Organic compound and organic electroluminescent device containing the compound

Abstract

The present invention provides an organic compound represented by the following general formula 1 and an organic electroluminescent device including the organic compound. [General formula 1]

Description

Technical Field

[0001] The present invention relates to the field of display screens, and more particularly to an organic compound used in the manufacture of an organic electroluminescent device of a display screen and an organic electroluminescent device containing the compound. Background Art

[0002] Until now, most flat panel displays are liquid crystal displays, but efforts have been actively made around the world to develop new flat panel displays that are more economical, have better performance, and are different from liquid crystal displays. Recently, organic electroluminescent devices have attracted attention as the next generation of flat panel displays. Compared with liquid crystal displays, they have the advantages of low driving voltage, fast response speed, and wide viewing angle.

[0003] According to the structure of the organic electroluminescent device, it is composed of a substrate, an anode, a hole injection layer that receives holes from the anode, a hole transport layer for transporting holes, an electron blocking layer that prevents electrons from entering the hole transport layer from the light-emitting layer, a light-emitting layer that emits light by combining holes and electrons, a hole blocking layer that prevents holes from entering the electron transport layer from the light-emitting layer, an electron transport layer that receives electrons from the cathode and transmits them to the light-emitting layer, an electron injection layer that receives electrons from the cathode, and a cathode. Depending on the situation, there is no need for an independent light-emitting layer, and a small amount of fluorescent or phosphorescent dye is doped into the electron transport layer or the hole transport layer to form a light-emitting layer. When using a polymer, generally speaking, one polymer can perform the roles of a hole transport layer, a light-emitting layer, and an electron transport layer at the same time. The organic thin film layer between the two electrodes can be formed by vacuum deposition, spin coating, inkjet printing, laser hot stamping, and other methods. As shown above, the reason why organic electroluminescent devices are made with a multi-layer thin film structure is to achieve interface stabilization between the electrode and the organic matter. When using organic matter, since the movement speeds of holes and electrons are very different, appropriate hole transport layers and electron transport layers are used to allow holes and electrons to be efficiently transmitted to the light-emitting layer, achieving a density balance of holes and electrons, thereby improving the light-emitting efficiency.

[0004] The driving principle of the organic electroluminescent device is as follows: when a voltage is applied between the anode and the cathode, the holes injected from the anode will move to the light-emitting layer via the hole injection layer and the hole transport layer. At the same time, electrons are injected from the cathode into the light-emitting layer via the electron injection layer and the electron transport layer, and recombine with carriers in the light-emitting layer to form excitons. In this state, the excitons change to the ground state, and thus, the fluorescent molecules in the light-emitting layer emit light to form an image. At this time, the excited state returns to the ground state through the singlet excited state, and the light emitted is called "fluorescence"; the light emitted by returning to the ground state through the triplet excited state is called "phosphorescence". The probability of returning to the ground state through the singlet excited state is 25% (the probability of passing through the triplet excited state is 75%), so the luminous efficiency is limited. If phosphorescence is used, 75% of the triplet excited state and 25% of the singlet excited state can be used for luminescence, so theoretically, the internal quantum efficiency can reach 100%.

[0005] The biggest problems with this type of organic electroluminescent device are its service life and luminous efficiency. As display screens become larger in area, service life and luminous efficiency have become issues that must be addressed.

[0006] Prior art documents related to the present application include: Korean Patent No. 1022021710000, Korean Patent No. 1018256120000 and Korean Patent No. 1012267000000. Summary of the invention

[0007] [Technical issues to be solved]

[0008] The present invention is proposed to solve the above-mentioned problems that occur in some situations of the conventional technology.

[0009] The object of the present invention is to provide a novel organic compound for use as a material for an organic electroluminescent device, thereby improving the luminous efficiency and luminous life of the organic electroluminescent device.

[0010] Another object of the present invention is to provide an organic electroluminescent device having improved driving voltage, luminous efficiency and luminous lifetime by including such an organic electroluminescent device material.

[0011] In addition, the present invention aims to provide an organic electroluminescent device, which further improves the driving voltage, luminous efficiency and luminous life of the device by combining materials comprising the organic electroluminescent device and a specific hole transport layer substance.

[0012]

Solutions to technical problems

[0013] The present invention provides an organic compound represented by the following general formula 1:

[0014] [General formula 1]

[0015]

[0016] In the above formula

[0017] R1 is deuterium, halogen, CN, CF3, a straight or branched chain alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a thiol group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, a substituted or unsubstituted phenyl group selected from the group consisting of anthracene, decalin, biphenyl, anthracene, phenanthryl, pyrene, 9,9-dimethylfluorene, carbazole, dibenzofuran, pyrrole, triazoles, aminobenzene, pyrazine, pyrimidine, quinoline, phenylpyridine, phenylpyrimidine, phenylimidazole or phenyltriazine, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms.

[0018] Deutzyl, halogen, CN, CF3, a straight or branched alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a thiol group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, one or more substituted or unsubstituted anthracenyl selected from the group consisting of anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorene, difluoroethylene, carbazole, dibenzofuran, pyrrole, triazoles, aminobenzene, pyrazine, pyrimidine, quinoline, phenylpyridine, phenylpyrimidine, phenylimidazole or phenyltriazine, and a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more elements selected from the group consisting of S, O, N, B and Si.

[0019] Z1, Z4, and Z5 are independently single bonds or C1-C10 straight or branched alkyl groups, C3-C12 cycloalkyl groups, C1-C10 alkoxy groups, halogen groups, CN, CF3, phenyl groups, decalin groups, biphenyl groups, phenylpyridine groups, phenylpyrimidine groups, phenylimidazole groups, and one or more substituted or unsubstituted aniline groups selected from the group consisting of Si(CH3)3.

[0020] Z2 and Z3 are each an independent single bond or one or more substituted or unsubstituted phenyl groups selected from the group consisting of halogen, CN, CF3, phenyl, decalin, phenylpyridine, phenylpyrimidine, phenylimidazole and Si(CH3)3.

[0021] a, b, c, d, e are independently 0 or 1,

[0022] Z6, Z7, Z8 are independent single bonds, C1-C2 alkylbenzene, phenyl or biphenyl,

[0023] f, g, h are independently 0 or 1,

[0024] M is boron, carbon or nitrogen,

[0025] G1, G2, G3 are independently carbon, nitrogen, oxygen or sulfur,

[0026] G4, G5, and G6 are each independently carbon or nitrogen.

[0027] R2, R3, R4, R5, R6, R7, R8 and R9 are independently hydrogen, deutrium, F, Cl, Br, I, CN, Si(CH3)3, B(OH)2, a straight or branched chain alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a thiol group having 1 to 40 carbon atoms, or a cycloalkyl group having 3 to 40 carbon atoms.

[0028] Deutzyl, F, Cl, Br, I, CN, Si(CH3)3, B(OH)2, a straight or branched chain alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a thiol group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, one or more substituted or unsubstituted anthracenyl groups selected from the group consisting of a phenyl group, a phenanthrenyl group, a pyrenyl group, 9,9-dimethylfluorene, carbazole, dibenzofuran, pyrrole, triazoles, aminobenzene, pyrazine, pyrimidine and quinoline groups, and one or more substituted or unsubstituted aromatic hydrocarbon groups having 6 to 60 carbon atoms selected from the group consisting of a quinoline group.

[0029] Deutzyl, F, Cl, Br, I, CN, Si(CH3)3, B(OH)2, a straight or branched alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a thiol group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, one or more substituted or unsubstituted anthracenyl groups selected from the group consisting of anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorene, difluoroethylene, carbazole, dibenzofuran, pyrrole, triazoles, aminobenzene, pyrazine, pyrimidine, and quinoline, and a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more elements selected from the group consisting of S, O, N, B and Si.

[0030] Deutz, F, Cl, Br, I, CN, Si(CH3)3, B(OH)2, a straight or branched alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a thiol group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, and one or more substituted or unsubstituted phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with phenyl, phenanthrenyl, pyrene, 9,9-dimethylfluorene, carbazole, quinoline, dibenzofuran, pyrrole, triazole, aminobenzene, pyrazine and pyrimidine.

[0031] [Effects of the invention]

[0032] The object of the present invention is to provide a novel organic compound for use as a material for an organic electroluminescent device, thereby improving the luminous efficiency and luminous life of the organic electroluminescent device.

[0033] In addition, the present invention provides an organic electroluminescent device having improved driving voltage, luminous efficiency and luminous life by including the above-mentioned organic electroluminescent device material.

[0034] In addition, the present invention aims to provide an organic electroluminescent device, which further improves the driving voltage, luminous efficiency and luminous life of the device by combining the material containing the above-mentioned organic electroluminescent device and a specific hole transport layer substance. DETAILED DESCRIPTION

[0035] The present invention relates to a novel organic compound represented by the following general formula 1:

[0036] [General formula 1]

[0037]

[0038] In the above formula

[0039] R1 is deuterium, halogen, CN, CF3, a straight or branched chain alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a thiol group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, a substituted or unsubstituted phenyl group selected from the group consisting of anthracene, decalin, biphenyl, anthracene, phenanthryl, pyrene, 9,9-dimethylfluorene, carbazole, dibenzofuran, pyrrole, triazoles, aminobenzene, pyrazine, pyrimidine, quinoline, phenylpyridine, phenylpyrimidine, phenylimidazole or phenyltriazine, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms.

[0040] Deutzyl, halogen, CN, CF3, a straight or branched alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a thiol group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, one or more substituted or unsubstituted anthracenyl selected from the group consisting of anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorene, difluoroethylene, carbazole, dibenzofuran, pyrrole, triazoles, aminobenzene, pyrazine, pyrimidine, quinoline, phenylpyridine, phenylpyrimidine, phenylimidazole or phenyltriazine, and a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more elements selected from the group consisting of S, O, N, B and Si.

[0041] Z1, Z4, and Z5 are independently single bonds or C1-C10 straight or branched alkyl groups, C3-C12 cycloalkyl groups, C1-C10 alkoxy groups, halogen groups, CN, CF3, phenyl groups, decalin groups, biphenyl groups, phenylpyridine groups, phenylpyrimidine groups, phenylimidazole groups, and one or more substituted or unsubstituted aniline groups selected from the group consisting of Si(CH3)3.

[0042] Z2 and Z3 are each an independent single bond or one or more substituted or unsubstituted phenyl groups selected from the group consisting of halogen, CN, CF3, phenyl, decalin, phenylpyridine, phenylpyrimidine, phenylimidazole and Si(CH3)3.

[0043] a, b, c, d, e are independently 0 or 1,

[0044] Z6, Z7, Z8 are independent single bonds, C1-C2 alkylbenzene, phenyl or biphenyl,

[0045] f, g, h are independently 0 or 1,

[0046] M is boron, carbon or nitrogen,

[0047] G1, G2, G3 are independently carbon, nitrogen, oxygen or sulfur,

[0048] G4, G5, and G6 are each independently carbon or nitrogen.

[0049] R2, R3, R4, R5, R6, R7, R8 and R9 are independently hydrogen, deutrium, F, Cl, Br, I, CN, Si(CH3)3, B(OH)2, a straight or branched chain alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a thiol group having 1 to 40 carbon atoms, or a cycloalkyl group having 3 to 40 carbon atoms.

[0050] Deutzyl, F, Cl, Br, I, CN, Si(CH3)3, B(OH)2, a straight or branched chain alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a thiol group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, one or more substituted or unsubstituted anthracenyl groups selected from the group consisting of a phenyl group, a phenanthrenyl group, a pyrenyl group, 9,9-dimethylfluorene, carbazole, dibenzofuran, pyrrole, triazoles, aminobenzene, pyrazine, pyrimidine and quinoline groups, and one or more substituted or unsubstituted aromatic hydrocarbon groups having 6 to 60 carbon atoms selected from the group consisting of a quinoline group.

[0051] Deutzyl, F, Cl, Br, I, CN, Si(CH3)3, B(OH)2, a straight or branched alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a thiol group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, one or more substituted or unsubstituted anthracenyl groups selected from the group consisting of anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorene, difluoroethylene, carbazole, dibenzofuran, pyrrole, triazoles, aminobenzene, pyrazine, pyrimidine, and quinoline, and a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more elements selected from the group consisting of S, O, N, B and Si.

[0052] Deutz, F, Cl, Br, I, CN, Si(CH3)3, B(OH)2, a straight or branched alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a thiol group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, and one or more substituted or unsubstituted phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with phenyl, phenanthrenyl, pyrene, 9,9-dimethylfluorene, carbazole, quinoline, dibenzofuran, pyrrole, triazole, aminobenzene, pyrazine and pyrimidine.

[0053] Specific examples of the above organic compound include any one of the following compounds 1 to 352:

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072] The organic electroluminescent device according to the present invention will be described below by way of example, but the following examples are not intended to limit the organic electroluminescent device according to the present invention.

[0073] The manufacturing method of the organic electroluminescent device of the present invention is as follows: First, the anode material is laminated on the surface of the substrate by conventional methods to form an anode, and the substrate used is a glass substrate or a transparent plastic substrate with good transparency, surface smoothness, operability and waterproofness. In addition, the anode material can use transparent and conductive indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO) and the like.

[0074] Then, a hole injection layer material (HIL) is vacuum thermally deposited or spin-coated on the anode surface by conventional methods to form a hole injection layer. The hole injection layer material can be CuPc, m-MTDATA, m-MTDAPB, TCTA of star amines, 2-TNATA, or IDE406 that can be purchased from Idemitsu Kosan Co., Ltd. of Japan.

[0075] The hole transport layer material (HTL) is vacuum thermally deposited or spin-coated on the surface of the hole injection layer by conventional methods to form the hole transport layer. The hole transport layer material can be α-NPD, NPB, or TPD. It is more desirable to use the chemical of general formula 2 of the present invention.

[0076] The light-emitting layer material (EML) is vacuum-heat-deposited or spin-coated on the surface of the hole transport layer by conventional methods to form a light-emitting layer. The light-emitting material can be a light-storing fluorescent material, a fluorescent brightener, a laser pigment, an organic scintillator, a fluorescent analysis reagent, etc. Specifically, there are carbazole compounds, phosphine oxide compounds, carbazole phosphine oxide compounds, FCN, Alq3, anthracene, phenanthrene, pyrene, chrysene, perylene, hexaphenylene, rubrene and polycyclic aromatic hydrocarbon compounds like quinacridone, phenylene compounds like quaterphenyl, 1,4-bis(2-methylphenylvinyl)benzene, 1,4-bis(4-methyl-5-phenyl-2-oxazolyl)benzene, 1,4-bis(5-phenyl-2-oxazolyl)phenyl, 2,5-bis(5-t-butyl-2-benzoxazolyl)thiophene, 1,4-biphenyl-1, 3-butadiene, 1,6-biphenyl-1,3,5-hexatriene, scintillators for liquid scintillation such as 1,1,4,4-tetraphenyl-1,3-butadiene, metal carriers of auxin derivatives, coumarin pigments, dicyanomethylene pigments, dicyanomethylenethiopyran pigments, polymethine pigments, hydroxybenzene anthracene pigments, xanthene pigments, quinolone pigments, perylene pigments, oxazine compounds, stilbene derivatives, spiro compounds, oxadiazoles, etc. In particular, in the case of blue organic electroluminescent devices, it is best to use the organic compound of the general formula 1 of the present invention as a dopant.

[0077] Optionally, an electron blocking layer (EBL) may be added between the hole transport layer and the light emitting layer.

[0078] The electron transport layer material (ETL) is vacuum thermally deposited or spin-coated on the surface of the light-emitting layer by conventional methods to form the electron transport layer. The electron transport layer material is not particularly limited, and Alq3 is preferably used.

[0079] Optionally, a hole blocking layer (HBL) may be added between the light-emitting layer and the electron transport layer, and phosphorescent dopants may be used in the light-emitting layer to prevent triplet excitons from diffusing into the electron transport layer.

[0080] The hole blocking layer material (HBL) is vacuum thermally deposited or spin-coated on the surface of the light-emitting layer by conventional methods to form a hole blocking layer. The hole blocking layer material is not particularly limited, and preferably Liq, 2-methyl-8-hydroxyquinoline-4-hydroxybiphenyl aluminum (BAlq), BCP, and LiF.

[0081] The electron injection layer material (EIL) is vacuum thermally deposited or spin-coated on the surface of the electron transport layer by conventional methods to form the electron injection layer. The electron injection layer material can be LiF, Liq, Li2O, BaO, NaCl, CsF, etc.

[0082] The cathode material is vacuum-thermally deposited or spin-coated on the electron injection layer by conventional methods to form the cathode. The cathode material can be Li, Al, Al-Li, Ca, Mg, Mg-In, Mg-Ag, etc. In addition, the organic electroluminescent device uses indium tin oxide (ITO) or indium zinc oxide (IZO) to make a light-transmitting transparent cathode.

[0083] According to the above-mentioned covering layer composition, a covering layer (CPL) may be further formed on the surface of the cathode.

[0084] According to the above-mentioned method for manufacturing an organic electroluminescent device, it can be manufactured in the order of anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode. Similarly, it can also be manufactured in the order of cathode / electron injection layer / electron transport layer / light-emitting layer / hole transport layer / hole injection layer / anode.

[0085] The following is an example of the synthesis method of the compound of Formula 1. However, the following method does not limit the synthesis method of the compound of the present invention, and the compound of the present invention can be prepared according to the following method and methods known in the art.

[0086] <Synthesis of Compounds of Formula 1>

[0087] <Synthesis of Intermediate 1-3>

[0088]

[0089] In a 2L three-necked round-bottom flask, 100g (591mmol) of 1-1 and 185.8g (591mmol) of 1-2, 11.3g (177mmol) of copper, 245.0g (1.77mol) of potassium carbonate, and 1L of nitrobenzene were added and heated under reflux for 12 hours. After the reaction was completed, the mixture was washed with EA, filtered through diatomaceous earth, and concentrated. The organic solvent was concentrated and passed through a chromatography column to obtain 126.5g of 1-3 with a yield of 66%.

[0090] Intermediate 1-3MS(FAB):324(M+)

[0091] <Synthesis of Intermediate 1-4>

[0092]

[0093] In a 3L three-necked round-bottom flask, 1-3 126.5g (390mmol) and aniline 72.6g (780mmol) were added, dissolved in 1.5L toluene, and sodium tert-butoxide 112.4g (1.17mol) and palladium acetate 1.75g ​​(8mmol), tri-tert-butylphosphine (50% in toluene) 6.31g (16mmol) were added, and then heated to reflux. After the reaction was completed, the temperature of the reactant dropped to room temperature, EA1L and water 1L were added, and the organic layer was extracted. The organic layer was concentrated and passed through a chromatography column and recrystallized to obtain 1-4 114.2g with a yield of 87%.

[0094] Intermediate 1-4MS(FAB):336(M+)

[0095] <Synthesis of Intermediate 1-6>

[0096]

[0097] In a 2L three-necked round-bottom flask, add 1-4 114.2g (339mmol) and 1-5 128.0g (407mmol), copper 6.47g (102mmol), potassium carbonate 140.7g (1.02mol), nitrobenzene 1L, and heat to reflux for 12 hours. After the reaction is completed, wash with EA, filter with diatomaceous earth and concentrate. After concentrating the organic solvent, pass through a chromatography column to obtain 1-6 123.4g with a yield of 74%.

[0098] Intermediate 1-6MS(FAB):491(M+)

[0099] <Synthesis of Intermediate 1-8>

[0100]

[0101] Add 1-6 123.4g (251mmol) and 1-7 85.0g (502mmol) to a 3L three-necked round-bottom flask and dissolve in THF 1.2L. Add sodium tert-butoxide 72.4g (753mmol) and palladium acetate 1.13g (5mmol), tri-tert-butylphosphine (50% in toluene) 4.06g (10mmol) and heat to reflux. After the reaction is completed, the temperature of the reactant drops to room temperature, and EA 1L and water 1L are added to extract the organic layer. After concentrating the organic layer, pass it through a chromatography column and recrystallize it to obtain 1-8 116.5g with a yield of 80%.

[0102] Intermediate 1-8MS(FAB):579(M+)

[0103] <Synthesis of Intermediate 1-10>

[0104]

[0105] 1-9 100g (591mmol) was added to a 2L three-necked round-bottom flask, dissolved in DMF 1L, and then an ice bath was set to maintain 0 degrees. 133.0g (591mmol) of N-iodosuccinimide was slowly added while maintaining 0 degrees. After the reaction, DMF was concentrated, and EA 1L and water 1L were added to extract the organic layer. The concentrated organic layer was passed through a chromatography column and then recrystallized to obtain 1-10 157.0g with a yield of 90%.

[0106] Intermediate 1-10MS(FAB):295(M+)

[0107] <Synthesis of Intermediate 1-11>

[0108]

[0109] Add 157.0 g (532 mmol) of 1-10 to a 3L three-necked round-bottom flask and dissolve in 1.5L of acetonitrile. Add 142.5 g (638 mmol) of copper (II) bromide and slowly add 91.4 g (798 mmol) of tert-butyl nitrite while heating at 60 degrees. After heating under reflux for 1 hour, the reaction is complete. After the temperature of the reactant drops to room temperature, add 1L of EA and 1L of water and extract the organic layer. After concentrating the organic layer, pass it through a chromatography column to obtain 116.5 g of 1-11 with a yield of 61%.

[0110] Intermediate 1-11MS(FAB):359(M+)

[0111] <Synthesis of Intermediate 1-12>

[0112]

[0113] In a 3L three-necked round-bottom flask, 1-8 116.5g (201mmol) and 1-11 86.5g (241mmol) were added and dissolved in 1.2L of toluene. After adding 57.9g (603mmol) of sodium tert-butoxide, 900mg (4mmol) of palladium acetate, and 3.25g (8mmol) of tri-tert-butylphosphine (50% in toluene), the mixture was heated to reflux. After confirming that the reaction was completed, the temperature of the reactant dropped to room temperature, 1L of EA and 1L of water were added, and the organic layer was extracted. The organic layer was concentrated and passed through a chromatography column and then recrystallized to obtain 105.9g of 1-12 with a yield of 65%.

[0114] Intermediate 1-12MS(FAB):810(M+)

[0115] <Synthesis of Compound 1>

[0116]

[0117] Add 1-12 105.9g (131mmol) and THF500ml to a 3L three-necked round-bottom flask, fill with nitrogen and use a dry ice bath to maintain minus 78 degrees. After adding 1.6M n-butyl lithium 261ml (418mmol), remove the dry ice bath and stir at room temperature. After 1 hour, set a dry ice bath to maintain minus 78 degrees and slowly add boron bromide 32.7g (131mmol), remove the dry ice bath and gradually heat up at room temperature, add xylene 1L and heat, when the internal thermometer reaches 140 degrees, distill and remove THF, set a condenser when only xylene is left, and heat to reflux for 3 days. After the reaction is completed, the temperature of the reactant drops to room temperature and then is concentrated, passed through a chromatography column and recrystallized to obtain 27.1g of compound-1 with a yield of 28%.

[0118] NMR (DMSO, 300Hz): δ (ppm) = 8.86 ~ 8.95 (t, 1H), 7.81 ~ 8.28 (m, 3H), 7.56 ~ 7.73 (m, 2H), 7.37 ~7.48(m, 7H), 7.17~7.34(m, 11H), 7.01~7.11(m, 7H), 6.74~6.96(m, 5H), 5.69~5.91(d, 2H)

[0119] MS(FAB):739(M+)

[0120] <Synthesis of Intermediate 45-3>

[0121]

[0122] In a 3L three-necked round-bottom flask, 100g (670mmol) of 45-1 and 212.6g (670mmol) of 45-2 were added and dissolved in 1.5L of toluene, and then 322g (3.35mol) of sodium tert-butoxide was added, and 3.01g (13.4mmol) of palladium acetate and 7.78g (26.8mmol) of tri-tert-butylphosphine tetrafluoroborate were added, and then heated to reflux for 5 hours. After the reaction was completed, the temperature of the reactant dropped to room temperature, and 1.5L of water was added to extract the organic layer. The water layer was washed again with 1L of EA, and the organic layer was concentrated and passed through a chromatography column and recrystallized to obtain 145.2g of 45-3 with a yield of 64%.

[0123] Intermediate 45-3MS(FAB):338(M+)

[0124] <Synthesis of Intermediate 45-4>

[0125]

[0126] In a 3L three-necked round-bottom flask, 145g (429mmol) of 45-3 was dissolved in 1.5L of dimethylacetamide, and 419g (1.286mol) of cesium carbonate was added. 1.93g (9mmol) of palladium acetate and 4.98g (17mmol) of tri-tert-butylphosphine tetrafluoroborate were added, and the mixture was heated under reflux for 5 hours. After the reaction was completed, the temperature of the reactant dropped to room temperature, and 2L of EA and 2L of water were added to extract the organic layer. The organic layer was concentrated and passed through a chromatography column and recrystallized to obtain 72.6g of 45-4 with a yield of 56%.

[0127] Intermediate 45-4MS(FAB):302(M+)

[0128] <Synthesis of Intermediate 45-5>

[0129]

[0130] Add 45-4 72.6g (240mmol) to a 2L three-necked round-bottom flask and dissolve in DMF 700ml. Dissolve NaOH 28.8g (720mmol) in 100ml water and stir for 30 minutes. Slowly add benzyl bromide 49.3g (288mmol) using a dropping funnel. After 1 hour of reaction, add EA 1L and water 1L and extract the organic layer. After concentrating the organic layer, pass it through a chromatography column to obtain 45-5 66.8g with a yield of 92%.

[0131] Intermediate 45-5MS(FAB):392(M+)

[0132] <Synthesis of Intermediate 45-7>

[0133]

[0134] Add 45-5 66.8g (170mmol) and 45-6 58.5g (187mmol) to a 2L three-necked round-bottom flask and dissolve in 1L of toluene. Add tert-butyl sodium 49.1g (511mmol) and palladium acetate 760mg (3mmol), tri-tert-butylphosphine (50% in toluene) 2.75g (7mmol) and heat to reflux. After confirming that the reaction is completed, the temperature of the reactant drops to room temperature, EA1L and water 1L are added, and the organic layer is extracted. The organic layer is concentrated and then passed through a chromatography column and recrystallized to obtain 45-7 73.7g with a yield of 73%.

[0135] Intermediate 45-7MS(FAB):592(M+)

[0136] <Synthesis of Intermediate 45-8>

[0137]

[0138] 45-7 73.7 g (124 mmol) was added to a 2L three-necked round-bottom flask, dissolved in 700 ml of THF, and 6.6 g (6 mmol) of palladium carbon (10%) was added. After bubbling with hydrogen, the mixture was stirred. After confirming that the reaction was complete, nitrogen was bubbled for 1 hour, and the mixture was filtered through diatomaceous earth. After concentrating THF, the mixture was recrystallized to obtain 45-8 59.3 g in a yield of 95%.

[0139] Intermediate 45-8MS(FAB):502(M+)

[0140] <Synthesis of Intermediate 45-10>

[0141]

[0142] A mechanical stirrer was set in a 2L three-necked round-bottom flask, 45-9 100g (438mmol), water 200ml and concentrated hydrochloric acid 200ml were added, and an ice-salt bath was used to maintain minus 5 degrees, and sodium nitrite 60.5g (877mmol) dissolved in 100ml water was slowly added. After 30 minutes, potassium iodide 145.5g (877mmol) dissolved in 100ml water was slowly added. The dry ice bath was removed and the temperature was slowly raised at room temperature and stirred for 2 hours. After the reaction was determined to be complete, 500ml of water was added, stirred, and filtered. After recrystallization through a chromatography column, 45-10 62.4g was obtained with a yield of 41%.

[0143] Intermediate 45-10MS(FAB):339(M+)

[0144] <Synthesis of Intermediate 45-11>

[0145]

[0146] In a 1L three-necked round-bottom flask, add 45-8 59.3g (118mmol) and 45-10 48.0g (142mmol), then add 600ml of xylene. Add 4.5g (24mmol) of cuprous iodide, 2.84g (24mmol) of ethylenediamine, and 32.6g (236mmol) of potassium carbonate, and heat to reflux. After the reaction is complete, wash with EA, filter and concentrate with diatomaceous earth, and recrystallize through a chromatography column to obtain 45-11 64.9g with a yield of 77%.

[0147] Intermediate 45-11MS(FAB):713(M+)

[0148] <Synthesis of Compound-45>

[0149]

[0150] Add 45-11 64.9g (91mmol) and THF 300ml to a 1L three-necked round-bottom flask, fill with nitrogen and use a dry ice bath to maintain minus 78 degrees. After adding 1.6M n-butyl lithium 187ml (300mmol), remove the dry ice bath and stir at room temperature. After 1 hour, set a dry ice bath to maintain minus 78 degrees and slowly add boron bromide 22.8g (91mmol). After removing the dry ice bath, slowly heat up at room temperature, add xylene 500ml and heat. When the internal thermometer reaches 140 degrees, distill and remove THF. When the only component left is xylene, set a condenser and heat to reflux for 3 days. After the reaction is completed, the reactant temperature drops to room temperature and is concentrated, passed through a chromatography column and recrystallized to obtain compound-45 22.8g with a yield of 39%.

[0151] NMR (DMSO, 300Hz): δ (ppm) = 8.91 ~ 8.98 (s, 1H), 8.21 ~ 8.29 (d, 1H), 7.82 ~ 7.89 (m, 1H), 7.62 ~ 7.68 (m, 1H), 7.41 ~ 7.53(m, 4H), 7.25~7.35(m, 2H), 7.01~7.15(m, 7H), 5.62~5.78(s, 2H), 1.43~1.52(s, 18H), 1.28~1.39(s, 18H)

[0152] MS(FAB):642(M+)

[0153] <Synthesis of Intermediate 107-2>

[0154]

[0155] In a 1L high pressure reactor, 100g (405mmol) of 107-1, 200ml of ammonia (25-30%), 400ml of PEG300, and 7.7g (40mmol) of cuprous iodide were added, and stirred overnight at 180 degrees. After the temperature of the reactant dropped to room temperature, 1L of EA and 1L of water were added to the reaction solution, and the organic layer was extracted. The organic layer was concentrated and recrystallized to obtain 107-271.9g with a yield of 97%.

[0156] Intermediate 107-2MS(FAB):183(M+)

[0157] <Synthesis of Intermediate 107-3>

[0158]

[0159] 107-5 50g (178mmol) was added to a 2L three-necked round-bottom flask, melted in DMF 500ml, and then set an ice bath to maintain 0 degrees. While maintaining 0 degrees, 88.3g (393mmol) of N-iodosuccinimide was slowly added. After the reaction was completed, DMF was concentrated, and EA 500ml and water 500ml were added to extract the organic layer. After the organic layer was concentrated, it was recrystallized through a chromatography column to obtain 107-3 51.0g with a yield of 42%.

[0160] Intermediate 107-3MS(FAB):309(M+)

[0161] <Synthesis of Intermediate 107-4>

[0162]

[0163] Add 107-3 51.0g (165mmol) to a 1L three-necked round-bottom flask and dissolve in acetonitrile 500ml. Add copper (II) bromide 44.2g (198mmol), and slowly add tert-butyl nitrite 28.3g (247mmol) while heating at 60 degrees. After heating under reflux for 1 hour, the reaction is complete. After the temperature of the reactant drops to room temperature, EA1L and water 1L are added and the organic layer is extracted. After concentrating the organic layer, pass through a chromatography column to obtain 107-4 44.9g with a yield of 73%.

[0164] Intermediate 107-4MS(FAB):372(M+)

[0165] <Synthesis of Intermediate 107-6>

[0166]

[0167] 107-5 50g (178mmol) was added to a 1L three-necked round-bottom flask, dissolved in DMF 500ml and then set in an ice bath to maintain 0 degrees. N-bromosuccinimide 31.6g (178mmol) was slowly added while maintaining 0 degrees. After the reaction, DMF was distilled, concentrated and passed through a chromatography column to obtain 107-6 58.3g with a yield of 91%.

[0168] Intermediate 107-6MS(FAB):360(M+)

[0169] <Synthesis of Intermediate 107-7>

[0170]

[0171] In a 1L three-necked round-bottom flask, 44.9 g (120 mmol) of 107-4 and 43.4 g (120 mmol) of 107-6, 2.3 g (36 mmol) of copper, 49.9 g (361 mmol) of potassium carbonate, and 500 ml of nitrobenzene were added and heated to reflux for 12 hours. After the reaction was completed, it was washed with EA, filtered through diatomaceous earth, and concentrated. The organic solvent was concentrated and passed through a chromatography column to obtain 40.8 g of 107-7 with a yield of 56%.

[0172] Intermediate 107-7MS(FAB):605(M+)

[0173] <Synthesis of Compound-107>

[0174]

[0175] Add 107-7 40.8g (67mmol) to a 1L three-necked round-bottom flask and dissolve in THF 400ml. Set a dry ice bath to maintain minus 78 degrees, slowly add 1.6M n-butyl lithium 177ml (283mmol), remove the dry ice bath and stir at room temperature. After 1 hour, add phenylmagnesium chloride (3M) 23ml (67mmol) again, remove the dry ice bath and slowly heat at room temperature, add xylene 500ml and heat. When the internal thermometer reaches 140 degrees, distill and remove THF, set a condenser when only xylene is left, and heat to reflux for 3 days. After the reaction is completed, the temperature of the reactant drops to room temperature and then is concentrated, passed through a chromatography column and recrystallized, and compound-107 12.5g is obtained with a yield of 35%.

[0176] NMR (DMSO, 300Hz): δ (ppm) = 7.81 ~ 8.28 (m, 2H), 7.52 ~ 7.73 (m, 5H), 7.31-7.46 (m, 6H), 7.13~7.25(m, 4H), 6.94-7.09(d, 1H), 1.43~1.53(s, 9H), 1.28~1.39(s, 9H),

[0177] MS(FAB):533(M+)

[0178] <Synthesis of Intermediate 165-3>

[0179]

[0180] 107-2 71.92g (393mmol) was added to a 2L three-necked round-bottom flask, dissolved in DMF 700ml and set in an ice bath to maintain 0 degrees. While maintaining 0 degrees, 88.3g (393mmol) of N-iodosuccinimide was slowly added. After the reaction was completed, DMF was concentrated, EA 500ml and water 500ml were added, and the organic layer was extracted. After the organic layer was concentrated, it was passed through a chromatography column and recrystallized to obtain 165-3 43.7g with a yield of 36%.

[0181] Intermediate 165-3MS(FAB):309(M+)

[0182] <Synthesis of Intermediate 165-4>

[0183]

[0184] Add 165-3 43.7g (141mmol) to a 1L three-necked round-bottom flask and dissolve in acetonitrile 500ml. Add copper bromide 37.9g ​​(170mmol), and slowly add tert-butyl nitrite 24.3g (212mmol) while heating at 60 degrees. After heating under reflux for 1 hour, the reaction is complete. After the temperature of the reactant drops to room temperature, add EA1L and water 1L and extract the organic layer. After concentrating the organic layer, pass it through a chromatography column to obtain 165-4 39.5g with a yield of 75%.

[0185] Intermediate 165-4MS(FAB):372(M+)

[0186] <Synthesis of Intermediate 165-7>

[0187]

[0188] In a 1L three-necked round-bottom flask, 165-4 39.5g (106mmol) and 107-6 39.2g (106mmol), copper 2.0g (32mmol), potassium carbonate 44.0g (318mmol), nitrobenzene 500ml were added and heated to reflux for 12 hours. After the reaction was completed, it was washed with EA, filtered through diatomaceous earth and concentrated. The organic solvent was concentrated and passed through a chromatography column to obtain 165-7 39.1g with a yield of 61%.

[0189] Intermediate 165-7MS(FAB):605(M+)

[0190] <Synthesis of Compound-165>

[0191]

[0192] Add 165-7 39.1g (65mmol) to a 1L three-necked round-bottom flask and dissolve in THF400ml. Use a dry ice bath to maintain minus 78 degrees, add 1.6M n-butyl lithium 170ml (272mmol), remove the dry ice bath, slowly heat up at room temperature and stir for 1 hour. Set a dry ice bath to maintain minus 78 degrees and slowly add boron bromide 32.7g (131mmol), remove the dry ice bath and gradually heat up at room temperature, add xylene 500ml and heat. When the internal thermometer reaches 140 degrees, distill and remove THF. When only xylene is left, set a condenser and heat to reflux for 3 days. After the reaction is completed, the reactant temperature drops to room temperature and is concentrated, passed through a chromatography column and recrystallized to obtain compound-165 13.2g with a yield of 38%.

[0193] NMR (DMSO, 300Hz): δ (ppm) = 7.73 ~ 8.28 (m, 3H), 7.57 ~ 7.69 (m, 2H), 7.31-7.48 (m, 8H), 7.14~7.25(m, 4H), 6.94-7.09(d, 1H), 1.43~1.52(s, 9H), 1.29~1.39(s, 9H),

[0194] MS(FAB):533(M+)

[0195] <Synthesis of Intermediate 201-2>

[0196]

[0197] 100 g (546 mmol) of 201-1 was added to a 2L three-necked round-bottom flask, dissolved in 1L of DMF and set in an ice bath to maintain 0 degrees, and 122.8 g (546 mmol) of N-iodosuccinimide was slowly added while maintaining 0 degrees. After the reaction, DMF was concentrated, 1L of EA and 1L of water were added, and the organic layer was extracted. The organic layer was concentrated and recrystallized by chromatography column to obtain 201-2121.5 g with a yield of 72%.

[0198] Intermediate 201-2MS(FAB):309(M+)

[0199] <Synthesis of Intermediate 201-3>

[0200]

[0201] 201-2 121.5 g (393 mmol) was added to a 2L three-necked round-bottom flask, dissolved in 1L of DMF and set in an ice bath to maintain at 0 degrees, and 69.9 g (393 mmol) of bromosuccinimide was slowly added while maintaining at 0 degrees. After the reaction, DMF was concentrated, 1L of EA and 1L of water were added, and the organic layer was extracted. The organic layer was concentrated and recrystallized by chromatography column to obtain 201-3 134.2 g with a yield of 88%.

[0202] Intermediate 201-3MS(FAB):388(M+)

[0203] <Synthesis of Intermediate 201-4>

[0204]

[0205] In a 3L three-necked round-bottom flask, add 201-3 134.2g (346mmol) and ethanol 1.3L, then slowly add 270ml sulfuric acid, and slowly add sodium nitrite 123.1g (692mmol) in batches while heating and refluxing. After the addition is completed, heat and reflux for 3 hours. After the reaction is completed, the temperature of the reactant drops to room temperature. After adding 1.5L water, filter and pass the solid produced by chromatography column to obtain 201-4 80.0g with a yield of 62%.

[0206] Intermediate 201-4MS(FAB):372(M+)

[0207] <Synthesis of Intermediate 201-6>

[0208]

[0209] In a 3L three-necked round-bottom flask, 201-4 80.0g (214mmol) and D-5 67.1g (214mmol), copper 4.1g (64mmol), potassium carbonate 88.9g (643mmol), and nitrobenzene 800ml were added and heated to reflux for 12 hours. After the reaction was completed, it was washed with EA, filtered through diatomaceous earth, and concentrated. The organic solvent was concentrated and passed through a chromatography column to obtain 201-6 72.3g with a yield of 64%.

[0210] Intermediate 201-6MS(FAB):526(M+)

[0211] <Synthesis of Intermediate 201-7>

[0212]

[0213] In a 2L three-necked round-bottom flask, 201-6 72.3g (137mmol), DMF 350ml, and cuprous iodide 58.1g (274mmol) were added, and sodium methoxide (30% in MeOH) 321g (1.78mol) was slowly added, and the mixture was heated to reflux. After the reaction was completed, the temperature of the reactants dropped to room temperature, and EA 1L and water 1L were added to extract the organic layer. The organic layer was concentrated and passed through a chromatography column to obtain 201-7 61.0g with a yield of 93%.

[0214] Intermediate 201-7MS(FAB):477(M+)

[0215] <Synthesis of Intermediate 201-8>

[0216]

[0217] In a 2L three-necked round-bottom flask, 61 g (128 mmol) of 201-7 was added to 600 ml of THF, and a dry ice bath was used to maintain minus 78 degrees. After 88 ml (140 mmol) of n-butyl lithium (1.6 M) was added dropwise, the dry ice bath was removed, and the temperature was slowly raised at room temperature and stirred for 30 minutes. A dry ice bath was set to maintain minus 78 degrees, 21.0 g (153 mmol) of isobutyl bromide was slowly added, and the temperature was gradually raised at room temperature after the dry ice bath was removed. After the reaction was completed, the mixture was concentrated, and the organic layer was extracted after adding 500 ml of EA and 500 ml of water. After concentration, the mixture was passed through a chromatography column to obtain 57.2 g of 201-8 with a yield of 84%.

[0218] Intermediate 201-8MS(FAB):533(M+)

[0219] <Synthesis of Intermediate 201-9>

[0220]

[0221] Add 201-8 57.2g (107mmol) to a 1L three-necked round-bottom flask, dissolve in MC 600ml, set an ice bath to maintain 0 degrees, and slowly add boron bromide 29.5g (118mmol) dropwise while maintaining 0 degrees. After the reaction is completed, add 500ml of water. After extracting the organic layer, concentrate and recrystallize to obtain 201-9 50.1g with a yield of 90%.

[0222] Intermediate 201-9MS(FAB):519(M+)

[0223] <Synthesis of Intermediate 201-10>

[0224]

[0225] In a 1L three-necked round-bottom flask, add 201-9 50.1g (96mmol) and 45-10 32.7g (96mmol), tripotassium phosphate 41.0g (193mmol), DMSO 500ml, cuprous iodide 3.7g (19mmol) and ferric acetylacetonate 6.8g (19mmol), and heat to 110 degrees. After the reaction is completed, the temperature of the reactant is reduced to room temperature, EA1L and water 1L are added, and the organic layer is extracted and concentrated. After passing through a chromatography column, 201-10 50.8g is obtained with a yield of 72%.

[0226] Intermediate 201-10MS(FAB):730(M+)

[0227] <Synthesis of Compound-201>

[0228]

[0229] Add 201-10 50.8g (69mmol) to a 1L three-necked round-bottom flask and dissolve in THF400ml. Set a dry ice bath to maintain minus 78 degrees, slowly add 1.6M n-butyl lithium 139ml (222mmol), remove the dry ice bath, heat at room temperature and stir for 1 hour, set a dry ice bath to maintain minus 78 degrees, slowly add boron bromide 17.4g (69mmol), remove the dry ice bath and slowly heat at room temperature, add 500ml of xylene and heat. When the internal thermometer reaches 140 degrees, distill and remove THF. When only xylene is left, set a condenser and heat to reflux for 3 days. After the reaction is completed, the temperature of the reactant drops to room temperature and is concentrated. After passing through a chromatography column, it is recrystallized to obtain 14.6g of compound-201 with a yield of 32%.

[0230] NMR (DMSO, 300Hz): δ (ppm) = 7.92 ~ 8.05 (d, 1H), 7.56 ~ 7.69 (m, 2H), 7.29-7.48 (m, 4H), 7.02 ~ 7.21 (m, 6H), 6.84 -6.98(d, 1H), 2.47~2.54(d, 2H), 1.91~1.99(m, 1H), 1.42~1.53(s, 18H), 1.28~1.39(s, 9H), 0.91~0.99(d, 6H)

[0231] MS(FAB):659(M+)

[0232] <Synthesis of Intermediate 249-3>

[0233]

[0234] In a 2L three-necked round-bottom flask, 100g (598mmol) of 249-1 and 92.8g (658mmol) of 249-2, 584.5g (1.79mol) of cesium carbonate, and 1L of DMF were added and heated to reflux. After the reaction was completely terminated, the temperature of the reactant dropped to room temperature and concentrated. 1L of EA and 1L of water were added to extract the organic layer, which was dried, filtered, and concentrated. After recrystallization, 117.3g of 249-3 was obtained with a yield of 68%.

[0235] Intermediate 249-3MS(FAB):288(M+)

[0236] <Synthesis of Intermediate 249-4>

[0237]

[0238] In a 2L three-necked round-bottom flask, 117.3g (407mmol) of 249-3 and 183.5g (813mmol) of dihydrated tin chloride were added, and then 1L of ethanol was added and heated to reflux. After the reaction was confirmed to be complete, the temperature of the reactant dropped to room temperature and concentrated. 1L of EA and 1L of water were added to extract the organic layer, and then concentrated. After recrystallization through a chromatography column, 88.2g of 249-4 was obtained with a yield of 84%.

[0239] Intermediate 249-4MS(FAB):258(M+)

[0240] <Synthesis of Intermediate 249-5>

[0241]

[0242] 249-4 88.2g (342mmol), acetic acid 880ml, sulfuric acid 88g were added to a 3L three-necked round bottom flask. Sodium nitrite 47.1g (683mmol) dissolved in 88ml water was added dropwise and heated to reflux. After the reaction was completed, the temperature of the reactant was lowered to room temperature, acetic acid was distilled, EA1L and water 1L were added for extraction, and the organic layer was concentrated and recrystallized by chromatography column to obtain 249-546.2g with a yield of 56%.

[0243] Intermediate 249-5MS(FAB):241(M+)

[0244] <Synthesis of Intermediate 249-6>

[0245]

[0246] Add 46.2 g (191 mmol) of 249-5 to a 1L three-necked round-bottom flask and dissolve in 500 ml of MC. Set an ice bath to maintain 0 degrees and then slowly add 34.1 g (191 mmol) of N-bromosuccinimide ammonia. After the reaction is completed, add 500 ml of water to extract the organic layer, concentrate it, and recrystallize it through a chromatography column to obtain 44.1 g of 249-6 with a yield of 72%.

[0247] Intermediate 249-6MS(FAB):320(M+)

[0248] <Synthesis of Intermediate 249-8>

[0249]

[0250] 100 g (379 mmol) of 249-7 and 1 L of ethanol were added to a 2 L three-necked round-bottom flask, and 35.3 g (379 mmol) of aniline was added while stirring. The mixture was heated to reflux, and after the reaction was completed, the temperature of the reactant was lowered to room temperature, and filtered to obtain 125.9 g of 249-8 with a yield of 98%.

[0251] Intermediate 249-8MS(FAB):339(M+)

[0252] <Synthesis of Intermediate 249-10>

[0253]

[0254] In a 2L three-necked round-bottom flask, 125.9g (477mmol) of 249-8 and 74.7g (477mmol) of 249-9 were added, and then 1L of EtOH was added for stirring. Then, 57.2g (1.43mol) of sodium hydroxide was slowly added and heated to reflux. After confirming that the reaction was completed, the temperature of the reactants dropped to room temperature, filtered, and recrystallized to obtain 198.3g of 249-10 with a yield of 89%.

[0255] Intermediate 249-10MS(FAB):467(M+)

[0256] <Synthesis of Intermediate 249-11>

[0257]

[0258] 198.3 g (425 mmol) of 249-10 was added to a 3L three-necked round-bottom flask and dissolved in 2L of THF. The temperature was maintained at -78°C using a dry ice bath, and 271 ml (433 mmol) of n-butyl lithium (1.6 M) was added dropwise. After 30 minutes, 48.5 g (467 mmol) of trimethyl borate was added. After the reaction was completed, the mixture was concentrated, and 1L of 2N HCl and 1L of EA were added for extraction. The organic layer was concentrated and recrystallized to obtain 122.9 g of 249-11 with a yield of 67%.

[0259] Intermediate 249-11MS(FAB):432(M+)

[0260] <Synthesis of Intermediate 249-13>

[0261]

[0262] In a 1L three-necked round-bottom flask, 50 g (347 mmol) of 249-12 was added to 500 ml of THF, and the temperature was maintained at -78 degrees Celsius using a dry ice bath. 221 ml (354 mmol) of n-butyl lithium (1.6 M) was added dropwise, and 96.8 g (381 mmol) of iodine was added after 30 minutes, and the temperature was raised at room temperature. After confirming that the reaction was completed, the mixture was concentrated, and the organic layer was extracted after adding 500 ml of EA and 500 ml of water. After recrystallization, 127.4 g of 249-13 was obtained with a yield of 85%.

[0263] Intermediate 249-13MS(FAB):270(M+)

[0264] <Synthesis of Intermediate 249-14>

[0265]

[0266] In a 3L three-necked round-bottom flask, 249-11 100g (231mmol) and 249-13 75.0g (278mmol), Pd(PPh3)4 13.4g (12mmol), 2M K2CO3 347ml (694mmol), THF1L were added and heated to reflux. After confirming that the reaction was completed, the temperature of the reactant dropped to room temperature and concentrated. After adding MC500ml and water 500ml, the organic layer was extracted and concentrated. After recrystallization through a chromatography column, 249-14 67.5g was obtained with a yield of 55%.

[0267] Intermediate 249-14MS(FAB):530(M+)

[0268] <Synthesis of Intermediate 249-15>

[0269]

[0270] In a 2L three-necked round-bottom flask, 67.5 g (127 mmol) of 249-14 was added and dissolved in 700 ml of THF. A dry ice bath was used to maintain the temperature at -78 degrees Celsius. 81 ml (130 mmol) of n-butyl lithium (1.6 M) was added dropwise. After 30 minutes, 14.6 g (140 mmol) of trimethyl borate was added. After the reaction was completed, the mixture was concentrated, and 500 ml of 2N HCl and 500 ml of EA were added for extraction. The organic layer was extracted and recrystallized to obtain 37.2 g of 249-15 with a yield of 59%.

[0271] Intermediate 249-15MS(FAB):495(M+)

[0272] <Synthesis of Compound-249>

[0273]

[0274] In a 1L three-necked round-bottom flask, 49-15 37.2g (75mmol) and 249-6 24.1g (75mmol), Pd(PPh3)4 4.3g (4mmol), 2M K2CO3 113ml (225mmol), THF400ml were added and heated to reflux. After confirming that the reaction was completed, the temperature of the reactant dropped to room temperature and concentrated. After adding MC500ml and water 500ml, the organic layer was extracted and concentrated. . Compound-249 34.7g was obtained by recrystallization through a chromatography column with a yield of 67%.

[0275] NMR (DMSO, 300Hz): δ (ppm) = 8.31 ~ 8.45 (m, 4H), 8.15 ~ 8.26 (d, 2H), 7.95 ~ 8.11 (m, 3H), 7.64~7.83(m, 2H), 7.46-7.61(m, 14H), 7.32~7.41(m, 2H), 7.11~7.20(m, 3H)

[0276] The present invention will be described in detail below through examples and comparative examples of organic electroluminescent devices. The following examples and comparative examples are only for illustrating the present invention, and the scope of the present invention is not limited to the following examples and comparative examples.

[0277] <Organic electroluminescent device manufacturing>

[0278] Example 1

[0279] ITO is used as the reflective layer anode substrate material, and its surface is treated with plasma or UV-Ozone. Above the anode substrate, HAT-CN with a thickness of 10nm is deposited on the HIL layer, and then NPD with a thickness of 120nm is deposited on the HTL layer. Above the above HTL layer, 25nm of compound 1 in the general formula 1 of the present invention is deposited on the EML layer to prepare blue EML; wherein, 5% 9,10-bis(2-naphthalene)anthracene (ADN) is doped in the blue EML. A 30nm thick ETL layer is deposited on the above anode to prepare a cathode, which is obtained by ET-254 and LiQ in a mass ratio of 1:1, and then LiQ with a thickness of 10nm is deposited on the EIL. Finally, a mixture of magnesium and silver mixed in a mass ratio of 9:1 is deposited on the cathode with a thickness of 15nm. In addition, above the cathode treated by the above method, 65nm of DNTPD is deposited on its cappinglayer. A seal cap containing a moisture absorbent is bonded on the capping layer with a UV curable adhesive to protect the organic electroluminescent device from being corroded by oxygen or moisture in the atmosphere, thereby preparing an organic electroluminescent device.

[0280] Examples 2 to 51

[0281] The difference between Examples 2 to 51 and Example 1 is that the compound 1 in Example 1 as the dopant of blue EML is replaced by compounds 3, 19, 24, 27, 35, 37, 45, 55, 56, 64, 72, 88, 93, 102, 107, 123, 140, 145, 151, 158, 161, 165, 178, 184, 201, 215, 221, 224, 226, 230, 236, 242, 249, 263, 264, 265, 268, 275, 290, 293, 301, 320, 337, 339, 344, 346, 348, 349, 350 and 352 respectively, and the preparation method of the organic electroluminescent device is the same as that of Example 1.

[0282] Comparative Example 1

[0283] The preparation method of the organic electroluminescent device is the same as that of Example 1, except that 2,5,8,11-Tetra-butyl-Perylene (t-Bu-Perylene) is used as the dopant of the light emitting layer (EML) blue EML.

[0284] The structures of the compounds used in the above Examples 1 to 51 and Comparative Example 1 are as follows.

[0285]

[0286] Example: Performance evaluation of organic electroluminescent devices

[0287] The performance of the organic electroluminescent devices prepared in the above-mentioned Examples 1 to 51 and Comparative Example 1 was tested at a current density of 10 mA / cm 2 The results are shown in Table 1.

[0288]

Table 1

[0289]

[0290]

[0291]

[0292] It can be seen from the experimental results shown above that the organic electroluminescent devices prepared in Examples 1 to 51 using the organic compound of general formula 1 of the present invention as a dopant to prepare the light-emitting layer have improved efficiency and reduced driving voltage compared with the existing organic electroluminescent device described in Control Example 1.

[0293] In addition, it can be seen from the T95 results that the life of the organic electroluminescent device of Control Example 1 is less than 100 hours, while the life of the organic electroluminescent devices prepared in Examples 1 to 51 is more than 300 hours, and in particular, the organic electroluminescent devices of Examples 9, 12, 26, 28, 33, 38, 43, 45, 46, 48, and 49 have a long life of more than 400 hours, which overcomes the shortcoming of the limited life of the existing Blue material and further expands the scope of application of the organic electroluminescent device.

[0294] In addition, the organic electroluminescent devices prepared in Examples 1 to 51 using the compound of the general formula 1 of the present invention as a dopant in the light-emitting layer have significantly improved efficiency and voltage characteristics compared with the existing organic electroluminescent device in Control Example 1.

[0295] In summary, the organic compound of Formula 1 of the present invention is used as a dopant to prepare a light-emitting layer, and the efficiency, driving voltage and life of the obtained organic electroluminescent device are significantly improved compared with the prior art.

Claims

1. An organic compound, characterized in that The organic compound is any one of the following compounds:

2. An organic electroluminescent device, wherein one or more organic thin film layers including at least a light-emitting layer are stacked between a cathode and an anode, wherein the light-emitting layer comprises one or more of the organic compounds of claim 1.

3. An organic electroluminescent device, wherein one or more organic thin film layers including at least a light-emitting layer are stacked between a cathode and an anode, wherein the organic thin film layers other than the light-emitting layer comprise one or more of the organic compounds of claim 1.

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