090] 13 C NMR (151MHz, CDCl3) δ174.12,164.52,158.41,158.22,149.54,137.41,130.16,127.95, 126.66,120.83,120.37(d,J=257.6Hz),118.79,117.96,117.67,115.22,100.49,55.95.

[0091] 19 FNMR (565MHz, CDCl3) δ -57.73

[0092] Example 13 3-((4-chlorophenyl)sulfonyl)-4H-benzopyran-4-one

[0093]

[0094] Compound (I) 3-dimethylamino-1-(2-hydroxyphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-chlorobenzenesulfonyl chloride (0.4 mmol), PTH 6 (0.02 mmol), and NaHCO3 (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetonitrile was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W white light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 51%.

[0095] 1 H NMR (600MHz, CDCl3) δ8.25 (dd, J=8.0, 1.5Hz, 1H), 8.24 (s, 1H), 7.74–7.70 (m, 1H), 7. 50(d,J=8.4Hz,1H),7.46(t,J=7.6Hz,1H),7.34(d,J=8.6Hz,2H),7.28–7.24(m,2H).

[0096] 13 C NMR (151MHz, CDCl3) δ174.96,157.88,156.39,134.16,133.16,132.81,130.95,129.29,126.49,125.92,123.76,119.32,118.21.

[0097] Example 14 3-Toluenesulfonyl-4H-benzopyran-4-one

[0098]

[0099] Compound (I) 3-(dimethylamino)-1-(2-hydroxyphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-toluenesulfonyl chloride (0.4 mmol), PTH 6 (0.02 mmol), and Et3N (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetonitrile was added as a solvent to the mixture. The reaction was stirred at room temperature for 12 hours under 25 W white light irradiation. 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 70%.

[0100] 1 H NMR(600MHz, CDCl3)δ8.24(dd,J=8.0,1.7Hz,1H),8.04(s,1H),7.68(ddd,J=8.7,7.1, 1.7Hz,1H),7.48–7.41(m,1H),7.38–7.33(m,2H),7.11(d,J=7.9Hz,1H),2.31(s,3H).

[0101] 13 C NMR (151MHz, CDCl3) δ175.10,156.33,156.26,137.62,133.88,131.04,130.07,129.85,126.43,125.62,123.61,121.17,118.11,21.09.

[0102] Example 15 7-Methyl-3-((4-fluorophenyl)sulfonyl)-4H-benzopyran-4-one

[0103]

[0104] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-fluorobenzenesulfonyl chloride (0.4 mmol), PTH 6 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetonitrile was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W white light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 72%.

[0105] 1 H NMR (600MHz, CDCl3) δ8.12 (d, J = 8.7Hz, 2H), 7.47–7.43 (m, 2H), 7.28–7.24 (m, 2H), 7.03–6.97 (m, 2H), 2.50 (s, 3H).

[0106] 13 C NMR (151MHz, CDCl3) δ174.86,163.06,161.42,156.74,156.42,145.50,132.61 (d,J=8.3Hz), 128.97(d,J=3.9Hz),127.23,126.07,121.39,120.20,117.76,116.22(d,J=22.1Hz),21.75.

[0107] 19 F NMR (565MHz, CDCl3) δ -114.35.

[0108] Example 16 7-Methyl-3-((4-bromophenyl)sulfonyl)-4H-benzopyran-4-one

[0109]

[0110] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-bromobenzenesulfonyl chloride (0.4 mmol), PTH 6 (0.02 mmol), and K2CO3 (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetonitrile was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W white light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 69%.

[0111] 1 H NMR (600MHz, CDCl3) δ8.22(s,1H),8.14(d,J=8.1Hz,1H),7.43–7.37(m,2H),7.29(s,2H),7.26(dd,J=9.0,2.3Hz,2H),2.52(s,3H).

[0112] 13 C NMR (151MHz, CDCl3) δ174.81,157.92,156.54,145.72,133.81,132.16,130.87,127.44,126.24,121.55,120.90,118.81,117.89,21.85.

[0113] Example 17 7-Methyl-3-((4-chlorophenyl)sulfonyl)-4H-benzopyran-4-one

[0114]

[0115] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-chlorobenzenesulfonyl chloride (0.4 mmol), PTH 6 (0.02 mmol), and DIPEA (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetonitrile was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W white light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 12%.

[0116] 1 H NMR (600MHz, CDCl3) δ8.15 (s, 1H), 8.07 (d, J = 8.2Hz, 1H), 7.29–7.26 (m, 2H), 7.23–7.22 (m, 2H), 7.20–7.18 (m, 2H), 2.46 (s, 3H).

[0117] 13 C NMR (151MHz, CDCl3) δ174.84,157.79,156.53,145.71,133.05,133.01,130.77,129.25,127.42,126.22,121.54,119.02,117.89,21.85.

[0118] Example 18 7-Methyl-3-toluenesulfonyl-4H-benzopyran-4-one

[0119]

[0120] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-toluenesulfonyl chloride (0.4 mmol), PTH 6 (0.02 mmol), and Na2HPO4 (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetonitrile was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W white light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 34%.

[0121] 1 H NMR (600MHz, CDCl3) δ8.11(d,J=8.3Hz,1H),8.00(s,1H),7.34(d,J=8.2Hz,2H),7.22(d,J=7.8Hz,2H),7.10(d,J=8.0Hz,2H),2.48(s,3H),2.31(s,3H). 13 C NMR (151MHz, CDCl3) δ174.99,156.48,156.18,145.34,137.47,130.87,130.09,130.02,127.14,126.17,121.40,120.85,117.79,21.82,21.08.

[0122] Example 19 7-Methyl-3-((4-tert-butylphenyl)sulfonyl)-4H-benzopyran-4-one

[0123]

[0124] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-tert-butylbenzenesulfonyl chloride (0.4 mmol), PTH 5 (0.02 mmol), and Et3N (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of DMSO was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 21%.

[0125] 1 H NMR (600MHz, CDCl3) δ8.13(d,J=8.8Hz,1H),8.03(s,1H),7.36–7.35(m,2H),7.32–7.30(m,2H),7.23(d,J=7.3Hz,2H),2.49(s,3H),1.28(s,9H).

[0126] 13 C NMR (151MHz, CDCl3) δ175.06,156.50,150.53,145.37,130.30,130.24,127.17,126.32,126.19,121.42,120.53,117.80,34.53,31.24,21.82.

[0127] Example 20 7-Methyl-3-((4-(trifluoromethyl)phenyl)sulfonyl)-4H-benzopyran-4-one

[0128]

[0129] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) p-trifluoromethylbenzenesulfonyl chloride (0.4 mmol), PTH 5 (0.02 mmol), and Et3N (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 74%.

[0130] 1 H NMR (400MHz, CDCl3) δ8.32 (s, 1H), 8.13 (d, J = 8.1Hz, 1H), 7.49 (s, 1H), 7.47 (s, 1H), 7.37–7.36(m,1H),7.34(s,1H),7.31–7.30(m,1H),7.29–7.27(m,1H),2.52(s,3H).

[0131] 13 C NMR (101MHz, CDCl3) δ174.71,159.22,156.60,145.99,140.30,127.66,127 .52,126.31,125.86(q,J=3.7Hz),122.69,121.59,117.98,117.08,21.90.

[0132] 19 F NMR (376MHz, CDCl3) δ -62.52.

[0133] Example 21 7-Methyl-3-((3-fluorophenyl)sulfonyl)-4H-benzopyran-4-one

[0134]

[0135] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) 3-fluorobenzenesulfonyl chloride (0.4 mmol), PTH 5 (0.02 mmol), and Et3N (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetonitrile was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 69%.

[0136] 1 H NMR (400MHz, CDCl3) δ8.26 (s, 1H), 8.14 (d, J = 8.1Hz, 1H), 7.31–7.27 (m, 2H), 7.25– 7.20(m,1H),7.15–7.09(m,1H),7.05–6.97(m,1H),6.92–6.84(m,1H),2.52(s,1H).

[0137] 13 C NMR (101MHz, CDCl3) δ174.82, 162.89 (d, J = 248.3Hz), 158.62, 156.57, 145.80, 137.25 (d, J = 7.7Hz), 130.34 (d, J = 8.4H z), 127.51, 126.29, 124.09 (d, J = 2.9Hz), 121.59, 118.06, 117.94, 115.35 (d, J = 23.5Hz), 113.63 (d, J = 21.3Hz), 21.88.

[0138] 19 F NMR (376MHz, CDCl3) δ -111.94.

[0139] Example 22 7-Methyl-3-(m-toluenesulfonyl)-4H-benzopyran-4-one

[0140]

[0141] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) 3-methylbenzenesulfonyl chloride (0.4 mmol), PTH 5 (0.02 mmol), and Et3N (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of THF was added as a solvent, and the mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was complete, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate, and the combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain an off-white solid in 35% yield.

[0142] 1 H NMR(600MHz, CDCl3)δ8.15(d,J=8.1Hz,1H),8.11(s,1H),7.28(d,J=3.3Hz,2H), 7.24(s,1H),7.21–7.17(m,2H),7.05(d,J=7.0Hz,1H),2.52(s,3H),2.32(s,3H).

[0143] 13 C NMR (151MHz, CDCl3) δ174.99,157.04,156.53,145.43,139.03,133.84,130.42, 129.02,127.99,127.21,126.89,126.25,121.49,119.94,117.83,21.83,21.33.

[0144] Example 23 7-Methyl-3-((3-trifluoromethylphenyl)sulfonyl)-4H-benzopyran-4-one

[0145]

[0146] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) 3-trifluoromethylbenzenesulfonyl chloride (0.4 mmol), PTH 5 (0.02 mmol), and Et3N (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of DCM was added as a solvent. The mixture was stirred at room temperature under 25 W blue light for 12 hours. After the reaction was complete, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid in 21% yield.

[0147] 1 H NMR (600MHz, CDCl3) δ8.28(s,1H),8.12(d,J=8.2Hz,1H),7.58(s,1H),7.50(d,J=7.8Hz ,1H),7.43(d,J=6.9Hz,1H),7.37(t,J=7.8Hz,1H),7.28(d,J=12.9Hz,2H),2.51(s,3H).

[0148] 13 C NMR (151MHz, CDCl3) δ174.64,158.58,156.50,145.79,136.36,131.74,129.36,127.4 8,126.20,125.20(q,J=3.9Hz),123.33(q,J=3.8Hz),121.51,117.88,117.78,21.79.

[0149] 19 FNMR (376MHz, CDCl3) δ -62.73.

[0150] Example 24 3-((3-bromophenyl)sulfonyl)-4H-benzopyran-4-one

[0151]

[0152] Compound (I) 3-dimethylamino-1-(2-hydroxyphenyl)prop-2-en-1-one (0.2 mmol), compound (II) 3-bromobenzenesulfonyl chloride (0.4 mmol), PTH 6 (0.02 mmol), and Et3N (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The reaction was stirred at room temperature under 25 W white light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 64%.

[0153] 1 H NMR (600MHz, CDCl3) δ8.27(s,1H),8.25(d,J=8.0Hz,1H),7.72(t,J=7.8Hz,1H),7. 51(s,1H),7.49–7.44(m,2H),7.31(dd,J=15.3,7.9Hz,2H),7.13(t,J=7.9Hz,1H).

[0154] 13 C NMR (151MHz, CDCl3) δ174.88,158.52,156.42,136.89,134.22,131.45,130.39,129.94,127.61,126.56,125.99,123.83,122.96,118.51,118.25.

[0155] Example 25 6-Chloro-3-toluenesulfonyl-4H-benzopyran-4-one

[0156]

[0157] Compound (I) 1-(5-chloro-2-hydroxyphenyl)-3-(dimethylamino)prop-2-en-1-one (0.2 mmol), compound (II) p-toluenesulfonyl chloride (0.4 mmol), PTH 6 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The reaction was stirred at room temperature for 12 hours under 25 W blue light irradiation. 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid in 75% yield.

[0158] 1 H NMR (600MHz, CDCl3) δ8.19(d,J=2.6Hz,1H),7.98(s,1H),7.61(dd,J=8.9,2.6Hz,1H ),7.41(d,J=8.9Hz,1H),7.35(d,J=8.2Hz,2H),7.12(d,J=8.2Hz,2H),2.32(s,3H).

[0159] 13 C NMR (151MHz, CDCl3) δ173.98,155.82,154.63,138.00,134.11,131.57,131.45,130.17,129.20,125.73,124.39,121.77,119.86,21.12.

[0160] Example 26 7-Methyl-3-(benzenesulfonyl)-4H-benzopyran-4-one

[0161]

[0162] Compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) benzenesulfonyl chloride (0.4 mmol), PTH 6 (0.02 mmol), and NaOAc (0.4 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stir bar. 2 mL of acetone was added as a solvent to the mixture. The mixture was stirred at room temperature under 25 W ultraviolet light for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The mixture was then separated and purified by rapid column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to give an off-white solid with a yield of 12%.

[0163] 1 H NMR (600MHz, CDCl3) δ8.15–8.09(m,2H),7.39(d,J=7.1Hz,2H),7.28(d,J=7.2Hz,3H),7.25–7.19(m,2H),2.49(s,3H).

[0164] 13C NMR (151MHz, CDCl3) δ174.98,157.28,156.53,145.49,134.28,129.72,129.17,127.27,127.01,126.24,121.50,119.70,117.84,21.83.

[0165] Example 27 Synthesis of phenothiazine derivative PTH4

[0166]

[0167] Step 1: Under a nitrogen atmosphere, a mixture of 0.05 mol of 2,3-dihydroxynaphthalene, 0.05 mmol of 2-aminothiophenol, and 30 mL of 1,2,4-trichlorobenzene was placed in a 100 mL round-bottom flask equipped with a magnetic stirrer and a water separator. The mixture was heated to 200 °C and reacted for 6 hours. Water generated during the reaction was collected using the water separator. After the reaction was complete, the product was recrystallized from n-hexane to obtain a yellow crude product, which was then purified by silica gel rapid column chromatography using petroleum ether and ethyl acetate in a volume ratio of 100:1 as eluents, yielding compound B as a yellow powder in 45% yield.

[0168] Step 2: Under a nitrogen atmosphere, palladium acetate (0.02 mmol), tri-tert-butylphosphine (0.08 mmol), and toluene (8 mL) were added to a round-bottom flask equipped with a magnetic stirrer. After stirring at room temperature for 10 min, compound B (2.0 mmol), 1-iodonaphthalene (2.6 mmol), and sodium tert-butoxide (3.0 mmol) prepared in Step 1 were added sequentially to the reaction solution. The mixture was stirred overnight at 120 °C. After the reaction was completed, the reaction solution was extracted three times with ethyl acetate and evaporated to dryness. Subsequently, it was purified by silica gel rapid column chromatography using petroleum ether and dichloromethane at a volume ratio of 200:1 as the eluent, and the coupling product PTH 4 was obtained in 32% yield.

[0169] 1 H NMR (400MHz, CDCl3) δ8.10–8.01(m,2H),7.77–7.66(m,2H),7.59–7.49(m,2H),7.48–7 .42(m,1H),7.21–7.08(m,4H),6.84–6.70(m,2H),6.27(s,1H),6.06(d,J=8.0Hz,1H).

[0170] 13C NMR (101MHz, CDCl3) δ142.43,141.00,137.02,135.40,132.95,130.99,129.94,129.07(d,J=19.9Hz),128.54,126.6 9,126.56,126.44,126.19,125.91,125.67,124.02(d,J=10.8Hz),123.38,121.88,121.79,118.91,115.92,110.78.

[0171] Example 28 Synthesis of phenothiazine derivative PTH5

[0172]

[0173] The synthesis of compound B is the same as in Example 27.

[0174] Under a nitrogen atmosphere, palladium acetate (0.02 mmol), tri-tert-butylphosphine (0.08 mmol), and toluene (8 mL) were added to a round-bottom flask equipped with a magnetic stirrer. After stirring at room temperature for 10 min, compound B (498.7 mg, 2.0 mmol), 1,3-dimethoxy-5-iodobenzene (2.6 mmol), and sodium tert-butoxide (3.0 mmol) were added sequentially to the reaction solution. The mixture was stirred overnight at 120 °C. After the reaction was completed, the reaction solution was extracted three times with ethyl acetate and evaporated to dryness. Subsequently, it was purified by silica gel rapid column chromatography using petroleum ether and dichloromethane in a volume ratio of 200:1 as the eluent, and the coupling product PTH 5 was given in 30% yield.

[0175] 1 H NMR (400MHz, CDCl3) δ7.79–7.76(m,1H),7.65–7.61(m,1H),7.49(d,J=2.2Hz,2H),7.40(dd,J=6.0,3.3Hz,2H),7. 32–7.27(m,2H),7.22–7.18(m,1H),7.10–7.06(m,1H),6.35(d,J=2.0Hz,2H),6.19(t,J=2.2Hz,1H),3.65(s,6H).

[0176] 13C NMR (101MHz, CDCl3) δ163.30,144.34,143.49,143.11,133.17,130.32,129.84,128.22,128.11, 127.16,126.95,126.54,126.12,123.54,122.98,122.14,118.88,114.74,104.62,94.78,55.63.

[0177] The preparation steps of PTH 6 are the same as those of PTH 4 in Example 27, except that in the second step, 1-iodonaphthalene is replaced with an equal molar amount of 1,3-di-tert-butyl-5-iodobenzene, and the other conditions remain unchanged, finally yielding the coupling product PTH 6.

[0178] 1 H NMR (600MHz, CDCl3) δ7.59(t,J=1.8Hz,1H),7.54(d,J=9.4Hz,1H),7.48(s,1H),7.30(d,J=7.6Hz,1H),7.26(d,J=1.7Hz,2H),7.23–7. 13(m,2H),7.07(dd,J=7.5,1.7Hz,1H),6.87(t,J=7.7Hz,1H),6.81(t,J=8.3Hz,1H),6.39(s,1H),6.19(d,J=8.6Hz,1H),1.40(s,18H).

[0179] 13 C NMR (151MHz, CDCl3) δ153.85,143.60,142.12,140.08,133.23,126.89,126.36,126.17,125. 94,124.90,124.21,124.08,122.16,122.03,121.70,119.05,116.14,110.82,35.15,31.50.

[0180] The preparation steps of PTH 7 are the same as those of PTH 4 in Example 27, except that in the second step, 1-iodonaphthalene is replaced with an equal molar amount of 2-iodo-1,3,5-trimethylbenzene, and the other conditions remain unchanged, and the coupling product PTH 7 is finally obtained.

[0181] 1H NMR (400MHz, CDCl3) δ7.48–7.42(m,1H),7.35(s,1H),7.27–7.24(m,1H),7.19–7.12(m,2H),7.11(s,2H),6.96(dd,J=7.6,1.6Hz, 1H),6.79(dd,J=7.2,1.6Hz,1H),6.73(td,J=7.6,1.6Hz,1H),6.11(s,1H),5.93(dd,J=7.2,1.6Hz,1H),2.41(s,3H),2.15(s,6H).

[0182] 13 C NMR (101MHz, CDCl3) δ140.14,138.56,138.33,137.81,137.69,134.86,133.74,130.42,130.11,127. 14,126.63,126.12,126.10,125.78,123.92,121.49,121.21,117.86,114.36,108.67,21.10,17.83.

[0183] The preparation steps of PTH 8 are the same as those of PTH 4 in Example 27, except that in the second step, 1-iodonaphthalene is replaced with an equal molar amount of 3,5-bis(trifluoromethyl)iodobenzene, and the other conditions remain unchanged, finally yielding the coupling product PTH 8.

[0184] 1 H NMR (400MHz, CDCl3) δ7.89–7.86(m,1H),7.78–7.83(m,1H),7.66–7.61(m,1H),7.55(t,J=2.0Hz,2H),7.5 0(dd,J=6.0,3.3Hz,2H),7.37–7.33(m,2H),7.29(d,J=2.2Hz,2H),7.21–7.18(m,1H),7.12–7.09(m,1H).

[0185] 13C NMR (101MHz, CDCl3) δ143.53,143.39,143.04(p,J=3.7Hz),133.14,133.02(q,J=7.5Hz),132.58(q,J=7.4Hz),130.18,129.76,128 .33,128.04,127.21,127.09,126.30,126.06,123.54,123.31(q,J=3.7Hz),123.14,122.01,121.78(q,J=7.2Hz),118.85,114.68.

[0186] 19 FNMR (376MHz, CDCl3) δ -79.65.

[0187] The preparation steps of PTH 9 are the same as those of PTH 4 in Example 27, except that in the first step, 2,3-dihydroxynaphthalene is replaced with an equal amount of 4-bromocatechol and 2-aminothiophenol is replaced with an equal amount of 2-amino-5-bromobenzenethiophenol; in the second step, 1-iodonaphthalene is replaced with an equal amount of 1-bromo-4-iodobenzene, and the other conditions remain unchanged, finally yielding the coupling product PTH 9.

[0188] 1 H NMR (400MHz, CDCl3) δ7.62(d,J=2.1Hz,2H),7.41–7.38(m,4H),7.23(d,J=8.2Hz,2H),7.06–7.02(m,2H).

[0189] 13 C NMR (101MHz, CDCl3) δ142.56,139.35,134.04,132.07,130.21,128.59,122.50,121.05,117.32,114.89.

[0190]

[0191] The corresponding compound from Example 20 was synthesized and applied (refer to J. Org. Chem. 2018, 83, 2361-2368, CN202210901189) to generate a compound capable of detecting Cu. 2+ Zn 2+ ,ClO - The functional fluorescent probes are described below:

[0192]

[0193] The above-described embodiments further illustrate the present invention in detail. Obviously, based on the above-described content of the present invention and according to common technical knowledge and conventional methods in the art, various other modifications, substitutions, or alterations can be made without departing from the basic technical concept of the present invention. However, this should not be construed as limiting the scope of the present invention to the following examples. All technologies implemented based on the above-described content of the present invention fall within the scope of the present invention.

Claims

1. A method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives, characterized in that, The o-hydroxyphenyl enamine ketone shown in Formula I, the aryl sulfonyl chloride shown in Formula II, the photocatalyst, and the additives were added to a solvent and reacted under light source irradiation with stirring. After the reaction was completed, post-treatment was performed to obtain the 3-sulfonyl substituted chromone derivative shown in Formula III, and its reaction formula is as follows: ； Wherein: R1 is hydrogen, C1-C4 alkyl, halogen or C1-C4 alkoxy, R2 is hydrogen, C1-C4 alkyl, halogen, C1-C4 alkoxy or trifluoromethyl, and the substituents R1 and R2 are each independently monosubstituted or polysubstituted. The photocatalyst is a PTH phenothiazine derivative, which is selected from PTH 1-9; the structural formula of the photocatalyst is as follows: ； The light source is blue light, white light, or violet light; The additives mentioned are K2CO3, NaOAc, or Et3N.

2. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 1, characterized in that: The photocatalyst is selected from PTH 5 or PTH 6.

3. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 1, characterized in that: The solvent is selected from one or any combination of the following: THF, acetone, C1-C4 alkyl alcohol, acetonitrile, DMF, DMA, DMSO; the concentration of compound I in the solvent is 0.01-0.5 mol / L.

4. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 3, characterized in that: The solvent is acetone or acetonitrile; the concentration of compound I in the solvent is 0.05-0.2 mol / L.

5. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 1, characterized in that: The light source is blue light or white light; the illuminance of the light source is 10-100W.

6. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 5, characterized in that: The light source has a power of 20-50W.

7. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 1, characterized in that: The molar ratio of the additive to compound I is 1-5:

1.

8. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 7, characterized in that: The molar ratio of the additive to compound I is 1.5-3:

1.

9. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 1, characterized in that: The molar ratio of compound I to compound II is 1.0 : 1.0 to 3.0; the molar ratio of compound I to photocatalyst is 1.0 : 0.01 to 0.

02.

10. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 9, characterized in that: The molar ratio of compound I to compound II is 1.0 : 1.5 to 2.

0.

11. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 1, characterized in that: The reaction temperature is 10–40°C, and the reaction time is 8–24 hours.

12. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 11, characterized in that: The reaction temperature is room temperature, and the reaction time is 10-15 hours.

13. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 1, characterized in that: The post-processing steps are as follows: water is added to quench the reaction, followed by extraction with ethyl acetate. The combined organic layers are dried with anhydrous Na2SO4 and concentrated under reduced pressure before being separated by column chromatography to obtain the product.

Images