A method for preparing sulfonamide benzo[a]fluorene-5-one derivatives

Abstract

This invention discloses a method for preparing sulfonamide-modified benzo[a]fluorene-5-one derivatives, using 1,7-enyne and N Using sulfonylaminopyridine salts as raw materials, a series of sulfonated benzo[a]fluorene-5-one compounds were successfully synthesized by catalyzing the sulfonation / cyclization tandem reaction of 1,7-enynes under photocatalytic conditions. This method has excellent functional group tolerance and high economic applicability.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, specifically to a method for preparing sulfonamide benzo[a]fluorene-5-one derivatives. Background Technology

[0002] Benzo[a]fluorene-5-one is a structural framework found in bioactive natural products, possessing biological activities such as antitumor, anti-inflammatory, and anti-infective effects. The Jiang Bo research group has reported several examples of the synthesis of functionalized benzo[a]fluorene-5-one, such as... Figure 1 As shown. On the other hand, sulfonamide groups are common structural units in drug molecules. They often act as bioisosteres of carboxylic acids and amide groups, enhancing the physicochemical properties of drug molecules and improving their overall bioavailability and efficacy. Based on the important value of the benzo[a]fluorene-5-one skeleton and sulfonamide groups in drug activity, introducing sulfonamide fragments into benzo[a]fluorene-5-one to synthesize sulfonated benzo[a]fluorene-5-one in a one-step process is of significant research importance. Currently, the synthesis of sulfonated benzo[a]fluorene-5-one has not been reported. Summary of the Invention

[0003] The purpose of this invention is to provide a method for preparing sulfonamide-treated benzo[a]fluorene-5-one derivatives, using 1,7-enyne and N Using sulfonylaminopyridine salts as raw materials, a series of sulfonated benzo[a]fluorene-5-one compounds were successfully synthesized by catalyzing the sulfonation / cyclization tandem reaction of 1,7-enynes under photocatalytic conditions. This method has excellent functional group tolerance and high economic applicability.

[0004] To achieve the above objectives, the solution of the present invention is: A method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative includes the following steps: Step 1: Weigh out 1,7-enyne and... (The sentence is incomplete and requires more context to translate accurately.) N -Sulfonamide pyridine salt, placed in a reaction vessel, yields the reaction substrate; Step 2: Then, solvent and photocatalyst are added sequentially to the reaction substrate. The volume ratio of the solvent to the molar amount of the 1,7-enyne is 1 mL : 0.1 mmol, and the molar ratio of the photocatalyst to the 1,7-enyne is 1:5. Step 3: Then, under a nitrogen atmosphere and at room temperature, the reaction is carried out under blue light irradiation. After the reaction product 1,7-enyne is completely consumed as monitored by thin-layer chromatography, deionized water and ethyl acetate are added to the reaction solution for extraction multiple times. The organic phases are then combined and concentrated by rotary evaporation to obtain the crude product. Step 4: Finally, the crude product is purified by chromatography to obtain the sulfonamide-modified benzo[a]fluorene-5-one derivative; In step 1, the chemical structural formula of the 1,7-enyne is shown in Formula I: Formula I; R1 is selected from one of hydrogen, 4-methyl, 4-methoxy, 4-tert-butyl, 4-fluoro, 4-chloro, 4-trifluoromethyl, 3-methyl and 2-chloro; R2 is selected from one of hydrogen, 4-methyl, 4-fluoro, and 4-chloro; R3 is selected from one of hydrogen, 3-fluoro, 3-chloro, 3-methoxy, 4-methyl, and 4-fluoro; In step 1, the N The chemical structural formula of sulfonamide pyridine salt is shown in Formula II: Formula II; Wherein, R is selected from one of hydrogen, 4-methyl, 4-methoxy, 4-tert-butyl, 4-fluoro, 4-chloro, 4-bromo, 4-trifluoromethoxy, 4-trifluoromethyl, 4-acetyl, 4-cyano, 3,5-dichloro, 2-fluoro, and 2-chloro; or: In step 1, the chemical structural formula of the 1,7-enyne is shown in Formula III. N The chemical structural formula of sulfonamide pyridine salt is shown in Formula II: Formula III; Alternatively, in step 1, the chemical structural formula of the 1,7-enyne is shown in Formula I. N The chemical structural formula of sulfonamide pyridine salt is shown in Formula IV: Formula IV.

[0005] In step 2, the solvent is acetonitrile, dichloromethane, tetrahydrofuran, acetone, 1,2-dichloroethane, methanol, dimethyl sulfoxide, 1,4-dioxane, and... N , N One of the dimethylformamides.

[0006] In step 2, the solvent is dimethyl sulfoxide.

[0007] In step 2, the photocatalyst is one of the following: 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile, Acid Red 94, 2,4,5,6-penta(9H-carbazolyl-9-yl)benzonitrile, tris(2,2-bipyridine)chloride hexahydrate, Rhodamine B, Solvent Red 43, 2,4,6-tris(9H-carbazolyl-9-yl)-5-chloroisophthalonitrile, and (OC-6-21)-tris[2-(2-pyridyl-κN)phenyl-κC]iridium. All of the above photocatalysts are commercially available Adamas brand reagents.

[0008] In step 2, the photocatalyst is 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile.

[0009] In step 3, the wavelength of the blue light is 445~450 nm, the power of the light is 5~20 W, and the duration of the light is 1~20 hours.

[0010] In step 3, the power of the light is 10 W, and the duration of the light exposure is 12 hours.

[0011] The chemical structural formula of the sulfonamide benzo[a]fluorene-5-one derivative is shown in Formula V, Formula VI or Formula VII: Formula V; R1 is selected from one of hydrogen, 4-methyl, 4-methoxy, 4-tert-butyl, 4-fluoro, 4-chloro, 4-trifluoromethyl, 3-methyl and 2-chloro; R2 is selected from one of hydrogen, 4-methyl, 4-fluoro, and 4-chloro; R3 is selected from one of hydrogen, 3-fluoro, 3-chloro, 3-methoxy, 4-methyl, and 4-fluoro; R is selected from one of hydrogen, 4-methyl, 4-methoxy, 4-tert-butyl, 4-fluoro, 4-chloro, 4-bromo, 4-trifluoromethoxy, 4-trifluoromethyl, 4-acetyl, 4-cyano, 3,5-dichloro, 2-fluoro, and 2-chloro; Formula VI; Formula VII.

[0012] The synthetic route for sulfonamide-modified benzo[a]fluorene-5-one derivatives of the present invention is shown in Formula VIII, Formula IX and Formula X: VIII; Formula IX; Formula X.

[0013] The synthetic route for the reactant 1,7-enyne in this invention is as follows:

[0014] Furthermore, the specific method for synthesizing the reaction raw material 1,7-enyne in this invention is as follows: (1) Synthesis of compound S2: In a 100 mL reaction flask, compound S1 (1 equivalent), palladium dichloride bis(triphenylphosphine) (5 mol% of the amount of compound S1), cuprous iodide (10 mol% of the amount of compound S1), and solvent triethylamine were added sequentially. A magnetic stir bar was placed in the flask, and then phenylacetylene series compounds (1.2 equivalents) were slowly added dropwise under stirring. The mixture was heated to 50 °C under nitrogen protection and reacted for 12 hours. After the reaction was completed, the reaction solution was washed with saturated ammonium chloride aqueous solution, extracted three times with ethyl acetate, concentrated by rotary evaporation, and the organic phases were combined. The organic phase was then purified by silica gel column chromatography (petroleum ether-ethyl acetate elution) to obtain the target product S2. (2) Synthesis of compound S3: 2-phenyl-1-propene series compounds (1 equivalent) were added sequentially to a 100 mL reaction flask. N 1-Bromosuccinimide (1.1 equivalents) and p-toluenesulfonic acid (10 mol% of the amount of 2-phenyl-1-propene series compounds) were added, followed by anhydrous tetrahydrofuran (1 mmol:1 mL ratio of 2-phenyl-1-propene series compounds to anhydrous tetrahydrofuran). A magnetic stir bar was placed, and the mixture was heated to 90°C with stirring and refluxed using a condenser. The reaction was carried out for 4 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the mixture was purified by silica gel column chromatography (petroleum ether-ethyl acetate elution) to obtain the target product S3. (3) Synthesis of compound S4: In a 100 mL reaction flask, compounds S2 (1 equivalent) and S3 (1.2 equivalent) were dissolved in a mixed solution of tetrahydrofuran and water (volume ratio = 1:1). Indium powder (1.2 equivalent) and a magnetic stir bar were then added. The flask was sealed with a rubber stopper and heated to 60 °C. After stirring for 48 h, the reaction was stopped. The reaction solution was first filtered through diatomaceous earth to remove insoluble solids. Then, it was extracted three times with ethyl acetate. The organic phases were combined, and the organic solvent was removed by rotary evaporation. The solution was then purified by silica gel column chromatography (petroleum ether-ethyl acetate elution) at a mesh of 300-400 to obtain the target product S4. (4) Synthesis of 1,7-enynes: Compound S4 was dissolved in dichloromethane in a 100 mL reaction flask. Then, under ice bath conditions at 0°C, a magnetic stir bar was added, and Desmartin oxidant was added while stirring. After S4 was completely oxidized by thin-layer chromatography, the reaction was quenched by adding saturated sodium bicarbonate solution. The mixture was then extracted three times with dichloromethane. The organic phases were combined, and the organic solvent was removed by rotary evaporation. The mixture was then purified by silica gel column chromatography (petroleum ether-ethyl acetate elution) using a 300-400 mesh silica gel column to obtain 1,7-enyne.

[0015] The reaction raw materials in this invention N The synthetic route for sulfonamide pyridine salts is as follows:

[0016] Furthermore, the reaction raw materials in this invention N The specific method for synthesizing sulfonylaminopyridine salts is as follows: (1) Synthesis of compound S6: Under nitrogen protection (0℃, ice-water bath), 4-dimethylaminopyridine (10 mol%), potassium carbonate (3.6 equivalents), and arylsulfonyl chloride (1 equivalent) were added sequentially to a 100 mL reaction flask containing compound S5 (1 equivalent) and acetonitrile solvent. The ice-water bath was then removed, and the mixture was stirred at room temperature for 6 hours. After the reaction was completed, the mixture was extracted three times with dichloromethane, and the organic phases were combined. The organic solvent was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether-ethyl acetate elution) to obtain the target product S6. (2) N Synthesis of -aminopyridine salts: In a 100 mL reaction flask, compound S6 (1 equivalent), dichloromethane, and a magnetic stir bar were added sequentially. 40 μL of the mixture was then added at room temperature. wt A 1.3 equivalent aqueous solution of tetrahydroboric acid was stirred for 30 minutes, followed by precipitation. The product was then filtered to obtain a crude product, which was washed three times each with pentane and diethyl ether, and dried under vacuum to obtain a pure product. N -Aminopyridine salt.

[0017] Following the adoption of the above technical solution, the present invention provides a method for preparing sulfonamide-modified benzo[a]fluorene-5-one derivatives, using 1,7-enyne and N Using sulfonylaminopyridine salts as raw materials, a series of sulfonated benzo[a]fluorene-5-one compounds were successfully synthesized by catalyzing the sulfonation / cyclization tandem reaction of 1,7-enynes under photocatalytic conditions. This method is simple and easy to control, with excellent functional group tolerance and high economic applicability. Attached Figure Description

[0018] Figure 1This is a schematic diagram of the structure of benzo[a]fluorene-5-one in the prior art; Figure 2 This is a schematic diagram of the free radical capture experiment of sulfonamide benzo[a]fluorene-5-one derivatives of the present invention; Figure 3 This is a diagram illustrating the reaction mechanism of sulfonamide benzo[a]fluorene-5-one derivatives of the present invention. Detailed Implementation

[0019] To further explain the technical solution of the present invention, the present invention will be described in detail below through specific embodiments.

[0020] 1. Optimization of preparation conditions for sulfonamide-treated benzo[a]fluorene-5-one derivatives 1.1 Influence of Solvent A method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative includes the following steps: Step 1: Weigh out 0.2 mmol of 1,7-enyne and 0.24 mmol of... N -Sulfonylaminopyridine salt was placed in a quartz test tube of a photocatalytic reactor (model WP-TEC-1020SL) to obtain the reaction substrate; Step 2: Then, add 2.0 mL of solvent and 0.04 mmol of 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile to the reaction substrate in sequence; Step 3: Then, under a nitrogen atmosphere and at room temperature, the reaction is carried out under blue light with a wavelength of 445~450 nm and a power of 20W for 12 hours. After the thin-layer chromatography shows that the reactant 1,7-enyne has been completely consumed, 20 mL of deionized water is added to the reaction solution, and then 15 mL of ethyl acetate is added for extraction. The extraction is repeated three times, and the three organic phases are combined and concentrated by rotary evaporation to obtain the crude product. Step 4: Finally, the crude product is purified by chromatography to obtain sulfonamide-modified benzo[a]fluorene-5-one derivatives, wherein the chemical structural formula of the 1,7-enyne is shown in Formula XI: Formula XI; N The chemical structural formula of sulfonamide pyridine salt is shown in Formula XII: Formula XII; The chemical structural formula of the sulfonamide benzo[a]fluorene-5-one derivative is shown in Formula XIII: Formula XIII; The choice of solvent and the corresponding product yield in step 2 are shown in Table 1.

[0021] Table 1. Effect of solvent selection on the reaction

[0022] Initially, acetonitrile was used as the solvent, but the yield of the target product was only 27%. Subsequently, different solvents (such as dichloromethane, tetrahydrofuran, acetone, 1,2-dichloroethane, methanol, dimethyl sulfoxide, 1,4-dioxane, etc.) were tested. N , N We investigated dimethylformamide and found that the yield of the target product could be increased to 64% when dimethyl sulfoxide was used as a solvent. Therefore, we chose dimethyl sulfoxide as the optimal solvent for this reaction.

[0023] 1.2 The Influence of Photocatalysts A method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative includes the following steps: Step 1: Weigh out 0.2 mmol of 1,7-enyne and 0.24 mmol of... N A sulfonylaminopyridine salt was placed in a quartz test tube of a photocatalytic reactor (model WP-TEC-1020SL) to obtain the reaction substrate, wherein the chemical structural formula of 1,7-enyne is shown in Formula XI. N The chemical structural formula of sulfonamide pyridine salt is shown in Formula XII; Step 2: Then, add 2.0 mL of dimethyl sulfoxide and 0.04 mmol of photocatalyst to the reaction substrate in sequence; Step 3: Then, under a nitrogen atmosphere and at room temperature, the reaction is carried out under blue light with a wavelength of 445~450 nm and a power of 20W for 12 hours. After the thin-layer chromatography shows that the reactant 1,7-enyne has been completely consumed, 20 mL of deionized water is added to the reaction solution, and then 15 mL of ethyl acetate is added for extraction. The extraction is repeated three times, and the three organic phases are combined and concentrated by rotary evaporation to obtain the crude product. Step 4: Finally, the crude product is purified by chromatography to obtain sulfonamide benzo[a]fluorene-5-one derivative, with the chemical structure shown in Formula XIII.

[0024] The selection of photocatalysts and the corresponding product yields in step 2 are shown in Table 2.

[0025] Table 2. Effect of photocatalyst selection on the reaction

[0026] After determining the optimal reaction solvent, the effect of the photocatalyst on the reaction was further investigated. Different types of photocatalysts were selected to explore their effects on the yield of the target product. When 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile was successively replaced with Acid Red 94, 2,4,5,6-penta(9H-carbazolyl-9-yl)benzonitrile, tris(2,2-bipyridine)chloride hexahydrate, Rhodamine B, Solvent Red 43, 2,4,6-tris(9H-carbazolyl-9-yl)-5-chloroisophthalonitrile, and (OC-6-21)-tris[2-(2-pyridyl-κN)phenyl-κC]iridium, the yield of the target product decreased significantly. Therefore, the non-metallic catalyst 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile was selected as the most suitable photocatalyst for this reaction.

[0027] 1.3 Effect of substrate ratio on the reaction A method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative includes the following steps: Step 1: First, weigh out 1,7-enyne and... according to the proportions in Table 3. N A sulfonylaminopyridine salt was placed in a quartz test tube of a photocatalytic reactor (model WP-TEC-1020SL) to obtain the reaction substrate, wherein the chemical structural formula of 1,7-enyne is shown in Formula XI. N The chemical structural formula of sulfonamide pyridine salt is shown in Formula XII; Step 2: Then, add 2.0 mL of dimethyl sulfoxide and 0.04 mmol of 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile to the reaction substrate in sequence. Step 3: Then, under a nitrogen atmosphere and at room temperature, the reaction is carried out under blue light with a wavelength of 445~450 nm and a power of 20W for 12 hours. After the thin-layer chromatography shows that the reactant 1,7-enyne has been completely consumed, 20 mL of deionized water is added to the reaction solution, and then 15 mL of ethyl acetate is added for extraction. The extraction is repeated three times, and the three organic phases are combined and concentrated by rotary evaporation to obtain the crude product. Step 4: Finally, the crude product is purified by chromatography to obtain sulfonamide benzo[a]fluorene-5-one derivative, with the chemical structure shown in Formula XIII.

[0028] Table 3 Effect of substrate ratio on the reaction

[0029] The feed ratio of the reaction substrates was screened, and when 1,7-enyne and N When the molar ratio of the sulfonylaminopyridine salt was increased from 1:1.2 to 1:1.5 and 1:2, the yield of the target product decreased significantly. Therefore, a substrate molar ratio of 1:1.2 was chosen as the appropriate condition for this reaction.

[0030] 1.4 The effect of light source on the reaction A method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative includes the following steps: Step 1: Weigh out 0.2 mmol of 1,7-enyne and 0.24 mmol of... N A sulfonylaminopyridine salt was placed in a quartz test tube of a photocatalytic reactor (model WP-TEC-1020SL) to obtain the reaction substrate, wherein the chemical structural formula of 1,7-enyne is shown in Formula XI. N The chemical structural formula of sulfonamide pyridine salt is shown in Formula XII; Step 2: Then, add 2.0 mL of dimethyl sulfoxide and 0.04 mmol of 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile to the reaction substrate in sequence. Step 3: Then, under a nitrogen atmosphere and at room temperature, the reaction is carried out under blue light with a wavelength of 445~450 nm and a power of 5~20W (specific power is shown in Table 4) for 12 hours. After the reaction is completely consumed by thin-layer chromatography, 20 mL of deionized water is added to the reaction solution, and then 15 mL of ethyl acetate is added for extraction. The extraction is repeated three times, and the three organic phases are combined and concentrated by rotary evaporation to obtain the crude product. Step 4: Finally, the crude product is purified by chromatography to obtain sulfonamide benzo[a]fluorene-5-one derivative, with the chemical structure shown in Formula XIII.

[0031] Table 4. Effect of light source on the reaction

[0032] The effect of adjusting blue light sources with different powers on the reaction was investigated. When the light source power was adjusted to 5 W, 6 W, and 8 W, the yield of the target product remained almost unchanged. When the light source power was 10 W, the yield of the target product increased to 75%. Further increasing the light source power resulted in a decrease in the yield of the target product. When the reaction was not irradiated by the light source, no target product was produced. Finally, based on the experimental results, a light source power of 10 W was determined as the optimal condition for this reaction.

[0033] 1.5 Effect of reaction time on the reaction A method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative includes the following steps: Step 1: Weigh out 0.2 mmol of 1,7-enyne and 0.24 mmol of... N A sulfonylaminopyridine salt was placed in a quartz test tube of a photocatalytic reactor (model WP-TEC-1020SL) to obtain the reaction substrate, wherein the chemical structural formula of 1,7-enyne is shown in Formula XI. N The chemical structural formula of sulfonamide pyridine salt is shown in Formula XII; Step 2: Then, add 2.0 mL of dimethyl sulfoxide and 0.04 mmol of 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile to the reaction substrate in sequence. Step 3: Then, under a nitrogen atmosphere and at room temperature, the reaction is carried out under blue light with a wavelength of 445-450 nm and a power of 10 W for 1-20 hours (the specific time is shown in Table 5). After the reaction product 1,7-enyne is completely consumed as monitored by thin-layer chromatography, 20 mL of deionized water is added to the reaction solution, and then 15 mL of ethyl acetate is added for extraction. The extraction is repeated three times, and the three organic phases are combined and concentrated by rotary evaporation to obtain the crude product. Step 4: Finally, the crude product is purified by chromatography to obtain sulfonamide benzo[a]fluorene-5-one derivative, with the chemical structure shown in Formula XIII.

[0034] Table 5. Effect of reaction time on the reaction

[0035] Further investigation into the effect of reaction time revealed that when the reaction time was 1–3 hours, the yield of the target product was low, and some substrate remained unreacted. At a reaction time of 12 hours, the yield reached 75%. Extending the reaction time further to 20 hours significantly reduced the yield, likely due to the prolonged exposure to the light source causing the degradation of some of the target product. Therefore, based on the experimental results, a reaction time of 12 hours was determined to be the optimal condition for this reaction.

[0036] 1.6 N Generalization study of sulfonylaminopyridine salts A method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative includes the following steps: Step 1: Weigh out 0.2 mmol of 1,7-enyne and 0.24 mmol of... N A sulfonylaminopyridine salt was placed in a quartz test tube of a photocatalytic reactor (model WP-TEC-1020SL) to obtain the reaction substrate, wherein the chemical structural formula of 1,7-enyne is shown in Formula XI. N The chemical structural formulas of sulfonamide pyridine salts are shown in Table 6. Step 2: Then, add 2.0 mL of dimethyl sulfoxide and 0.04 mmol of 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile to the reaction substrate in sequence. Step 3: Then, under a nitrogen atmosphere and at room temperature, the reaction is carried out under blue light with a wavelength of 445~450 nm and a power of 10 W for 12 hours. After the reaction is completely consumed by thin-layer chromatography, 20 mL of deionized water is added to the reaction solution, and then 15 mL of ethyl acetate is added for extraction. The extraction is repeated three times, and the three organic phases are combined and concentrated by rotary evaporation to obtain the crude product. Step 4: Finally, the crude product was purified by chromatography to obtain sulfonamide benzo[a]fluorene-5-one derivatives, the chemical structure of which is shown in Table 6.

[0037] Table 6 N Results of the general applicability study of sulfonylaminopyridine salts

[0038] We examined the reaction substrates N Structural diversity of sulfonylaminopyridine salts: in reactions with 1,7-enynes N -The aromatic ring of the sulfonamide pyridine salt has different substituents (including H, Me, MeO, ...) attached to the para position. t The reaction proceeds smoothly with the presence of Bu, F, Cl, Br, CF3O, CF3, CH3CO and CN, yielding the target product in 58% to 75% yield.

[0039] Immediately afterwards, we N The effects of ortho- and meta-substituents on the aromatic ring of sulfonylaminopyridine salts were investigated. Dichloro-substituted... N- The reaction involved sulfonylaminopyridine salts, yielding the desired product in 64% yield. Furthermore, substrates with ortho-halogen substituents also showed good compatibility, with yields of 57% and 68% respectively. Notably, the reaction was also effective for heterocyclic substrates, including those with thiophene groups. N -Sulfoamide pyridine salts also reacted smoothly, yielding the target product in 66% yield.

[0040] 1.7, 1,7-Enyne Generalization Study A method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative includes the following steps: Step 1: Weigh out 0.2 mmol of 1,7-enyne and 0.24 mmol of... N 1,7-sulfonylaminopyridine salt was placed in a quartz test tube of a photocatalytic reactor (WP-TEC-1020SL) to obtain the reaction substrate. The chemical structural formula of 1,7-enyne is shown in Table 7. N The chemical structural formula of sulfonamide pyridine salt is shown in Formula XII; Step 2: Then, add 2.0 mL of dimethyl sulfoxide and 0.04 mmol of 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile to the reaction substrate in sequence. Step 3: Then, under a nitrogen atmosphere and at room temperature, the reaction is carried out under blue light with a wavelength of 445-450 nm and a power of 10 W for 1-20 hours (the specific time is shown in Table 5). After the reaction product 1,7-enyne is completely consumed as monitored by thin-layer chromatography, 20 mL of deionized water is added to the reaction solution, and then 15 mL of ethyl acetate is added for extraction. The extraction is repeated three times, and the three organic phases are combined and concentrated by rotary evaporation to obtain the crude product. Step 4: Finally, the crude product was purified by chromatography to obtain sulfonamide benzo[a]fluorene-5-one derivatives, the chemical structure of which is shown in Table 7.

[0041] Table 71, Results of the generalization study of 7-enynes

[0042] After completing the N Following our investigation of sulfonylaminopyridine salts, we then... N Using sulfonylaminopyridine salts as template substrates, the substrate applicability for 1,7-enynes was investigated. First, the effect of substituents (R1) on the aryynyl group in the enyne molecule was explored. Experiments showed that the reaction is effective for substituents including methyl (Me), methoxy (MeO), and tert-butyl (...). t The product exhibits good compatibility with various functional groups, including Bu, fluorine (F), chlorine (Cl), and trifluoromethyl (CF3), and the corresponding target products were obtained in yields ranging from 47% to 81%.

[0043] We then turned our attention to the substituents (R2) on the alkenyl benzene ring. Substrates with methyl, fluorine, or chlorine substituents at the para-position of the benzene ring underwent successful transformation to yield the corresponding products.

[0044] Finally, we investigated substrates with electron-withdrawing or electron-donating groups attached to the C4 or C5 position of the inner aromatic ring (i.e., the fused ring portion) of the 1,7-enyne. These substrates also reacted readily, yielding the corresponding benzo[a]fluorene-5-one products in 59% to 70% yields. Notably, substrates replacing the inner aromatic ring with a thiophene ring also performed excellently, yielding benzo[a]fluorene-5-one derivatives in 85% yield.

[0045] All reagents used in this invention are known in the art (unless otherwise specified, their synthesis methods are given separately).

[0046] 2. Product structural formula and NMR characterization The chemical structural formulas of sulfonamide-treated benzo[a]fluorene-5-one derivatives are shown in formulas V, VI, or VII: Formula V; R1 is selected from one of hydrogen, 4-methyl, 4-methoxy, 4-tert-butyl, 4-fluoro, 4-chloro, 4-trifluoromethyl, 3-methyl and 2-chloro; R2 is selected from one of hydrogen, 4-methyl, 4-fluoro, and 4-chloro; R3 is selected from one of hydrogen, 3-fluoro, 3-chloro, 3-methoxy, 4-methyl, and 4-fluoro; R is selected from one of hydrogen, 4-methyl, 4-methoxy, 4-tert-butyl, 4-fluoro, 4-chloro, 4-bromo, 4-trifluoromethoxy, 4-trifluoromethyl, 4-acetyl, 4-cyano, 3,5-dichloro, 2-fluoro, and 2-chloro; Formula VI; Formula VII.

[0047] ① When R1, R2, R3, and R in formula V are all selected from hydrogen, the product is named N -((5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0048] White solid, yield: 75%, melting point: 195~197℃.

[0049] 1 H NMR (400 MHz, CDCl3) δ 8.04 (dd, J = 7.6, 1.3 Hz, 1H), 7.53 – 7.43(m, 6H), 7.39 (d, J = 6.8 Hz, 2H), 7.35 – 7.21 (m, 8H), 7.05 – 6.99 (m, 1H), 4.08 (t, J = 6.2 Hz, 1H), 3.49 (dd, J = 12.5, 5.7 Hz, 1H), 3.31 – 3.18 (m, 2H), 2.55 (d, J = 16.8 Hz, 1H). 13100 MHz C NMR (CDCl3) δ 196.0, 146.7, 145.6, 141.3, 139.3, 138.1, 134.8, 133.9, 133.8, 132.5, 130.1, 129.1, 129.0, 128.6, 128.4, 128.2, 127.7, 127.6, 126.8, 126.8, 122.0, 121.8, 55.4, 47.7, 45.8. HRMS (ESI) m / z calcd for C 30 H 24 NO3S [M+H] + 478.1477, found478.1476. ② When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 4-methyl, the product is named 4-methyl- N- ((5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]-fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0050] White solid, yield: 59%. Melting point: 197~199℃.

[0051] 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 7.6, 1.5 Hz, 1H), 7.51 –7.43 (m, 3H), 7.37 (d, J = 8.2 Hz, 4H), 7.33 – 7.25 (m, 4H), 7.25 – 7.18 (m,2H), 7.09 (d, J = 8.1 Hz, 2H), 7.05 – 7.00 (m, 1H), 4.22 (t, J = 6.2 Hz, 1H), 3.46 (dd, J = 12.4, 5.9 Hz, 1H), 3.28 – 3.14 (m, 2H), 2.52 (d, J = 16.8 Hz, 1H), 2.36 (s, 3H). 13C10 NMR (100 MHz, CDCl3) δ 196.1, 146.8, 145.5, 143.2, 141.3, 138.1, 136.3, 134.8, 133.9, 133.7, 130.1, 129.6, 129.1, 129.1, 128.5, 128.4, 128.1, 127.7, 127.5, 126.9, 126.7, 122.0, 121.9, 55.4, 47.7, 45.8, 21.5. HRMS (ESI) m / z calcd for C 31 H 26 NO3S [M+H] + 492.1633, found 492.1636. ③ When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 4-methoxy, the product is named 4-methoxy- N -((5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0052] White solid, yield: 67%, melting point: 196~198℃.

[0053] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.05 – 7.99 (m, 1H), 7.50 – 7.35 (m, 7H), 7.33 – 7.19 (m, 6H), 7.02 (dd, J = 7.6, 1.2 Hz, 1H), 6.78 – 6.71 (m, 2H), 4.19 (t, J = 6.2 Hz, 1H), 3.81 (s, 3H), 3.46 (dd, J = 12.4, 5.9 Hz, 1H), 3.28 –3.14 (m, 2H), 2.52 (d, J = 16.7 Hz, 1H). 13C10 NMR (100 MHz, CDCl3) δ 196.1, 162.7, 146.8, 145.5, 141.3, 138.1, 134.8, 133.9, 133.7, 130.7, 130.1, 129.1, 129.0, 128.5, 128.4, 128.1, 127.7, 127.5, 126.7, 122.0, 121.9, 114.1, 55.6, 55.3, 47.6, 45.9. HRMS (ESI) m / z calcd for C 31 H 26 NO4S [M+H] + 508.1583, found 508.1580. ④ When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 4-tert-butyl, the product is named 4-(butyl)- N -((5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0054] White solid, yield: 65%, melting point: 251~252℃.

[0055] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.07 – 8.01 (m, 1H), 7.52 – 7.44 (m, 3H), 7.40 (t, J = 7.0 Hz, 4H), 7.34 – 7.21 (m, 8H), 7.06 – 7.00 (m, 1H), 4.07 (t, J = 6.3 Hz, 1H), 3.49 (dd, J = 12.5, 5.8 Hz, 1H), 3.30 – 3.18 (m, 2H), 2.55 (d, J = 16.8 Hz, 1H), 1.30 (s, 3H). 13100 MHz C NMR (CDCl3) δ 196.0, 156.2, 146.8, 145.5, 141.2, 138.2, 136.3, 134.8, 133.9, 133.7, 130.1, 129.1, 129.0, 128.5, 128.4, 128.2, 127.7, 127.6, 126.7, 126.0, 122.0, 121.8, 55.4, 47.7, 45.9, 35.1, 31.1. HRMS (ESI) m / z calcd for C 34 H 32 NO3S [M+H] + 534.2103, found 534.2105. ⑤ When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 4-fluoro, the product is named 4-fluoro- N -(5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0056] White solid, yield: 65%, melting point: 213~215℃.

[0057] 1 H NMR (400 MHz, CDCl3) δ 8.03 (dd, J = 7.6, 1.4 Hz, 1H), 7.55 –7.44 (m, 5H), 7.41 – 7.35 (m, 2H), 7.34 – 7.26 (m, 4H), 7.25 – 7.20 (m, 2H),7.02 – 6.92 (m, 3H), 4.22 (t, J = 6.1 Hz, 1H), 3.51 (dd, J = 12.5, 5.8 Hz, 1H),3.28 – 3.17 (m, 2H), 2.54 (d, J = 16.7 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 196.0, 164.9 (d, J = 254.6 Hz), 146.6,145.5, 141.4, 137.9, 135.4 (d, J= 3.2 Hz), 134.7, 133.8, 133.8, 130.0, 129.6(d, J = 9.4 Hz), 129.1, 129.0, 128.6, 128.5, 128.3, 127.6, 126.8, 122.1,121.8, 116.2 (d, J = 22.6 Hz), 55.3, 47.7, 45.9. 19 F-NMR (376 MHz, CDCl3) δ -105.40 (s). HRMS (ESI) m / z calcd forC 30 H 23 FNO3S [M+H] + 496.1383, found 496.1387. ⑥ When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 4-chloro, the product is named 4-chlorothium-(5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, and the corresponding chemical structural formula is:

[0058] White solid, yield: 60%, melting point: 177~178℃.

[0059] 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 7.7, 1.5 Hz, 1H), 7.51 –7.44 (m, 3H), 7.42 – 7.26 (m, 8H), 7.25 – 7.19 (m, 4H), 6.97 (dd, J = 7.8, 1.0Hz, 1H), 4.24 (t, J = 6.0 Hz, 1H), 3.53 (dd, J = 12.5, 5.7 Hz, 1H), 3.28 – 3.16(m, 2H), 2.53 (d, J = 16.8 Hz, 1H). 13100 MHz C NMR (CDCl3) δ 196.0, 146.6, 145.5, 141.4, 139.0, 137.8, 134.6, 133.8, 130.0, 129.3, 129.1, 129.0, 128.6, 128.5, 128.2, 127.6, 127.6, 126.8, 55.3, 47.6, 45.9. HRMS (ESI) m / z calcd for C 30 H 23 ClNO3S [M+H] + 512.1087, found 512.1086. ⑦ When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 4-bromine, the product is named 4-bromoplutonium-(5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, and the corresponding chemical structural formula is:

[0060] White solid, yield: 65%, melting point: 210~211℃.

[0061] 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 7.6, 1.4 Hz, 1H), 7.51 –7.44 (m, 3H), 7.42 – 7.25 (m, 10H), 7.25 – 7.19 (m, 2H), 6.96 (dd, J = 7.7, 0.9 Hz, 1H), 4.24 (t, J = 6.1 Hz, 1H), 3.53 (dd, J = 12.5, 5.7 Hz, 1H), 3.28 –3.17 (m, 2H), 2.53 (d, J = 16.8 Hz, 1H). 13100 MHz C NMR (CDCl3) δ 195.93, 146.5, 145.5, 141.4, 138.4, 137.8, 134.6, 133.8, 133.8, 132.2, 130.0, 129.1, 129.0, 128.6, 128.5, 128.3, 128.2, 127.6, 127.6, 127.5, 126.9, 122.1, 121.8, 55.3, 47.6, 45.9. HRMS (ESI) m / z calcd for C 30 H 23 BrNO3S [M+H] + 556.0582, found 556.0574. ⑧. When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 4-trifluoromethoxy, the product is named N -((5-oxy-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)-4-(trifluoromethoxy)benzenesulfonamide, the corresponding chemical structural formula is:

[0062] White solid, yield: 71%, melting point: 185~186℃.

[0063] 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 7.7, 1.4 Hz, 1H), 7.53 –7.42 (m, 5H), 7.36 (dd, J = 5.5, 1.9 Hz, 2H), 7.33 – 7.16 (m, 6H), 7.10 (d, J =8.1 Hz, 2H), 6.99 (dd, J = 7.7, 0.8 Hz, 1H), 4.44 (d, J = 5.6 Hz, 1H), 3.55 (dd, J = 12.6, 6.0 Hz, 1H), 3.29 – 3.18 (m, 2H), 2.52 (d, J = 16.8 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 196.0, 151.8, 146.7, 145.5, 141.5, 137.8, 137.8, 134.7, 133.8, 133.7, 130.1, 129.1, 129.0, 128.9, 128.6, 128.5, 128.3, 127.6, 126.7, 122.0, 121.8, 120.8, 120.2 (q, J = 259.1 Hz), 55.3, 47.7, 45.8. 19 F-NMR (376 MHz, CDCl3) δ -57.62 (s). HRMS (ESI) m / z calcd forC 31 H 23 F3NO4S [M+H] + 562.1300, found 562.1305. 9. When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 4-trifluoromethyl, the product is named N -((5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)-4-(trifluoromethyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0064] White solid, yield: 58%, melting point: 191~193℃.

[0065] 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 7.8, 1.3 Hz, 1H), 7.56 (q, J = 8.5 Hz, 4H), 7.51 – 7.44 (m, 3H), 7.36 (dd, J = 5.7, 1.8 Hz, 2H), 7.33 –7.23 (m, 4H), 7.23 – 7.15 (m, 2H), 6.99 – 6.93 (m, 1H), 4.38 (t, J = 6.0 Hz, 1H), 3.58 (dd, J = 12.6, 5.8 Hz, 1H), 3.32 – 3.18 (m, 2H), 2.53 (d, J = 16.8Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 195.9, 146.5, 145.5, 143.1, 141.5, 137.7, 134.6, 134.2, 133.9, 133.8, 133.7, 130.0, 129.1, 128.9, 128.7, 128.5, 128.3, 127.6, 127.5, 127.2, 126.8, 126.1 (q, J = 3.6 Hz), 123.2 (q, J = 272.9Hz), 122.1,121.7,55.3, 47.7, 45.8. 19 F-NMR (376 MHz, CDCl3) δ -63.12 (s). HRMS (ESI) m / z calcd forC 31 H 23 F3NO3S [M+H] + 546.1351, found 546.1355. ⑩ When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 4-acetyl, the product is named 4-acetyl- N -((5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0066] White solid, yield: 67%, melting point: 227~229℃.

[0067] 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 7.8, 1.2 Hz, 1H), 7.87 –7.82 (m, 2H), 7.60 – 7.53 (m, 2H), 7.52 – 7.43 (m, 3H), 7.41 – 7.34 (m, 2H),7.34 – 7.27 (m, 3H), 7.26 – 7.18 (m, 3H), 6.99 (dd, J = 7.8, 0.8 Hz, 1H), 4.28(t, J = 6.1 Hz, 1H), 3.54 (dd, J= 12.6, 5.7 Hz, 1H), 3.32 – 3.17 (m, 2H), 2.61(s, 3H), 2.55 (d, J = 16.8 Hz, 1H). 13 C10 NMR (100 MHz, CDCl3) δ 196.7, 195.9, 146.6, 145.5, 143.3, 141.5, 139.8, 137.8, 134.7, 133.8, 133.8, 130.0, 129.2, 129.0, 128.8, 128.7, 128.5, 128.2, 127.6, 127.1, 126.8, 122.1, 121.8, 55.3, 47.8, 45.8, 26.9. HRMS (ESI) m / z calcd for C 32 H 26 NO4S [M+H] + 520.1583, found 520.1580. When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 4-cyano, the product is named 4-cyano- N -((5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0068] White solid, yield: 58%, melting point: 194~196℃.

[0069] 1 H NMR (400 MHz, CDCl3) δ 8.04 (dd, J = 7.7, 1.3 Hz, 1H), 7.57 (s,4H), 7.53 – 7.46 (m, 3H), 7.39 – 7.26 (m, 6H), 7.25 – 7.20 (m, 2H), 6.97 (dd, J = 7.8, 0.7 Hz, 1H), 4.32 (t, J = 6.1 Hz, 1H), 3.58 (dd, J = 12.7, 5.7 Hz,1H), 3.32 – 3.17 (m, 2H), 2.55 (d, J = 16.7 Hz, 1H). 13 C10 NMR (100 MHz, CDCl3) δ 195.8, 146.4, 145.5, 143.8, 141.6, 137.6, 134.5, 133.8, 133.6, 132.8, 130.0, 129.2, 128.9, 128.8, 128.6, 128.4, 127.7, 127.5, 127.3, 126.9, 122.2, 121.7, 117.3, 116.2, 55.3, 47.8, 45.8. HRMS (ESI) m / z calcd for C 31 H 23 N₂O₃S [M+H] + 503.1429, found 503.1431. When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 3,5-dichloro, the product is named 3,5-dichloromolybdenum(5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, and the corresponding chemical structural formula is:

[0070] White solid, yield: 64%, melting point: 232~233℃. 1 H NMR (400 MHz, CDCl3) δ 8.06 (dd, J = 7.7, 1.4 Hz, 1H), 7.53 –7.43 (m, 3H), 7.41 – 7.26 (m, 9H), 7.26 – 7.20 (m, 2H), 6.99 (dd, J = 7.7, 0.9Hz, 1H), 4.27 (t, J = 6.0 Hz, 1H), 3.61 (dd, J = 12.8, 5.6 Hz, 1H), 3.33 (dd, J = 12.8, 6.6 Hz, 1H), 3.23 (d, J = 16.8 Hz, 1H), 2.56 (d, J = 16.8 Hz, 1H). 13C10 NMR (100 MHz, CDCl3) δ 195.8, 146.4, 145.5, 142.6, 141.6, 137.7, 135.8, 134.5, 133.9, 133.7, 132.6, 130.0, 129.2, 128.9, 128.9, 128.5, 128.4, 127.7, 127.4, 126.8, 125.1, 122.0, 121.7, 55.3, 47.7, 45.8. HRMS (ESI) m / z calcd for C 30 H 22 Cl2NO3S [M+H] + 546.0697, found 546.0698. When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 2-fluorine, the product is named 2-fluorotantalum-(5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, and the corresponding chemical structural formula is:

[0071] White solid, yield: 57%, melting point: 216~218℃.

[0072] 1 H NMR (400 MHz, CDCl3) δ 8.03 (dd, J = 7.6, 1.5 Hz, 1H), 7.58(td, J = 7.6, 1.7 Hz, 1H), 7.53 – 7.40 (m, 6H), 7.33 – 7.16 (m, 6H), 7.10 (td, J = 7.7, 0.8 Hz, 1H), 7.03 – 6.91 (m, 2H), 4.34 (t, J = 5.9 Hz, 1H), 3.61 (dd, J = 12.7, 5.8 Hz, 1H), 3.33 (dd, J = 12.7, 6.2 Hz, 1H), 3.23 (d, J = 16.8 Hz, 1H), 2.55 (d, J = 16.8 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 195.9, 158.4 (d, J = 254.3 Hz), 146.6,145.5, 141.5, 137.8, 134.7, 134.7, 134.6, 133.9, 133.8, 130.1, 129.9, 129.1(d, J = 12.6 Hz), 128.7, 128.3 (d, J = 22.4 Hz), 127.6, 127.56 (d, J = 12.9 Hz), 126.8, 124.3 (d, J = 3.7 Hz), 122.0, 121.7, 116.9 (d, J = 21.0 Hz), 55.4, 47.9, 45.8. 19 F-NMR (376 MHz, CDCl3) δ -110.23 (s). HRMS (ESI) m / z calcd forC 30 H 23 FNO3S [M+H] + 496.1383, found 496.1382. When R1, R2, and R3 in formula V are all selected from hydrogen, and R is selected from 2-chloro, the product is named 2-chlorotitanium-(5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, and the corresponding chemical structural formula is:

[0073] White solid, yield: 68%, melting point: 204~206℃.

[0074] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.05 – 8.00 (m, ¹H), 7.79 (dd, J = 7.8,1.6 Hz, 1H), 7.53 – 7.35 (m, 6H), 7.33 – 7.23 (m, 7H), 7.21 – 7.15 (m, 1H),7.07 – 7.01 (m, 1H), 4.51 (t, J = 5.8 Hz, 1H), 3.56 (dd, J= 12.6, 5.8 Hz, 1H), 3.28 (dd, J = 12.6, 6.0 Hz, 1H), 3.20 (d, J = 16.8 Hz, 1H), 2.53 (d, J = 16.8Hz, 1H). 13 C10 NMR (100 MHz, CDCl3) δ 195.9, 146.6, 145.5, 141.4, 137.9, 136.6, 134.6, 133.8 (d, J = 1.4 Hz), 133.5, 131.5, 131.2, 130.9, 130.0, 129.1,129.0, 128.6, 128.5, 128.3, 127.7, 127.6, 127.0, 126.8, 122.1, 121.6, 55.4,48.0, 46.1. HRMS (ESI) m / z calcd for C 30 H 23 ClNO3S [M+H] + 512.1087, found 512.1089. When the chemical structural formula of the sulfonamide benzo[a]fluorene-5-one derivative is shown in Formula VII, the product is named N -((5-O-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)thiophene-2-sulfonamide, white solid, yield: 66%, melting point: 231~232℃.

[0075] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.07 – 8.01 (m, 1H), 7.52 – 7.36 (m, 6H), 7.35 – 7.28 (m, 4H), 7.27 – 7.22 (m, 3H), 7.09 – 7.04 (m, 1H), 6.89 (dd, J = 5.0, 3.8 Hz, 1H), 4.29 (t, J = 6.0 Hz, 1H), 3.56 (dd, J = 12.4, 5.7 Hz,1H), 3.36 – 3.21 (m, 2H), 2.56 (d, J = 16.8 Hz, 1H). 13 C10 NMR (100 MHz, CDCl3) δ 196.1, 146.7, 145.5, 141.4, 140.2, 138.0, 134.8, 133.9, 133.8, 132.2, 132.0, 130.1, 129.1, 129.1, 128.6, 128.4, 128.3, 127.8, 127.6, 127.2, 126.8, 122.1, 121.8, 55.3, 48.0, 45.9. HRMS (ESI) m / z calcd for C 28 H 22 NO3S2[M+H] + 484.1041, found 484.1053. When R, R2, and R3 in formula V are all selected from hydrogen, and R1 is selected from 4-methyl, the product is named... N -((5-oxo-11-(p-toryl)-5,6-dihydro-6aH-benzo[a]fluoro-6a-acylmethyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0076] White solid, yield: 61%, melting point: 188~189℃. 1 ¹H NMR (400 MHz, CDCl₃) δ 8.06 – 8.00 (m, 1H), 7.53 – 7.43 (m, 3H), 7.36 – 7.18 (m, 13H), 7.07 (dd, J = 4.3, 2.4 Hz, 1H), 4.11 – 4.06 (m,1H), 3.48 (dd, J = 12.4, 5.7 Hz, 1H), 3.28 – 3.19 (m, 2H), 2.53 (d, J = 16.8Hz, 1H), 2.45 (s, 3H). 13C10 NMR (100 MHz, CDCl3) δ 196.1, 146.7, 145.7, 141.3, 139.3, 138.2, 137.7, 134.9, 133.8, 132.5, 130.7, 130.1, 129.8, 129.0, 128.9, 128.5, 128.1, 127.7, 127.5, 126.8, 126.7, 122.1, 121.7, 55.3, 47.7, 45.8, 21.5. HRMS (ESI) m / z calcd for C 31 H 26 NO3S[M+H] + 492.1633, found 492.1639. When R, R2, and R3 in formula V are all selected from hydrogen, and R1 is selected from 4-methoxy, the product is named... N -((11-(4-methoxyphenyl)-5-oxy-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0077] White solid, yield: 47%, melting point: 174~175℃. 1 ¹H NMR (400 MHz, CDCl₃) δ 8.05 – 8.00 (m, 1H), 7.51 – 7.43 (m, 3H), 7.35 – 7.26 (m, 8H), 7.25 – 7.19 (m, 2H), 7.11 – 7.06 (m, 1H), 7.01 (d, J = 8.8 Hz, 2H), 4.11 (t, J = 6.2 Hz, 1H), 3.89 (s, 3H), 3.48 (dd, J = 12.4, 5.8Hz, 1H), 3.28 – 3.16 (m, 2H), 2.52 (d, J = 16.8 Hz, 1H). 13C10 NMR (100 MHz, CDCl3) δ 196.1, 159.6, 146.7, 145.7, 141.0, 139.3, 137.7, 135.0, 133.8, 132.5, 130.3, 130.1, 129.0, 128.5, 128.1, 127.6, 127.5, 126.8, 126.7, 125.9, 122.0, 121.8, 114.5, 55.4, 55.2, 47.7, 45.8. HRMS (ESI) m / z calcd for C 31 H 26 NO4S[M+H] + 508.1583, found 508.1587. When R, R2, and R3 in formula V are all selected from hydrogen, and R1 is selected from 4-tert-butyl, the product is named (S)- N -((11-(4-(tert-butyl)phenyl)-5-oxo-5,6-dihydro-6aH-benzo[a]fluorene-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0078] White solid, yield: 59%, melting point: 195~197℃.

[0079] 1 H NMR (400 MHz, CDCl3) δ 8.05 – 8.00 (m, 1H), 7.50 – 7.44 (m, 5H), 7.35 – 7.24 (m, 9H), 7.23 – 7.17 (m, 1H), 7.12 – 7.08 (m, 1H), 4.22 (t, J =5.9 Hz, 1H), 3.47 (dd, J = 12.4, 5.8 Hz, 1H), 3.30 – 3.17 (m, 2H), 2.53 (d, J =16.8 Hz, 1H), 1.39 (s, 9H). 13C10 NMR (100 MHz, CDCl3) δ 196.2, 151.4, 146.7, 145.7, 141.3, 139.3, 137.7, 135.0, 133.8, 132.5, 130.7, 130.1, 129.0, 128.7, 128.5, 128.1, 127.7, 127.5, 126.8, 126.7, 125.9, 122.2, 121.8, 55.3, 47.7, 45.8, 34.8, 31.4. HRMS (ESI) m / z calcd for C 34 H 32 NO3S[M+H] + 534.2103, found 534.2108. When R, R2, and R3 in formula V are all selected from hydrogen, and R1 is selected from 4-fluorine, the product is named N -((11-(4-fluorophenyl)-5-oxo-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methylbenzenesulfonamide, the corresponding chemical structural formula is:

[0080] White solid, yield: 63%, melting point: 226~228℃.

[0081] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.06 – 8.01 (m, 1H), 7.51 – 7.44 (m, 3H), 7.40 – 7.29 (m, 7H), 7.29 – 7.14 (m, 5H), 7.03 – 6.98 (m, 1H), 4.19 (t, J = 6.2 Hz, 1H), 3.48 (dd, J = 12.5, 5.7 Hz, 1H), 3.30 – 3.17 (m, 2H), 2.52 (d, J = 16.8 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 195.9, 162.7 (d, J= 247.9 Hz), 146.6,145.4, 140.2, 139.3, 138.5, 134.6, 133.9, 132.6, 130.9, 130.9, 130.1, 129.8(d, J = 3.5 Hz), 129.0, 128.6, 128.4, 127.6 (d, J = 8.7 Hz), 126.9, 126.8,121.9, 121.8, 116.3 (d, J = 21.4 Hz), 55.4, 47.7, 45.8. 19 F-NMR (376 MHz, CDCl3) δ -112.81 (s). HRMS (ESI) m / z calcd forC 30 H 23 FNO3S[M+H] + 496.1383, found496.1393. When R, R2, and R3 in formula V are all selected from hydrogen, and R1 is selected from 4-chloro, the product is named N -((11-(4-chlorophenyl)-5-oxo-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0082] White solid, yield: 62%, melting point: 223~225℃.

[0083] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.05 – 8.00 (m, ¹H), 7.45 (dd, J = 14.2,8.2 Hz, 5H), 7.35 – 7.26 (m, 8H), 7.20 (dd, J = 16.8, 7.4 Hz, 2H), 7.01 (dd, J = 6.6, 2.3 Hz, 1H), 4.38 (t, J = 6.2 Hz, 1H), 3.47 (dd, J = 12.5, 5.9 Hz, 1H),3.28 – 3.16 (m, 2H), 2.50 (d, J = 16.8 Hz, 1H). 13 C10 NMR (100 MHz, CDCl3) δ 195.9, 146.7, 145.1, 139.9, 139.3, 138.7, 134.5, 134.3, 133.9, 132.5, 132.4, 130.5, 130.1, 129.4, 129.0, 128.6, 128.4, 127.6, 127.6, 126.9, 126.8, 121.9, 121.7, 55.5, 47.7, 45.8. HRMS (ESI) m / z calcd for C 30 H 23 ClNO3S[M+H] + 512.1087, found 512.1082. When R, R2, and R3 in formula V are all selected from hydrogen, and R1 is selected from 4-trifluoromethyl, the product is named n-((5-oxo-11-(4-(trifluoromethyl)benzoyl)-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, and the corresponding chemical structural formula is:

[0084] White solid, yield: 81%, melting point: 203~205℃.

[0085] 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 7.6, 1.5 Hz, 1H), 7.71 (d, J = 8.1 Hz, 2H), 7.57 – 7.41 (m, 5H), 7.36 – 7.26 (m, 6H), 7.20 (dd, J = 10.8,3.9 Hz, 1H), 7.17 – 7.11 (m, 1H), 6.95 (dd, J = 7.6, 1.0 Hz, 1H), 4.60 (q, J =6.0 Hz, 1H), 3.49 (dd, J = 12.6, 6.1 Hz, 1H), 3.31 – 3.13 (m, 2H), 2.51 (d, J =16.8 Hz, 1H). 13C10 NMR (100 MHz, CDCl3) δ 195.8, 146.78, 144.9, 139.7, 139.4, 139.2, 137.9, 134.3, 134.0, 132.5, 130.4 (q, J = 32.7 Hz), 130.2, 129.6,129.0, 128.6, 127.7, 127.6, 127.0, 126.8, 126.1, 126.1, 126.0, 126.0, 124.1(q, J = 272.8 Hz), 122.0, 121.7,55.7, 47.8, 45.8. 19 F-NMR (376 MHz, CDCl3) δ -62.45 (s). HRMS (ESI) m / z calcd forC 31 H 23 F3NO3S[M+H] + 546.1351, found 546.1366. When R, R2, and R3 in formula V are all selected from hydrogen, and R1 is selected from 3-methyl, the product is named... N -((5-oxy-11-(m-torilyl)-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0086] White solid, yield: 60%, melting point: 196~198℃.

[0087] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.06 – 8.00 (m, 1H), 7.52 – 7.43 (m, 3H), 7.39 – 7.26 (m, 7H), 7.25 – 7.13 (m, 4H), 7.07 – 7.02 (m, 1H), 4.17 – 4.07 (m, 1H), 3.48 (dd, J = 12.4, 5.8 Hz, 1H), 3.29 – 3.18 (m, 2H), 2.54 (d, J = 16.7 Hz, 1H), 2.40 (s, 3H). 13C10 NMR (100 MHz, CDCl3) δ 196.1, 146.7, 145.6, 141.5, 139.3, 138.8, 137.8, 134.9, 133.8, 132.5, 130.1, 129.5, 129.1, 129.0, 128.5, 128.2, 127.7, 127.5, 126.8, 126.7, 126.0, 122.1, 121.7, 55.3, 47.7, 45.8, 21.5. HRMS (ESI) m / z calcd for C 31 H 26 NO3S[M+H] + 492.1633, found 492.1637. When R, R2, and R3 in formula V are all selected from hydrogen, and R1 is selected from 2-chloro, the product is named N -((11-(2-chlorophenyl)-5-oxo-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methylbenzenesulfonamide, the corresponding chemical structural formula is:

[0088] White solid, yield: 63%, melting point: 180~181℃.

[0089] 1 H NMR (400 MHz, CDCl3) δ 8.04 (dd, J = 7.6, 1.5 Hz, 1H), 7.64 –7.59 (m, 1H), 7.55 – 7.41 (m, 6H), 7.36 – 7.22 (m, 7H), 7.06 (d, J = 7.5 Hz,1H), 6.96 – 6.91 (m, 1H), 4.08 (t, J = 6.1 Hz, 1H), 3.50 (dd, J = 12.5, 5.3 Hz,1H), 3.40 – 3.11 (m, 1H), 2.58 (d, J = 16.5 Hz, 1H). 13C10 NMR (100 MHz, CDCl3) δ 196.0, 146.5, 145.3, 140.3, 139.4, 138.2, 135.3, 134.2, 132.8, 132.7, 132.6, 131.6, 130.5, 129.9, 129.4, 129.0, 128.7, 128.5, 127.5, 127.2, 126.9, 126.8, 126.4, 121.8, 121.7, 55.8, 47.8, 46.2. HRMS (ESI) m / z calcd for C 30 H 23 ClNO3S[M+H] + 512.1087, found 512.1084. When R, R1, and R3 in formula V are all selected from hydrogen, and R2 is selected from 4-methyl, the product is named n-((9-methyl-5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methylbenzenesulfonamide, and the corresponding chemical structural formula is:

[0090] White solid, yield: 65%, melting point: 248~250℃.

[0091] 1 H NMR (400 MHz, CDCl3) δ 8.03 (dd, J = 7.6, 1.5 Hz, 1H), 7.53 –7.44 (m, 6H), 7.38 (d, J = 6.6 Hz, 2H), 7.35 – 7.23 (m, 4H), 7.16 (d, J = 7.5Hz, 1H), 7.08 – 6.97 (m, 3H), 4.00 (t, J = 6.2 Hz, 1H), 3.46 (dd, J = 12.4, 5.4Hz, 1H), 3.30 – 3.16 (m, 2H), 2.54 (d, J = 16.7 Hz, 1H), 2.35 (s, 3H). 13C10 NMR (100 MHz, CDCl3) δ 196.1, 145.8, 143.8, 141.3, 139.4, 138.6, 138.3, 134.8, 134.0, 133.8, 132.5, 130.1, 129.1, 129.0, 129.0, 128.4, 128.1, 127.6, 127.6, 127.6, 126.8, 122.7, 121.5, 55.0, 47.8, 46.0, 21.6. HRMS (ESI) m / z calcd for C 31 H 26 NO3S[M+H] + 492.1633, found 492.1635. When R, R1, and R3 in formula V are all selected from hydrogen, and R2 is selected from 4-fluorine, the product is named N -((9-fluoro-5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0092] White solid, yield: 93%, melting point: 223~225℃.

[0093] 1 H NMR (400 MHz, CDCl3) δ 8.05 (dd, J = 7.7, 1.4 Hz, 1H), 7.49(dt, J = 7.3, 6.7 Hz, 6H), 7.40 – 7.27 (m, 6H), 7.20 (dd, J = 8.2, 4.8 Hz, 1H), 7.04 (dd, J = 7.6, 1.0 Hz, 1H), 6.88 (dd, J = 13.5, 5.7 Hz, 2H), 4.11 (t, J =6.3 Hz, 1H), 3.48 (dd, J = 12.7, 6.2 Hz, 1H), 3.29 – 3.16 (m, 2H), 2.54 (d, J =16.8 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 195.6, 163.4 (d, J = 246.1 Hz), 147.7,147.6, 142.2, 142.1, 140.5, 140.5, 140.0, 139.4, 134.4, 133.9, 133.3, 132.6,130.1, 129.3, 129.0, 128.9, 128.7 (d, J = 4.4 Hz), 127.6, 126.8, 122.8 (d, J =9.2 Hz), 113.4 (d, J = 23.4 Hz), 109.3 (d, J = 24.0 Hz), 55.0, 47.7, 45.8. 19 F-NMR (376 MHz, CDCl3) δ -113.00 (s). HRMS (ESI) m / z calcd forC 30 H 23 FNO3S[M+H] + 496.1383, found 496.1389. When R, R1, and R3 in formula V are all selected from hydrogen, and R2 is selected from 4-chloro, the product is named N -((9-chloro-5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0094] White solid, yield: 71%, melting point: 246~247℃.

[0095] 1 H NMR (400 MHz, CDCl3) δ 8.05 (dd, J = 7.6, 1.3 Hz, 1H), 7.50 (d, J = 7.5 Hz, 6H), 7.39 – 7.28 (m, 6H), 7.20 – 7.12 (m, 3H), 7.07 – 7.02 (m,1H), 4.10 (t, J = 6.4 Hz, 1H), 3.49 (dd, J= 12.8, 6.4 Hz, 1H), 3.30 – 3.17 (m,2H), 2.53 (d, J = 16.8 Hz, 1H). 13 C10 NMR (100 MHz, CDCl3) δ 195.5, 147.2, 145.0, 140.4, 139.6, 139.4, 134.7, 134.3, 133.9, 133.2, 132.6, 130.1, 129.3, 129.0, 128.9, 128.7, 127.7, 127.7, 126.7, 126.6, 122.7, 122.1, 55.2, 47.6, 45.5. HRMS (ESI) m / z calcd for C 30 H 23 ClNO3S[M+H] + 512.1087, found 512.1089. When R, R1, and R2 in formula V are all selected from hydrogen, and R3 is selected from 3-fluorine, the product is named N -((3-fluoro-5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0096] White solid, yield: 69%, melting point: 178-180℃.

[0097] 1 H NMR (400 MHz, CDCl3) δ 7.68 (dd, J = 8.9, 2.6 Hz, 1H), 7.54 –7.43 (m, 6H), 7.41 – 7.29 (m, 5H), 7.28 – 7.20 (m, 3H), 7.05 – 6.93 (m, 2H), 4.11 (t, J = 6.3 Hz, 1H), 3.47 (dd, J = 12.5, 5.5 Hz, 1H), 3.30 – 3.17 (m, 2H), 2.54 (d, J = 16.8 Hz, 1H). 13C10 NMR (100 MHz, CDCl3) δ 195.1, 162.2 (d, J = 250.8 Hz), 146.3,145.5, 141.1, 139.4, 137.1, 133.7, 132.6, 132.1, 132.0, 131.2 (d, J = 3.1 Hz), 129.9 (d, J = 7.3 Hz), 129.2, 129.0 (d, J = 6.8 Hz), 128.7, 128.5, 126.8,126.8, 122.1, 121.8, 121.5 (d, J = 22.6 Hz), 113.6 (d, J = 22.5 Hz), 55.4, 47.8, 45.6. 19 F-NMR (376 MHz, CDCl3) δ -110.71 (s). HRMS (ESI) m / z calcd forC 30 H 23 FNO3S[M+H] + 496.1383, found 496.1380. When R, R1, and R2 in formula V are all selected from hydrogen, and R3 is selected from 3-chloro, the product is named N -((3-chloro-5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0098] White solid, yield: 70%, melting point: 200-202℃.

[0099] 1 H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 2.3 Hz, 1H), 7.53 – 7.44(m, 6H), 7.39 – 7.27 (m, 6H), 7.26 – 7.17 (m, 3H), 6.95 (d, J = 8.5 Hz, 1H), 4.19 (t, J = 6.2 Hz, 1H), 3.48 (dd, J= 12.6, 5.6 Hz, 1H), 3.29 – 3.16 (m, 2H), 2.52 (d, J = 16.8 Hz, 1H). 13 C10 NMR (100 MHz, CDCl3) δ 194.9, 146.5, 145.4, 141.9, 139.3, 137.0, 134.4, 133.8, 133.6, 133.2, 132.6, 131.2, 129.2, 129.1, 129.0, 128.9, 128.7, 128.6, 127.4, 127.0, 126.8, 122.2, 121.8, 55.2, 47.7, 45.6. HRMS (ESI) m / z calcd for C 30 H 23 ClNO3S[M+H] + 512.1087, found 512.1091. When R, R1, and R2 in formula V are all selected from hydrogen, and R3 is selected from 3-methoxy, the product is named... N -((3-methoxy-5-oxy-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0100] White solid, yield: 70%, melting point: 200~202℃.

[0101] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.52 – 7.42 (m, 7H), 7.40 – 7.23 (m, 6H), 7.22 – 7.15 (m, 2H), 6.95 (d, J = 8.7 Hz, 1H), 6.83 (dd, J = 8.7, 2.8 Hz, 1H), 4.24 (t, J = 6.2 Hz, 1H), 3.83 (s, 3H), 3.48 (dd, J = 12.4, 5.9 Hz, 1H),3.28 – 3.16 (m, 2H), 2.52 (d, J = 16.8 Hz, 1H). 13 C10 NMR (100 MHz, CDCl3) δ 196.1, 159.5, 146.4, 145.7, 139.4, 138.0, 134.1, 132.5, 131.5, 129.2, 129.1, 129.1, 129.0, 128.5, 128.3, 127.9, 126.8, 126.4, 122.2, 121.8, 121.6, 109.5, 55.6, 55.3, 48.0, 45.7. HRMS (ESI) m / z calcd for C 31 H 26 NO4S[M+H] + 508.1583, found 508.1587. When R, R1, and R2 in formula V are all selected from hydrogen, and R3 is selected from 4-methyl, the product is named N -((2-methyl-5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0102] White solid, yield: 59%, melting point: 191~193℃.

[0103] 1 H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.0 Hz, 1H), 7.52 – 7.43(m, 6H), 7.41 – 7.35 (m, 2H), 7.32 (dd, J = 11.0, 4.5 Hz, 3H), 7.27 – 7.18 (m,3H), 7.11 (dd, J = 8.0, 1.0 Hz, 1H), 6.77 (s, 1H), 4.14 (t, J = 6.2 Hz, 1H), 3.48 (dd, J = 12.4, 5.7 Hz, 1H), 3.30 – 3.15 (m, 2H), 2.51 (d, J = 16.7 Hz, 1H), 2.12 (s, 3H). 13C10 NMR (100 MHz, CDCl3) δ 195.8, 146.7, 145.45, 144.5, 141.0, 139.3, 138.3, 134.7, 133.9, 132.4, 129.4, 129.0, 129.0, 128.9, 128.5, 128.4, 128.0, 127.9, 127.6, 126.9, 126.7, 122.0, 121.8, 55.4, 47.8, 45.8, 21.9. HRMS (ESI) m / z calcd for C 31 H 26 NO3S[M+H] + 492.1633, found 492.1630. When R, R1, and R2 in formula V are all selected from hydrogen, and R3 is selected from 4-fluorine, the product is named N -((2-fluoro-5-oxo-11-phenyl-5,6-dihydro-6aH-benzo[a]fluoro-6a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0104] White solid, yield: 66%, melting point: 193~195℃.

[0105] 1 H NMR (400 MHz, CDCl3) δ 8.04 (dd, J = 8.8, 6.0 Hz, 1H), 7.48(dt, J = 14.2, 7.4 Hz, 6H), 7.39 – 7.28 (m, 6H), 7.27 – 7.20 (m, 2H), 6.94(td, J = 8.4, 2.5 Hz, 1H), 6.54 (dd, J = 9.8, 2.5 Hz, 1H), 4.33 (dd, J = 7.0, 5.5 Hz, 1H), 3.51 (dd, J = 12.6, 5.3 Hz, 1H), 3.29 – 3.16 (m, 2H), 2.50 (d, J =16.8 Hz, 1H). 13C10 NMR (100 MHz, CDCl3) δ 194.7, 165.6 (d, J = 255.7 Hz), 146.6,145.3, 142.7, 139.4, 137.5 (d, J = 10.2 Hz), 137.0 (d, J = 2.3 Hz), 133.3,132.6, 130.7 (d, J = 10.1 Hz), 129.3, 129.0, 128.8, 128.7, 128.7, 127.2,126.8, 126.7, 126.7, 122.3, 121.9, 115.9 (d, J = 22.6 Hz), 113.8 (d, J = 23.3Hz), 55.5, 47.7, 45.6. 19 F-NMR (376 MHz, CDCl3) δ -102.26 (s). HRMS (ESI) m / z calcd forC 30 H 23 FNO3S[M+H] + 496.1383, found 496.1385. When the chemical structural formula of the sulfonamide benzo[a]fluorene-5-one derivative is shown in Formula VI, the product is named N -((4-oxo-10-phenyl-4,5-dihydro-5aH-fluoroxonium[2,1-b]thiophene-5a-yl)methyl)benzenesulfonamide, the corresponding chemical structural formula is:

[0106] White solid, yield: 85%, melting point: 188~189℃.

[0107] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.56 – 7.41 (m, 9H), 7.38 – 7.22 (m, 6H), 6.71 (d, J = 5.1 Hz, 1H), 4.24 (t, J = 6.4 Hz, 1H), 3.48 (dd, J = 12.6, 5.7Hz, 1H), 3.35 (dd, J= 12.6, 7.4 Hz, 1H), 3.16 (d, J = 16.5 Hz, 1H), 2.58 (d, J = 16.5 Hz, 1H). 13 C10 NMR (100 MHz, CDCl3) δ 190.5, 146.7, 145.5, 142.7, 141.0, 139.6, 136.1, 136.1, 134.8, 133.5, 132.6, 129.1, 129.0, 128.9, 128.7, 127.0, 126.8, 126.3, 122.3, 122.1, 57.1, 49.2, 45.1. HRMS (ESI) m / z calcd forC 28 H 22 NO3S2[M+H] + 484.1041, found 484.1050. 3. Investigation of the reaction mechanism To further elucidate the reaction mechanism, we designed a free radical capture experiment (such as...). Figure 2 Under standard reaction conditions [using 3-phenyl-1-(2-(phenylethynyl)phenyl)but-3-en-1-one (0.2 mmol) and 1-phenyl-3-(benzenesulfonyl)triazole tetrafluoroborate (0.24 mmol) as substrates, 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile (0.04 mmol, 2 mol%) as photocatalyst, dimethyl sulfoxide as solvent, and reacting at room temperature for 12 hours under 10 W blue light irradiation], 3 equivalents of 2,2,6,6-tetramethylpiperidin-1-oxy radical and 2,6-di-tert-butyl-4-methylphenol were added respectively. It was found that the former completely inhibited the reaction, and the target product 3aa was not detected; the latter significantly inhibited the reaction, yielding the product only in 42% of the standard product (compared to 75% under standard conditions). Furthermore, the corresponding radical structures were captured by high-resolution mass spectrometry. These results consistently suggest that free radical intermediates are likely involved in the reaction process.

[0108] Based on literature reports and the above-mentioned mechanistic experiments, we hypothesize a possible reaction mechanism, such as... Figure 3 As shown. First, under visible light irradiation, the photocatalyst 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile (4CzIPN) absorbs energy and transitions from its ground state to the excited state 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile (4CzIPN). *Subsequently, the excited state 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile (4CzIPN) * )and N A single-electron transfer process occurs between 2a and 2a of sulfonamide pyridine salts, generating sulfonamide radical A and oxidized 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile (4CzIPN). •+ The generated free radical A then adds to the carbon-carbon double bond in 1a, forming free radical intermediate B. Intermediate B then undergoes intramolecular six-membered external cyclization to give intermediate C. Intermediate C further undergoes five-membered internal cyclization to transform into intermediate D. Finally, intermediate D is oxidized to 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile (4CzIPN). •+ It undergoes single-electron oxidation, followed by deprotonation, to produce the final product 3aa.

[0109] The above embodiments and figures are not intended to limit the product form and style of the present invention. Any appropriate changes or modifications made by those skilled in the art should be considered as not departing from the patent scope of the present invention.

Claims

1. A method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative, characterized in that: Includes the following steps: Step 1: Weigh out 1,7-enyne and... (The sentence is incomplete and requires more context to translate accurately.) N -Sulfonamide pyridine salt, placed in a reaction vessel, yields the reaction substrate; Step 2: Then, solvent and photocatalyst are added sequentially to the reaction substrate. The volume ratio of the solvent to the molar amount of the 1,7-enyne is 1 mL : 0.1 mmol, and the molar ratio of the photocatalyst to the 1,7-enyne is 1:

5. Step 3: Then, under a nitrogen atmosphere and at room temperature, the reaction is carried out under blue light irradiation. After the reaction product 1,7-enyne is completely consumed as monitored by thin-layer chromatography, deionized water and ethyl acetate are added to the reaction solution for extraction multiple times. The organic phases are then combined and concentrated by rotary evaporation to obtain the crude product. Step 4: Finally, the crude product is purified by chromatography to obtain the sulfonamide-modified benzo[a]fluorene-5-one derivative; In step 1, the chemical structural formula of the 1,7-enyne is shown in Formula I: Formula I; R1 is selected from one of hydrogen, 4-methyl, 4-methoxy, 4-tert-butyl, 4-fluoro, 4-chloro, 4-trifluoromethyl, 3-methyl and 2-chloro; R2 is selected from one of hydrogen, 4-methyl, 4-fluoro, and 4-chloro; R3 is selected from one of hydrogen, 3-fluoro, 3-chloro, 3-methoxy, 4-methyl, and 4-fluoro; In step 1, the N The chemical structural formula of sulfonamide pyridine salt is shown in Formula II: Formula II; Wherein, R is selected from one of hydrogen, 4-methyl, 4-methoxy, 4-tert-butyl, 4-fluoro, 4-chloro, 4-bromo, 4-trifluoromethoxy, 4-trifluoromethyl, 4-acetyl, 4-cyano, 3,5-dichloro, 2-fluoro, and 2-chloro; or: In step 1, the chemical structural formula of the 1,7-enyne is shown in Formula III. N The chemical structural formula of sulfonamide pyridine salt is shown in Formula II: Formula III; Alternatively, in step 1, the chemical structural formula of the 1,7-enyne is shown in Formula I. N The chemical structural formula of sulfonamide pyridine salt is shown in Formula IV: Formula IV.

2. The method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative according to claim 1, characterized in that: In step 2, the solvent is acetonitrile, dichloromethane, tetrahydrofuran, acetone, 1,2-dichloroethane, methanol, dimethyl sulfoxide, 1,4-dioxane, and... N , N One of the dimethylformamides.

3. The method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative according to claim 2, characterized in that: In step 2, the solvent is dimethyl sulfoxide.

4. The method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative according to claim 1, characterized in that: In step 2, the photocatalyst is one of 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile, Acid Red 94, 2,4,5,6-penta(9H-carbazolyl-9-yl)benzonitrile, tris(2,2-bipyridine)chloride hexahydrate, Rhodamine B, Solvent Red 43, 2,4,6-tris(9H-carbazolyl-9-yl)-5-chloroisophthalonitrile, and (OC-6-21)-tris[2-(2-pyridyl-κN)phenyl-κC]iridium.

5. The method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative according to claim 4, characterized in that: In step 2, the photocatalyst is 2,4,5,6-tetracarbazolyl-1,3-isophthalonitrile.

6. The method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative according to claim 1, characterized in that: In step 3, the wavelength of the blue light is 445~450 nm, the power of the light is 5~20 W, and the duration of the light is 1~20 hours.

7. The method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative according to claim 6, characterized in that: In step 3, the power of the light is 10 W, and the duration of the light exposure is 12 hours.

8. The method for preparing a sulfonamide-modified benzo[a]fluorene-5-one derivative according to claim 1, characterized in that: The chemical structural formula of the sulfonamide benzo[a]fluorene-5-one derivative is shown in Formula V, Formula VI or Formula VII: Formula V; R1 is selected from one of hydrogen, 4-methyl, 4-methoxy, 4-tert-butyl, 4-fluoro, 4-chloro, 4-trifluoromethyl, 3-methyl and 2-chloro; R2 is selected from one of hydrogen, 4-methyl, 4-fluoro, and 4-chloro; R3 is selected from one of hydrogen, 3-fluoro, 3-chloro, 3-methoxy, 4-methyl, and 4-fluoro; R is selected from one of hydrogen, 4-methyl, 4-methoxy, 4-tert-butyl, 4-fluoro, 4-chloro, 4-bromo, 4-trifluoromethoxy, 4-trifluoromethyl, 4-acetyl, 4-cyano, 3,5-dichloro, 2-fluoro, and 2-chloro; Formula VI; Formula VII.

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