Sulfonylated benzoazepine [1, 2-a] indolone compound and preparation method thereof

Abstract

The invention belongs to the field of organic synthesis, and discloses a sulfonylated benzoazepine [1, 2-a] indolone compound and a preparation method thereof. According to the preparation method, under the conditions of room temperature and visible light irradiation, 1-(2-(arylethynyl) benzoyl) indole, aryl thianthrene salt and 4-diazabicyclo [2.2. 2] octane-1, 4-dionium-1, 4-disulfinic acid are used as raw materials, tris (4-methoxyphenyl) amine is used as a catalyst, and the preparation of the sulfonylated benzazepine [1, 2-a] indolone compound is realized. The method has the advantages of mild reaction conditions, simplicity and convenience in operation, no photosensitizer, wide substrate application range and the like. The sulfonylated benzazepine [1, 2-a] indolone compound has potential application value in the research fields of organic synthesis and the like, a novel preparation method is provided for synthesis of the sulfonylated benzazepine [1, 2-a] indolone compound, and part of the synthesized compound has certain antitumor activity.

Description

Technical Field

[0001] The present invention relates to the field of organic synthesis, and in particular to a method for preparing benzazepine [1,2-a] indole one. Background Art

[0002] Benzazepin[1,2-a]indolones are widely found in various natural indole alkaloids, such as Arborescidine C and Akagerine (Eur. J. Med. Chem., 2009, 44, 3810-3815). Because Benzazepin[1,2-a]indolone molecules often possess significant biological activity and potential applications, the synthesis of novel Benzazepin[1,2-a]indolone derivatives is of great significance for the discovery of new bioactive molecules. Sulfonyl groups are important reactive functional groups in drug molecules, possessing unique physiological activities. Among them, arylsulfonates, as precursors of aryl radicals, undergo sulfonylation through the insertion of sulfur dioxide, requiring transition metal catalysts, additives, or high temperatures (ACS Catal. 2023, 13, 11580-11588; Org. Lett. 2024, 26, 1845-1850). Currently, reports on the synthesis of sulfonylated benzazepine[1,2-a]indolones are relatively rare, and they face limitations such as harsh reaction conditions and a limited substrate applicability. For example, the preparation method proposed in Org. Lett., 2024, 26, 10982-10987, involves the synthesis of arylsulfonyl hydrazides, which often require the reaction of sulfonyl chloride with hydrazine hydrate. The preparation of arylsulfonyl chlorides often requires starting from the corresponding aromatic hydrocarbons and using toxic chlorosulfonic acid or thionyl chloride through multiple steps. This presents a significant challenge for the preparation of the corresponding arylsulfonyl chlorides from complex aromatic hydrocarbon drugs. Furthermore, this method requires the use of an equivalent amount of the strong oxidant K2S2O8, which has poor compatibility with sensitive functional groups such as aldehydes. Therefore, the synthesis of sulfonylated benzazepine[1,2-a]indolones using arylsulfonates under mild conditions holds great research value and significance. Summary of the Invention

[0003] In response to the above technical problems, the present invention provides a sulfonylated benzazepine [1,2-a] indole one compound and a preparation method thereof.

[0004] To achieve the above object, the technical solution of the present invention is implemented as follows:

[0005] A method for preparing a sulfonylated benzazepine [1,2-a] indole one compound comprises the following steps:

[0006] A magnetic stirrer, catalyst tris(4-methoxyphenyl)amine (TMPA), 1-(2-(arylalkynyl)benzoyl)indole, arylthianthrene salt, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid (DABSO), and solvent were sequentially added to a Schlenk reaction tube. The tube was refrigerated and degassed, and the atmosphere was purged with nitrogen three times. The tube was sealed and allowed to react at room temperature under 10-20W blue light at 430nm for 24-48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The resulting crude product was purified by silica gel column chromatography to obtain the sulfonylated benzazepine[1,2-a]indole one compound.

[0007] The reaction equation is:

[0008]

[0009] Among them, the structural formula of 1-(2-(aryl alkynyl)benzoyl)indole compounds is The structural formula of arylthianthrene salt is Wherein, R is H, Me, OMe, Cl, t Bu; Ar is an aromatic ring or an aromatic heterocyclic ring.

[0010] Furthermore, the above Ar is

[0011] Any one of .

[0012] The molar ratio of the 1-(2-(arylalkynyl)benzoyl)indole compound, arylthianthrene salt, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid and tri(4-methoxyphenyl)amine is 1:1.5-2.5:1.5-2.5:0.1-0.2. For example, the molar ratio of 1-(2-(arylalkynyl)benzoyl)indole compounds, arylthianthrene salts, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid and tri(4-methoxyphenyl)amine is 1:1.5-2:1.5-2:0.1-0.2, 1:2-2.5:2-2.5:0.1-0.2, 1:2:2:0.2, 1:1.5:2.5:0.1, 1:2.5:2:0.2, etc., as long as the molar ratio of the four is within the range of 1:1.5-2.5:1.5-2.5:0.1-0.2.

[0013] The solvent is any one of acetonitrile, ethyl acetate, dichloromethane and 1,2-dichloroethane.

[0014] The reaction mechanism is as follows: The process begins with the interaction between TMPA and aryl thianthrene salts to form an electron donor-acceptor (EDA) complex. Under visible light irradiation, the complex undergoes a single electron transfer process to generate an aryl radical, thianthrene, and TMPA. ·+ Species. Subsequently, the aryl radical reacts with DABSO to generate a sulfonyl radical and release DABCO. The sulfonyl radical selectively adds to the carbon-carbon triple bond of compound 1 to form an olefinic radical intermediate 4a. Intermediate 4a then undergoes a cyclization reaction to generate radical species 4b. Radical 4b is subsequently converted to TMPA through single electron transfer (SET). ·+ Oxidation forms cationic intermediate 4c, and regenerates TMPA to participate in the next cycle. Cationic intermediate 4c is then deprotonated by DABCO to finally generate product 4. The specific reaction mechanism is shown in the figure below. Figure 1 shown.

[0015] The sulfonylated benzazepine [1,2-a] indole one compound prepared by the above-mentioned preparation method has the following general structural formula:

[0016] Wherein, R is H, Me, OMe, Cl, t Bu; Ar is an aromatic ring or an aromatic heterocyclic ring.

[0017] Furthermore, the sulfonylated benzazepine [1,2-a] indole one compound is any one of the following compounds:

[0018]

[0019]

[0020] The present invention provides a novel method for constructing sulfonylated benzazepin[1,2-a]indolones. This method utilizes TMPA as a catalyst under visible light irradiation to achieve the synthesis of sulfonylated benzazepin[1,2-a]indolones. The method utilizes mild conditions, readily available and inexpensive raw materials, is simple to operate, and requires no metals. Preliminary experimental results demonstrate that the method can effectively link sulfonylated drug molecules to benzazepin[1,2-a]indolones. Biological activity tests demonstrate that some of the synthesized compounds exhibit moderate anti-tumor activity. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0022] Figure 1 The figure is a reaction mechanism diagram of the sulfonylated benzazepine [1,2-a] indole one compounds of the present invention.

[0023] Figure 2 This is a graph showing the in vitro anti-tumor activity test results of the target product prepared in Example 5 of the present invention. DETAILED DESCRIPTION

[0024] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without creative work are within the scope of protection of the present invention.

[0025] A method for preparing 1-(2-(arylalkynyl)benzoyl)indole, comprising the following steps:

[0026]

[0027] To a three-necked flask equipped with a magnetic rod, 0.2 g of NaH was added, the atmosphere replaced with nitrogen, and 5 ml of DMF was added, followed by stirring at 0°C. Subsequently, 0.65 g of 3-methylindole was dissolved in 25 ml of ultra-dry DMF and added dropwise to the round-bottom flask. After stirring the reaction system at room temperature for 1 hour, 1.3 g of o-iodobenzoyl chloride dissolved in 5 ml of DMF was added to the reaction system, and the reaction was stirred at 75°C for 18 hours. After completion of the reaction, cold water was added to quench the reaction, and the mixture was extracted with ethyl acetate. The organic layers were combined, dried over anhydrous sodium sulfate, filtered, and concentrated on a rotary evaporator. The reaction system was then purified by silica gel column chromatography to obtain the product, 1-(2-iodobenzoyl)indole.

[0028]

[0029] To a three-necked flask equipped with a magnetic field, 1.8 g of 1-(2-iodobenzoyl)indole, 6 mmol of a phenylacetylene derivative, 70 mg of Pd(PPh3)2Cl2, and 19 mg of CuI were added. The atmosphere in the reaction system was replaced with nitrogen. Subsequently, 30 ml of triethylamine was added to the reaction system, and the reaction was stirred at 50°C for 12 hours. After the reaction, the mixture was extracted with ethyl acetate / water. The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated on a rotary evaporator. The product, 1-(2-(arylalkynyl)benzoyl)indole 1, was then purified by silica gel column chromatography.

[0030]

[0031] A magnetic stirrer, catalyst tris(4-methoxyphenyl)amine (TMPA), 1-(2-(arylalkynyl)benzoyl)indole, arylthianthrene salt, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid (DABSO), and solvent were sequentially added to a Schlenk reaction tube. The tube was refrigerated and degassed, and the atmosphere was purged with nitrogen three times. The tube was sealed and allowed to react at room temperature under 10-20W blue light at 430nm for 24-48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The resulting crude product was purified by silica gel column chromatography to obtain the sulfonylated benzazepine[1,2-a]indole one compound.

[0032] Example 1

[0033] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0034] A Schlenk reaction tube was sequentially added with a magnetic stirrer, 0.1 mmol of 1-(2-(arylalkynyl)benzoyl)indole (i.e., (3-methyl-1H-indol-1-yl)(2-(phenylethynyl)phenyl)methanone), 0.2 mmol of p-tolylthianthrene salt, 0.2 mmol of 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid, 20 mol% of the catalyst TMPA, and 1 mL of CH3CN. The tube was refrigerated and degassed, the atmosphere was purged with nitrogen three times, and the reaction was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain the sulfonylated benzazepine[1,2-a]indolone in a 39% yield. 1H NMR(600MHz,Chloroform-d)δ8.32(d,J=8.5Hz,1H),8.14(d,J=8.0Hz,1H),8.02–7.98(m,1H),7.79(d,J=7.9Hz,1H),7.56–7.51(m,2H),7.49–7.45(m,2H) ),7.42–7.36(m,3H),7.30–7.27(m,1H),7.20–7.16(m,2H),6.99(t,J=7.6Hz ,1H),6.92(d,J=8.1Hz,2H),6.34(d,J=8.6Hz,1H),2.25(s,3H),1.45(s,3H). 13 C{ 1 H}NMR(151MHz,Chloroform-d)δ168.0,144.5,141.2,140.0,136.6,135.3,133.1,132.3,131.1,130.5,130.0,12 9.7,129.4,129.3,129.0,128.2,128.0,127.6,127.4,123.7,119.2,114.2,21.5,10.5.HRMS(ESI-TOF)m / z:[M+H] + Calcdfor C 31 H 24 NO3S + ,490.1471,found:490.1473.

[0035]

[0036] Example 2

[0037] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0038] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolylethynyl)phenyl ketone 0.1 mmol, p-tolylthianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the reaction was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone with a yield of 76%. 1 H NMR(600MHz,Chloroform-d)δ8.31(d,J=8.4Hz,1H),8.13(d,J=8.0Hz,1H),7.88(d,J =7.8Hz,1H),7.77(d,J=7.9Hz,1H),7.55–7.49(m,1H),7.49–7.43(m,1H),7.44–7.40 (m,1H),7.41–7.36(m,1H),7.32–7.26(m,2H),7.23–7.16(m,2H),6.93(d,J=8.1Hz,2 H),6.84–6.79(m,1H),6.27(d,J=7.9Hz,1H),2.40(s,3H),2.26(s,3H),1.49(s,3H). 13 C{ 1 H}NMR(151MHz,Chloroform-d)δ168.0,144.3,143.2,140.0,136.5,135.55,135.50,133.1,131.2,130.5,130.1,129.7,129. 5,129.36,129.30,129.1,128.9,128.8,128.4,128.0,127.6,127.5,123.7,119.2,114.2,21.5,21.4,10.5.HRMSm / z:[M+Na] + Calcd for C 32 H 25 NNaO3S + ,526.1447,found:526.1441.

[0039]

[0040] Example 3

[0041] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0042] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., 0.1 mmol of (3-methyl-1H-indol-1-yl)(2-((4-methoxyphenyl)ethynyl)phenylmethanone, 0.2 mmol of p-tolylthianthrene salt, 0.2 mmol of 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid, 20 mol% of catalyst TMPA, and 1 mL of CH3CN were sequentially added to a Schlenk reaction tube. The tube was refrigerated and degassed, nitrogen was purged three times, and the reaction was carried out at room temperature under 10 W blue light at 430 nm for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone with a yield of 66%. 1 H NMR(600MHz,Chloroform-d)δ8.31(d,J=8.5Hz,1H),8.14–8.09(m,1H),7.93(d, J=8.5Hz,1H),7.79–7.75(m,1H),7.55–7.51(m,1H),7.47–7.38(m,3H),7.31–7.2 7(m,1H),7.21(d,J=8.1Hz,2H),7.00(d,J=8.5Hz,1H),6.94(d,J=8.0Hz,2H),6.5 3(d,J=8.6Hz,1H),6.27(d,J=7.2Hz,1H),3.86(s,3H),2.26(s,3H),1.52(s,3H). 13 C{ 1 H}NMR(151MHz,Chloroform-d)δ168.1,161.0,143.9,143.1,138.4,138.3,136.6,135.5,134.7,131.5,131.4,130.7,130.5,130.1,12 9.6,129.4,129.3,128.9,128.8,128.4,127.6,127.4,123.7,119.2,114.7,114.2,112.0,55.3,21.4,10.6.HRMS(ESI-TOF)m / z:[M+K] + Calcd for C 32 H 25 KNO4S + ,558.1136,found:558.1137.

[0043]

[0044] Example 4

[0045] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0046] A Schlenk reaction tube was sequentially added with a magnetic stirrer, 0.1 mmol of 1-(2-(arylalkynyl)benzoyl)indole (i.e., (3-methyl-1H-indol-1-yl)(2-((4-chlorophenyl)ethynyl)phenyl)methanone), 0.2 mmol of p-tolylthianthrene salt, 0.2 mmol of 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid, 20 mol% of the catalyst TMPA, and 1 mL of CH3CN. The tube was refrigerated and degassed, the atmosphere was purged with nitrogen three times, and the reaction was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution was added and extracted with dichloromethane, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain the sulfonylated benzazepine[1,2-a]indolone in a 66% yield. 1 H NMR(600MHz,Chloroform-d)δ8.31(d,J=8.5Hz,1H),8.12(d,J=7.9Hz,1H),7.95(d,J=8.2Hz,1H),7.78(d,J=7.8Hz,1H),7.55–7.52(m,1H),7.49–7 .46(m,2H),7.44–7.39(m,2H),7.30(d,J=7.5Hz,1H),7.21(d,J=8.2Hz,2H ),6.98(d,J=8.3Hz,3H),6.32(d,J=8.3Hz,1H),2.28(s,3H),1.53(s,3H). 13 C{ 1 H}NMR(151MHz,Chloroform-d)δ167.8,143.6,142.7,139.7,138.0,136.7,136.6,136.1,135.5,134.3,131.1,130.69,130.61,129. 9,129.4,129.3,129.2,129.1,129.0,128.7,128.3,127.8,127.7,127.5,123.8,119.3,114.2,21.4,10.7.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 31 H23 ClNO3S + ,524.1082,found:524.1084.

[0047]

[0048] Example 5

[0049] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0050] A Schlenk reaction tube was sequentially added with a magnetic stirrer, 0.1 mmol of 1-(2-(arylalkynyl)benzoyl)indole (i.e., (3-methyl-1H-indol-1-yl)(2-((4-tert-butylphenyl)ethynyl)phenyl)methanone), 0.2 mmol of p-tolylthianthrene salt, 0.2 mmol of 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid, 20 mol% of the catalyst TMPA, and 1 mL of CH3CN. The tube was refrigerated and degassed, the atmosphere was purged with nitrogen three times, and the reaction was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution was added and extracted with dichloromethane, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain the sulfonylated benzazepine[1,2-a]indolone in a yield of 72%. 1 H NMR(600MHz,Chloroform-d)δ8.26(d,J=8.5Hz,1H),8.06(d,J=7.9Hz,1H),7.83(d,J=8.0Hz,1H),7.77(d,J=7.9Hz,1H),7.52–7.47(m,1H),7.42–7.35( m,3H),7.33(d,J=7.8Hz,1H),7.24–7.18(m,1H),7.08(d,J=8.2Hz,2H),6.85 –6.78(m,3H),6.04(d,J=8.2Hz,1H),2.17(s,3H),1.34(s,3H),1.27(s,9H). 13 C{ 1H}NMR(151MHz,Chloroform-d)δ168.1,153.0,143.9,142.9,139.4,138.4,136.5,135.36,135.31,132.9,131.3,130.5,130.0,129.7 ,129.5,129.4,129.3,129.0,128.8,128.3,127.6,127.3,125.4,124.0,123.7,119.2,114.2,34.7,31.3,21.4,10.2.HRMSm / z:[M+H] + Calcd for C 35 H 32 NO3S + ,546.2097,found:546.2098.

[0051]

[0052] Example 6

[0053] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0054] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, phenylthianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the tube was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone with a yield of 60%. 1H NMR(600MHz,Chloroform-d)δ8.31(d,J=8.5Hz,1H),8.12(d,J=8.0Hz,1H),7.89(d,J=7.7Hz,1H),7.78(d,J=7.8Hz,1H),7.57–7.51(m,1H),7.4 7(t,J=1.3Hz,1H),7.44–7.38(m,2H),7.34–7.27(m,5H),7.17–7.10(m, 2H),6.80–6.76(m,1H),6.22(d,J=8.0Hz,1H),2.39(s,3H),1.49(s,3H). 13 C{ 1 H}NMR(151MHz,Chloroform-d)δ168.0,144.5,141.3,140.0,138.6,136.6,135.5,135.3,133.1,132.3,131.1,130.5,130.0 ,129.7,129.4,129.39,129.37,129.0,128.5,128.2,128.0,127.6,127.4,123.7,119.2,114.2,21.4,10.5.HRMSm / z:[M+Na] + Calcd for C 31 H 23 NNaO3S + ,512.1291,found:512.1288.

[0055]

[0056] Example 7

[0057] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0058] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, p-methoxyphenylthianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the tube was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone in a yield of 66%. 1 H NMR(400MHz,Chloroform-d)δ8.38–8.30(m,1H),8.16(d,J=8.0Hz,1H),7.91(d,J=8.3Hz,1H),7.80(d,J=7.7Hz,1H),7.55(d,J=7.7Hz,1H),7.51–7.40( m,3H),7.36–7.26(m,3H),7.26(d,J=8.8Hz,3H),6.90–6.83(m,1H),6.62(d, J=8.9Hz,2H),6.30(d,J=8.0Hz,1H),3.77(s,3H),2.42(s,3H),1.51(s,3H). 13 C{ 1 H}NMR(151MHz,Chloroform-d)δ168.0,162.7,144.0,139.9,139.1,136.5,135.58,135.53,133.0,132.7,131.3,130.4,130.1,1 29.7,129.68,129.65,129.3,129.2,128.9,128.3,128.0,127.5,123.7,119.2,114.2,113.5,55.5,21.5,10.5.HRMSm / z:[M+Na] + Calcd for C 32 H 25 NNaO4S + ,542.1397,found:542.1386.

[0059]

[0060] Example 8

[0061] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0062] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, biphenylthianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the tube was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone with a yield of 46%. 1 H NMR(600MHz,Chloroform-d)δ8.33(d,J=8.5Hz,1H),8.15(d,J=7.9Hz,1H),7.93–7.89(m,1H),7.82(d,J=7.8Hz,1H),7.56(d ,J=7.6Hz,1H),7.48–7.40(m,7H),7.40–7.26(m,7H),6.74(d,J=7.9Hz,1H),6.20(d,J=7.9Hz,1H),2.40(s,3H),1.48(s,3H). 13 C{ 1 H}NMR(151MHz,Chloroform-d)δ168.0,145.2,144.3,140.0,139.8,139.3,136.6,135.5,135.4,133.2,131.1,130.5,130.0,129.9,129.45 ,129.40,129.3,129.2,129.0,128.9,128.49,128.40,128.0,127.9,127.6,127.2,126.8,123.7,119.2,114.2,21.5,10.5.HRMSm / z:[M+Na] + Calcd for C 37 H 27 NNaO3S + ,588.1604,found:588.1601.

[0063]

[0064] Example 9

[0065] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0066] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, p-tert-butylphenylthianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the reaction was carried out at room temperature under 10 W blue light at 430 nm for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone in a yield of 62%. 1 H NMR(400MHz,Chloroform-d)δ8.36(d,J=8.4Hz,1H),8.14(d,J=7.9Hz,1H),7.94–7.83(m,2H),7.60(d,J=7.6Hz,1H),7.52–7.39(m,3H),7.33 –7.26(m,3H),7.21(d,J=8.6Hz,2H),7.12(d,J=8.6Hz,2H),6.70–6.58(m,1H),6.07(d,J=8.0Hz,1H),2.39(s,3H),1.48(s,3H),1.25(s,9H). 13 C{ 1 H}NMR(151MHz,Chloroform-d)δ168.0,155.9,143.7,139.7,139.6,138.1,136.5,135.4,135.3,133.1,131.2,130.4,130.0,129. 9,129.4,129.39,129.30,128.9,128.2,127.9,127.5,127.2,125.1,123.7,119.1,114.2,34.9,30.9,21.4,10.4.HRMSm / z:[M+Na] + Calcd for C 35 H 31 NNaO3S + ,568.1917,found:568.1906.

[0067]

[0068] Example 10

[0069] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0070] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, p-fluorophenylthianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the tube was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone with a yield of 46%. 1 H NMR(600MHz,Chloroform-d)δ8.32(d,J=8.5Hz,1H),8.12–8.08(m,1H),7.88(d,J=7.8Hz,1H),7.81(d,J=7.8Hz,1H),7.55(d,J=1.4Hz ,1H),7.49–7.46(m,1H),7.43(d,J=7.5Hz,2H),7.34–7.29(m,4H),6.86–6.79(m,3H),6.24(d,J=7.9Hz,1H),2.40(s,3H),1.49(s,3H). 19 F NMR(376MHz,Chloroform-d)δ-104.7. 13 C{ 1 H} NMR (151MHz, Chloroform-d) δ 167.9, 164.8 (d, J = 255.4Hz), 144.6, 140.3, 138.5, 137.3 (d, J = 3.2Hz) 136.6, 135.5, 135.3, 133.2, 131.0, 130.6, 130. 2(d,J=9.6Hz),130.0,129.8,129.4,129.4,129.3,129.2,129.1,128.7,12 8.1,127.8,123.8,119.3,115.5,115.4,114.2,21.5,10.5.HRMSm / z:[M+Na] + Calcd for C 31H 22 FNNaO3S + ,530.1197,found:530.1192.

[0071]

[0072] Example 11

[0073] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0074] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., 0.1 mmol of (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone, 0.2 mmol of p-trifluoromethylphenylthianthrene salt, 0.2 mmol of 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid, 20 mol% of catalyst TMPA, and 1 mL of CH3CN were sequentially added to a Schlenk reaction tube. The tube was refrigerated and degassed, and nitrogen was purged three times. After sealing, the reaction was irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone in a yield of 56%. 1 H NMR(400MHz,Chloroform-d)δ8.37(d,J=8.4Hz,1H),8.12(d,J=8.0Hz,1H),7.95–7.84(m,2H),7.61(d,J=1.5Hz ,1H),7.55–7.37(m,7H),7.33–7.25(m,2H),6.71(d,J=8.1Hz,1H),6.15–6.07(m,1H),2.41(s,3H),1.50(s,3H). 19 F NMR(376MHz,Chloroform-d)δ-63.3. 13 C{ 1H}NMR(151MHz,Chloroform-d)δ167.8,144.9,144.7,140.4,138.4,136.7,1 35.4,135.0,133.7(q,J=32.7Hz),133.2,130.75,130.71,130.07,130.03,12 9.7,129.5,129.3,129.2,129.0,128.7,128.1,127.9,127.8,125.2(q,J=3.7 Hz),123.9,123.1(q,J=272.8Hz),119.3,114.3,21.4,10.6.HRMSm / z:[M+Na] + Calcd for C 32 H 22 F3NNaO3S + ,580.1165,found:580.1163.

[0075]

[0076] Example 12

[0077] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0078] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenylmethanone 0.1 mmol, p-formyl methylphenylthianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the tube was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone in a yield of 59%. 1H NMR(600MHz,Chloroform-d)δ8.33(d,J=8.5Hz,1H),8.16–8.12(m,1H),8.12–8.08( m,2H),7.91(d,J=7.7Hz,1H),7.82(d,J=7.9Hz,1H),7.58–7.55(m,1H),7.54–7.50( m,2H),7.49–7.45(m,1H),7.44–7.38(m,4H),7.35(d,J=8.5Hz,2H),7.33–7.28(m,2 H),6.77–6.72(m,1H),6.22(d,J=7.9Hz,1H),3.94(s,3H),2.40(s,3H),1.49(s,3H). 13 C{ 1 H}NMR(101MHz,Chloroform-d)δ168.0,166.6,144.5,143.9,143.6,140.7,140.1,138.7,136.6,135.5,135.3,133.2,131.0,130.6,130.2,130.0,12 9.98,129.90,129.5,129.3,129.26,129.22,129.1,128.7,128.1,128.0,1 27.7,127.2,127.0,123.8,119.3,114.2,52.3,21.5,10.6.HRMSm / z:[M+K] + Calcd for C 33 H 25 KNO5S + ,586.1085,found:586.1069.

[0079]

[0080] Example 13

[0081] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0082] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, p-cyanophenylthianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the reaction was carried out at room temperature under 10 W blue light at 430 nm for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone in a yield of 78%. 1 H NMR(400MHz,Chloroform-d)δ8.35(d,J=8.4Hz,1H),8.09(d,J=7.9Hz,1H),7.94–7.84(m,2H),7.64–7.57(m,1H ),7.54–7.43(m,7H),7.34(d,J=7.6Hz,2H),6.87–6.80(m,1H),6.21(d,J=7.9Hz,1H),2.44(s,3H),1.51(s,3H). 13 C{ 1 H}NMR(101MHz,Chloroform-d)δ167.6,145.9,145.4,140.7,137.6,136.7,135.7,135.0,133.4,131.8,130.7,130.6,130.0,129 .9,129.6,129.37,129.31,129.1,128.7,128.2,127.98,127.92,123.8,119.3,117.0,115.9,114.3,21.3,10.4.HRMSm / z:[M+Na] + Calcd for C 32 H 22 N2NaO3S + ,537.1243,found:537.1236.

[0083]

[0084] Example 14

[0085] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0086] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, 3,4-dimethoxyphenylthianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the reaction was carried out at room temperature under 10 W blue light at 430 nm for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone with a yield of 42%. 1 H NMR(400MHz,Chloroform-d)δ8.36–8.29(m,1H),8.15–8.09(m,1H),7.93(d,J=7.8Hz, 1H),7.81(d,J=7.8Hz,1H),7.56(d,J=7.6Hz,1H),7.51–7.40(m,3H),7.37–7.29(m,2H ),7.04(d,J=8.5,2.1Hz,1H),6.88(d,J=7.9Hz,1H),6.72(d,J=2.1Hz,1H),6.65(d,J= 8.6Hz,1H),6.29(d,J=7.9Hz,1H),3.85(s,3H),3.73(s,3H),2.42(s,3H),1.51(s,3H). 13 C{ 1 H}NMR(101MHz,Chloroform-d)δ168.1,152.6,148.6,144.3,139.9,139.4,136.6,135.8,135.7,133.3,131.5,130.8,130.3,130.2,129 .9,129.8,129.5,129.2,128.9,128.1,128.0,127.5,123.7,121.7,119.2,114.2,110.6,110.5,56.1,55.9,21.4,10.3.HRMSm / z:[M+Na] + Calcdfor C 33 H 27 NNaO5S + ,572.1502,found:572.1499.

[0087]

[0088] Example 15

[0089] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0090] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., 0.1 mmol of (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone, 0.2 mmol of benzothiophene thianthrene salt, 0.2 mmol of 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid, 20 mol% of catalyst TMPA, and 1 mL of CH3CN were sequentially added to a Schlenk reaction tube. The tube was refrigerated and degassed, nitrogen was purged three times, and the tube was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone in a yield of 43%. 1 H NMR(400MHz,Chloroform-d)δ8.33(d,J=8.4Hz,1H),8.15(d,J=7.9Hz,1H),7.97–7.86(m,2H),7.7 6–7.62(m,3H),7.52–7.29(m,8H),6.75–6.63(m,1H),5.85–5.72(m,1H),2.39(s,3H),1.36(s,3H). 13 C{ 1 H}NMR(101MHz,Chloroform-d)δ167.6,144.4,140.2,139.4,136.5,135.7,135.6,135.0,134.3,133.2,132.9,131.1,130.4,129.9,12 9.6,129.38,129.31,129.1,129.0,128.0,127.8,127.4,125.8,125.5,123.5,122.6,122.4,119.0,114.3,21.3,10.2.HRMSm / z:[M+Na] + Calcd for C 33 H 23 NNaO3S2 + ,568.1012,found:568.1007.

[0091]

[0092] Example 16

[0093] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0094] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, dibenzofuran thianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the tube was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone in a yield of 33%. 1 H NMR(600MHz,Chloroform-d)δ8.32(d,J=8.5Hz,1H),8.18(d,J=7.8Hz,1H),7.96–7.93(m,1H),7.86–7.80(m,3H),7.61–7.57(m,1H),7.56(d,J= 8.1Hz,1H),7.54–7.41(m,5H),7.39–7.30(m,4H),7.28(d,J=7.5Hz,1H) ,6.41(d,J=7.9Hz,1H),6.00(d,J=7.9Hz,1H),2.08(s,3H),1.43(s,3H). 13 C{ 1 H}NMR(151MHz,Chloroform-d)δ168.0,157.7,156.8,144.0,140.1,139.7,136 .5,135.6,135.4,135.2,133.2,131.1,130.5,130.0,129.9,129.49,129.45,12 9.3,129.16,129.14,128.4,128.3,127.9,127.6,126.2,123.9,123.7,123.5, 122.8,121.9,121.0,119.2,114.2,111.9,111.8,21.2,10.4.HRMSm / z:[M+NH4] + Calcd for C 37 H 29 N2O4S2 + ,597.1843,found:597.1798.

[0095]

[0096] Example 17

[0097] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0098] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, 2-bromopyridine thianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the tube was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone in a yield of 54%. 1 H NMR(400MHz,Chloroform-d)δ8.37(d,J=8.4Hz,1H),8.19(s,1H),8.10(d,J=7.9Hz,1H),7.96–7.87(m,2H),7.64–7 .60(m,1H),7.57–7.41(m,5H),7.37–7.24(m,3H),6.94–6.85(m,1H),6.28–6.18(m,1H),2.46(s,3H),1.52(s,3H). 13 C{ 1 H}NMR(101MHz,Chloroform-d)δ167.5,148.8,146.1,144.9,141.1,137.5,136.8,136.4,135.6,134.9,133.2,130. 7,129.9,129.7,129.5,129.4,129.2,128.6,128.3,128.0,127.5,123.9,119.2,114.4,21.4,10.4.HRMSm / z:[M+Na] + Calcd for C 30 H 21 BrN2NaO3S + ,591.0348,found:591.0338.

[0099]

[0100] Example 18

[0101] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0102] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, benzbromarone thianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the tube was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone in an 18% yield. 1 H NMR(600MHz,Chloroform-d)δ8.32(d,J=8.5Hz,1H),8.14(d,J=7.9Hz,1H),7.91(d,J=7.7H z,1H),7.87(s,2H),7.82(d,J=7.8Hz,1H),7.59–7.55(m,1H),7.49–7.38(m,4H),7.33(d,J= 7.7Hz,1H),7.30–7.26(m,2H),7.17(d,J=8.3Hz,1H),6.60(d,J=7.9Hz,1H),6.09(d,J=8.0H z,1H),3.97(s,3H),2.90(q,J=7.5Hz,2H),2.35(s,3H),1.47(s,3H),1.35(t,J=7.5Hz,3H). 13 C{ 1H}NMR(151MHz,Chloroform-d)δ169.8,167.9,158.1,151.9,144.3,140.1,137.7,136.6,136.3,135.3,133.5,133.2,131.0,130.5,130.0,129.9, 129.8,129.5,129.3,129.1,128.8,128.0,127.7,123.8,122.6,120.8,1 19.2,118.7,114.3,111.9,60.9,22.1,21.4,11.9,10.6.HRMSm / z:[M+Na] + Calcd for C 43 H 31 Br2NNaO6S + ,870.0131,found:870.0117.

[0103]

[0104] Example 19

[0105] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0106] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, gemfibrozil thianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the tube was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone with a yield of 80%. 1H NMR(600MHz,Chloroform-d)δ8.36(d,J=8.4Hz,1H),8.11(d,J=7.9Hz,1H),7.88–7.83(m,2H),7 .60–7.54(m,1H),7.49–7.38(m,3H),7.29(d,J=7.5Hz,1H),7.27–7.25(m,1H),6.92(s,1H),6.6 6–6.63(m,1H),6.35(s,1H),6.10(d,J=7.8Hz,1H),3.83(q,J=2.7Hz,2H),3.64(s,3H),2.35(s, 3H),2.33(s,3H),1.89(s,3H),1.72–1.66(m,2H),1.67–1.62(m,2H),1.44(s,3H),1.20(s,6H). 13 C{ 1 H}NMR(151MHz,Chloroform-d)δ178.1,168.2,159.9,143.0,139.7,139.5,136.5 ,136.2,135.24,135.22,132.8,132.1,131.4,130.4,130.1,130.0,129.6,129.42 ,129.40,129.1,128.9,128.1,127.7,127.5,123.7,123.6,119.1,114.3,113.4, 68.2,51.7,42.0,36.8,25.2,25.1,24.9,21.4,20.4,15.1,10.4.HRMSm / z:[M+Na] + Calcdfor C 41 H 41 NNaO6S + ,698.2547,found:698.2547.

[0107]

[0108] Example 20

[0109] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0110] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., 0.1 mmol of (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone, 0.2 mmol of indomethacin thianthrene salt, 0.2 mmol of 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid, 20 mol% of catalyst TMPA, and 1 mL of CH3CN were sequentially added to a Schlenk reaction tube. The tube was refrigerated and degassed, and nitrogen was purged three times. After sealing, the reaction was irradiated at room temperature under 10 W blue light at 430 nm for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone in a yield of 23%. 1 H NMR(400MHz,Chloroform-d)δ8.35(d,J=8.4Hz,1H),7.93(d,J=7.9Hz,1H),7.85(d ,J=7.7Hz,1H),7.66(d,J=7.7Hz,1H),7.58(s,2H),7.53–7.37(m,6H),7.28(d,J=7 .4Hz,1H),7.03(d,J=7.7Hz,1H),6.70(s,1H),6.63(s,1H),6.30(s,1H),5.90(s,1 H),3.79(s,3H),3.69(s,3H),3.60(s,2H),2.44(s,3H),2.17(s,3H),1.41(s,3H). 13 C{ 1 H}NMR(101MHz,Chloroform-d)δ170.5,168.4,167.3,152.9,141.7,140.1,139.5 ,139.1,136.4,135.8,135.1,133.8,132.8,132.4,131.7,130.9,130.1,130.0,12 9.7,129.4,129.3,129.2,129.0,128.7,128.3,127.2,127.0,126.9,123.4,118.9 ,116.4,114.1,112.2,100.5,56.5,51.9,29.8,21.0,13.0,10.0.HRMSm / z:[M+Na] + Calcd for C 45 H 35 ClN2NaO7S + ,805.1746,found:805.1743.

[0111]

[0112] Example 21

[0113] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0114] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, flurbiprofen thianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the tube was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone with a yield of 58%. 1 H NMR(400MHz,Chloroform-d)δ8.34(d,J=8.5Hz,1H),8.18–8.12(m,1H),7.92–7.84(m,2H),7.60–7.56(m,1H),7.50–7.41(m,3H),7.33–7.23(m,7 H),7.17–7.11(m,2H),6.71(d,J=8.0Hz,1H),6.15–6.09(m,1H),3.78–3. 73(m,1H),3.70(s,3H),2.38(s,3H),1.52(d,J=7.1Hz,3H),1.47(s,3H). 19 F{ 1 H}NMR(376MHz,Chloroform-d)δ-117.0. 13 C{ 1H}NMR(101MHz,Chloroform-d)δ174.0,167.9,159.8(d,J=249.2Hz),144.2,140 .6,140.0,139.6,136.6,135.6,135.3,133.2,131.2,130.5,130.4,130.1,129.9 ,129.4,129.3,128.9,128.6(d,J=3.3Hz),127.9,127.5,127.4,123.7(d,J=9.0 Hz),119.1,115.4(d,J=23.3Hz),114.2,52.0,44.9,18.2,10.3.HRMSm / z:[M+Na] + Calcd for C 41 H 32 FN1O5S + ,692.1887,found:692.1875.

[0115]

[0116] Example 22

[0117] The preparation method of the sulfonylated benzazepine [1,2-a] indole one compound of this embodiment comprises the following steps:

[0118] A magnetic stirrer, 1-(2-(arylalkynyl)benzoyl)indole, i.e., (3-methyl-1H-indol-1-yl)(2-(p-tolueneethynyl)phenyl ketone 0.1 mmol, p-formylbiphenylthianthrene salt 0.2 mmol, 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid 0.2 mmol, catalyst TMPA 20 mol%, and CH3CN 1 mL were added to a Schlenk reaction tube in sequence. The tube was refrigerated and degassed, nitrogen was purged three times, and the tube was sealed and irradiated with 10 W blue light at 430 nm at room temperature for 48 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain sulfonylated benzazepine[1,2-a]indolone in a yield of 42%. 1H NMR(600MHz,Chloroform-d)δ10.06(s,1H),8.32(d,J=8.4Hz,1H),8.14(d,J=7.9Hz, 1H),7.98–7.89(m,3H),7.81(d,J=7.8Hz,2H),7.62(d,J=8.1Hz,2H),7.56(d,J=7.6H z,2H),7.47(d,J=7.9Hz,1H),7.42(d,J=9.5Hz,3H),7.37(d,J=8.6Hz,2H),7.31(d,J =13.6Hz,2H),6.76(d,J=8.1Hz,1H),6.24(d,J=8.0Hz,1H),2.40(s,3H),1.49(s,3H). 13 C{ 1 H}NMR(151MHz,Chloroform-d)δ191.6,167.9,143.6,138.6,133.2,130.6,130.3,130.0,129.8,129.4,129 .3,129.2,129.1,128.1,127.8,127.7,127.1,123.8,119.2,114.2,21.5,10.5.HRMS(ESI-TOF)m / z:[M+Na] + Calcd for C 38 H 27 NNaO4S + ,616.1553,found:616.1548.

[0119]

[0120] Application Examples

[0121] The in vitro anti-cancer cell proliferation test was conducted using the cervical cancer cell Hela line, human colon cancer cell HCT116 line and A549 line as models, using the CellTiter-Glo (Promega, USA) test method. The specific test method is as follows: After diluting the cancer cell suspension to an appropriate concentration using culture medium, 95 μL was added to a 96-well plate. After adding 5 μL of the test compound at different concentrations, the culture plate was incubated at 37°C and 5% CO2 for 72 hours. The culture plate was removed and placed at room temperature to start the test. 20 μL of CellTiter-Glo reagent was added to each well and mixed on a shaker for 2 minutes to induce cell lysis. Incubate at room temperature for 10 minutes to stabilize the fluorescence signal. The fluorescence intensity was recorded using a multifunctional microplate reader. The cell viability was calculated according to the formula and the fluorescence intensity of the blank control group, and then the IC of the target compound was calculated. 50The results of some compounds are shown in Table 1.

[0122] Table 1 Antiproliferation activity of some compounds on tumor cell lines

[0123]

[0124] Figure 2 The graph shows the in vitro anti-tumor activity test results of the target product in Example 5. It can be seen that the compound exhibits certain anti-cancer activity against HELA cervical cancer cells, IC 50 =23.43 μmol / L. Therefore, the above results indicate that the compound prepared in the present invention has certain anti-tumor activity.

[0125] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a sulfonylated benzazepine [1,2-a] indole ketone compound, characterized in that: The steps are as follows: tri(4-methoxyphenyl)amine, 1-(2-(arylalkynyl)benzoyl)indole compound, arylthianthrene salt, and 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinic acid are added to a solvent, reacted at room temperature under inert gas conditions and visible light irradiation, and then post-processed to obtain; wherein the structural formula of the 1-(2-(arylalkynyl)benzoyl)indole compound is The structural formula of arylthianthrene salt is Wherein, R is H, Me, OMe, Cl, t Bu; Ar is an aromatic ring or an aromatic heterocyclic ring.

2. The method for preparing the sulfonylated benzazepine [1,2-a] indole one compound according to claim 1, characterized in that: The Ar is Any one of .

3. The method for preparing the sulfonylated benzazepine [1,2-a] indole one compound according to claim 2, characterized in that: The molar ratio of the 1-(2-(arylalkynyl)benzoyl)indole compound, arylthianthrene salt, 1,4-diazabicyclo[2.2.2]octane-1,4-disulfinic acid and tri(4-methoxyphenyl)amine is 1:1.5-2.5:1.5-2.5:0.1-0.

2.

4. The method for preparing the sulfonylated benzazepine [1,2-a] indole one compound according to claim 3, characterized in that: The solvent is any one of acetonitrile, ethyl acetate, dichloromethane and 1,2-dichloroethane.

5. The method for preparing the sulfonylated benzazepine [1,2-a] indole one compound according to any one of claims 1 to 4, characterized in that: The visible light is blue light, and the wavelength and power are 430nm and 10-20W respectively.

6. The method for preparing the sulfonylated benzazepine [1,2-a] indole one compound according to claim 5, characterized in that: The reaction time is 24-48 hours.

7. The method for preparing the sulfonylated benzazepine [1,2-a] indole one compound according to claim 6, characterized in that: The post-treatment steps are: after the reaction is completed, extraction is performed, the organic phase is collected, and purification is performed to obtain the product.

8. The method for preparing the sulfonylated benzazepine [1,2-a] indole one compound according to claim 7, characterized in that: The extraction solution used is saturated sodium chloride solution and dichloromethane.

9. A sulfonylated benzazepine [1,2-a] indole one compound prepared by the preparation method according to any one of claims 1 to 4 or 6 to 8, characterized in that: The general structural formula of the sulfonylated benzazepine [1,2-a] indole one compound is as follows: Wherein, R is H, Me, OMe, Cl, t Bu; Ar is an aromatic ring or an aromatic heterocyclic ring.

10. The sulfonylated benzazepine [1,2-a] indole one compound according to claim 9, characterized in that: The sulfonylated benzazepine [1,2-a] indole one compound is any one of the following compounds:

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