A boron-containing organic compound and use thereof

Abstract

The application discloses a boron-containing organic compound and application thereof, and belongs to the technical field of semiconductors. The structure of the organic compound is shown in general formula (1). The compound has a narrow half-peak width and a high fluorescence quantum yield, and can be used as a green light doping material of a light-emitting layer of an organic electroluminescent device, so that the light-emitting color purity and efficiency of the device are improved, and the service life of the device is prolonged.

Description

Technical Field

[0001] This invention relates to the field of semiconductor technology, and in particular to a boron-containing organic compound and its application in organic electroluminescent devices. Background Technology

[0002] Traditional fluorescent doped materials, limited by early technologies, can only emit light using 25% of singlet excitons generated by electrical excitation. This results in low internal quantum efficiency (maximum 25%) and external quantum efficiency generally below 5%, significantly lower than that of phosphorescent devices. Phosphorescent materials, due to the strong spin-orbit coupling at their heavy atom centers, enhance intersystem crossing and can effectively utilize both singlet and triplet excitons generated by electrical excitation, achieving an internal quantum efficiency of 100%. However, most phosphorescent materials are expensive, have poor material stability, low color purity, and suffer from severe efficiency roll-off, limiting their application in OLEDs.

[0003] With the advent of the 5G era, higher requirements have been placed on color rendering standards. In addition to high efficiency and stability, luminescent materials also need narrower half-widths (HWHMs) to improve the purity of the emitted color in devices. Fluorescent dopants can achieve high fluorescence quantum density and narrow HWHM through molecular engineering. Significant breakthroughs have been achieved in blue fluorescent dopants, with the HWHM of boron-based materials reduced to below 30 nm. However, research on the green light region, which is more sensitive to the human eye, has mainly focused on phosphorescent dopants. However, the peak shape of these dopants is difficult to narrow using simple methods. Therefore, researching efficient green fluorescent dopants with narrow HWHMs is of great significance in meeting higher color rendering standards.

[0004] In addition, TADF-sensitized fluorescence (TSF) technology combines TADF materials with fluorescent doping materials. By using TADF materials as exciton sensitization media, triplet excitons formed by electrical excitation are converted into singlet excitons. Energy is then transferred to the fluorescent doping material through long-range energy transfer of singlet excitons, achieving 100% in-device quantum efficiency. This technology can compensate for the insufficient exciton utilization of fluorescent doping materials and effectively leverage the high fluorescence quantum yield, high device stability, high color purity, and low cost of fluorescent doping materials, showing broad prospects for OLED applications.

[0005] Boron compounds with resonant structures are more likely to achieve narrow half-width emission (HWHM). When applied to TADF-sensitized fluorescence technology, these materials can enable the fabrication of devices with high efficiency and narrow HWHM emission. For example, CN 107507921 A and CN110492006 A disclose a luminescent layer combination technique using a TADF material with a minimum singlet and triplet energy level difference of less than or equal to 0.2 eV as the main body and boron-containing materials as dopants; CN 110492005 A and CN 110492009 A disclose a luminescent layer combination scheme using an exciton complex as the main body and boron-containing materials as dopants; both achieve efficiencies comparable to phosphorescence and relatively narrow HWHM. Therefore, developing TADF-sensitized fluorescence technology based on narrow HWHM boron-based luminescent materials has unique advantages and strong potential for achieving BT.2020 display performance. Summary of the Invention

[0006] To address the aforementioned problems in the existing technology, this invention provides a boron-containing organic compound and its applications. The compound of this invention exhibits a narrow full width at half maximum (FWHM) and high fluorescence quantum yield, and can be used as a green light doping material for the emitting layer of organic electroluminescent devices, thereby improving the emission color purity and efficiency of the device and extending its lifetime.

[0007] The technical solution of the present invention is as follows: a boron-containing organic compound, the structure of which is shown in general formula (1):

[0008]

[0009] In general formula (1), dashed lines indicate no connection or connection via a single key;

[0010] Z is represented as N or C-R1;

[0011] Each occurrence of R1, whether identical or different, represents a hydrogen atom, deuterium atom, tritium atom, halogen atom, or substituted or unsubstituted C1-C1 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10 Aryloxy group, substituted or unsubstituted aromatic amino group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0012] Adjacent R1s can also be connected to form a ring;

[0013] Z1 and Z2 represent CR respectively. a CR b ;

[0014] R a R b Represented independently as hydrogen atoms, deuterium atoms, tritium atoms, halogen atoms, and substituted or unsubstituted C1 to C2 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10 Aryloxy group, substituted or unsubstituted aromatic amino group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0015] R a With R b They can also be connected to form a ring;

[0016] When a dashed line indicates no connection, R a With R b Connect them into a ring;

[0017] A1 indicates C3 to C4 with or without substitution. 10 Cycloalkyl, substituted or unsubstituted C3-C 10 Cycloalkenyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0018] The substituents used for the substituent groups are selected from deuterium atoms, tritium atoms, halogen atoms, and C1-C2 atoms. 10 Alkyl groups, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2~C 30 One or more of the heteroaryl groups.

[0019] In a preferred embodiment, the structure of the boron-containing organic compound is shown in general formula (1-1):

[0020]

[0021] In general formula (1-1), Z is represented as N or C-R1;

[0022] Each occurrence of R1, whether identical or different, represents a hydrogen atom, deuterium atom, tritium atom, halogen atom, or substituted or unsubstituted C1-C1 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10 Aryloxy group, substituted or unsubstituted aromatic amino group, substituted or unsubstituted C6-C 30Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0023] Adjacent R1s can also be connected to form a ring;

[0024] Each occurrence of R, whether the same or different, represents a hydrogen atom, deuterium atom, tritium atom, halogen atom, or substituted or unsubstituted C1-C1 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10 Aryloxy group, substituted or unsubstituted aromatic amino group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0025] A1 indicates C3 to C4 with or without substitution. 10 Cycloalkyl, substituted or unsubstituted C3-C 10 Cycloalkenyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0026] Ar1 represents C3 to C4 with or without substitution. 10 Cycloalkyl, substituted or unsubstituted C3-C 10 Cycloalkenyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0027] Ar1 can be connected to a nearby Z to form a ring;

[0028] The substituents used for the substituent groups are selected from deuterium atoms, tritium atoms, halogen atoms, and C1-C2 atoms. 10 Alkyl groups, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2~C 30 One or more of the heteroaryl groups.

[0029] In a preferred embodiment, the structure of the boron-containing organic compound is shown in general formula (1-2):

[0030]

[0031] In general formula (1-2), the meanings of Z, A1, and R are the same as those defined above.

[0032] In a preferred embodiment, the structure of the boron-containing organic compound is shown in general formula (2) or general formula (3):

[0033]

[0034] In general formulas (2) and (3), the meaning of Z is the same as the limitation mentioned above.

[0035] In a preferred embodiment, the structure of the boron-containing organic compound is shown in any one of general formulas (4) to (20):

[0036]

[0037]

[0038] In general formulas (4) to (20), the meaning of Z is the same as the limitation mentioned above;

[0039] X1 and X2 can be independently represented as one of O, S, Se, N(R2), C(R3)(R4) or Si(R5)(R6);

[0040] R2-R6 are independently represented as substituted or unsubstituted C1-C6 groups. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C2-C 30 It is one of the heteroaryl groups; R3 and R4, and R5 and R6 can also be linked to form a ring.

[0041] The substituents used for the substituent groups are selected from deuterium atoms, tritium atoms, halogen atoms, and C1-C2 atoms. 10 Alkyl groups, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2~C 30 One or more of the heteroaryl groups.

[0042] In a preferred embodiment, the structure of the boron-containing organic compound is shown in any one of general formulas (4-1) to (16-1):

[0043]

[0044]

[0045] In general formulas (4-1) to (16-1), the definitions of Z, X1, and X2 are the same as those in the above text.

[0046] In a preferred embodiment, the structure of the boron-containing organic compound is shown in any one of general formulas (A-1) to (A-11):

[0047]

[0048] In general formulas (A-1) to (A-11), the definitions of Z, X1, and X2 are the same as those in the above description;

[0049] R1, R, and R0 are independently represented as hydrogen atom, deuterium atom, tritium atom, halogen atom, adamantyl group, methyl group, deuterated methyl group, tritated methyl group, trifluoromethyl group, ethyl group, deuterated ethyl group, tritated ethyl group, isopropyl group, deuterated isopropyl group, tritated isopropyl group, tert-butyl group, deuterated tert-butyl group, tritated tert-butyl group, cyclopentyl group, deuterated cyclopentyl group, tritated cyclopentyl group, methyl-substituted cyclopentyl group, cyclohexyl group, and benzene group. alkyl, deuterated phenyl, tritated phenyl, diphenyl, deuterated diphenyl, tritated diphenyl, terphenyl, deuterated terphenyl, tritated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracene, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazole, N-phenylcarbazole, 9, 9-Dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, diphenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, phenyl-substituted triazineyl, phenyl-substituted boroalkyl, methoxy, tert-butoxy;

[0050] In the preferred embodiment, R1, R a R bEach of these can be independently represented as a hydrogen atom, deuterium atom, tritium atom, halogen atom, adamantyl, methyl, deuterated methyl, tritated methyl, trifluoromethyl, ethyl, deuterated ethyl, tritated ethyl, isopropyl, deuterated isopropyl, tritated isopropyl, tert-butyl, deuterated tert-butyl, tritated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl. Tritium-substituted phenyl, diphenyl, deuterated diphenyl, triphenyl, deuterated terphenyl, tritium terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthraceneyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazole, N-phenylcarbazole, 9,9-dimethyl Fluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, diphenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, phenyl-substituted triazineyl, phenyl-substituted boraneyl, methoxy, tert-butoxy;

[0051] R3-R6 are independently represented as hydrogen atom, deuterium atom, tritium atom, halogen atom, adamantyl, methyl, deuterated methyl, tritated methyl, trifluoromethyl, ethyl, deuterated ethyl, tritated ethyl, isopropyl, deuterated isopropyl, tritated isopropyl, tert-butyl, deuterated tert-butyl, tritated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, and benzene. alkyl, deuterated phenyl, tritated phenyl, diphenyl, deuterated diphenyl, tritated diphenyl, terphenyl, deuterated terphenyl, tritated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracene, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazole, N-phenylcarbazole 9,9-Dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, phenyl-substituted triazineyl, phenyl-substituted boroalkyl, methoxy, tert-butoxy;

[0052] R2 represents phenyl, deuterated phenyl, tritated phenyl, diphenyl, deuterated diphenyl, tritated diphenyl, terphenyl, deuterated terphenyl, tritated terphenyl, naphthyl, anthraceneyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazoyl, N-phenylcarbazoyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl. One of the following: ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, and phenyl-substituted triazineyl.

[0053] The A1 represents substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthraquinone, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrene, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiopheneyl or substituted or unsubstituted N-phenylcarbazoyl.

[0054] The substituents used for the substituent groups are selected from deuterium, tritium, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, and naphthyl.

[0055] In a preferred embodiment, A1 is represented by any of the following ring structures:

[0056]

[0057] The definition of Z in the above formula is the same as the limitation mentioned above.

[0058] In a preferred embodiment, the boron-containing organic compound has any one of the following structures:

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075] An organic electroluminescent device includes a cathode and an anode, and an organic light-emitting functional layer therebetween, the organic light-emitting functional layer including a light-emitting layer containing the boron-containing organic compound.

[0076] The organic electroluminescent device further includes a substrate, which may be adjacent to the anode or the cathode.

[0077] Preferably, the light-emitting layer comprises a host material and a dopant material, wherein the dopant material contains the boron-containing organic compound.

[0078] Further preferably, the light-emitting layer comprises a first host material, a second host material, and a dopant material, wherein at least one of the first host material and the second host material is a TADF material, and the dopant material is the boron-containing organic compound.

[0079] Preferably, the light-emitting layer comprises a host material, an exciton-sensitizing material, and a dopant material, wherein the exciton-sensitizing material is a complex containing a metal element, and the dopant material is the boron-containing organic compound.

[0080] The beneficial technical effects of this invention are as follows:

[0081] (1) The compound of the present invention can be used as a doping material for OLED devices, and can emit green fluorescence under the action of an electric field. It can be applied to OLED lighting or OLED display fields.

[0082] (2) The compound of the present invention has a high fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%;

[0083] (3) The compound of the present invention is used as a doping material, and TADF sensitizer is introduced as a second host, which can effectively improve device efficiency;

[0084] (4) The compounds of the present invention have a narrower FWHM spectrum, which can effectively improve the color gamut of the device and improve the luminous efficiency of the device. Attached Figure Description

[0085] Figure 1 This is a schematic diagram of the structure of an OLED device in which the materials listed in this invention are applied;

[0086] Wherein, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer. Detailed Implementation

[0087] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but this is not intended to limit the scope of the invention.

[0088] The following examples are intended to better explain the present invention, but the scope of the invention is not limited thereto.

[0089] All raw materials involved in the synthesis embodiments of the present invention can be purchased from the market or obtained by conventional preparation methods in the art;

[0090] Example 1: Synthesis of Compound 3:

[0091]

[0092] Under nitrogen protection, 10 mmol of starting material A-1 and 12 mmol of NaH were added to a three-necked flask, followed by 50 mL of anhydrous DMF. The mixture was stirred at room temperature for 0.5 hours. Then, 10 mmol of starting material B-1 was added, and the mixture was heated to 80 °C and reacted for 18 hours. After the reaction was complete, 100 mL of deionized water was added, the precipitate was filtered, dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered, and separated by column chromatography to obtain intermediate a-1. LC-MS: Measured value: 322.09 ([M+H)) + Theoretical value: 321.02.

[0093] Under nitrogen protection, 10 mmol of intermediate a-1, 10 mmol of starting material D-1, 20 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, 50 mL of tetrahydrofuran, and 5 mL of water were added to a three-necked flask, and the mixture was refluxed for 8 hours. After the reaction, the organic phase was collected by separation, the organic layer was concentrated under reduced pressure, and then purified by silica gel column chromatography to obtain intermediate b-1. LC-MS: Measured value: 521.22 ([M+H) + Theoretical value: 520.29.

[0094] In a sealed, pressure-resistant tube under nitrogen protection, 10 mmol of intermediate b-1 and 5 ml of o-dichlorobenzene were added. A solution of 12 mmol of n-butyllithium in n-hexane was added at 0°C, the system was heated to 60°C and reacted for 2 hours. Then, 15 mmol of boron tribromide was added at 0°C, and the mixture was transferred to room temperature and reacted for another 2 hours. Next, 20 mmol of N,N-diisopropylethylamine was added at 0°C, the system was heated to 200°C and reacted for 2 hours. After the reaction was complete, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 3.

[0095] 1¹H NMR (400 MHz, deuterated chloroform) δ 8.73 (d, 1H), 8.30 (d, 1H), 8.15 (dd, 1H), 7.89–7.82 (m, 2H), 7.73–7.68 (m, 2H), 7.62 (t, 1H), 7.59 (dd, 1H), 7.56–7.45 (m, 3H), 7.43–7.30 (m, 2H), 6.77 (dd, 1H), 1.31 (s, 9H), 1.28 (s, 9H).

[0096] Example 2: Synthesis of Compound 17:

[0097]

[0098] In a three-necked flask under nitrogen protection, 10 mmol of starting material A-2, 11 mmol of NaH, and 50 mL of DMF were added. The mixture was stirred at room temperature for 0.5 h, followed by the addition of 10 mmol of starting material B-2. The mixture was heated to 80 °C and reacted for 12 h. After the reaction was complete, the reactants were precipitated with 100 mL of water and filtered. The precipitate was dissolved in dichloromethane, dried over anhydrous sodium sulfate, and filtered again. The organic phase was concentrated and subjected to column chromatography to obtain intermediate a-2. LC-MS: Measured value: 333.20 ([M+H)) + Theoretical value: 332.13.

[0099] Under nitrogen protection, 10 mmol of intermediate a-2, 10 mmol of NBS, and 20 mL of glacial acetic acid were added to a three-necked flask, and the reaction was carried out at 0°C in the dark for 3 hours. After the reaction was completed, a saturated aqueous solution of anhydrous sodium sulfite was added, the organic phase was collected by separation, the organic layer was concentrated, and then purified by silica gel column chromatography to obtain intermediate b-2. LC-MS: Measured value: 411.01 ([M+H)) + Theoretical value: 410.04; 1 H NMR (400MHz, Chloroform-d) δ8.50–8.47(m,2H),8.27–8.13(m,1H),7.98–7.85(m,2H),7.79–7.65(m,6H),7.56–7.47(m,3H),7.34(m,1H).

[0100] Under nitrogen protection, 10 mmol of intermediate b-2, 10 mmol of pinacol diboronate, 5 mmol of potassium acetate, 0.1 mmol of Pd(dppf)Cl2, and 30 mL of 1,4-dioxane were added to a three-necked flask, and the mixture was refluxed for 18 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate c-2. LC-MS: Measured value: 459.21 ([M+H)) + Theoretical value: 458.22.

[0101] In a three-necked flask, under nitrogen protection, 10 mmol of intermediate a-1, 10 mmol of intermediate c-2, 10 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, and 200 mL of toluene were added and refluxed for 14 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate d-2. LC-MS: Measured value: 574.25 ([M+H) + Theoretical value: 573.22.

[0102] In a sealed, pressure-resistant tube under nitrogen protection, 10 mmol of intermediate d-2 and 5 ml of o-dichlorobenzene were added. A solution of 12 mmol of n-butyllithium in n-hexane was added at 0 °C, the system was heated to 60 °C and reacted for 1 hour. Then, 15 mmol of boron tribromide was added at 0 °C, and the mixture was transferred to room temperature and reacted for another 2 hours. Next, 20 mmol of N,N-diisopropylethylamine was added at 0 °C, the system was heated to 200 °C and reacted for 2 hours. After the reaction was complete, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 17.

[0103] 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.11 (m, 2H), 8.05–7.91 (m, 1H), 7.89 (m, 1H), 7.83 (m, 1H), 7.75 (d, 1H), 7.68–7.53 (m, 6H), 7.51–7.49 (m, 5H), 7.45–7.34 (m, 5H), 7.25–7.16 (m, 1H), 6.80 (dd, 1H).

[0104] Example 3: Synthesis of Compound 19:

[0105]

[0106] In a three-necked flask under nitrogen protection, 10 mmol of intermediate a-2, 20 mmol of NBS, and 50 mL of glacial acetic acid were added. The mixture was heated at 90 °C and reacted in the dark for 10 hours. After the reaction was complete, a saturated aqueous solution of anhydrous sodium sulfite was added. The organic phase was collected by separation, the organic layer was concentrated, and then purified by silica gel column chromatography to obtain intermediate a-3. LC-MS: Measured value: 488.99 ([M+H)) + Theoretical value: 487.95.

[0107] Intermediate a-3 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst (0.2 mmol), potassium carbonate (20 mmol), and DMAc (50 mL) were added sequentially to a two-necked flask. The mixture was then heated under nitrogen protection and stirred under reflux for 12 hours. After cooling, the organic phase was separated and collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated. The compounds were separated by silica gel column chromatography using petroleum ether:ethyl acetate (100:1) as the developing solvent to obtain intermediate b-3. LC-MS: Measured value: 409.07 ([M+H) + Theoretical value: 408.03.

[0108] 1 H NMR (400MHz, Chloroform-d) δ8.45–8.32(m,1H),8.12(dd,1H),7.79(dd,1H),7.43–7.25(m,5H),7.14–7.03(m,4H),6.95(m,1H).

[0109] Under nitrogen protection, 10 mmol of intermediate b-3, 10 mmol of pinacol diboronate, 5 mmol of potassium acetate, 0.1 mmol of Pd(dppf)Cl2, and 30 mL of 1,4-dioxane were added to a three-necked flask, and the mixture was refluxed for 19 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate c-3. LC-MS: Measured value: 457.25 ([M+H)) + Theoretical value: 456.20.

[0110] In a three-necked flask, under nitrogen protection, 10 mmol of intermediate a-1, 10 mmol of intermediate c-3, 10 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, and 200 mL of toluene were added and refluxed for 18 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate d-3. LC-MS: Measured value: 572.21 ([M+H) + Theoretical value: 571.20.

[0111] In a sealed, pressure-resistant tube under nitrogen protection, 10 mmol of intermediate d-3 and 5 ml of o-dichlorobenzene were added. A solution of 12 mmol of n-butyllithium in n-hexane was added at 0 °C, the system was heated to 60 °C and reacted for 2 hours. Then, 15 mmol of boron tribromide was added at 0 °C, and the mixture was transferred to room temperature and reacted for another 2 hours. Next, 20 mmol of N,N-diisopropylethylamine was added at 0 °C, the system was heated to 200 °C and reacted for 2 hours. After the reaction was complete, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 19.

[0112] 1 ¹H NMR (400MHz, deuterated chloroform) δ 8.16–8.05 (m, 3H), 7.92 (dd, 1H), 7.88 (m, 1H), 7.82 (t, 1H), 7.76 (d, 1H), 7.75–7.70 (m, 3H), 7.68 (dd, 1H), 7.64–7.59 (m, 1H), 7.53–7.48 (m, 2H), 7.36–7.11 (m, 7H), 6.92 (dd, 1H).

[0113] Example 4: Synthesis of compound 52:

[0114]

[0115] In a three-necked flask under nitrogen protection, 10 mmol of intermediate a-1, 10 mmol of starting material A-4, 10 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, and 200 mL of toluene were added and refluxed for 20 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate a-4. LC-MS: Measured value: 523.33 ([M+H) + Theoretical value: 522.30.

[0116] In a sealed, pressure-resistant tube under nitrogen protection, 10 mmol of intermediate a-4 and 5 ml of o-dichlorobenzene were added. A solution of 12 mmol of n-butyllithium in n-hexane was added at 0 °C, the system was heated to 60 °C and reacted for 1.5 h. Then, 15 mmol of boron tribromide was added at 0 °C, and the mixture was transferred to room temperature and reacted for another 2 h. Next, 20 mmol of N,N-diisopropylethylamine was added to the system at 0 °C, the mixture was heated to 200 °C and reacted for 2 h. After the reaction was complete, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 52.

[0117] 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.17–8.11 (m, 1H), 7.89 (d, 1H), 7.82 (m, 1H), 7.74 (m, 1H), 7.59 (d, 1H), 7.53 (t, 1H), 7.50 (dd, 1H), 7.43 (m, 1H), 7.37 (dd, 1H), 7.33 (m, 1H), 7.29 (dd, 1H), 7.24–7.17 (m, 3H), 7.13–7.06 (m, 2H), 6.85 (dd, 1H), 1.38 (d, 18H).

[0118] Example 5: Synthesis of Compound 85:

[0119]

[0120] Under nitrogen protection, 10 mmol of starting material A-5 and 12 mmol of NaH were added to a three-necked flask, followed by 50 mL of anhydrous DMF. The mixture was stirred at room temperature for 0.5 hours. Then, 10 mmol of starting material B-1 was added, and the mixture was heated to 80 °C and reacted for 17 hours. After the reaction was complete, 100 mL of deionized water was added, the precipitate was filtered, dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered, and separated by column chromatography to obtain intermediate a-5. LC-MS: Measured value: 474.09 ([M+H)) + Theoretical value: 473.08.

[0121] In a three-necked flask under nitrogen protection, 10 mmol of intermediate a-5, 10 mmol of starting material D-1, 10 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, and 200 mL of toluene were added and refluxed for 5 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate b-5. LC-MS: Measured value: 673.31 ([M+H) + Theoretical value: 672.35.

[0122] In a sealed, pressure-resistant tube under nitrogen protection, 10 mmol of intermediate b-5 and 5 ml of o-dichlorobenzene were added. A solution of 12 mmol of n-butyllithium in n-hexane was added at 0°C, the system was heated to 60°C and reacted for 2 hours. Then, 15 mmol of boron tribromide was added at 0°C, and the mixture was transferred to room temperature and reacted for another hour. Next, 20 mmol of N,N-diisopropylethylamine was added at 0°C, the system was heated to 200°C and reacted for 3 hours. After the reaction was complete, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 85.

[0123] 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.89 (d, 1H), 8.57 (d, 1H), 8.33 (d, 1H), 8.23–8.15 (m, 1H), 7.84 (m, 1H), 7.68 (d, 1H), 7.61 (t, 1H), 7.57–7.32 (m, 15H), 7.26–7.19 (m, 1H), 1.43 (s, 9H), 1.35 (s, 9H).

[0124] Example 6: Synthesis of Compound 136:

[0125]

[0126] Under nitrogen protection, 10 mmol of starting material A-6 and 12 mmol of NaH were added to a three-necked flask, followed by 50 mL of anhydrous DMF. The mixture was stirred at room temperature for 0.5 hours. Then, 10 mmol of starting material B-1 was added, and the mixture was heated to 80°C and reacted for 10 hours. After the reaction was complete, 100 mL of deionized water was added, the precipitate was filtered, dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered, and separated by column chromatography to obtain intermediate a-6. LC-MS: Measured value: 472.00 ([M+H)) + Theoretical value: 471.06.

[0127] In a three-necked flask under nitrogen protection, 10 mmol of intermediate a-6, 10 mmol of starting material D-1, 10 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, and 200 mL of toluene were added and refluxed for 12 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate b-6. LC-MS: Measured value: 671.30 ([M+H) + Theoretical value: 670.33.

[0128] In a sealed, pressure-resistant tube under nitrogen protection, 10 mmol of intermediate b-6 and 5 ml of o-dichlorobenzene were added. A solution of 12 mmol of n-butyllithium in n-hexane was added at 0 °C, the system was heated to 60 °C and reacted for 2 hours. Then, 15 mmol of boron tribromide was added at 0 °C, and the mixture was transferred to room temperature and reacted for another 2 hours. Next, 20 mmol of N,N-diisopropylethylamine was added at 0 °C, the system was heated to 200 °C and reacted for 4 hours. After the reaction was complete, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 136.

[0129] 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.99 (d, 1H), 8.81 (dd, 1H), 8.76 (d, 1H), 8.28 (d, 1H), 8.14–8.05 (m, 2H), 7.91 (m, 1H), 7.85 (dd, 1H), 7.77 (d, 1H), 7.73–7.22 (m, 12H), 1.51 (s, 9H), 1.40 (s, 9H).

[0130] Example 7: Synthesis of Compound 185:

[0131]

[0132] Under nitrogen protection, 10 mmol of starting material A-7 and 10 mmol of starting material B-7 were added to tetrahydrofuran. The reaction solution was sealed in a thick-walled pressure-resistant tube and microwave-heated to 150°C for 2 hours. After heating was stopped and the mixture was cooled to room temperature, the reaction solution was concentrated and separated by column chromatography to obtain intermediate a-7. LC-MS: Measured value: 280.23 ([M+H)) + Theoretical value: 279.20.

[0133] Under nitrogen protection, 10 mmol of intermediate a-7 and 12 mmol of NaH were added to a three-necked flask, followed by 50 mL of anhydrous DMF. The mixture was stirred at room temperature for 0.5 hours. Then, 10 mmol of starting material B-1 was added, and the mixture was heated to 80 °C and reacted for 20 hours. After the reaction was complete, 100 mL of deionized water was added, the precipitate was filtered, dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered, and separated by column chromatography to obtain intermediate b-7. LC-MS: Measured value: 434.12 ([M+H)) + Theoretical value: 433.14.

[0134] In a three-necked flask under nitrogen protection, 10 mmol of intermediate b-7, 10 mmol of starting material D-1, 10 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, and 200 mL of toluene were added and refluxed for 18 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate c-7. LC-MS: Measured value: 633.44 ([M+H)) + Theoretical value: 632.41.

[0135] In a sealed, pressure-resistant tube under nitrogen protection, 10 mmol of intermediate C-7 and 5 ml of o-dichlorobenzene were added. A solution of 12 mmol of n-butyllithium in n-hexane was added at 0 °C, the system was heated to 60 °C and reacted for 3 hours. Then, 15 mmol of boron tribromide was added at 0 °C, and the mixture was transferred to room temperature and reacted for another 2 hours. Next, 20 mmol of N,N-diisopropylethylamine was added at 0 °C, the system was heated to 200 °C and reacted for 3 hours. After the reaction was complete, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 185. 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.51 (d, 1H), 8.32 (d, 1H), 8.11 (d, 1H), 7.95–7.89 (m, 1H), 7.83 (d, 1H), 7.79 (t, 1H), 7.66 (dd, 1H), 7.60–7.37 (m, 6H), 1.44–1.41 (m, 27H), 1.33 (s, 9H).

[0136] Example 8: Synthesis of compound 283:

[0137]

[0138] Under nitrogen protection, 10 mmol of intermediate a-7 and 12 mmol of NaH were added to a three-necked flask, followed by 50 mL of anhydrous DMF. The mixture was stirred at room temperature for 0.5 hours. Then, 10 mmol of starting material A-8 was added, and the mixture was heated to 80 °C and reacted for 4 hours. After the reaction was complete, 100 mL of deionized water was added, the precipitate was filtered, dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered, and separated by column chromatography to obtain intermediate a-8. LC-MS: Measured value: 490.29 ([M+H)) + Theoretical value: 489.20.

[0139] In a three-necked flask under nitrogen protection, 10 mmol of intermediate a-8, 10 mmol of starting material D-1, 10 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, and 200 mL of toluene were added and refluxed for 24 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate b-8. LC-MS: Measured value: 689.45 ([M+H) + Theoretical value: 688.48.

[0140] In a sealed, pressure-resistant tube under nitrogen protection, 10 mmol of intermediate b-8 and 5 ml of o-dichlorobenzene were added. A solution of 12 mmol of n-butyllithium in n-hexane was added at 0°C, the system was heated to 60°C and reacted for 2 hours. Then, 15 mmol of boron tribromide was added at 0°C, and the mixture was transferred to room temperature and reacted for another 2 hours. Next, 20 mmol of N,N-diisopropylethylamine was added to the system at 0°C, the mixture was heated to 200°C and reacted for 2.5 hours. After the reaction was complete, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 283.

[0141] 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.75 (d, 1H), 8.39 (d, 1H), 8.11 (d, 1H), 7.82 (m, 1H), 7.67 (d, 1H), 7.59 (dd, 1H), 7.52–7.48 (m, 3H), 7.45–7.26 (m, 3H), 1.47–1.41 (m, 27H), 1.36 (d, 18H).

[0142] Example 9: Synthesis of compound 332:

[0143]

[0144] Under nitrogen protection, 10 mmol of starting material A-5 and 12 mmol of NaH were added to a three-necked flask, followed by 50 mL of anhydrous DMF. The mixture was stirred at room temperature for 0.5 hours. Then, 10 mmol of starting material B-7 was added, and the mixture was heated to 80°C and reacted for 6 hours. After the reaction was complete, 100 mL of deionized water was added, the precipitate was filtered, dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered, and separated by column chromatography to obtain intermediate a-9. LC-MS: Measured value: 530.19 ([M+H)) + Theoretical value: 529.14.

[0145] In a three-necked flask under nitrogen protection, 10 mmol of intermediate a-9, 10 mmol of starting material D-1, 10 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, and 200 mL of toluene were added and refluxed for 8 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate b-9. LC-MS: Measured value: 729.48 ([M+H)) + Theoretical value: 728.41.

[0146] In a sealed, pressure-resistant tube under nitrogen protection, 10 mmol of intermediate b-9 and 5 ml of o-dichlorobenzene were added. A solution of 12 mmol of n-butyllithium in n-hexane was added at 0°C, the system was heated to 60°C and reacted for 2 hours. Then, 15 mmol of boron tribromide was added at 0°C, and the mixture was transferred to room temperature and reacted for another 2 hours. Next, 20 mmol of N,N-diisopropylethylamine was added to the system at 0°C, the mixture was heated to 200°C and reacted for 1.5 hours. After the reaction was complete, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 332.

[0147] 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.70 (d, 1H), 8.58 (d, 1H), 8.34 (d, 1H), 8.17 (dd, 1H), 7.82 (m, 1H), 7.73 (d, 1H), 7.56–7.25 (m, 16H), 1.39 (s, 9H), 1.36 (d, 18H).

[0148] Example 10: Synthesis of compound 381:

[0149]

[0150] Under nitrogen protection, 10 mmol of starting material A-1, 10 mmol of starting material A-10, 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6, and 70 mL of dichlorobenzene were added to a three-necked flask, and the mixture was refluxed for 72 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate a-10. LC-MS: Measured value: 446.01 ([M+H)) + Theoretical value: 445.05.

[0151] In a three-necked flask under nitrogen protection, 10 mmol of intermediate a-10, 10 mmol of starting material D-1, 10 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, and 200 mL of toluene were added and refluxed for 10 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate b-10. LC-MS: Measured value: 645.33 ([M+H) + Theoretical value: 644.32.

[0152] In a sealed, pressure-resistant tube under nitrogen protection, 10 mmol of intermediate b-10 and 5 ml of o-dichlorobenzene were added. A solution of 12 mmol of n-butyllithium in n-hexane was added at 0 °C, the system was heated to 60 °C and reacted for 1 hour. Then, 15 mmol of boron tribromide was added at 0 °C, and the mixture was transferred to room temperature and reacted for another 2 hours. Next, 20 mmol of N,N-diisopropylethylamine was added at 0 °C, the system was heated to 200 °C and reacted for 1 hour. After the reaction was complete, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 381.

[0153] 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.72 (d, 1H), 8.34 (d, 1H), 8.16 (m, 1H), 8.03–7.95 (m, 2H), 7.93 (dd, 1H), 7.89–7.85 (m, 3H), 7.81–7.76 (m, 2H), 7.73–7.60 (m, 2H), 7.51 (d, 1H), 7.49–7.38 (m, 2H), 7.25–7.13 (m, 2H), 6.82 (dd, 1H), 1.37 (s, 9H), 1.28 (s, 9H).

[0154] Example 11 Synthesis of compound 396:

[0155]

[0156] Under nitrogen protection, 10 mmol of starting material A-1, 10 mmol of starting material A-11, 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6, and 70 mL of dichlorobenzene were added to a three-necked flask, and the mixture was refluxed for 24 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate a-11. LC-MS: Measured value: 368.13 ([M+H)) + Theoretical value: 367.08.

[0157] In a three-necked flask under nitrogen protection, 10 mmol of intermediate a-11, 10 mmol of starting material D-1, 10 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, and 200 mL of toluene were added and refluxed for 48 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate b-11. LC-MS: Measured value: 611.33 ([M+H) + Theoretical value: 610.30.

[0158] In a sealed, pressure-resistant tube under nitrogen protection, 10 mmol of intermediate b-11 and 5 ml of o-dichlorobenzene were added. A solution of 12 mmol of n-butyllithium in n-hexane was added at 0 °C, the system was heated to 60 °C and reacted for 2 hours. Then, 15 mmol of boron tribromide was added at 0 °C, and the mixture was transferred to room temperature and reacted for another 4 hours. Next, 20 mmol of N,N-diisopropylethylamine was added at 0 °C, the system was heated to 200 °C and reacted for 4 hours. After the reaction was complete, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 396.

[0159] 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.77 (d, 1H), 8.35 (d, 1H), 8.11 (d, 1H), 8.05–7.99 (m, 2H), 7.96 (dd, 1H), 7.92–7.89 (m, 2H), 7.85 (s, 1H), 7.64–7.60 (m, 2H), 7.55–7.49 (m, 1H), 7.48–7.43 (m, 1H), 7.39 (m, 2H), 7.33 (dd, 1H), 6.82 (dd, 1H), 1.38 (s, 9H), 1.26 (s, 9H).

[0160] Example 12 Synthesis of compound 457:

[0161]

[0162] Under nitrogen protection, 10 mmol of starting material A-5, 10 mmol of starting material A-11, 15 mmol of potassium carbonate, 0.5 mmol of copper, 15 mmol of 18-crown ether-6, and 70 mL of dichlorobenzene were added to a three-necked flask, and the mixture was refluxed for 24 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate a-12. LC-MS: Measured value: 520.11 ([M+H)) + Theoretical value: 519.14.

[0163] In a three-necked flask under nitrogen protection, 10 mmol of intermediate a-12, 10 mmol of starting material D-1, 10 mmol of potassium carbonate, 0.1 mmol of Pd(PPh3)4, and 200 mL of toluene were added and refluxed for 20 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain intermediate b-12. LC-MS: Measured value: 763.39 ([M+H)) + Theoretical value: 762.36.

[0164] In a sealed, pressure-resistant tube under nitrogen protection, 10 mmol of intermediate b-12 and 5 ml of o-dichlorobenzene were added. A solution of 12 mmol of n-butyllithium in n-hexane was added at 0°C, the system was heated to 60°C and reacted for 2 hours. Then, 15 mmol of boron tribromide was added at 0°C, and the mixture was transferred to room temperature and reacted for another 2 hours. Next, 20 mmol of N,N-diisopropylethylamine was added at 0°C, the system was heated to 200°C and reacted for 2 hours. After the reaction was complete, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain compound 457.

[0165] 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.76 (d, 1H), 8.50 (d, 1H), 8.29 (d, 1H), 8.14 (dd, 1H), 7.91 (dd, 1H), 7.82 (m, 1H), 7.73 (s, 1H), 7.70 (d, 1H), 7.53 (dd, 1H), 7.47–7.18 (m, 16H), 1.44 (s, 9H), 1.36 (s, 9H).

[0166] Example 13 Synthesis of Compound 499:

[0167]

[0168] Compound 17 (10.0 mmol), pinacol diboronate (15 mmol), [Ir(COD)(OCH3)]2 (0.06 mmol), and 50 mL of tetrahydrofuran were added sequentially to a single-necked flask. The reaction was carried out at room temperature for 16 hours under nitrogen protection. The reaction was then filtered, the organic phase was concentrated, and the compounds were separated by silica gel column chromatography using petroleum ether:ethyl acetate (1:1) as the developing solvent to give intermediate a-13. This reaction exhibited relatively good selectivity (see DOI: 10.31635 / ccschem.021.202101033), with the borate ester at the B position showing higher activity and selectivity. LC-MS: Measured value: 708.28 ([M+H) + Theoretical value: 707.29; 1 H NMR (400MHz, Chloroform-d) δ8.13(dd,1H),7.65–7.52(m,4H),7.43(d,2H),7.34(s,2H),7.30–7.00(m,12H),6.25(dd,2H),1.62(s,12H).

[0169] Intermediate a-13 (10.0 mmol), raw material A-13 (10.0 mmol), Pd(PPh3)4 catalyst 0.1 mmol, 50 mL tetrahydrofuran:water = 10:1 mixed solution, and potassium carbonate (20 mmol) were added sequentially to a two-necked flask. The mixture was then stirred at 80 °C for 3 hours under nitrogen protection. After cooling, the liquid was separated and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated. The compound was separated by silica gel column chromatography using petroleum ether:ethyl acetate = 5:1 as the developing solvent to obtain compound 499.

[0170] 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.82 (d, 1H), 8.67–8.58 (m, 4H), 8.49 (d, 1H), 8.15 (dd, 2H), 8.03 (dd, 1H), 7.88–7.82 (m, 2H), 7.69 (d, 1H), 7.63 (dd, 1H), 7.57–7.41 (m, 13H), 7.35–7.23 (m, 5H), 7.18 (m, 1H), 6.76 (dd, 1H).

[0171] The structural characterization of the compounds obtained in each embodiment is shown in Table 1.

[0172] Table 1

[0173]

[0174]

[0175] The compounds of this invention can be used as doping materials for the light-emitting layer in light-emitting devices. The physicochemical properties of the compounds prepared in the above embodiments of this invention were tested, and the results are shown in Table 2.

[0176] Table 2

[0177]

[0178] Note: PLQY (fluorescence quantum yield) and FWHM (full width at half maximum) were measured in thin film state using a Horiba Fluorolog-3 series fluorescence spectrometer.

[0179] As shown in the table above, the compound of the present invention, as a doping material, has a high fluorescence quantum efficiency, which is close to 100%. At the same time, the material has a narrow spectral FWHM, which can effectively improve the color gamut of the device and improve the luminous efficiency of the device.

[0180] The application effects of the OLED material synthesized in this invention in devices are described in detail below through device examples 1-13 and device comparative examples 1-4. Device examples 2-13 and device comparative examples 1-4 of this invention have the same fabrication process as device example 1, and use the same substrate material and electrode material, with the same electrode film thickness. The only difference is the replacement of the light-emitting layer material in the device. The layer structure and test results of each device example are shown in Tables 3-1 and 4, respectively.

[0181] Device Example 1

[0182] like Figure 1As shown, the transparent substrate layer 1 is a transparent PI film. The ITO anode layer 2 (film thickness 150nm) is washed sequentially with a cleaning agent (Semiclean M-L20), followed by washing with pure water, drying, and then ultraviolet-ozone washing to remove organic residues from the transparent ITO surface. After the above washing, HT-1 and HI-1 with a thickness of 10nm are deposited on the ITO anode layer 2 using a vacuum evaporation apparatus as a hole injection layer 3, with a mass ratio of HT-1 to HI-1 of 97:3. Next, a 60nm thick layer of HT-1 is deposited as a hole transport layer 4. Subsequently, a 30nm thick layer of EB-1 is deposited as an electron blocking layer 5. After the electron blocking materials are deposited, the light-emitting layer 6 of the OLED light-emitting device is fabricated, using GH-1 and GH-2 as the host materials and compound 3 as the dopant material, with a mass ratio of GH-1, GH-2, and compound 3 of 69:30:1, and a film thickness of 30nm. Following the aforementioned light-emitting layer 6, HB-1 is vacuum-deposited to a thickness of 5 nm; this layer serves as the hole-blocking layer 7. Following the hole-blocking layer 7, ET-1 and Liq are vacuum-deposited at a mass ratio of 1:1, resulting in a film thickness of 30 nm; this layer serves as the electron transport layer 8. On the electron transport layer 8, a LiF layer with a thickness of 1 nm is fabricated using a vacuum evaporation apparatus; this layer serves as the electron injection layer 9. On the electron injection layer 9, an 80 nm thick Mg:Ag electrode layer is fabricated using a vacuum evaporation apparatus, with a Mg:Ag mass ratio of 1:9; this layer serves as the cathode layer 10.

[0183] The application effects of the OLED material synthesized in this invention in devices are described in detail below using Device Examples 14-26 and Comparative Examples 5-8. Device Examples 15-26 and Comparative Examples 5-8 of this invention have the same fabrication process as Device Example 14, and use the same substrate and electrode materials, with consistent electrode film thickness. The only difference is the replacement of the light-emitting layer material. The layer structure and test results of each device example are shown in Tables 3-2 and 4, respectively.

[0184] Device Example 14

[0185] The transparent substrate layer 1 is a transparent PI film. The ITO anode layer 2 (film thickness 150nm) is washed sequentially with a cleaning agent (Semiclean M-L20), washed with pure water, dried, and then washed with ultraviolet light and ozone to remove organic residues from the transparent ITO surface. After the above washing, HT-1 and HI-1 with a thickness of 10nm are deposited on the ITO anode layer 2 using a vacuum evaporation apparatus as a hole injection layer 3, with a mass ratio of HT-1 to HI-1 of 97:3. Next, a 60nm thick layer of HT-1 is deposited as a hole transport layer 4. Subsequently, a 30nm thick layer of EB-1 is deposited as an electron blocking layer 5. After the electron blocking materials are deposited, the light-emitting layer 6 of the OLED light-emitting device is fabricated, using GH-1 and GH-2 as the host materials, GD-1 as the first dopant, and compound 3 as the second dopant, with a mass ratio of GH-1, GH-2, GD-1, and compound 3 of 66:30:3:1. The light-emitting layer has a film thickness of 30nm. Following the aforementioned light-emitting layer 6, HB-1 is vacuum-deposited to a thickness of 5 nm; this layer serves as the hole-blocking layer 7. Following the hole-blocking layer 7, ET-1 and Liq are vacuum-deposited at a mass ratio of 1:1, resulting in a film thickness of 30 nm; this layer serves as the electron transport layer 8. On the electron transport layer 8, a LiF layer with a thickness of 1 nm is fabricated using a vacuum evaporation apparatus; this layer serves as the electron injection layer 9. On the electron injection layer 9, an 80 nm thick Mg:Ag electrode layer is fabricated using a vacuum evaporation apparatus, with a Mg:Ag mass ratio of 1:9; this layer serves as the cathode layer 10.

[0186] The molecular structural formulas of the relevant materials are shown below:

[0187]

[0188] After completing the OLED light-emitting device as described above, the anode and cathode are connected using a known driving circuit, and the current efficiency, external quantum efficiency, and lifetime of the device are measured. Examples and comparisons of devices prepared using the same method are shown in Tables 3-1 and 3-2; the test results for the current efficiency, external quantum efficiency, and lifetime of the obtained devices are shown in Table 4.

[0189] Table 3-1

[0190]

[0191]

[0192] Table 3-2

[0193]

[0194]

[0195] Table 4

[0196]

[0197] Note: Voltage, current efficiency, and emission peak were measured using an IVL (current-voltage-brightness) testing system (Suzhou Fushida Scientific Instruments Co., Ltd.); the lifetime testing system was the EAS-62C OLED device lifetime tester from System Technology Inc., Japan; LT95 refers to the time it takes for the device brightness to decay to 95%; all data are within 10 mA / cm². 2 Next test.

[0198] As can be seen from the device data results in Table 4, compared with devices Comparative Examples 1-4, the compounds of the present invention exhibit higher current efficiency and device lifetime in the fluorescence-sensitized system devices; in the phosphorus-sensitized system devices, the device efficiency also shows a better effect, which is because this type of boron-nitrogen fused ring core can enhance the resonance intensity and improve the device efficiency; compared with devices Comparative Examples 5-8, the compounds of the present invention show a significant improvement in current efficiency and device lifetime in both the fluorescence-sensitized system devices and the phosphorus-sensitized system devices compared with OLED devices made of known materials.

[0199] In summary, the above are merely preferred embodiments of the present invention and are 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 within the protection scope of the present invention.

Claims

1. A boron-containing organic compound, characterized in that, The structures of the boron-containing organic compounds are shown in general formula (1-1) or general formula (1-2): In general formulas (1-1) and (1-2), Z is represented as C-R1; Each occurrence of R1, whether identical or different, represents a hydrogen atom, deuterium atom, halogen atom, or substituted or unsubstituted C1-C1 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, diphenyl-substituted amino, tert-butylbenzene-substituted amino, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups; Each occurrence of R, whether the same or different, represents a hydrogen atom, deuterium atom, halogen atom, or substituted or unsubstituted C1-C1 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups; A1 represents one of the following: substituted or unsubstituted phenyl, substituted or unsubstituted pyrene, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophene. Ar1 represents C6-C6 with or without substitution. 30 aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups; The substituents used for the substituent groups are optionally selected from deuterium atoms, halogen atoms, C1 to C2 atoms. 10 Alkyl groups, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2~C 30 One or more of the heteroaryl groups.

2. A boron-containing organic compound, characterized in that, The structure of the boron-containing organic compound is shown in general formula (2) or general formula (3): In general formulas (2) and (3), Z is represented as C-R1; Each occurrence of R1, whether identical or different, represents a hydrogen atom, deuterium atom, halogen atom, or substituted or unsubstituted C1-C1 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, diphenyl-substituted amino, tert-butylbenzene-substituted amino, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups; The substituents used for the substituent groups are optionally selected from deuterium atoms, halogen atoms, C1 to C2 atoms. 10 Alkyl groups, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2~C 30 One or more of the heteroaryl groups.

3. A boron-containing organic compound, characterized in that, The structure of the boron-containing organic compound is shown in any one of general formulas (16) to (20): In general formulas (4) to (20), Z is represented as C-R1; Each occurrence of R1, whether identical or different, represents a hydrogen atom, deuterium atom, halogen atom, or substituted or unsubstituted C1-C1 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, diphenyl-substituted amino, tert-butylbenzene-substituted amino, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups; The substituents used for the substituent groups are optionally selected from deuterium atoms, halogen atoms, C1 to C2 atoms. 10 Alkyl groups, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2~C 30 One or more of the heteroaryl groups; X2 represents one of O and S; X1 is represented as N(R2); R2 represents one of the following: phenyl, deuterated phenyl, diphenyl, deuterated diphenyl, naphthyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, and tert-butyl-substituted diphenyl.

4. A boron-containing organic compound, characterized in that, The structure of the boron-containing organic compound is shown in any one of general formulas (15-1) to (16-1): In general formulas (15-1) to (16-1), Z is represented as C-R1; Each occurrence of R1, whether identical or different, represents a hydrogen atom, deuterium atom, halogen atom, or substituted or unsubstituted C1-C1 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, diphenyl-substituted amino, tert-butylbenzene-substituted amino, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups; X2 represents one of O and S.

5. A boron-containing organic compound, characterized in that, The structure of the boron-containing organic compound is shown in any one of general formulas (A-1) to (A-11): In general formulas (A-1) to (A-11), Z is represented as C-R1; Each occurrence of R1, whether identical or different, represents a hydrogen atom, deuterium atom, halogen atom, or substituted or unsubstituted C1-C1 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, diphenyl-substituted amino, tert-butylbenzene-substituted amino, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups; X2 represents one of O and S; X1 is represented as N(R2); R2 represents one of the following: phenyl, deuterated phenyl, diphenyl, deuterated diphenyl, naphthyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, and tert-butyl-substituted diphenyl. R1, R, and R0 are independently represented as hydrogen atom, deuterium atom, halogen atom, adamantyl, methyl, deuterated methyl, trifluoromethyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, naphthyl, anthracene, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazoyl, N-phenylcarbazoyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted One of the following: phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, diphenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, phenyl-substituted triazineyl, methoxy, and tert-butoxy.

6. The boron-containing organic compound according to claim 1, characterized in that, R1 represents hydrogen atom, deuterium atom, halogen atom, adamantyl, methyl, deuterated methyl, trifluoromethyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, naphthyl, anthracene, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazoyl, N-phenylcarbazoyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted One of the following: phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, diphenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, phenyl-substituted triazineyl, methoxy, and tert-butoxy. The A1 represents a substituted or unsubstituted phenyl, a substituted or unsubstituted pyrene, a substituted or unsubstituted dibenzofuranyl, or a substituted or unsubstituted dibenzothiopheneyl. The substituents used for the substituent groups are selected from deuterium, tritium, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, and naphthyl.

7. The boron-containing organic compound according to claim 3, characterized in that, R1 represents hydrogen atom, deuterium atom, halogen atom, adamantyl, methyl, deuterated methyl, trifluoromethyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, naphthyl, anthracene, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazoyl, N-phenylcarbazoyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted One of the following: phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, diphenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, phenyl-substituted triazineyl, methoxy, and tert-butoxy. R2 represents one of phenyl, diphenyl, or naphthyl.

8. The boron-containing organic compound according to claim 5, characterized in that, The organic compound has a specific structure that is any one of the following:

9. An organic electroluminescent device, comprising a cathode and an anode, and an organic light-emitting functional layer therebetween, said organic light-emitting functional layer comprising a light-emitting layer, characterized in that, The light-emitting layer contains a boron-containing organic compound as described in any one of claims 1-8.

10. The organic electroluminescent device according to claim 9, characterized in that, The light-emitting layer comprises a host material and a dopant material, wherein the dopant material contains a boron-containing organic compound as described in any one of claims 1-8.

11. The organic electroluminescent device according to claim 9, wherein the light-emitting layer comprises a first host material, a second host material, and a dopant material, characterized in that, At least one of the first host material and the second host material is a TADF material, and the doping material is a boron-containing organic compound as described in any one of claims 1-8.

12. The organic light-emitting device according to claim 9, wherein the light-emitting layer comprises a host material, an exciton-sensitizing material, and a dopant material, characterized in that, The exciton sensitizing material is a complex containing a metal element, and the doping material is a boron-containing organic compound as described in any one of claims 1-8.

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