Method for photocatalytic synthesis of 3-position sulfonyl substituted chromone derivative

Abstract

The method comprises the following steps: adding o-hydroxyphenyl enaminone as shown in a formula I, aryl sulfonyl chloride as shown in a formula II, a photocatalyst and an additive into a solvent, stirring and reacting under the irradiation of a light source, filtering, washing, and drying to obtain the 3-position sulfonyl substituted chromone derivative. And after the reaction is finished, carrying out post-treatment to obtain the 3-position sulfonyl substituted chromone derivative as shown in a formula III, wherein the reaction formula of the 3-position sulfonyl substituted chromone derivative is as follows: # imgabs0 #. The method has the advantages of simple operation process, cheap and easily available raw materials, mild reaction conditions, high reaction yield and the like, and compared with the traditional process, the method avoids the use of high-temperature conditions and oxidizing agents, and is environment-friendly.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a method and application of using phenothiazine derivatives as small molecule photocatalysts to achieve visible light-induced 3-sulfonyl-substituted chromone derivatives. Background Art

[0002] As a heterocyclic compound, phenothiazine (PTH) has gradually attracted attention in the field of photoinitiators due to its unique optoelectronic properties and multifunctionality. Because its structure contains both S and N atoms, it can be used as a strong electron-donating group to construct materials with intramolecular electron transfer (ICT) properties. Modification of different sites of the phenothiazine structure will have different effects on the properties of the final compound. At present, the number of photocatalysts derived from its structural modification is still limited, and the scope of application is small. Therefore, it is necessary to further expand the structural modification and related applications of its derivatives.

[0003]

[0004] Chromone (benzo-γ-pyrone) is a high-quality heterocyclic lead compound skeleton that exists in large quantities in natural products and drug synthesis. Many chromone derivatives have been used in clinical treatment due to their anti-inflammatory, antioxidant, antibacterial, and anti-tumor biological activities. Therefore, the development of simple and efficient synthesis methods for the lead structure skeleton of chromone compounds with potential drug activity has received widespread attention.

[0005]

[0006] On the other hand, the sulfonyl group has many biological activities, such as anti-inflammatory and antiviral activities. It is worth noting that the sulfonyl group is similar to the carbonyl group in structure and electronic configuration, and can be used as its biological electronic isostere in drug design, which has great development value. Therefore, the introduction of sulfonyl groups in heterocyclic compounds has always been a research hotspot in the field of organic chemical synthesis. At the same time, 3-substituted sulfonyl chromones can be used as reaction intermediates for synthetic applications, and benzimidazole compounds are generated by reacting with o-diphenylamine, thereby further synthesizing fluorescent probes for bioimaging (J.Org.Chem.2018,83,2361-2368, CN202210901189).

[0007]

[0008] The current strategy is to use sulfonyl hydrazide as a functionalization agent to provide sulfonyl radicals and construct sulfonyl substituted heterocycles. For example, in 2017, Wan Jieping et al. reported the use of equivalent-level iodine catalysis, o-hydroxyphenyl enaminoketone as a substrate, benzenesulfonyl hydrazide as a substrate, and a cascade cyclization reaction to construct 3-sulfonyl substituted chromone (Eur. J. Org. Chem. 2017, 30, 4401–4404). Compared with this work, it is still challenging to avoid traditional thermodynamic conditions and the use of transition metal photocatalysts through visible light induction, and relatively less research has been done. Summary of the invention

[0009] In view of the above-mentioned technical problems existing in the prior art, the purpose of the present invention is to synthesize a class of phenothiazine derivatives, and use them as photocatalysts under visible light induction to provide a method for the synthesis of 3-substituted sulfonylated chromone derivatives with simple operation, mild reaction conditions, high product purity, and green and efficient.

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

[0011] The method for photocatalytically synthesizing a 3-sulfonyl-substituted chromone derivative comprises the following steps: adding o-hydroxyphenyl enaminoketone shown in formula I, aryl sulfonyl chloride shown in formula II, a photocatalyst and an additive to a solvent, stirring and reacting under irradiation with a light source, and after the reaction is completed, post-processing to obtain a 3-sulfonyl-substituted chromone derivative shown in formula III, wherein the reaction formula 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] Furthermore, the photocatalyst is Ir[dF(CF3)ppy]2(dtbbpy)PF6, Ir(ppy)3, 4CzIPN or a PTH phenothiazine derivative, and 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 can be selected from the following one or any combination of the following: THF, acetone, C1-C4 alkyl alcohol, acetonitrile, DMF, DMA, DMSO, preferably acetone or acetonitrile; the concentration of the 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 purple light, preferably blue light or white light; the illumination power of the light source is 10-100W, preferably 20-50W.

[0019] Furthermore, the additive is at least one of Na2HPO4, K3PO4, NaOH, K2CO3, Na2CO3, NaHCO3, NaOAc, Et3N, DBU, DIPEA, TMEDA, 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 1.0:1.0-3.0, preferably 1.0:1.5-2.0; the molar ratio of compound I to photocatalyst is 1.0:0.01-0.02.

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

[0022] Further, the post-treatment process is: adding water to quench the reaction, extracting with ethyl acetate, combining the organic layers, drying with anhydrous Na2SO4 and concentrating under reduced pressure, and then separating by column to obtain the product. The solvent used for column separation is a mixed solvent of petroleum ether / ethyl acetate with a volume ratio of 20-30:1.

[0023] By adopting the above technology, compared with the prior art, the present invention has the following significant beneficial effects:

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

[0025] 2) The present invention adopts a photocatalytic method to use arylsulfonyl chloride to carry out a tandem sulfonylation cyclization reaction on enaminone compounds to synthesize 3-sulfonyl-substituted chromone derivatives in one step, which has good regioselectivity. Compared with the traditional process, the use of oxidants and additives is avoided, the reaction yield is high, the process is environmentally friendly, and it is conducive to large-scale production.

[0026] Based on our previous work on visible light catalytic radical cyclization, we synthesized a series of phenothiazine derivatives by modifying the structure of phenothiazine derivatives, such as through the conjugated structure of benzoheterocycles, increasing or decreasing the electronic and steric effects of substituents on heteroatoms, and used them as small molecule photocatalysts. We used substituted arylsulfonyl chlorides as the sulfonyl source and o-hydroxyphenylenaminone as the substrate to construct a series of 3-substituted sulfonyl chromone compounds. DETAILED DESCRIPTION

[0027] The present invention will be further described below in conjunction with the embodiments, so that the professional and technical personnel in the field can more fully understand the present invention, but the scope of the present invention is not limited in any way. It is well known to those skilled in the art that due to the existence of objective factors such as sample preparation, sample purity, instrument conditions and other experimental conditions, the experimental results obtained will have certain errors.

[0028] Example 1 7-Tosyl-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 magnet. 2 mL of acetone was added to the mixture as a solvent. The mixture was stirred and reacted at room temperature for 12 hours under irradiation with 25 W blue light. 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain an off-white solid with a yield of 48%.

[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] In a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetone was added to the mixture as a solvent. Under irradiation with 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] In a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetone was added to the mixture as a solvent. Under the irradiation of 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] Into a 10 mL Schlenk tube equipped with a magnet, compound (I) 3-dimethylamino-1-(2-hydroxy-4-methylphenyl)prop-2-en-1-one (0.2 mmol), compound (II) 2-thiophenesulfonyl chloride (0.4 mmol), PTH 4 (0.02 mmol), and NaOAc (0.4 mmol) were added respectively, and 2 mL of acetone was added to the mixture as a solvent. Under the irradiation of 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] Into a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetone was added to the mixture as a solvent. Under the irradiation of 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the reaction was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] In a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetone was added to the mixture as a solvent. Under irradiation with 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] Into a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetone was added to the mixture as a solvent. Under irradiation with 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] Into a 10 mL Schlenk tube equipped with a magnet, compound (I) 3-dimethylamino-1-(2-hydroxy-4-methoxyphenyl)prop-2-en-1-one (0.2 mmol), compound (II) 4-bromobenzenesulfonyl chloride (0.4 mmol), PTH 8 (0.02 mmol), and NaOAc (0.4 mmol) were added respectively, and 2 mL of acetone was added to the mixture as a solvent. Under the irradiation of 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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 magnet. 2 mL of acetone was added to the mixture as a solvent. The mixture was stirred at room temperature for 12 hours under irradiation with 25 W blue light. After the reaction, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] Into a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetone was added to the mixture as a solvent. Under the irradiation of 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] Into a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetone was added to the mixture as a solvent. Under the irradiation of 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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 magnet. 2 mL of acetone was added to the mixture as a solvent. The mixture was stirred at room temperature for 12 hours under irradiation with 25 W blue light. After the reaction, 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] Into a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetonitrile was added to the mixture as a solvent. Under the irradiation of 25 W white light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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-Tosyl-4H-benzopyran-4-one

[0098]

[0099] Into a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetonitrile was added to the mixture as a solvent. Under irradiation with 25 W white light, the reaction was stirred at room temperature for 12 hours, and 10 mL of water was added to quench the reaction. The reaction was extracted three times with 5 mL of ethyl acetate, the organic layers were combined, dried over anhydrous Na2SO4 and concentrated under reduced pressure, and separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] In a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetonitrile was added to the mixture as a solvent. Under irradiation with 25 W white light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] In a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetonitrile was added to the mixture as a solvent. Under irradiation with 25 W white light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] Into a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetonitrile was added to the mixture as a solvent. Under irradiation with 25 W white light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] In a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetonitrile was added to the mixture as a solvent. Under irradiation with 25 W white light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] In a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL DMSO was added to the mixture as a solvent. Under irradiation with 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] In a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetone was added to the mixture as a solvent. Under the irradiation of 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] In a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetonitrile was added to the mixture as a solvent. Under the irradiation of 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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] In a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of THF was added to the mixture as a solvent. Under irradiation with 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain an off-white solid with a yield of 35%.

[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] In a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of DCM was added to the mixture as a solvent. Under irradiation with 25 W blue light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain an off-white solid with a yield of 21%.

[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] Into a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetone was added to the mixture as a solvent. Under the irradiation of 25 W white light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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 magnet. 2 mL of acetone was added to the mixture as a solvent. The mixture was stirred and reacted at room temperature for 12 hours under irradiation with 25 W blue light. 10 mL of water was added to quench the reaction. The mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain an off-white solid with a yield of 75%.

[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-(phenylsulfonyl)-4H-benzopyran-4-one

[0161]

[0162] In a 10 mL Schlenk tube equipped with a magnet, 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 respectively, and 2 mL of acetone was added to the mixture as a solvent. Under irradiation with 25 W purple light, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, 10 mL of water was added to quench the reaction, and the mixture was extracted three times with 5 mL of ethyl acetate. The organic layers were combined, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The mixture was separated and purified by flash column chromatography (petroleum ether / ethyl acetate = 25 / 1, v / v) to obtain 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 PTH 4

[0166]

[0167] Step 1: Under a nitrogen atmosphere, a mixture of 2,3-dihydroxynaphthalene (0.05 mol), 2-aminothiophenol (0.05 mmol) 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, heated to 200 ° C for 6 hours, and the water generated during the reaction was collected with a water separator. After the reaction, the yellow crude product was recrystallized from n-hexane, and then purified by silica gel flash column chromatography, using petroleum ether and ethyl acetate in a volume ratio of 100:1 as eluent to obtain compound B in a yellow powder with a yield of 45%.

[0168] Step 2: Under 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 the first step were added to the reaction solution in sequence, and stirred at 120°C overnight. After the reaction was completed, the reaction solution was extracted with ethyl acetate three times and dried by spin drying, and then purified by silica gel flash column chromatography, using petroleum ether and dichloromethane in a volume ratio of 200:1 as eluent, and the coupling product PTH 4 was obtained with a yield of 32%.

[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 PTH 5

[0172]

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

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

[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] Preparation steps of PTH 6 The preparation steps of PTH 4 in Example 27 were repeated, except that 1-iodonaphthalene was replaced with an equal molar amount of 1,3-di-tert-butyl-5-iodobenzene in the second step, and other conditions remained unchanged, to finally obtain 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] Preparation steps of PTH 7 The preparation steps of PTH 4 in Example 27 were repeated, except that 1-iodonaphthalene was replaced with an equal molar amount of 2-iodo-1,3,5-trimethylbenzene in the second step, and other conditions remained unchanged, to finally obtain the coupling product PTH7.

[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] Preparation steps of PTH 8 The preparation steps of PTH 4 in Example 27 were repeated, except that 1-iodonaphthalene was replaced with an equal molar amount of 3,5-bis(trifluoromethyl)iodobenzene in the second step, and other conditions remained unchanged, to finally obtain 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] Preparation steps of PTH 9 The preparation steps of PTH 4 in Example 27 were repeated, except that in the first step, 2,3-dihydroxynaphthalene was replaced by an equal molar amount of 4-bromocatechol, and 2-aminothiophenol was replaced by an equal molar amount of 2-amino-5-bromobenzenethiol; in the second step, 1-iodonaphthalene was replaced by an equal molar amount of 1-bromo-4-iodobenzene, and other conditions remained unchanged, to finally obtain 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 compounds in Example 20 were synthesized and applied (refer to J.Org.Chem.2018,83,2361-2368, CN202210901189) to generate Cu 2+ 、Zn 2+ , ClO - The functional fluorescent probe is as follows:

[0192]

[0193] The above specific implementation methods in the form of embodiments further describe the above contents of the present invention in detail. Obviously, according to the above contents of the present invention, according to the common technical knowledge and customary means in this field, without departing from the above basic technical ideas of the present invention, other various forms of modification, replacement or change can also be made. However, this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies realized based on the above contents of the present invention belong to 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 enamino ketone shown in formula I, the aryl sulfonyl chloride shown in formula II, a photocatalyst and an additive are added to a solvent, stirred and reacted under light source irradiation, and after the reaction, a 3-sulfonyl substituted chromone derivative shown in formula III is obtained by post-treatment, and the 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, trifluoromethyl or aryl, and the substituents R1 and R2 are each independently monosubstituted or polysubstituted.

2. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 1, characterized in that: 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:

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

4. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 1, characterized in that: The solvent can 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.

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, white light or purple light, preferably blue light or white light; the illumination power of the light source is 10-100W, preferably 20-50W.

6. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 1, characterized in that: The additive is at least one of 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.

7. 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 1.0:1.0-3.0, preferably 1.0:1.5-2.0; the molar ratio of compound I to photocatalyst is 1.0:0.01-0.

02.

8. 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. The reaction temperature is preferably room temperature, and the reaction time is preferably 10-15 hours.

9. The method for photocatalytic synthesis of 3-sulfonyl-substituted chromone derivatives according to claim 1, characterized in that: The post-treatment process is as follows: add water to quench the reaction, extract with ethyl acetate, combine the organic layers, dry over anhydrous Na2SO4 and concentrate under reduced pressure, and then separate by column to obtain the product.

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