Compound with nine-ring side chain and organic electroluminescent device thereof

Abstract

The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to a compound with a nine-ring side chain and an organic electroluminescent device.The series of compounds contain a large conjugate fragment and a benzo five-membered heterocyclic ring or five-membered heterocyclic ring structure, sulfur and other heavy atoms contained in the large conjugate fragment can improve the spin-orbit coupling capacity, and therefore the stability of the compound is improved. According to the invention, charge transfer in molecules is enhanced, so that a higher anti-intersystem crossing coefficient is achieved, efficient conversion of triplet excitons can be realized, and loss of the excitons is reduced; meanwhile, the compound structure has an extremely remarkable intramolecular distortion structure, molecular stacking is effectively reduced, annihilation of carriers and excitons is inhibited, triplet-state excitons can be converted more efficiently, combination of the excitons in a light-emitting layer is guaranteed through cooperation of the structures of all the parts, and the light-emitting efficiency is improved. Therefore, the comprehensive performance of the organic light-emitting device is improved.

Description

Technical Field

[0001] This invention belongs to the field of organic electroluminescent materials technology, and particularly relates to a compound with a 9-ring side chain and its organic electroluminescent device. Background Technology

[0002] Organic electroluminescence (OEC) technology has undergone several generations of development, but its core challenge has always been how to efficiently utilize excitons generated under electroexcitation. Driven by an electric field, electrons and holes recombine to generate excitons, with singlet excitons accounting for approximately 25% and triplet excitons accounting for approximately 75%. Traditional fluorescent materials can only utilize singlet excitons for luminescence, thus limiting the theoretical upper limit of the device's quantum efficiency to 25%. To overcome this bottleneck, second-generation phosphorescent materials have introduced noble metals such as iridium and platinum, utilizing their strong spin-orbit coupling effect to achieve the capture and radiative emission of triplet excitons, resulting in an internal quantum efficiency of 100%. However, the dependence of phosphorescent materials on rare metals leads to high costs, and the stability of blue light-emitting materials remains a technical challenge, restricting their large-scale application.

[0003] To address the aforementioned contradictions, researchers proposed a general strategy of "sensitized luminescence." The core of this strategy lies in functional separation: one material acts as a "sensitizer," responsible for efficiently capturing and managing excitons; the other material acts as a "luminescence center," responsible for achieving efficient and stable light output. The sensitizer, acting as an energy transfer station, typically involves three key steps: energy absorption, energy transfer, and energy release. First, the sensitizer is excited by external energy; then, through mechanisms such as Förster resonance energy transfer or Dexter energy transfer, energy is transferred to a neighboring luminescent object; finally, the luminescent object completes radiative luminescence, while the sensitizer returns to its ground state. In this architecture, the sensitizer itself does not directly participate in luminescence but acts as an energy medium, enabling luminescent materials that are difficult to excite directly and efficiently to achieve optimal performance.

[0004] The emergence of thermally activated delayed fluorescence (TADF) materials has provided an ideal material choice for sensitizers. As a third-generation organic electroluminescent material, TADF materials, through ingenious molecular design, possess extremely small singlet-triplet energy level differences. Under thermal activation, triplet excitons can be converted into singlet excitons through a reverse intersystem crossing process, theoretically achieving 100% exciton utilization without relying on noble metals. Based on this, superfluorescence technology has emerged. This technology uses TADF materials as sensitizers, leveraging their ability to efficiently manage all excitons, and then precisely transferring singlet energy to traditional fluorescent materials with high fluorescence quantum yield and narrow spectral characteristics as the luminescent terminal through resonant energy transfer. This combination of TADF sensitizer and fluorescent emitter retains the inherent advantages of high color purity and good stability of fluorescent materials while successfully breaking through the 25% exciton utilization efficiency bottleneck, achieving a balance between high efficiency and high color purity.

[0005] Therefore, superfluorescence technology using TADF materials as the core sensitizer represents the cutting edge of current OLED material design. Future research will focus on developing TADF sensitizer systems with higher energy transfer efficiency and better stability, and further promote the practical application of this technology in high-quality displays and lighting by optimizing its energy level matching and spatial distribution with fluorescent guests. Thus, developing novel TADF materials with high luminous efficiency has become a key research direction for further development of OLED technology. By continuously optimizing molecular configurations and exploring novel donor-acceptor units and their spatial arrangements, it is hoped that the overall performance of materials can be improved while advancing the practical application of TADF materials in next-generation display technologies. Summary of the Invention

[0006] To address the problems existing in the background art, the present invention provides a compound having a nine-ring side chain, the structure of which is shown in general formula (I):

[0007] L is selected from single bond, substituted or unsubstituted C6-C. 12 Aromatic rings, either substituted or unsubstituted, are C3-C6 heteroaromatic rings; A and B are each independently selected from substituted or unsubstituted C6-C. 12 Aromatic ring or (I)-1, (I)-2, (I)-3, (I)-4, and at least one of A and B is selected from (I)-1, (I)-2, (I)-3, (I)-4: ; C is selected from structure (I)-5 or (I)-6: ; D is selected from any structure from (I)-7 to (I)-11: ; X1 is independently selected from NR3, O, S, and Se; X2 is independently selected from N and CR5; and E is independently selected from R2-substituted C6-C. 12 Aromatic rings or C3-C6 heteroaromatic rings; X3 is selected from O, S, and Se, and X4 is selected independently from NR3, O, S, and Se; * indicates a linkage site. R1 to R5 are each independently selected from hydrogen, deuterium, cyano, C1-C6 alkyl, substituted or unsubstituted C6-C. 12 Aryl or C3-C 12 heteroaryl groups; When substitution is present, the substituents are each independently selected from deuterium, cyano, C1-C6 alkyl, C6 ... 12 The aryl group, C3-C6 heteroaryl group, n is from 1 to the largest substitution site number of the ring, and the heteroatom is N.

[0008] As a preferred embodiment of the present invention, E is selected from an R2-substituted benzene ring.

[0009] As a preferred embodiment of the present invention, L is a single bond, phenyl, naphthyl or pyridyl.

[0010] As a preferred embodiment of the present invention, one of A and B is selected from (I)-1, (I)-2, (I)-3, and (I)-4.

[0011] As a preferred embodiment of the present invention, A and B are each independently selected from (I)-1 or (I)-2.

[0012] As a preferred embodiment of the present invention, at least one X4 in (I)-7, (I)-8, (I)-9, (I)-10, and (I)-11 is S.

[0013] As a preferred embodiment of the present invention, R1 to R5 are each independently selected from hydrogen, deuterium, cyano, methyl, tert-butyl, phenyl, and pyridyl. When substitutions are present, the substituents are each independently selected from deuterium, cyano, methyl, tert-butyl, phenyl, and pyridyl.

[0014] As a preferred embodiment of the present invention, the specific structure of the compound having a nonacyclic side chain is as follows: ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; .

[0015] Another object of the present invention is to provide an organic electroluminescent device having an anode, a cathode, and an organic layer, wherein the organic layer includes a light-emitting layer comprising the aforementioned compound having a nonacyclic side chain.

[0016] As a preferred embodiment of the present invention, the organic electroluminescent device is used to manufacture display devices, lighting sources, signal lights, and signs. The display devices include mobile phone displays, computer displays, television displays, smartwatch displays, smart car display panels, and VR or AR helmet displays.

[0017] The beneficial effects of this invention are as follows: The compound with a quinone ring side chain provided by this invention contains a large conjugated segment (quinone ring side chain) and a benzo[5] quinone heterocyclic or quinone heterocyclic structure. The heavy atoms such as sulfur contained in the large conjugated segment can improve spin-orbit coupling ability, which is beneficial to enhancing intramolecular charge transfer, thereby having a higher antisystem crossing coefficient (k). RISCThis invention enables highly efficient conversion of triplet excitons, reducing exciton loss. Simultaneously, the material structure exhibits a remarkably pronounced intramolecular twisted structure, effectively reducing molecular stacking and suppressing carrier and exciton annihilation, thus allowing for more efficient conversion of triplet excitons. The benzo[a]-5-membered heterocyclic structure leads to electron localization, not only more effectively separating charge transfer between adjacent atoms within the molecule and suppressing exciton annihilation, thereby increasing the radiative transition rate of the molecule and achieving high fluorescence quantum efficiency, but also effectively increasing carrier injection into the emitting layer, effectively reducing device voltage, and obtaining a suitable bandgap. This ensures greater overlap between the emission peak position and the absorption peak position of the doped material, achieving efficient energy transfer. Through the coordination between the various structural components, more efficient exciton energy transfer can be achieved, ensuring exciton binding in the emitting layer, thereby improving the overall performance of the organic electroluminescent device. Attached Figure Description

[0018] The accompanying drawings, which are included to provide a further understanding of the invention and form part of this invention, illustrate exemplary embodiments of the invention and are used to explain the invention, but do not constitute an undue limitation of the invention. In the drawings: Figure 1 This is the 1H NMR spectrum of compound 1 in this invention; Figure 2 This is a transient lifetime decay curve of compound 1 in this invention. Detailed Implementation

[0019] The technical solution of the present invention will be clearly and completely described below with reference to synthetic embodiments and device embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] Synthesis Examples

[0021] Example 1: Synthesis of Compound 1

[0022] Synthesis of 1-3: Under nitrogen atmosphere, 1-1 (5.8 g, 15.5 mmol), 1-2 (2.9 g, 17 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (0.18 g, 0.16 mmol), and potassium phosphate (4.4 g, 32 mmol) were placed in a 500 mL three-necked flask, and toluene / water = 150 mL / 75 mL was added. The mixture was heated to 60 °C and reacted at this temperature for 12 hours. After the reaction system cooled to room temperature, the organic phase was collected by separation, washed with brine, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined and dried with anhydrous magnesium sulfate. After drying, the solvent was removed by rotary evaporation under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain 1-3 (4.6 g, 81%). The molecular weight determined by mass spectrometry was 369.42 (theoretical value 369.28).

[0023] Synthesis of 1-4: Under a nitrogen atmosphere, 1-3 (18.0 g, 48.7 mmol) was dissolved in dichloromethane (97 mL) in a three-necked flask and cooled to 0 °C using an ice bath. m-chloroperoxybenzoic acid (12.00 g, 48.7 mmol) was added, and the mixture was stirred at 0 °C for 4 hours. After the reaction was complete, 50 mL of sodium bicarbonate aqueous solution was added, the organic layer was separated, recovered, and the organic reagents were removed under reduced pressure using a rotary evaporator to obtain 1-4 (17.1 g, 91%). The molecular weight determined by mass spectrometry was 385.14 (theoretical value 385.28). Synthesis of 1-5: Under a nitrogen atmosphere, 1-4 (18.4 g, 47.4 mmol) and dichloromethane (415 mL) were placed in a 1 L three-necked flask and cooled to 0 °C using an ice bath. At 0 °C, trifluoromethanesulfonic anhydride (TFAH) (28.2 g, 100 mmol) was added to the reaction system, and the reaction was continued for 2 hours. Then, 50 mL of saturated sodium hydroxide aqueous solution was added, and the reaction system was heated to 40 °C and stirred for 3 hours. After the reaction system cooled to room temperature, the organic layer was recovered, and the organic reagents were removed under reduced pressure using a rotary evaporator to obtain 1-5 (11.7 g, 70%). The molecular weight determined by mass spectrometry was 353.34 (theoretical value 353.23). Synthesis of 1-7: Under a nitrogen atmosphere, 1-5 (4.3 g, 12.1 mmol), benzophenone imine (2.90 g, 15.7 mmol), sodium tert-butoxide (NaOt-Bu) (1.70 g, 18.0 mmol), tris(dibenzylacetone)dipalladium (Pd2(dba)3) (110 mg, 0.12 mmol), bis(2-diphenylphosphine)phenyl ether (DPEphos) (129 mg, 0.24 mmol), and toluene (50 mL) were added. The reaction mixture was heated to 100 °C and stirred for 18 hours. After the reaction was complete, the reaction system was cooled to room temperature, and two-thirds of the solvent was removed by rotary evaporation under reduced pressure. Then, ethanol (25 mL) and water (3 mL) were added to the resulting mixture, and a solid precipitated. After filtration, the filter cake was washed with ethanol (10 mL), collected, and dried in a vacuum oven to obtain the crude product. The crude product was dissolved in dichloromethane (100 mL), and concentrated hydrochloric acid (1.5 mL, 17.6 mmol) was added to the reaction system. The mixture was stirred at room temperature for 18 hours. Then, 1 M NaOH (25 mL) was added to the mixture, and the organic phase was collected by separation. The aqueous layer was then extracted with dichloromethane. The organic layers were combined, washed with brine, dried on anhydrous magnesium sulfate, filtered, and concentrated under vacuum using a rotary evaporator. The crude raw material was purified by silica gel chromatography to obtain 1-7 (2.8 g, 80%), with a molecular weight determined by mass spectrometry of 289.18 (theoretical value 289.35). Synthesis of 1-9: Under a nitrogen atmosphere, 1-7 (13.0 g, 45 mmol), 1-8 (17.5 g, 45 mmol), tris(dibenzylacetone)dipalladium(0) (0.8 g, 0.9 mmol), 2-biscyclohexylphosphine-2',4',6'-triisopropylbiphenyl (x-phos) (0.4 g, 0.9 mmol), sodium tert-butoxide (6.5 g, 68 mmol), and 400 mL of toluene were added to a 1 L three-necked flask. The reaction mixture was heated to 110 °C and stirred for 8 hours. After the reaction was complete, the reaction mixture was cooled to room temperature. Add 300 mL of deionized water to the reaction system, collect the organic phase by separation, dry with anhydrous sodium sulfate, remove organic reagents under reduced pressure using a rotary evaporator, and purify the crude product by silica gel column chromatography to obtain 1-9 (15.4 g, 62%). The molecular weight determined by mass spectrometry is 550.62 (theoretical value 550.49). Synthesis of 1-10: Under a nitrogen atmosphere, 1-9 (11.4 g, 20.7 mmol), 1,3-bis(26-diisopropylphenyl)imidazolium chloride (IPrHCl) (0.36 g, 0.82 mmol), palladium(II) acetate (0.093 g, 0.41 mmol), potassium carbonate (5.8 g, 42 mmol), and 60 mL of N,N-dimethylacetamide (DMAc) were added to a 500 mL three-necked flask. The reaction system was heated to 140 °C and stirred for 12 hours. After the reaction was complete, it was cooled to room temperature. The precipitated solid in the reaction system was filtered, and the filter cake was washed three times with acetone. The filter cake was collected and dried in a vacuum oven to obtain 1-10 (3.6 g, 37%). The molecular weight determined by mass spectrometry was 469.72 (theoretical value 469.58). Synthesis of 1-12: Under a nitrogen atmosphere, 1-11 (6.9 g, 25.4 mmol) and tetrahydrofuran solution (120 mL) were added to a 1 L three-necked flask. After the reaction system was cooled to -60 °C, lithium diisopropylaminolithium (LDA) (29.2 mL, 58.4 mmol) was slowly added dropwise to the reaction system. After stirring for 2 hours, dimethylformamide (DMF) (5.9 mL, 76.2 mmol) was added to the reaction system, and stirring was continued for 30 minutes. Water was added, and the mixture was brought to room temperature. The mixture was extracted with ethyl acetate, and the extracted organic layer was washed with brine and dried with anhydrous Na2SO4. After drying, the solvent was removed by rotary evaporation under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain 1-12 (7.2 g, 86%). The molecular weight determined by mass spectrometry was 328.04 (theoretical value 327.91). Synthesis of 1-14: 1-12 (7.9 g, 24 mmol), 1-13 (6.3 g, 50 mmol), and urea nitrate (0.9 g, 7 mmol) were placed together in a mortar under solvent-free conditions and ground and mixed at room temperature, with thin-layer chromatography (TCL) monitoring the process. After the reaction was complete, the crude product was poured into ice water and stirred for 30 minutes. The mixture was then filtered, and the solid residue was recrystallized from ethanol to obtain 1-14 (10.5 g, 81%). The molecular weight determined by mass spectrometry was 538.08 (theoretical value 538.22). Synthesis of 1-15: Under a nitrogen atmosphere, 1-14 (7.1 g, 13.2 mmol), cuprous cyanide (CuCN) (5.9 g, 66 mmol), and N,N-dimethylformamide (DMF) (40 mL) were placed in a 100 mL three-necked flask, heated to 150 °C, and stirred at this temperature for 8 hours. After the reaction was complete, the mixture was cooled to room temperature, and 18 mL of ammonia was added to the reaction system. The organic layer was extracted with dichloromethane, washed with water and brine, collected, and dried over anhydrous magnesium sulfate. After drying, the solvent was removed under reduced pressure using a rotary evaporator. The crude product obtained after solvent removal under reduced pressure was purified by silica gel column chromatography to obtain 1-15 (4.8 g, 84%). The molecular weight determined by mass spectrometry was 430.31 (theoretical value 430.45). Synthesis of 1-17: Under nitrogen atmosphere, 1-15 (4.3 g, 10 mmol), 1-16 (2.4 g, 10 mmol), cesium carbonate (8.2 g, 25 mmol), and N,N-dimethylformamide (50 mL) were added to a 250 mL two-necked flask. The reaction was carried out overnight at 120 °C under nitrogen protection. Heating was stopped, and after cooling to room temperature, 150 mL of water was added and stirred for 10 min. A large amount of white solid precipitated. The solid was filtered, and the filter cake was washed with ethanol for 2 h. After cooling, the solid was filtered again to obtain 1-17 (4.5 g, 69%). The molecular weight determined by mass spectrometry was 653.89 (theoretical value 653.75). Synthesis of Compound 1: Under a nitrogen atmosphere, 1-17 (6.5 g, 10 mmol), 1-10 (4.7 g, 10 mmol), cesium carbonate (8.2 g, 25 mmol), and N,N-dimethylformamide (50 mL) were added to a 250 mL two-necked flask. The reaction was carried out overnight at 120 °C under nitrogen protection. Heating was stopped, and after cooling to room temperature, 150 mL of water was added and stirred for 10 min. A large amount of white solid precipitated. The solid was filtered, and the filter cake was washed with ethanol for 2 h. After cooling, the solid was filtered again to obtain Compound 1 (8.1 g, 73%). The molecular weight determined by mass spectrometry was 1103.15 (theoretical value 1103.32).

[0024] Example 2: Synthesis of Chemical 20

[0025] Synthesizing method 20-2 is the same as that of 1-3, except that 1-1 is replaced by 20-1. Mass spectrometry analysis determined the molecular weight to be 369.14 (theoretical value 369.28). Synthesizing method 20-3 is the same as that of 1-4, except that 1-3 is replaced by 20-2. Mass spectrometry analysis determined the molecular weight to be 385.17 (theoretical value 385.28). Synthesizing method 20-4 is the same as that of 1-5, except that 1-4 is replaced by 20-3. Mass spectrometry analysis determined the molecular weight to be 353.09 (theoretical value 353.23). Synthesizing method 20-5 is the same as that of 1-7, except that 1-5 is replaced by 20-4. Mass spectrometry analysis determined the molecular weight to be 289.21 (theoretical value 289.35). The synthesis methods for 20-7 and 1-9 are the same, except that 1-7 is replaced by 20-5 and 1-8 by 20-6. The molecular mass determined by mass spectrometry is 550.33 (theoretical value 550.49). The synthesis methods for 20-8 and 1-10 are the same, except that 1-9 is replaced by 20-7. The molecular mass determined by mass spectrometry is 469.44 (theoretical value 469.58). Synthesis of 20-10: 20-9 (3.4 g, 24 mmol), 1-13 (3.1 g, 25 mmol), and urea nitrate (0.4 g, 3.5 mmol) were placed together in a mortar under solvent-free conditions and ground and mixed at room temperature, with thin-layer chromatography (TCL) monitoring the process. After the reaction was complete, the crude product was poured into ice water and stirred for 30 minutes. The mixture was then filtered, and the solid residue was recrystallized from ethanol to obtain 20-10 (5.2 g, 88%). The molecular weight determined by mass spectrometry was 247.12 (theoretical value 247.26). Synthesis of 20-11: Under a nitrogen atmosphere, 20-10 (5.3 g, 21.5 mmol), copper bromide (6 g, 42 mmol), palladium acetate (0.25 g, 1.1 mmol), and N,N-dimethylacetamide (DMA) (50 mL) were added to a dried 1 L round-bottom flask. The reaction mixture was placed in an oil bath at 120 °C and stirred for 12 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, and ethyl acetate (50 mL) was mixed with the reaction system. The organic layer was washed with saturated sodium bicarbonate solution and dried with anhydrous sodium sulfate. After drying, the organic solvent was removed by rotary evaporation under reduced pressure. The crude product was purified by silica gel column chromatography to give 20-11 (3.9 g, 45%), with a molecular weight determined by mass spectrometry of 404.91 (theoretical value 405.05). Synthesis of 20-12: 16.6 g (41 mmol) of 20-11 was placed in a 1 L three-necked flask, and anhydrous THF (400 mL) solution was added. Nitrogen gas was purged three times. At -78 °C, LDA (2.0 M, 49 mmol) was added dropwise to the reaction solution. After stirring for 1 hour at the same temperature, 21 g (82 mmol) of iodine in THF (200 mL) solution was added dropwise to the reaction system. The reaction mixture was stirred at -78 °C for another 1 hour and then gradually brought to room temperature. The reaction solution was quenched with HCl (3M, 100mL), and the mixture was stirred for 0.5h. The organic layer was separated, the aqueous layer was extracted with ethyl acetate, the organic phase was collected, and dried with anhydrous Na2SO4. After drying, the solvent was removed by rotary evaporation under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain 20-12 (17.4g, 80%). The molecular weight determined by mass spectrometry was 530.81 (theoretical value 530.95). Synthesis of 20-14: 20-12 (20.2 g, 38 mmol), 20-13 (5.0 g, 41 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (0.44 g, 0.38 mmol), and potassium carbonate (11 g, 76 mmol) were placed in a 1 L three-necked flask. The mixture was purged with nitrogen three times. Under a nitrogen atmosphere, toluene / ethanol / water = 400 mL / 100 mL / 200 mL was added. The mixture was heated to 60 °C and reacted at this temperature for 12 hours. After the reaction system cooled to room temperature, the organic phase was collected by separation and washed with brine. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, and dried with anhydrous magnesium sulfate. After drying, the solvent was removed by rotary evaporation under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain 20-14 (16.3 g, 89%). The molecular weight determined by mass spectrometry was 481.31 (theoretical value 481.15). Compound 20-15 was synthesized using the same method as compound 1-15, except that 1-14 was replaced by 20-14. The molecular weight determined by mass spectrometry was 373.26 (theoretical value 373.38). Compound 20-17 was synthesized using the same method as compound 1-17, except that 1-15 was replaced by 20-15 and 1-16 by 20-16. The molecular weight determined by mass spectrometry was 672.92 (theoretical value 672.78). Compound 20 was synthesized using the same method as compound 1, except that 1-17 was replaced by 20-17 and 1-10 by 20-8. The molecular weight determined by mass spectrometry was 1122.19 (theoretical value 1122.35).

[0026] Example 3: Synthesis of Compound 37

[0027] Synthesis of 37-3: Under a nitrogen atmosphere, 37-1 (14.5 g, 39 mmol), 37-2 (g, 43 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (9.4 g, 0.39 mmol), and potassium carbonate (80 mmol) were placed in a 1 L three-necked flask, along with 400 mL of dioxane and 200 mL of water. The reaction system was then heated to 65 °C and reacted at this temperature for 12 hours. After the reaction system cooled to room temperature, the organic phase was collected by separation, washed with brine, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined and dried with anhydrous magnesium sulfate. After drying, the solvent was removed by rotary evaporation under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain 37-3 (8.4 g, 64%). The molecular weight determined by mass spectrometry was 338.33 (theoretical value 338.2). Synthesis of 37-4: Under a nitrogen atmosphere, 37-3 (2.4 g, 7 mmol), 4 M HCl (17.5 mL, 70 mmol), and 25 mL acetonitrile were added to a 100 mL three-necked flask, and the mixture was stirred thoroughly. The reaction system was cooled to 0 °C, and at this temperature, an aqueous solution of NaNO2 (7.7 mL, 7.7 mmol, 1 M) was slowly added dropwise, and the mixture was stirred for 45 minutes. Subsequently, under stirring at 0 °C, an aqueous solution of KI (8.8 mL, 17.5 mmol, 2 M) was slowly added dropwise to the reaction system, and the mixture was stirred for 5 minutes. The temperature was then raised to room temperature, and the mixture was stirred for 2 hours until the reaction was complete. The mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the organic phase was removed by rotary evaporation under reduced pressure. The crude product was purified by silica gel column chromatography to obtain 37-4 (2.3 g, 74%), with a molecular weight determined by mass spectrometry of 449.24 (theoretical value 449.09). Synthesis of 37-5: Under a nitrogen atmosphere, 37-4 (2.2 g, 5 mmol) was dissolved in dichloromethane (30 mL) in a 100 mL three-necked flask. Then, m-CPBA (2.03 g, 10 mmol) was added in portions. After the m-CPBA was completely dissolved, the reaction solution was cooled to 0 °C. Trifluoroacetic acid (TfOH) (1.3 mL, 15 mmol) was then added dropwise to the reaction system. After the addition was complete, the reaction system was gradually brought back to room temperature, and stirring was continued for 2 hours. After the reaction was complete, dichloromethane was removed under reduced pressure using a rotary evaporator. 100 mL of diethyl ether was added to the reaction residue, and the mixture was stirred at room temperature for 30 minutes. The residue was filtered to obtain a filter cake, which was repeatedly washed with diethyl ether. The filter cake was collected and dried in a vacuum oven to obtain 37-5 (1.8 g, 60%). The molecular weight determined by mass spectrometry was 596.99 (theoretical value 597.14). Synthesis of 37-6: Under a nitrogen atmosphere, 37-5 (6.0 g, 10 mmol), cesium carbonate (13.0 g, 40 mmol), S8 (1.3 g, 5 mmol), and 200 mL of DMSO were added to a 500 mL three-necked flask. The resulting mixture was stirred at 95 °C for 2 hours. After the reaction system cooled to room temperature, 20 mL of water was added. The reaction mixture was extracted with ethyl acetate, and the organic layers were combined and dried over anhydrous sodium sulfate. The organic phase was purified by column chromatography after removing the solvent under reduced pressure using a rotary evaporator, yielding 37-6 (2.9 g, 81%) with a molecular weight determined by mass spectrometry of 353.38 (theoretical value 353.23). Synthesis of 37-7: Under a nitrogen atmosphere, 2,2,6,6-tetramethylpiperidine (26.1 mL, 153 mmol) and THF (236 mL) were added to a 1 L three-necked flask and cooled to 0 °C using an ice bath. Then, n-butyllithium (1.6 M hexane solution) (96 mL, 153 mmol) was slowly added dropwise to the reaction system. Stirring was continued at 0 °C for 30 minutes. The reaction system was then cooled to -78 °C, and triisopropyl borate (33.3 g, 177 mmol) and 37-6 (41.7 g, 118 mmol) were added sequentially. The reaction system was then slowly heated from -78 °C to room temperature. After the reaction was complete, 100 mL of 10% hydrochloric acid was added dropwise. Subsequently, liquid-liquid extraction was performed, the organic layer was collected, and washed with petroleum ether to obtain 37-7 (32.8 g, 54%). The molecular weight determined by mass spectrometry was 397.19 (theoretical value 397.05). Synthesis of 37-8: Under a nitrogen atmosphere, 37-7 (41.3 g, 104 mmol), N-chlorosuccinimide (NCS) (13.94 g, 104 mmol), cuprous chloride (I) (10.34 g, 104 mmol), and acetonitrile (348 mL) were added to a 1 L three-necked flask and stirred at 65 °C for 6 hours. After the reaction was complete, 250 mL of dichloromethane and 150 mL of water were added. The organic phase was collected by separation, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure using a rotary evaporator. The crude product was purified by silica gel column chromatography to obtain 37-8 (27.4 g, 68%). The molecular weight determined by mass spectrometry was 387.79 (theoretical value 387.68). Synthesized by the same method as 1-9, 37-10 is synthesized by replacing 1-8 with 37-8 and 1-7 with 37-9. The molecular weight determined by mass spectrometry is 505.89 (theoretical value 506.03). Synthesized by the same method as 1-10, 37-11 is synthesized by replacing 1-9 with 37-10. The molecular weight determined by mass spectrometry is 469.43 (theoretical value 469.58). Synthesis of 37-12: Under a nitrogen atmosphere, 1-1 (6.9 g, 25.4 mmol) and tetrahydrofuran solution (60 mL) were added to a 1 L three-necked flask. After the reaction system was cooled to -60 °C, lithium diisopropylaminolithium (LDA) (14.6 mL, 29.2 mmol) was slowly added dropwise to the reaction system. After stirring for 2 hours, dimethylformamide (DMF) (3.0 mL, 38.1 mmol) was added to the reaction system, and stirring was continued for 30 minutes. Water was added, and the mixture was brought to room temperature. The mixture was extracted with ethyl acetate, and the extracted organic layer was washed with brine and dried with anhydrous Na2SO4. After drying, the solvent was removed by rotary evaporation under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain 37-12 (5.9 g, 78%). The molecular weight determined by mass spectrometry was 299.76 (theoretical value 299.90). Synthesis of 37-14: Under nitrogen protection, 37-12 (4.3 g, 14.4 mmol), 37-13 (1.3 g, 12 mmol), and sodium cyanide (0.6 g, 12 mmol) were added sequentially to a 1 L three-necked flask and dissolved in 60 mL of N,N-dimethylformamide (DMF). The reaction was carried out in an oil bath at 100 °C for 6 hours. After the reaction was completed by TLC monitoring, the reaction system was cooled to room temperature, and 80 mL of water was added for extraction with ethyl acetate. The organic phase was concentrated and then purified by column chromatography to obtain 37-14 (2.1 g, 45%). The molecular weight determined by mass spectrometry was 388.82 (theoretical value 388.99). The synthesis method of 37-15 is the same as that of 20-12, except that 20-11 is replaced by 37-14. The molecular mass determined by mass spectrometry is 514.75 (theoretical value 514.89). The synthesis method of 37-16 is the same as that of 20-14, except that 20-12 is replaced by 37-15. The molecular mass determined by mass spectrometry is 464.95 (theoretical value 465.09). The synthesis method of 37-17 is the same as that of 1-15, except that 1-14 is replaced by 37-16. The molecular mass determined by mass spectrometry is 357.15 (theoretical value 357.32). The synthesis method of 37-19 is the same as that of 1-17, except that 1-15 is replaced by 37-17 and 1-16 is replaced by 37-18. The molecular mass determined by mass spectrometry is 670.56 (theoretical value 670.70). Compound 37 was synthesized using the same method as compound 1, except that 37-19 replaced 1-17 and 37-11 replaced 1-10. The molecular mass determined by mass spectrometry was 1120.37 (theoretical value 1120.27).

[0028] Example 4: Synthesis of Compound 68

[0029] Synthesis of 68-1: Under a nitrogen atmosphere, 37-5 (6.0 g, 10 mmol), KOt-Bu (4.5 g, 40 mmol), Se (2.4 g, 30 mmol), and 200 mL of DMSO were added to a 500 mL three-necked flask. The resulting mixture was stirred at 100 °C for 2 hours. After the reaction system cooled to room temperature, 15 mL of water was added. The reaction mixture was extracted with ethyl acetate, and the organic layers were combined and dried over anhydrous sodium sulfate. The organic phase was purified by column chromatography after removing the solvent under reduced pressure using a rotary evaporator, yielding 68-1 (3.2 g, 79%) with a molecular weight determined by mass spectrometry of 400.00 (theoretical value 400.14). Synthesis of 68-2: Under a nitrogen atmosphere, 68-1 (30.4 g, 76 mmol), tert-butylcarbamate (NH₂BOC) (124 mg, 106 mmol), Pd₂(dba)₃.CHCl₃ (104 mg, 10.0 mmol), 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl (X-phos) (145 mg, 34.0 mmol), sodium tert-butoxide (NaOt-Bu) (107 mg, 111.0 mmol), and toluene (300 mL) were added to a 500 mL three-necked flask. The reaction mixture was then heated to 60 °C and reacted for 12 hours. After the reaction was complete, the mixture was diluted with ethyl acetate and water, and neutralized with 1 M hydrochloric acid. The organic layer was separated, washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. The crude product obtained in the previous step was dissolved in a mixed solution of dioxane (0.49 mL, 1.97 mmol) and dichloromethane (1.5 mL) containing 4 M hydrochloric acid. The solution was stirred at room temperature for 3 hours. The mixture was diluted with ethyl acetate, poured into ice water, neutralized with saturated sodium bicarbonate solution, washed with brine, dried over anhydrous sodium sulfate, and then concentrated. The crude product was purified by silica gel column chromatography to give 68-2 (21.7 g, 85%), with a molecular weight determined by mass spectrometry of 336.12 (theoretical value 336.26). The synthesis method of 68-3 is the same as that of 1-9, the difference being that 1-7 is replaced by 68-2 and 1-8 is replaced by 20-6. The molecular mass determined by mass spectrometry is 552.81 (theoretical value 552.95). The synthesis method of 68-4 is the same as that of 1-10, the difference being that 1-9 is replaced by 68-3. The molecular mass determined by mass spectrometry is 516.32 (theoretical value 516.49). Synthesis of 68-5: Under nitrogen protection, 1-12 (3.3 g, 10 mmol), 37-13 (2.6 g, 24 mmol) and sodium cyanide (1.2 g, 24 mmol) were added sequentially to a 1 L three-necked flask and dissolved in 60 mL of N,N-dimethylformamide (DMF). The reaction was carried out in an oil bath at 100 °C for 6 hours. After the reaction was completed by TLC monitoring, the reaction system was cooled to room temperature, 80 mL of water was added, and the mixture was extracted with ethyl acetate. The organic phase was concentrated and then purified by column chromatography to obtain 68-5 (2.3 g, 45%). The molecular weight determined by mass spectrometry was 505.97 (theoretical value 506.10). Compound 68-6 was synthesized using the same method as compound 1-15, except that 1-14 was replaced with 68-5. The molecular weight determined by mass spectrometry was 398.17 (theoretical value 398.33). Compound 68-8 was synthesized using the same method as compound 1-7, except that 1-15 was replaced with 68-6 and 1-16 with 68-7. The molecular weight determined by mass spectrometry was 698.45 (theoretical value 698.59). Compound 68 was synthesized using the same method as compound 1, except that 1-17 was replaced with 68-8 and 1-10 with 68-5. The molecular weight determined by mass spectrometry was 1194.89 (theoretical value 1195.07).

[0030] Example 5: Synthesis of Compound 106

[0031] The synthesis methods for 106-2 and 37-3 are the same, except that 106-1 is used instead of 37-1. Mass spectrometry analysis determined the molecular weight to be 338.34 (theoretical value 338.2). The synthesis methods for 106-3 and 37-4 are the same, except that 106-2 is used instead of 37-3. Mass spectrometry analysis determined the molecular weight to be 449.23 (theoretical value 449.09). The synthesis methods for 106-4 and 37-5 are the same, except that 106-3 is used instead of 37-4. Mass spectrometry analysis determined the molecular weight to be 597.01 (theoretical value 597.14). The synthesis methods for 106-5 and 68-1 are the same, except that 106-4 is used instead of 37-5. Mass spectrometry analysis determined the molecular weight to be 399.97 (theoretical value 400.14). The synthesis methods for 106-6 and 68-2 are the same, except that 68-1 is replaced by 106-5. The molecular mass determined by mass spectrometry is 336.38 (theoretical value 336.26). The synthesis methods for 106-8 and 1-9 are the same, except that 1-7 is replaced by 106-6 and 1-8 is replaced by 106-7. The molecular mass determined by mass spectrometry is 552.78 (theoretical value 552.95).The synthesis methods for 106-9 and 1-10 are the same, except that 1-9 is replaced by 106-8. The molecular weight determined by mass spectrometry is 516.62 (theoretical value 516.49). The synthesis methods for 106-10 and 20-12 are the same, except that 20-11 is replaced by 1-1. The molecular weight determined by mass spectrometry is 397.64 (theoretical value 397.78). The synthesis methods for 106-12 and 20-14 are the same, except that 20-12 is replaced by 106-10 and 20-13 is replaced by 106-11. The molecular weight determined by mass spectrometry is 419.21 (theoretical value 419.08). The synthesis methods for 106-13 and 20-12 are the same, except that 20-11 is replaced by 106-12. The molecular weight determined by mass spectrometry is 544.81 (theoretical value 544.98). The synthesis methods of 106-15 and 20-14 are the same, the difference being that 106-13 replaces 20-12 and 106-14 replaces 20-13. The molecular mass determined by mass spectrometry is 502.05 (theoretical value 502.19).Compound 106-16 was synthesized using the same method as compound 1-15, except that 1-14 was replaced by 106-15. The molecular weight determined by mass spectrometry was 394.30 (theoretical value 394.42). Compound 106-18 was synthesized using the same method as compound 1-17, except that 1-15 was replaced by 106-16 and 1-16 by 106-17. The molecular weight determined by mass spectrometry was 549.53 (theoretical value 549.67). Compound 106 was synthesized using the same method as compound 1, except that 1-17 was replaced by 106-18 and 1-10 by 106-19. The molecular weight determined by mass spectrometry was 1045.98 (theoretical value 1046.15).

[0032] Example 6: Synthesis of Compound 125

[0033] Synthesis of 125-3: Under a nitrogen atmosphere, 125-1 (10.6 g, 38 mmol), 125-2 (10.4 g, 41 mmol), tetra(triphenylphosphine)palladium (Pd(PPh3)4) (0.44 g, 0.38 mmol), tetrabutylammonium bromide (TBAB) (38 mmol), and potassium carbonate (11 g, 76 mmol) were placed in a 1 L three-necked flask. The mixture was purged with nitrogen three times. Under a nitrogen atmosphere, 300 mL of dioxane and 100 mL of water were added. The reaction system was heated to 80 °C and reacted for 12 hours. After the reaction system cooled to room temperature, the organic phase was collected by separation, washed with brine, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined and dried with anhydrous magnesium sulfate. After drying, the solvent was removed by rotary evaporation under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain 125-3 (10.1 g, 65%). The molecular weight determined by mass spectrometry was 407.84 (theoretical value 407.68). Synthesis of 125-4: Under nitrogen atmosphere, 125-3 (25.1 g, 61.6 mmol) and DMF (168 mL) were added to a 250 mL three-necked flask and dissolved. Cesium carbonate (30.11 g, 61.6 mmol) was added to the reaction system, and the temperature was raised to 75 °C for 4 hours. After the reaction solution cooled to room temperature, deionized water (200 mL) was added. A large amount of solid precipitated with stirring. After stirring for another hour, the mixture was filtered, and the filter cake was washed with petroleum ether to obtain 125-4 (19.6 g, 82%). The molecular weight determined by mass spectrometry was 387.54 (theoretical value 387.68). The synthesis method of 125-6 is the same as that of 1-9, the difference being that 1-8 is replaced by 125-4 and 1-7 is replaced by 125-5. The molecular mass determined by mass spectrometry is 550.35 (theoretical value 550.49). The synthesis method of 125-7 is the same as that of 1-10, the difference being that 1-9 is replaced by 125-6. The molecular mass determined by mass spectrometry is 469.44 (theoretical value 469.58). Synthesis of 125-8: Under a nitrogen atmosphere, 37-17 (4.5 g, 12.5 mmol), 70 mL of dioxane, and 40 mL of water were added to a 1 L three-necked flask. Then, 1.5 mL of ammonia (30 wt%) was added to the flask. The reaction system was heated to 80 °C and stirred for 10 hours at this temperature. After the reaction was complete, the reaction solvent was cooled to room temperature. Extraction was performed with ethyl acetate, and the organic phase was collected and dried with anhydrous sodium sulfate. The solvent was removed from the organic phase using a rotary evaporator under reduced pressure, and the residue was purified by silica gel column chromatography to obtain a solid, yielding 125-8 (4.2 g, 95%). The molecular weight determined by mass spectrometry was 354.22 (theoretical value 354.34). Synthesis of 125-9: Under a nitrogen atmosphere, 125-8 (18.1 g, 51 mmol), iodine (26 g, 102 mmol), and 125 mL of acetonitrile were added to a 500 mL three-necked flask. Then, tert-butyl nitrite (t-BuONO) (10 g, 102 mmol) was added to the reaction system, and the mixture was stirred at 25 °C for 8 hours. After the reaction was complete, 50 mL of saturated sodium bisulfite aqueous solution was added to the reaction solution. The reaction system was separated, and the organic phase was collected and dried using anhydrous sodium sulfate. The organic phase was subjected to reduced pressure to remove the solvent from the obtained solution using a rotary evaporator, and purified by silica gel column chromatography to obtain 125-9 (14.2 g, 60%). The molecular weight determined by mass spectrometry was 465.06 (theoretical value 465.23). Compound 125-11 was synthesized using the same method as compound 20-14, except that 20-12 was replaced by 125-9 and 20-13 by 125-10. The molecular weight determined by mass spectrometry was 656.58 (theoretical value 656.72). Compound 125 was synthesized using the same method as compound 1, except that 1-17 was replaced by 125-11 and 1-10 by 125-7. The molecular weight determined by mass spectrometry was 1106.42 (theoretical value 1106.29).

[0034] Example 7: Synthesis of Compound 215

[0035] Synthesis of 215-2: Under nitrogen protection and at -78°C, a THF / hexane solution of LDA (10.5 mL, 2.0 M, 21 mmol) was slowly added to a THF solution of 215-1 (2.3 g, 10 mmol) (60 mL). After the addition was complete, the mixture was stirred at -78°C for 1 hour. Subsequently, trichlorosilane (3.3 g, 21 mmol) was added to the reaction mixture, and the mixture was slowly heated to room temperature and stirred for 12 hours. After the reaction was complete, the reaction solution was filtered through a diatomaceous earth filter and washed with dichloromethane. The filtrate was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (petroleum ether) to give 215-2 (3.1 g, 82%), with a molecular weight determined by mass spectrometry of 375.42 (theoretical value 375.53). Synthesis of 215-3: Under a nitrogen atmosphere, 215-2 (0.55 g, 1.46 mmol) was dissolved in 3 mL of carbon tetrachloride, and the reaction system was lowered to -15 °C. Then, 3.0 mL of a carbon tetrachloride solution containing bromine (1.20 mL, 2.96 mmol) was slowly added dropwise to the reaction system. After the addition was complete, the mixture was stirred at -15 °C for 60 minutes, then slowly heated to room temperature and stirred for another 60 minutes. After the reaction was complete, water was added to quench the reaction. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and the organic reagents were removed under reduced pressure using a rotary evaporator to obtain 215-3 (0.49 g, 86%). The molecular weight determined by mass spectrometry was 388.84 (theoretical value 388.96). Synthesis of 215-4: Under a nitrogen atmosphere, 215-3 (25.0 g, 64.3 mmol) and THF (tetrahydrofuran) (643 mL) were placed in a 1000 mL three-necked flask. The reaction system was cooled to -78 °C, and then n-BuLi solution (2.7 M hexane solution) (24.47 mL, 67.5 mmol) was added dropwise. After the addition was complete, the mixture was stirred at -78 °C for 2 hours. Then, iodine (19.59 g, 77 mmol) was added to the reaction system while stirring and slowly restoring to room temperature. After restoring to room temperature, saturated sodium bisulfite aqueous solution (100 mL) was added to the reaction system. The organic layer was extracted with ethyl acetate, collected, dried over anhydrous magnesium sulfate, and the organic solvent was removed under reduced pressure using a rotary evaporator. The concentrated compound was purified by silica gel column chromatography to obtain 215-4 (23.0 g, 82%), and the molecular weight determined by mass spectrometry was 435.82 (theoretical value 435.96). The synthesis method of 215-5 is the same as that of 1-3, except that 1-1 is replaced by 215-4. The molecular mass determined by mass spectrometry is 432.11 (theoretical value 432.25). The synthesis method of 215-6 is the same as that of 1-4, except that 1-3 is replaced by 215-5. The molecular mass determined by mass spectrometry is 448.11 (theoretical value 448.25). The synthesis method of 215-7 is the same as that of 1-5, except that 1-4 is replaced by 215-6. The molecular mass determined by mass spectrometry is 416.09 (theoretical value 416.21). The synthesis method of 215-8 is the same as that of 106-6, except that 106-5 is replaced by 215-7. The molecular mass determined by mass spectrometry is 352.18 (theoretical value 352.32). The synthesis method of 215-9 is the same as that of 1-9. The difference is that 215-8 is used to replace 1-7 and 20-6 is used to replace 1-8. The molecular mass determined by mass spectrometry is 613.35 (theoretical value 613.46).The synthesis methods of 215-10 and 1-10 are the same, except that 1-9 is replaced by 2115-9. The molecular mass determined by mass spectrometry analysis is 532.42 (theoretical value 532.55). Synthesis of 215-11: Under nitrogen protection and at -78°C, a THF / hexane solution of LDA (10.5 mL, 2.0 M, 21 mmol) was slowly added to a THF solution of 1-1 (5.4 g, 20 mmol) (60 mL). After the addition was complete, the mixture was stirred at -78°C for 1 hour. Subsequently, trichlorosilane (3.3 g, 30 mmol) was added to the reaction mixture, and the mixture was slowly heated to room temperature while stirring for 12 hours. After the reaction was complete, the reaction solution was filtered through a diatomaceous earth filter and washed with dichloromethane. The filtrate was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (petroleum ether) to give 215-11 (5.4 g, 78%). The molecular weight determined by mass spectrometry was 344.25 (theoretical value 344.07). The synthesis methods for 215-12 and 37-12 are the same, except that 1-11 is replaced by 215-11. The molecular weight determined by mass spectrometry is 372.22 (theoretical value 372.08). The synthesis methods for 215-13 and 37-14 are the same, except that 37-12 is replaced by 215-12. The molecular weight determined by mass spectrometry is 461.31 (theoretical value 461.18). Synthesis of 215-14: Under a nitrogen atmosphere, 215-13 (8.1 g, 17.5 mmol) and 20 mL of dichloromethane were added to a 100 mL round-bottom flask. Iodine monochloride (2.8 g, 17.5 mmol) was dissolved in 10 mL of dichloromethane and added dropwise at 0 °C. The mixture was then stirred at 40 °C for 4 hours. After stirring, the mixture was allowed to return to room temperature, and 10 mL of saturated sodium bisulfite aqueous solution was added. The organic layer was extracted with dichloromethane. The extracted layers were washed with water and brine, and the washed organic layers were dried with magnesium sulfate. The dried organic layers were concentrated using a rotary evaporator. The concentrated compound was purified by silica gel chromatography to obtain 215-14 (6.3 g, 70%). The molecular weight determined by mass spectrometry was 514.75 (theoretical value 514.89). The synthesis methods for 215-15 and 20-14 are the same, except that 20-12 is replaced by 215-14. The molecular weight determined by mass spectrometry is 465.27 (theoretical value 465.09). The synthesis methods for 215-16 and 1-15 are the same, except that 1-14 is replaced by 215-15. The molecular weight determined by mass spectrometry is 357.19 (theoretical value 357.32). The synthesis methods for 215-18 and 1-17 are the same, except that 1-15 is replaced by 215-16, and 1-16 is replaced by 215-17. The molecular weight determined by mass spectrometry is 657.44 (theoretical value 657.58). Compound 215 was synthesized using the same method as compound 1, except that 215-18 replaced 1-17 and 215-10 replaced 1-10. The molecular mass determined by mass spectrometry was 1169.97 (theoretical value 1170.12).

[0036] Example 8: Synthesis of Compound 305

[0037] Synthesizing method 305-2 is the same as that of 1-3, except that 1-1 is replaced by 305-1. Mass spectrometry analysis determined the molecular weight to be 369.15 (theoretical value 369.28). Synthesizing method 305-3 is the same as that of 1-4, except that 1-3 is replaced by 305-2. Mass spectrometry analysis determined the molecular weight to be 385.45 (theoretical value 385.28). Synthesizing method 305-4 is the same as that of 1-5, except that 1-4 is replaced by 305-3. Mass spectrometry analysis determined the molecular weight to be 353.09 (theoretical value 353.23). Synthesizing method 305-5 is the same as that of 1-7, except that 1-5 is replaced by 305-4. Mass spectrometry analysis determined the molecular weight to be 289.49 (theoretical value 289.35). The synthesis methods of 305-6 and 1-9 are the same. The difference is that 305-5 is used to replace 1-7 and 20-6 is used to replace 1-8. The molecular mass determined by mass spectrometry analysis is 550.35 (theoretical value 550.49).Synthesized as 305-7, 1-10 is synthesized using the same method, except that 1-9 is replaced by 305-6. The molecular weight determined by mass spectrometry is 469.75 (theoretical value 469.58). Synthesized as 305-8, 20-10 is synthesized using the same method, except that 20-9 is replaced by 37-12. The molecular weight determined by mass spectrometry is 405.24 (theoretical value 405.05). Synthesized as 305-9, 20-12 is synthesized using the same method, except that 20-11 is replaced by 305-8. The molecular weight determined by mass spectrometry is 530.81 (theoretical value 530.95). Synthesized as 305-10, 20-14 is synthesized using the same method, except that 20-12 is replaced by 305-9. The molecular weight determined by mass spectrometry is 481.32 (theoretical value 481.15). The synthesis methods of 305-11 and 1-15 are the same, except that 305-10 is used instead of 1-14. The molecular mass determined by mass spectrometry analysis is 373.50 (theoretical value 373.38).Compound 305-13 was synthesized using the same method as compound 1-17, except that 1-15 was replaced by 305-11 and 1-16 by 305-12. The molecular weight determined by mass spectrometry was 596.82 (theoretical value 596.68). Compound 305 was synthesized using the same method as compound 1, except that 1-17 was replaced by 305-13 and 1-10 by 305-7. The molecular weight determined by mass spectrometry was 1046.11 (theoretical value 1046.25).

[0038] Example 9: Synthesis of Compound 331

[0039] Synthesizing method 331-2 is the same as that of 1-9, except that 1-7 is replaced by 215-8 and 1-8 is replaced by 331-1. The molecular weight determined by mass spectrometry is 613.59 (theoretical value 613.46). Synthesizing method 331-3 is the same as that of 1-10, except that 1-9 is replaced by 331-2. The molecular weight determined by mass spectrometry is 532.67 (theoretical value 532.55). Synthesizing method 331-4 is the same as that of 20-12, except that 20-11 is replaced by 215-11. The molecular weight determined by mass spectrometry is 470.11 (theoretical value 469.97). Synthesizing method 331-6 is the same as that of 20-14, except that 20-12 is replaced by 331-4 and 20-13 is replaced by 331-5. The molecular weight determined by mass spectrometry is 460.33 (theoretical value 460.19). The synthesis methods of 331-7 and 215-14 are the same, except that 215-13 is replaced by 331-6. The molecular mass determined by mass spectrometry analysis is 514.04 (theoretical value 513.90).Synthesized as 331-8 and 20-14, the difference being that 20-12 is replaced by 331-7. The molecular weight determined by mass spectrometry is 464.22 (theoretical value 464.10). Synthesized as 331-9 and 1-15, the difference being that 1-14 is replaced by 331-8. The molecular weight determined by mass spectrometry is 356.47 (theoretical value 356.33). Synthesized as 331-11 and 1-17, the difference being that 1-15 is replaced by 331-9, and 1-16 is replaced by 331-10. The molecular weight determined by mass spectrometry is 580.76 (theoretical value 580.62). Compound 331 was synthesized using the same method as compound 1, except that 331-11 replaced 1-17 and 331-3 replaced 1-10. The molecular mass determined by mass spectrometry was 1093.01 (theoretical value 1093.16).

[0040] Example 10: Synthesis of Compound 341

[0041] Synthesizing methods for 341-3 and 37-3 are the same, except that 37-1 is replaced by 341-1. The molecular weight determined by mass spectrometry is 338.31 (theoretical value 338.20). Synthesizing methods for 341-4 and 37-4 are the same, except that 37-3 is replaced by 341-3. The molecular weight determined by mass spectrometry is 449.23 (theoretical value 449.09). Synthesizing methods for 341-5 and 37-5 are the same, except that 37-4 is replaced by 341-4. The molecular weight determined by mass spectrometry is 597.27 (theoretical value 597.14). Synthesizing methods for 341-6 and 37-6 are the same, except that 37-5 is replaced by 341-5. The molecular weight determined by mass spectrometry is 353.38 (theoretical value 353.23). The synthesis method of 341-7 is the same as that of 1-7. The difference is that 1-5 is replaced by 341-6. The molecular mass determined by mass spectrometry is 289.49 (theoretical value 289.35).Synthesized as 341-8, the method is the same as that of 1-8, except that 1-7 is replaced by 341-7 and 1-8 is replaced by 20-6. The molecular weight determined by mass spectrometry is 550.66 (theoretical value 550.49). Synthesized as 341-9, the method is the same as that of 1-10, except that 1-9 is replaced by 341-8. The molecular weight determined by mass spectrometry is 469.72 (theoretical value 469.58). Synthesized as 341-11, the method is the same as that of 20-14, except that 20-12 is replaced by 106-7 and 20-13 is replaced by 341-10. The molecular weight determined by mass spectrometry is 464.23 (theoretical value 464.10). The synthesis methods for 341-12 and 20-12 are the same, except that 20-11 is replaced by 241-11. The molecular mass determined by mass spectrometry is 590.14 (theoretical value 590.00). The synthesis methods for 341-13 and 20-14 are the same, except that 20-12 is replaced by 341-12. The molecular mass determined by mass spectrometry is 540.34 (theoretical value 540.20).Compound 341-14 was synthesized using the same method as compound 1-15, except that 1-14 was replaced by 341-13. The molecular weight determined by mass spectrometry was 432.56 (theoretical value 432.43). Compound 341-16 was synthesized using the same method as compound 1-17, except that 1-15 was replaced by 341-14, and 1-16 by 341-15. The molecular weight determined by mass spectrometry was 655.87 (theoretical value 655.73). Compound 341 was synthesized using the same method as compound 1, except that 1-17 was replaced by 341-16, and 1-10 by 341-9. The molecular weight determined by mass spectrometry was 1105.41 (theoretical value 1105.30).

[0042] The above synthetic examples illustrate representative synthetic routes. Unless otherwise specified, all reagents and instruments used are commercially available conventional products. Some reaction compounds were purchased from a supplier (Zhengzhou Alpha Chemical Co., Ltd.), while some compounds that could not be directly purchased were prepared from commercially available raw materials through simple reactions. All percentages refer to mass percentages. The principles, procedures, routine post-processing, silica gel column chromatography, recrystallization purification, and other techniques of this method are well-known to those skilled in the art and can be fully implemented to obtain the target product.

[0043] In addition, it should be noted that other compounds in this application can be obtained by referring to the synthetic routes of the synthetic examples listed above, so they will not be listed one by one here.

[0044] Device Examples To evaluate the luminescence performance of the compounds described in this invention in organic electroluminescent devices, a series of OLED devices based on multilayer organic thin film structures were designed and constructed, and the specific fabrication process is shown below:

[0045] Preparation of Example 1: The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol, baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam. The treated ITO transparent conductive layer was placed in a vacuum evaporation chamber. After the system reached a high vacuum, a hole injection layer (HIL) with a thickness of 10 nm was first deposited. This layer used a co-evaporation combination of HT and HI-1 (mass ratio 97:3, w / w), with the two materials placed in different evaporation sources. Precise ratio control was achieved by adjusting the evaporation rate. This doping system aims to improve the energy level matching between the anode and the organic layer and reduce the hole injection barrier. A 15 nm thick HT-1 layer is deposited on top of the hole injection layer as a hole transport layer (HTL). The main function of this layer is to efficiently transport holes and suppress electron back injection, maintaining a good charge balance in the device. Subsequently, a 20 nm thick HT-2 layer is deposited as an electron blocking layer (EBL) to restrict electron penetration to the hole transport layer, thereby effectively improving the exciton binding ability and recombination efficiency in the light-emitting region. A 30nm thick light-emitting layer (EML) was deposited on the electron blocking layer using a multi-source co-evaporation process. The host material was HOST, compound 1 was the sensitizing material MH, and the dopant was GD-1. They were placed in independent evaporation sources, and the co-doped composite light-emitting film was formed by controlling their evaporation rate ratio to 49:50:1 (w / w / w). A 5nm thick HB-1 layer is deposited on the light-emitting layer as a hole blocking layer (HBL) to block holes from escaping into the electron region and enhance the electron injection interface. A 30 nm thick electron transport layer (ETL) was deposited on the hole blocking layer using an ET-1 and LiQ doping system (mass ratio 50:50, w / w). This combination helps to improve the electron transport rate and interface injection efficiency. Depositing 1 nm of Yb on the electron transport layer as an electron injection layer (EIL) helps to form an interfacial dipole and improve the injection efficiency of electrons from the Al cathode to the electron transport layer. A Mg:Ag electrode layer with a thickness of 13 nm is deposited on top of the electron injection layer, wherein the mass ratio of Mg to Ag is 1:9. This layer serves as the cathode layer. A CP-1 layer with a thickness of 65 nm was vacuum-deposited on the cathode as a light extraction layer (CPL). The entire organic layer and cathode evaporation process is completed in a continuous vacuum to avoid interface oxidation or contamination, with the deposition rate set to 0.1 nm / s.

[0046] In the glove box, the vapor-deposited device is coated with UV adhesive using a coating equipment. The coated cover plate is then moved to the lamination section, where the vapor-deposited substrate is placed on top of the cover plate. Finally, the substrate and cover plate are laminated using a bonding equipment and cured with UV adhesive.

[0047] Preparation of Examples 2-30: When forming the light-emitting layer (EML), the corresponding compounds in Tables 2-1 and 2-2 were used to replace compound 1 in Example 1, and the organic electroluminescent device was prepared using the same method as in Example 1.

[0048] Preparation of Comparative Examples 1-12: Except that, when forming the light-emitting layer (EML), the corresponding compound in Table 3 was used to replace compound 1 in Example 1, the organic electroluminescent device was prepared using the same method as in Example 1.

[0049] The structures of the compounds used in the device are as follows:

[0050] Evaluation of compounds: The emission peak positions, photoluminescence quantum yield (PLQY), and antisystem crossing coefficients (k) of the compounds in Tables 1-1 and 1-2 were analyzed. RISC ) and radiative transition rate coefficient (k r ), singlet-triplet bandgap (ΔE) ST The PLQY test: Dissolve the sample in nitrogen-saturated toluene and prepare 10... -5 The phosphorescence and fluorescence of the mol / L solution were measured using a Hamamatsu PLQY spectrometer; the emission peak positions were determined using a fluorescence spectrometer; and phosphorescence and fluorescence at 77 K were obtained using a HITACHI F-7000 spectrometer. RISC and k r The results were obtained through testing and calculation using FLS1000 and are shown in Tables 1-1 and 1-2 below: ;

[0051] Device evaluation: The voltage was increased at a rate of 0.1V per second, and the brightness of the device embodiment and the comparative example was measured when they reached lcd / m². 2The voltage at which it is turned on is 10 mA / cm. 2 The driving voltage and current efficiency of the device embodiments and comparative examples were determined at a current density of 35 mA / cm². The driving voltage and current efficiency were measured using an IVL (current-voltage-luminance) testing system (Suzhou Fushida Scientific Instruments Co., Ltd.). 2 The time required for the brightness to decrease to 95% of the initial brightness at a given current density (LT95) was measured. The lifetime testing system was the OLED lifetime testing system from Suzhou Fosstar Scientific Instruments Co., Ltd.; at 10 cd / m 2 The wavelength of the maximum emission peak, the full width at half maximum (FWHM), and the corresponding CIE color coordinates were obtained. The results are shown in Tables 2-1, 2-2, and 3 below. ; ;

[0052] As shown in Tables 1-3, the compounds of this invention exhibit excellent properties at the molecular level: their band gap (ΔE) ST The voltage is extremely small (<0.01 eV), and therefore possesses an extremely high anti-inter-system crossing rate (k). RISC ) and radiative transition rate (k r These properties directly translate into superior photophysical performance, manifested as high fluorescence quantum efficiency (PLQY) and a suitable emission peak position. Ultimately, when used as a sensitizer in organic electroluminescent devices, these advantages combine to result in lower turn-on voltage, higher current efficiency, and longer lifespan, achieving optimized overall performance.

[0053] The above embodiments only list the effect data of devices made from a portion of the structures. This is a representative sampling test. Based on the experimental data, the overall data is not significantly different and can represent the effects of other unlisted structures.

[0054] Those skilled in the art will readily recognize that many modifications and variations can be made to this invention without departing from its spirit and scope. Therefore, it is anticipated that this invention covers the modifications and variations provided within the scope of the appended claims and their equivalents. This invention has been illustrated by the above embodiments with respect to the organic electroluminescent materials and organic electroluminescent devices of this invention, but the invention is not limited to the above embodiments, i.e., it does not mean that the invention must rely on the above embodiments to be implemented.

Claims

1. A compound having a nine-ring side chain, characterized in that, Its structure is shown in general formula (I): ； L is selected from single bond, substituted or unsubstituted C6-C. 12 Aromatic rings, either substituted or unsubstituted, are C3-C6 heteroaromatic rings; A and B are each independently selected from substituted or unsubstituted C6-C. 12 Aromatic ring or (I)-1, (I)-2, (I)-3, (I)-4, and at least one of A and B is selected from (I)-1, (I)-2, (I)-3, (I)-4: ； C is selected from structure (I)-5 or (I)-6: ； D is selected from any structure from (I)-7 to (I)-11: ； X1 is independently selected from NR3, O, S, and Se; X2 is independently selected from N and CR5; and E is independently selected from R2-substituted C6-C. 12 Aromatic rings or C3-C6 heteroaromatic rings; X3 is selected from O, S, and Se, and X4 is selected independently from NR3, O, S, and Se; * indicates a linkage site. R1 to R5 are each independently selected from hydrogen, deuterium, cyano, C1-C6 alkyl, substituted or unsubstituted C6-C. 12 Aryl or C3-C 12 heteroaryl groups; When substitution is present, the substituents are each independently selected from deuterium, cyano, C1-C6 alkyl, C6 ... 12 The aryl group, C3-C6 heteroaryl group, n is from 1 to the largest substitution site number of the ring, and the heteroatom is N.

2. The compound having a nine-ring side chain according to claim 1, characterized in that, E is selected from a benzene ring substituted with R2.

3. The compound having a nine-ring side chain according to claim 1, characterized in that, L can be a single bond, phenyl, naphthyl, or pyridyl.

4. The compound having a nine-ring side chain according to claim 1, characterized in that, One of A and B is selected from (I)-1, (I)-2, (I)-3, (I)-4.

5. The compound having a nine-ring side chain according to claim 1, characterized in that, A and B are each independently selected from (I)-1 or (I)-2.

6. The compound having a nine-ring side chain according to claim 1, characterized in that, At least one of (I)-7, (I)-8, (I)-9, (I)-10, and (I)-11 is S.

7. The compound having a nine-ring side chain according to claim 1, characterized in that, R1 to R5 are each independently selected from hydrogen, deuterium, cyano, methyl, tert-butyl, phenyl, and pyridyl. When substitutions are present, the substituents are each independently selected from deuterium, cyano, methyl, tert-butyl, phenyl, and pyridyl.

8. The compound having a nonacyclic side chain according to any one of claims 1-7, characterized in that, The specific structure of this compound is as follows: ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； 。 9. An organic electroluminescent device, comprising an anode, a cathode, and an organic layer, wherein the organic layer includes a light-emitting layer, characterized in that, The luminescent layer comprises any one of the compounds described in claims 1-8 having a nonacyclic side chain.

10. The organic electroluminescent device according to claim 9, characterized in that, This organic electroluminescent device is used to manufacture display devices, lighting sources, signal lights, and signs. The display devices include mobile phone displays, computer displays, television displays, smartwatch displays, smart car display panels, and VR or AR helmet displays.

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