Organic compound and organic electroluminescent device containing same

Abstract

The invention relates to the field of organic electroluminescent device materials, in particular to an organic compound and an organic electroluminescent device containing the same. The organic compound has good photoelectric properties, can be applied to an organic electroluminescent device as a phosphorescent host material, and can improve the luminous efficiency and prolong the service life of the device by matching with a proper guest material. The OLED prepared from the organic compound provides a solution of a light-emitting device which is low in manufacturing cost, high in efficiency and long in service life.

Description

Technical Field

[0001] The invention relates to the field of organic electroluminescent device materials, in particular to an organic compound and an organic electroluminescent device containing the same. Background Art

[0002] Organic Light-emitting Diode (OLED) technology is an active light-emitting technology of organic semiconductor thin films under the action of an external electric field. It has many advantages such as flexibility, light weight, high brightness and low power consumption. It has been widely used in smart phones, televisions, wearable devices, car displays and other fields.

[0003] Organic electroluminescent devices usually include an anode, a cathode, and an organic functional layer formed between the two electrodes, wherein the organic functional layer may include a hole injection layer, a hole transport layer, a hole auxiliary layer, an electron blocking layer, a light-emitting layer (containing a host material and a guest material), a hole blocking layer, an electron transport layer, an electron injection layer, etc. Its working principle is: under the drive of an external electric field, electrons enter the electron transport layer from the cathode, and holes enter the hole transport layer from the anode. The two recombine in the light-emitting layer to generate excitons, and the excitons radiatively transition back to the ground state and emit light. The luminescence process is divided into the following points: carrier injection, carrier transport, and exciton radiative recombination luminescence.

[0004] The luminescent materials in OLED devices can be divided into two categories according to the luminescence mechanism: electrofluorescence and electrophosphorescence. Electrofluorescence is the radiative decay transition of singlet excitons, while electrophosphorescence is the light emitted by triplet excitons radiatively decaying to the ground state. According to the spin quantum statistics theory, the probability ratio of singlet excitons and triplet excitons is 1:3; therefore, the internal quantum efficiency of electrofluorescent materials does not exceed 25%, while electrophosphorescent materials have a strong spin-orbit coupling effect, which can simultaneously utilize singlet and triplet excitons, so that the internal quantum efficiency of phosphorescent electroluminescent devices reaches 100% in theory. However, the excited state lifetime of phosphorescent materials is long, and when the concentration of triplet excitons is high, triplet-triplet annihilation and triplet-polaron annihilation are easily formed; therefore, phosphorescent materials are usually doped into host materials as guests to reduce the self-concentration quenching process. Therefore, phosphorescent host materials have a significant effect on reducing the driving voltage of devices, improving the luminous efficiency of devices, and improving the service life of devices.

[0005] Therefore, it is necessary to continue to develop new phosphorescent host materials to further improve the performance of organic electroluminescent devices. Summary of the invention

[0006] The object of the present invention is to provide an organic compound which can be used as a phosphorescent host material in an OLED device to effectively improve the luminous efficiency and service life of the OLED.

[0007] The technical solution of the present invention is as follows:

[0008] An organic compound having a structure as shown in the general formula (I):

[0009] (I)

[0010] Where: -Z- each occurrence is selected from none or a single bond;

[0011] Each occurrence of R1, R2, R3, and R5 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, substituted or unsubstituted straight-chain alkyl having 1 to 20 carbon atoms, substituted or unsubstituted straight-chain or cyclic alkyl having 3 to 20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;

[0012] Each occurrence of R4 is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, substituted or unsubstituted straight chain alkyl having 1 to 20 carbon atoms, substituted or unsubstituted straight chain or cyclic alkyl having 3 to 20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;

[0013] m is selected from 0, 1, 2, 3, 4 or 5;

[0014] "Substituted or unsubstituted" means that the defined group is unsubstituted or substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a straight-chain or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups.

[0015] In one embodiment, the organic compound according to the present invention has any structure as shown in general formula (II-1) or (II-2):

[0016] .

[0017] Further, in a specific embodiment, the organic compound is selected from any of the following general formulas:

[0018] .

[0019] In one embodiment, the term "substituted or unsubstituted" means that the defined group is unsubstituted or substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 10 carbon atoms, a straight-chain or cyclic alkyl group having 3 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a heteroaromatic group having 5 to 15 ring atoms, or a group formed by a combination of the above groups.

[0020] In one embodiment, each occurrence of R1, R2, R3, and R5 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, substituted or unsubstituted straight-chain alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted straight-chain or cyclic alkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms, and substituted or unsubstituted heteroaromatic groups having 5 to 10 ring atoms.

[0021] Furthermore, each occurrence of R1, R2, R3, and R5 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, substituted or unsubstituted straight-chain alkyl having 1 to 10 carbon atoms, substituted or unsubstituted straight-chain or cyclic alkyl having 3 to 10 carbon atoms, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, and substituted or unsubstituted naphthyl.

[0022] In one embodiment, each occurrence of R1 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched-chain alkyl group or a cyclic alkyl group having 3 to 6 carbon atoms, a phenyl group, a pyridyl group, or a group formed by a combination of the above groups.

[0023] In one embodiment, each occurrence of R2 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a linear alkyl group having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 6 carbon atoms, phenyl, pyridyl, or a group formed by a combination of the above groups.

[0024] Preferably, each occurrence of R2 is independently selected from -H or -D.

[0025] In one embodiment, each occurrence of R5 is independently selected from --H, -D, -F, -Cl, -Br, -I, cyano, nitro, a linear alkyl group having 1-6 carbon atoms, or a branched or cyclic alkyl group having 3-6 carbon atoms.

[0026] Preferably, each occurrence of R5 is independently selected from -H or -D.

[0027] In one embodiment, each occurrence of R3 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a linear alkyl group having 1 to 6 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, phenyl, pyridyl, or a group formed by a combination of the above groups.

[0028] In one embodiment, each occurrence of R4 is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a linear alkyl group having 1 to 6 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, phenyl, pyridyl, naphthyl, or a group formed by a combination of the above groups.

[0029] In one embodiment, m is selected from 0, 1 or 2.

[0030] In one implementation, the organic compound is selected from any of the following general formulas:

[0031]

[0032]

[0033]

[0034] ;

[0035] in:

[0036] Each occurrence of R1 is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched-chain alkyl group or a cyclic alkyl group having 3 to 6 carbon atoms, a phenyl group, a pyridyl group, or a group formed by a combination of the above groups;

[0037] Each occurrence of R2 is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 6 carbon atoms, phenyl, pyridyl, or a group formed by a combination of the above groups.

[0038] In a specific embodiment, the organic compound according to the present invention is selected from the following structures but not limited thereto:

[0039] .

[0040] In one embodiment, the organic compound according to the present invention can be used as a host material in a light-emitting layer of an organic electroluminescent device.

[0041] Furthermore, the organic compound according to the present invention can be used as a phosphorescent host material in the light-emitting layer of an organic electroluminescent device.

[0042] The present invention also provides a mixture, which comprises the organic compound as described above and at least one organic functional material; the at least one organic functional material is preferably a self-luminous layer guest material.

[0043] In one embodiment, the guest material of the light-emitting layer is selected from metal complexes containing Ir.

[0044] The present invention also provides an organic electroluminescent device, comprising a cathode, an anode and at least one functional layer located between the cathode and the anode, wherein the at least one functional layer comprises the organic compound as described above.

[0045] Preferably, the at least one functional layer comprises a light-emitting layer, the light-emitting layer comprises a host material and a guest material, the host material comprises an organic compound as described above.

[0046] Specifically, the organic electroluminescent device according to the present invention comprises an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer cathode stacked in sequence from bottom to top; the light-emitting layer comprises the organic compound as described above.

[0047] The present invention also relates to the application of organic electroluminescent devices in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

[0048] Compared with the prior art, the beneficial technical effects of the present invention are:

[0049] The organic compound provided by the present invention has good photoelectric properties and can be used as a phosphorescent host material in an organic electroluminescent device. By combining with a suitable guest material, the luminous efficiency and life of the device can be improved. Furthermore, the present invention also provides a solution for a light-emitting device with low manufacturing cost, high efficiency and long life. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0051] Figure 1 It is a schematic diagram of the structure of the OLED device shown in device embodiment 1 of the present invention.

[0052] Among them, 101 is a substrate; 102 is an anode layer; 103 is a hole injection layer; 104 is a first hole transport layer; 105 is a second hole transport layer; 106 is a light emitting layer; 107 is an electron transport layer; 108 is an electron injection layer; and 109 is a cathode layer. DETAILED DESCRIPTION

[0053] In order to make the purpose, technical solution and advantages of the present application more clear, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present application and are not used to limit the present application.

[0054] In the present invention, when describing electrodes and organic electroluminescent devices, as well as other structures, the words "upper", "lower", "top" and "bottom" used to indicate orientation only indicate the orientation in a certain state, and do not mean that the related structure can only exist in the orientation described; on the contrary, if the structure can change its position, such as inverted, the orientation of the structure will be changed accordingly. Specifically, in the present invention, the "bottom" or "lower" side of the electrode refers to the side of the electrode close to the substrate during the preparation process, and the opposite side away from the substrate is the "top" or "upper" side.

[0055] The terms "and / or", "or / and", and "and / or" used in this article include any one of two or more related listed items, and also include any and all combinations of related listed items, and the arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions that are all connected by "logical and", and undoubtedly includes technical solutions that are all connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution that is all connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the combination of four of A, B, C, and D (that is, the technical solution that is all connected by "logical AND").

[0056] In the present invention, "substituted" means that one or more hydrogen atoms in a substituted group are replaced by a substituent.

[0057] In the present invention, when the same substituent appears multiple times, it can be independently selected from different groups. If the general formula contains multiple R, then R can be independently selected from different groups.

[0058] In the present invention, the "number of ring atoms" refers to the number of atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, the number of ring atoms of a thienyl group is 5, and the number of ring atoms of a carbazolyl group is 13.

[0059] "Aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom, which can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. For example, "substituted or unsubstituted aromatic group having 6 to 40 ring atoms" refers to an aromatic group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aromatic group having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted aromatic group having 6 to 14 ring atoms, and the aromatic group is optionally further substituted; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylene, pyrenyl, perylene, naphthyl, fluorenyl, dinaphthylenyl, acenaphthene and derivatives thereof. It is understandable that multiple aromatic groups may also be interrupted by short non-aromatic units (e.g. <10% non-H atoms, such as C, N or O atoms), specifically acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, diaryl ether systems should also be included in the definition of aromatic groups.

[0060] "Heteroaryl or heteroaromatic group" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an aryl group, and the non-carbon atom can be an N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" means a heteroaryl having 5 to 40 ring atoms, preferably a substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably a substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and the heteroaryl group is optionally further substituted, and suitable examples include but are not limited to: thienyl, furanyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidyl, Triazine, acridinyl, pyridazinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothiophenyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-naphthyl, phenanthridinyl, primary pyridyl, quinazolinone, dibenzothiophenyl, dibenzofuranyl, carbazolyl and derivatives thereof.

[0061] In the present invention, "alkyl" may mean a straight chain, branched chain or cyclic alkyl. The carbon number of the alkyl group may be 1 to 20, 1 to 10 or 1 to 6. Phrases containing this term, non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2 -ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, etc.

[0062] In the present invention, when the same group contains multiple substituents with the same symbol, the substituents may be the same or different from each other. , the six Rs on the benzene ring may be the same or different from each other.

[0063] In the present invention, the single bond to which the substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example R is connected to any substitutable position of the benzene ring.

[0064] In the present invention, the description method "independently selected" can mean that in different groups, the specific options expressed by the same symbols do not affect each other, or it can mean that in the same group, the specific options expressed by the same symbols do not affect each other.

[0065] The “combination thereof”, “any combination thereof”, “combination of groups”, “combination” and the like used in the present invention include all suitable combinations of any two or more items in the listed groups.

[0066] In the present invention, “further”, “furthermore”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0067] In the present invention, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel solutions of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0068] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0069] Compound Synthesis Examples

[0070] Synthesis Example 1: Synthesis of Compound (1)

[0071]

[0072] Synthesis of compound 1-1:

[0073] Accurately weigh 9-phenyl-4-bromocarbazole (32.2 g, 0.1 mol) and potassium carbonate (27.6 g, 0.2 mol) and add them into a 1000 ml three-necked flask. Under nitrogen protection, add tetrakistriphenylphosphine palladium (1.15 g 1 mmol) and 300 ml of 1,4-dioxane into the reaction flask and stir to dissolve. The nitrogen was replaced three times, the temperature was raised to 100°C, and then 200 ml of a mixed solution of 2-bromophenylboronic acid (22.1 g, 0.11 mol) in 1,4-dioxane and methanol (1:1 volume ratio) was added dropwise. After the addition was completed, the reaction solution was refluxed for 6 h until the raw materials were completely reacted, cooled to room temperature, filtered, and the filtrate was concentrated to remove the solvent. Then, dichloromethane and water were added to extract the liquids, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain an off-white solid. The solid was then purified by slurrying with a mixed solvent of petroleum ether and dichloromethane in a ratio of 10:1 (volume ratio) to obtain about 28.59 g of compound 1-1 with a yield of 71.8% and MS: 398.15.

[0074] Synthesis of compound 1-2:

[0075] Accurately weigh compound 1-1 (27.9 g, 70 mmol) and 400 ml of anhydrous tetrahydrofuran were placed in a 1000 ml three-necked flask, stirred and dissolved, and nitrogen was replaced three times. The reaction solution was cooled to -78 °C, and then 34 ml of butyl lithium (2.5 M) was slowly added dropwise, and the temperature was controlled to react for 1 h. Then, a tetrahydrofuran solution of phosphorus trichloride (10.6 g 0.77 mol) was added dropwise. After the addition was complete, the cooling device was removed, and the reaction solution was warmed to room temperature. After 2 h, TLC showed that the reaction was over. 100 ml of water was added to the reaction solution under stirring, and the tetrahydrofuran was removed by vacuum concentration. The residue was extracted with dichloromethane and water, and the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. Then, 100 ml of petroleum ether was used for pulping and purification to obtain about 20.65 g of compound 1-2, with a yield of 70.1%, and MS: 421.03.

[0076] Synthesis of compound 1-3:

[0077] Accurately weigh compound 2.2-dibromobiphenyl (25 g, 80 mmol) and 250 ml of anhydrous tetrahydrofuran, place in a 500 ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78 °C, then slowly add 36 ml of butyl lithium (2.5 M) dropwise to control the temperature and react for 1 h, then add a solution of compound 1-2 (16.8 g 40 mmol) in anhydrous tetrahydrofuran, remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. TLC shows that the reaction is complete after 2 h. 100 ml of water was added to the reaction solution under stirring, and then the solvent tetrahydrofuran was removed by concentration. The residue was extracted with dichloromethane and water, and the organic phases were combined. The organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. Then, it was purified by slurrying with a mixed solvent of petroleum ether and dichloromethane in a ratio of 10:1 (volume ratio) to obtain about 13.07 g of compound 1-3 with a yield of 65.2% and MS: 501.32.

[0078] Synthesis of compound (1):

[0079] Accurately weigh compound 1-3 (10 g, 20 mmol) and 150 ml of anhydrous dichloromethane, place in a 500 ml three-necked flask, stir and dissolve, cool the reaction solution to 5°C, then slowly drop 20 ml of hydrogen peroxide (36%), remove the cooling device after the dropwise addition is complete, and the reaction solution is warmed to room temperature. The reaction ends after 2 hours. Add 100 ml of water to the reaction solution under stirring, combine the organic phases, wash the organic phases with saturated sulfurous acid aqueous solution and saturated saline in turn, dry over anhydrous sodium sulfate, filter, concentrate the filtrate, and then recrystallize with toluene to obtain about 8.33 g of compound (1), with a yield of 80.4%, MS: 518.24.

[0080] Synthesis Example 2: Synthesis of Compound (3)

[0081]

[0082] Synthesis of compound 3-1:

[0083] Accurately weigh 9-(4-tert-butyl)phenyl-4-bromocarbazole (37.8 g, 0.1 mol) and potassium carbonate (27.6 g, 0.2 mol) and add them into a 1000 ml three-necked flask. Under nitrogen protection, add tetrakistriphenylphosphine palladium (1.15 g 1 mmol) and 300 ml of 1,4-dioxane into the reaction flask and stir to dissolve. The nitrogen was replaced three times, the temperature was raised to 100°C, and then 200 ml of a mixed solution of 2-bromophenylboronic acid (22.1 g, 0.11 mol) in 1,4-dioxane and methanol (1:1 volume ratio) was added dropwise. After the addition was completed, the reaction solution was refluxed for 6 h until the raw materials were completely reacted, cooled to room temperature, filtered, and the filtrate was concentrated to remove the solvent. Then, dichloromethane and water were added to extract the liquids, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain an off-white solid. The solid was then purified by slurrying with a mixed solvent of petroleum ether and dichloromethane in a ratio of 10:1 (volume ratio) to obtain about 32.93 g of compound 3-1 with a yield of 72.5% and MS: 454.22.

[0084] Synthesis of compound 3-2:

[0085] Accurately weigh compound 3-1 (31.8g, 70mmol) and 400ml of anhydrous tetrahydrofuran, place in a 1000ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78°C, then slowly add 34ml of butyl lithium (2.5M), control the temperature and react for 1h, then add a tetrahydrofuran solution of phosphorus trichloride (10.57g 0.77mol), remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. After 2h, TLC shows that the reaction is over. Add 100ml of water to the reaction solution under stirring, then concentrate under reduced pressure to remove tetrahydrofuran, extract the residue with dichloromethane and water, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then purify with 100ml of petroleum ether to obtain about 22.73g of compound 3-2, with a yield of 68.1%, MS: 476.85.

[0086] Synthesis of compound 3-3:

[0087] Accurately weigh compound 2.2-dibromobiphenyl (25 g, 80 mmol) and 250 ml of anhydrous tetrahydrofuran, place in a 500 ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78 °C, then slowly add 36 ml of butyl lithium (2.5 M) dropwise to control the temperature for 1 h, then add a solution of compound 3-2 (19 g, 40 mmol) in anhydrous tetrahydrofuran, remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. TLC shows that the reaction is complete after 2 h. 100 ml of water was added to the reaction solution with stirring, and then the tetrahydrofuran solvent was removed by concentration. The residue was extracted with dichloromethane and water, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to remove the solvent. The mixture was then purified by slurrying with a mixed solvent of petroleum ether and dichloromethane in a ratio of 10:1 (volume ratio) to obtain about 14.19 g of compound 3-3 with a yield of 63.6% and MS: 557.42.

[0088] Synthesis of compound (3):

[0089] Accurately weigh compound 3-3 (11.15 g, 20 mmol) and 150 ml of anhydrous dichloromethane, place in a 500 ml three-necked flask, stir and dissolve, cool the reaction solution to 5°C with an ice-salt bath, then slowly drop 20 ml of hydrogen peroxide (36%), remove the cooling device after the dropwise addition, warm to room temperature, and the reaction ends after 2 hours. Add 100 ml of water to the reaction solution under stirring, combine the organic phases, wash the organic phases with saturated sulfurous acid aqueous solution and saturated brine in turn, dry with anhydrous sodium sulfate, filter, concentrate the filtrate to obtain an off-white solid, and then recrystallize from toluene to obtain about 9.46 g of compound (3), with a yield of 82.3%, MS: 574.39.

[0090] Synthesis Example 3: Synthesis of Compound (12)

[0091]

[0092] Synthesis of compound 12-1:

[0093] Accurately weigh 2,2'-dibromo-6-iodo-1,1'-biphenyl (43.8 g, 0.1 mol) and potassium carbonate (27.6 g, 0.2 mol) and add them into a 1000 ml three-necked flask. Under nitrogen protection, add tetrakistriphenylphosphine palladium (1.15 g 1 mmol) and 300 ml of 1,4-dioxane into the reaction flask and stir to dissolve. The nitrogen was replaced three times, the temperature was raised to 100°C, and then 200 ml of a mixed solution of 2-bromophenylboronic acid (22.1 g, 0.11 mol) in 1,4-dioxane and methanol (1:1 volume ratio) was added dropwise. After the addition was completed, the reaction solution was refluxed for 6 h until the raw materials were completely reacted, cooled to room temperature, filtered, and the filtrate was concentrated to remove the solvent. Then dichloromethane and water were added to extract the liquid, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain an off-white solid. The solid was then purified by slurrying with a mixed solvent of petroleum ether and dichloromethane in a ratio of 10:1 (volume ratio) to obtain about 22.76 g of compound 12-1, with a yield of 58.6%. MS: 388.61.

[0094] Synthesis of compound 12-2:

[0095] Accurately weigh compound 12-1 (15.5 g, 40 mmol) and 150 ml of anhydrous tetrahydrofuran, place in a 500 ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78 ° C, then slowly add 18 ml of butyl lithium (2.5 M) to control the temperature for 1 hour, then add compound 1-2 (8.4 g 20 mmol) in anhydrous tetrahydrofuran solution, remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. After 2 hours, TLC shows that the reaction is over. Add 100 ml of water to the reaction solution under stirring, then concentrate to remove the solvent tetrahydrofuran, extract the residue with dichloromethane and water, combine the organic phases, wash the organic phase with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then slurry and purify with a mixed solvent of petroleum ether and dichloromethane in a ratio of 10:1 (v / v), to obtain about 7.93 g of compound 12-2, with a yield of 68.7%. MS:577.33.

[0096] Synthesis of compound (12):

[0097] Accurately weigh compound 12-2 (5.77 g, 10 mmol) and 100 ml of anhydrous dichloromethane, place in a 500 ml three-necked flask, stir and dissolve, cool the reaction solution to 5°C, then slowly drop 12 ml of hydrogen peroxide (36%), remove the cooling device after the dropwise addition is complete, and the reaction solution is warmed to room temperature. The reaction ends after 2 hours. Add 100 ml of water to the reaction solution under stirring, combine the organic phases, wash the organic phases with saturated sulfurous acid aqueous solution and saturated salt water in turn, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then recrystallize with toluene to obtain 4.6 g of compound (12), with a yield of 77.6%. MS: 593.14.

[0098] Synthesis Example 4: Synthesis of Compound (13)

[0099]

[0100] Synthesis of compound 13-1:

[0101] Accurately weigh 9-phenyl-2-bromocarbazole (32.2 g, 0.1 mol) and potassium carbonate (27.6 g, 0.2 mol) and add them into a 1000 ml three-necked flask. Under nitrogen protection, add tetrakistriphenylphosphine palladium (1.15 g 1 mmol) and 300 ml of 1,4-dioxane into the reaction flask and stir to dissolve. The nitrogen was replaced three times, the temperature was raised to 100°C, and then 200 ml of a mixed solution of 2-bromophenylboronic acid (22.1 g, 0.11 mol) in 1,4-dioxane and methanol (1:1 volume ratio) was added dropwise. After the addition was completed, the reaction solution was refluxed for 6 h until the raw materials were completely reacted, cooled to room temperature, filtered, and the filtrate was concentrated to remove the solvent. Then dichloromethane and water were added to extract the liquid, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain an off-white solid. The solid was then purified by slurrying with a mixed solvent of petroleum ether and dichloromethane in a ratio of 10:1 (volume ratio) to obtain about 29.73 g of compound 13-1, with a yield of 74.7%. MS: 398.11.

[0102] Synthesis of compound 13-2:

[0103] Accurately weigh compound 13-1 (27.9 g, 70 mmol) and 400 ml of anhydrous tetrahydrofuran, place in a 1000 ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78 ° C, then slowly add 34 ml of butyl lithium (2.5 M), control the temperature and react for 1 hour, then add phosphorus trichloride (10.57 g 0.11 mol) tetrahydrofuran solution, remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. After 2 hours, TLC shows that the reaction is over. Add 100 ml of water to the reaction solution under stirring, concentrate under reduced pressure to remove tetrahydrofuran, extract the residue with dichloromethane and water, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then slurry and purify with 100 ml of petroleum ether to obtain about 21.59 g of compound 13-2, with a yield of 73.5%. MS: 419.84.

[0104] Synthesis of compound 13-3:

[0105] Accurately weigh compound 2.2-dibromobiphenyl (25 g, 80 mmol) and 250 ml of anhydrous tetrahydrofuran, place in a 500 ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78 °C, then slowly add 36 ml of butyl lithium (2.5 M) dropwise to control the temperature and react for 1 h, then add a solution of compound 13-2 (16.8 g 40 mmol) in anhydrous tetrahydrofuran, remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. TLC shows that the reaction is complete after 2 h. 100 ml of water was added to the reaction solution under stirring, and then the solvent tetrahydrofuran was removed by concentration. The residue was extracted with dichloromethane and water, and the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. Then, it was purified by slurrying with a mixed solvent of petroleum ether and dichloromethane in a ratio of 10:1 (volume ratio), and a total of 14.18 g of compound 13-3 was obtained, with a yield of 70.8%. MS: 501.03.

[0106] Synthesis of compound (13):

[0107] Accurately weigh compound 13-3 (10 g, 20 mmol) and 150 ml of anhydrous dichloromethane, place in a 500 ml three-necked flask, stir and dissolve, cool the reaction solution to 5°C, then slowly drop 20 ml of hydrogen peroxide (36%), remove the cooling device after the dropwise addition is complete, and the reaction solution is warmed to room temperature. The reaction ends after 2 hours. Add 100 ml of water to the reaction solution under stirring, combine the organic phases, wash the organic phases with saturated sulfurous acid aqueous solution and saturated brine in turn, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then recrystallize with toluene to obtain 8.65 g of compound (13), with a yield of 83.4%. MS: 518.29.

[0108] Synthesis Example 5: Synthesis of Compound (15)

[0109]

[0110] Synthesis of compound 15-1:

[0111] Accurately weigh compound 2.2-dibromo-(4.4-di-tert-butyl)biphenyl (33.94 g, 80 mmol) and 300 ml of anhydrous tetrahydrofuran, place in a 500 ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78 °C, then slowly add 36 ml of butyl lithium (2.5 M) dropwise to control the temperature and react for 1 h, then add a solution of compound 13-2 (16.8 g 40 mmol) in anhydrous tetrahydrofuran, remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. After 2 h, TLC shows that the reaction is complete. 100 ml of water was added to the reaction solution under stirring, and then the solvent tetrahydrofuran was removed by concentration. The residue was extracted with dichloromethane and water, and the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. Then, it was purified by slurrying with a mixed solvent of petroleum ether and dichloromethane in a ratio of 10:1 (volume ratio), and about 11.09 g of compound 15-1 was obtained, with a yield of 45.2%. MS: 613.35.

[0112] Synthesis of compound (15):

[0113] Accurately weigh compound 15-1 (9.2 g, 15 mmol) and 150 ml of anhydrous dichloromethane, place in a 500 ml three-necked flask, stir and dissolve, cool the reaction solution to 5°C, then slowly drop 15 ml of hydrogen peroxide (36%), remove the cooling device after the dropwise addition, warm the reaction solution to room temperature, and the reaction ends after 2 hours. Add 100 ml of water to the reaction solution under stirring, combine the organic phases, wash the organic phases with saturated sulfurous acid aqueous solution and saturated salt water in turn, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then recrystallize with toluene to obtain 7.33 g of compound (15), with a yield of 77.5%. MS: 630.41.

[0114] Synthesis Example 6: Synthesis of Compound (23)

[0115]

[0116] Synthesis of compound 23-1:

[0117] Accurately weigh 9-phenyl-3-bromocarbazole (32.2 g, 0.1 mol) and potassium carbonate (27.6 g, 0.2 mol) and add them into a 1000 ml three-necked flask. Under nitrogen protection, add tetrakistriphenylphosphine palladium (1.15 g 1 mmol) and 300 ml of 1,4-dioxane into the reaction flask and stir to dissolve. The nitrogen was replaced three times, the temperature was raised to 100°C, and then 200 ml of a mixed solution of 2-bromophenylboronic acid (22.1 g, 0.11 mol) in 1,4-dioxane and methanol (1:1 volume ratio) was added dropwise. After the addition was completed, the reaction solution was refluxed for 6 h until the raw materials were completely reacted, cooled to room temperature, filtered, and the filtrate was concentrated to remove the solvent. Then dichloromethane and water were added to extract the liquid, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain an off-white solid. The solid was then purified by pulping with petroleum ether and dichloromethane (10:1 volume ratio) to obtain about 31.96 g of compound 23-1, with a yield of 80.4%. MS: 397.74.

[0118] Synthesis of compound 23-2:

[0119] Accurately weigh compound 23-1 (27.8g, 70mmol) and 400ml of anhydrous tetrahydrofuran, place in a 1000ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78°C, then slowly add 34ml of butyl lithium (2.5M), control the temperature and react for 1h, then add a tetrahydrofuran solution of phosphorus trichloride (10.57g 0.77mol), remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. After 2H, TLC shows that the reaction is over. Add 100ml of water to the reaction solution under stirring, concentrate under reduced pressure to remove tetrahydrofuran, extract the residue with dichloromethane and water, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then slurry and purify with 100ml of petroleum ether to obtain about 21.32g of compound 23-2, with a yield of 72.5%. MS: 420.16.

[0120] Synthesis of compound 23-3:

[0121] Accurately weigh compound 12-1 (15.52g, 40mmol) and 250ml of anhydrous tetrahydrofuran were placed in a 500ml three-necked flask and stirred to dissolve. The nitrogen was replaced three times. The reaction solution was cooled to -78°C, and then 20ml of butyl lithium (2.5M) was slowly added to control the temperature for 1h. Then, a solution of compound 23-2 (16.8g 40mmol) in anhydrous tetrahydrofuran was added. After the addition was complete, the cooling device was removed, and the reaction solution was warmed to room temperature. After 2h, TLC showed that the reaction was over. 100ml of water was added to the reaction solution under stirring, and then the solvent tetrahydrofuran was concentrated to remove. The residue was extracted with dichloromethane and water, and the organic phases were combined. The organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. Then, a mixed solvent of petroleum ether and dichloromethane was used to slurry and purify at a volume ratio of 10:1 to obtain about 11.59g of compound 23-3, with a yield of 50.2%. MS:577.29.

[0122] Synthesis of compound (23):

[0123] Accurately weigh compound 23-3 (5.77 g, 10 mmol) and 100 ml of anhydrous dichloromethane, place in a 500 ml three-necked flask, stir and dissolve, cool the reaction solution to 5°C, then slowly drop 12 ml of hydrogen peroxide (36%), remove the cooling device after the dropwise addition, and warm the reaction solution to room temperature. The reaction ends after 2 hours. Add 100 ml of water to the reaction solution under stirring, combine the organic phases, wash the organic phases with saturated sulfurous acid aqueous solution and saturated salt water in turn, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then recrystallize with toluene to obtain 4.66 g of compound (23), with a yield of 78.4%. MS: 594.48.

[0124] Synthesis Example 7: Synthesis of Compound (27)

[0125]

[0126] Synthesis of compound 27-1:

[0127] Accurately weigh 3-bromo-9-(3-hexylphenyl)-9H-carbazole (40.43 g, 0.1 mol) and potassium carbonate (27.6 g, 0.2 mol) and add them into a 1000 ml three-necked flask. Under nitrogen protection, add tetrakistriphenylphosphine palladium (1.15 g 1 mmol) and 400 ml of 1,4-dioxane into the reaction flask and stir to dissolve. The nitrogen was replaced three times, the temperature was raised to 100°C, and then 200 ml of a mixed solution of 2-bromophenylboronic acid (22.1 g, 0.11 mol) in 1,4-dioxane and methanol (1:1 volume ratio) was added dropwise. After the addition was completed, the reaction solution was refluxed for 6 h until the raw materials were completely reacted, cooled to room temperature, filtered, and the filtrate was concentrated to remove the solvent. Then dichloromethane and water were added to extract the liquid, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain an off-white solid. The solid was then purified by slurrying with a mixed solvent of petroleum ether and dichloromethane in a ratio of 10:1 (volume ratio) to obtain about 34.25 g of compound 27-1, with a yield of 71.2%. MS: 480.73.

[0128] Synthesis of compound 27-2:

[0129] Accurately weigh compound 27-1 (33.6 g, 70 mmol) and 400 ml of anhydrous tetrahydrofuran, place in a 1000 ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78 ° C, then slowly add 34 ml of butyl lithium (2.5 M), control the temperature and react for 1 hour, then add a tetrahydrofuran solution of phosphorus trichloride (10.57 g 0.11 mol), remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. After 2 hours, TLC shows that the reaction is over. Add 100 ml of water to the reaction solution under stirring, concentrate under reduced pressure to remove tetrahydrofuran, extract the residue with dichloromethane and water, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then slurry and purify with 100 ml of petroleum ether to obtain about 23.24 g of compound 27-2, with a yield of 66.1%. MS: 502.16.

[0130] Synthesis of compound 27-3:

[0131] Accurately weigh compound 2.2-dibromobiphenyl (25g, 80mmol) and 250ml of anhydrous tetrahydrofuran, place in a 500ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78°C, then slowly add 36ml of butyl lithium (2.5M) to control the temperature for 1h, then add compound 27-2 (20.09g 40mmol) in anhydrous tetrahydrofuran solution, remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. After 2h, TLC shows that the reaction is over. Add 100ml of water to the reaction solution under stirring, then concentrate to remove the solvent tetrahydrofuran, extract the residue with dichloromethane and water, combine the organic phases, wash the organic phase with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then use petroleum ether and dichloromethane with a mixed solvent of 10:1 (volume ratio) to slurry and purify, to obtain about 12.88g of compound 27-3, with a yield of 55.2%. MS:583.44.

[0132] Synthesis of compound (27):

[0133] Accurately weigh compound 27-3 (11.67 g, 20 mmol) and 150 ml of anhydrous dichloromethane, place in a 500 ml three-necked flask, stir and dissolve, cool the reaction solution to 5°C, then slowly drop 20 ml of hydrogen peroxide (36%), remove the cooling device after the dropwise addition is complete, and the reaction solution is warmed to room temperature. The reaction ends after 2 hours. Add 100 ml of water to the reaction solution under stirring, combine the organic phases, wash the organic phases with saturated sulfurous acid aqueous solution and saturated salt water in turn, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then recrystallize with toluene to obtain about 9.52 g of compound (27), with a yield of 79.4%. MS: 599.47.

[0134] Synthesis Example 8: Synthesis of Compound (31)

[0135]

[0136] Synthesis of compound 31-1:

[0137] Accurately weigh N-(4-bromophenyl)-N,N-bis(1,1'-biphenyl-4-yl)amine (47.6 g, 0.1 mol) and potassium carbonate (27.6 g, 0.2 mol) and add them into a 1000 ml three-necked flask. Under nitrogen protection, add tetrakistriphenylphosphine palladium (1.15 g 1 mmol) and 300 ml of 1,4-dioxane into the reaction flask and stir to dissolve. The nitrogen was replaced three times, the temperature was raised to 100°C, and then 200 ml of a mixed solution of 2-bromophenylboronic acid (22.1 g, 0.11 mol) in 1,4-dioxane and methanol (1:1 (volume ratio)) was added dropwise. After the addition was completed, the reaction solution was refluxed for 6 h until the raw materials were completely reacted, cooled to room temperature, filtered, and the filtrate was concentrated to remove the solvent. Then dichloromethane and water were added to extract the liquid, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain an off-white solid. The solid was then purified by slurrying with a mixed solvent of petroleum ether and dichloromethane in a ratio of 5:1 (volume ratio) to obtain about 38.66 g of compound 31-1, with a yield of 69.9%. MS: 553.24.

[0138] Synthesis of compound 31-2:

[0139] Accurately weigh compound 31-1 (33.2g, 60mmol) and 400ml of anhydrous tetrahydrofuran, place in a 1000ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78°C, then slowly add 28ml of butyl lithium (2.5M), control the temperature and react for 1h, then add a tetrahydrofuran solution of phosphorus trichloride (9.86g 0.72mol), remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. After 2h, TLC shows that the reaction is over. Add 100ml of water to the reaction solution under stirring, concentrate under reduced pressure to remove tetrahydrofuran, extract the residue with dichloromethane and water, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then slurry and purify with 100ml of petroleum ether to obtain about 24.98g of compound 31-2, with a yield of 72.5%. MS: 574.25.

[0140] Synthesis of compound 31-3:

[0141] Accurately weigh compound 2.2-dibromobiphenyl (25g, 80mmol) and 250ml of anhydrous tetrahydrofuran, place in a 500ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78°C, then slowly add 36ml of butyl lithium (2.5M) to control the temperature for 1h, then add a solution of compound 31-2 (23g 40mmol) in anhydrous tetrahydrofuran, remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. After 2h, TLC shows that the reaction is over. Add 100ml of water to the reaction solution under stirring, then concentrate to remove the solvent tetrahydrofuran, extract the residue with dichloromethane and water, combine the organic phases, wash the organic phase with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then slurry and purify with a mixed solvent of petroleum ether and dichloromethane in a ratio of 10:1 (volume ratio), to obtain about 14.47g of compound 31-3, with a yield of 55.2%. MS:655.46.

[0142] Synthesis of compound (31):

[0143] Accurately weigh compound 31-3 (13.1 g, 20 mmol) and 150 ml of anhydrous dichloromethane, place in a 500 ml three-necked flask, stir and dissolve, cool the reaction solution to 5°C, then slowly drop 20 ml of hydrogen peroxide (36%), remove the cooling device after the dropwise addition is complete, and the reaction solution is warmed to room temperature. The reaction ends after 2 hours. Add 100 ml of water to the reaction solution under stirring, combine the organic phases, wash the organic phases with saturated sulfurous acid aqueous solution and saturated brine in turn, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then recrystallize with toluene to obtain about 10.38 g of compound (31), with a yield of 77.3%. MS: 671.30.

[0144] Synthesis Example 9: Synthesis of Compound (37)

[0145]

[0146] Synthesis of compound 37-1:

[0147] Accurately weigh 4-bromo-N-(4-2-naphthyl)-N-phenylamine (45.04 g, 0.1 mol) and potassium carbonate (27.6 g, 0.2 mol) and add them into a 1000 ml three-necked flask. Under nitrogen protection, add tetrakistriphenylphosphine palladium (1.15 g 1 mmol) and 300 ml of 1,4-dioxane into the reaction flask and stir to dissolve. The nitrogen was replaced three times, the temperature was raised to 100°C, and then 200 ml of a mixed solution of 2-bromophenylboronic acid (22.1 g, 0.11 mol) in 1,4-dioxane and methanol (1:1 (volume ratio)) was added dropwise. After the addition was completed, the reaction solution was refluxed for 6 h until the raw materials were completely reacted, cooled to room temperature, filtered, and the filtrate was concentrated to remove the solvent. Then dichloromethane and water were added to extract the liquid, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain an off-white solid. The solid was then purified by slurrying with a mixed solvent of petroleum ether and dichloromethane in a ratio of 5:1 (volume ratio) to obtain about 41.68 g of compound 37-1, with a yield of 79.1%. MS: 527.21.

[0148] Synthesis of compound 37-2:

[0149] Accurately weigh compound 37-1 (37g, 70mmol) and 400ml of anhydrous tetrahydrofuran, place in a 1000ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78°C, then slowly drop 34ml of butyl lithium (2.5M), control the temperature and react for 1h, then drop phosphorus trichloride (10.57g 0.77mol) tetrahydrofuran solution, remove the cooling device after the dropwise addition, and the reaction solution is warmed to room temperature. After 2h, TLC shows that the reaction is over. Add 100ml of water to the reaction solution under stirring, concentrate under reduced pressure to remove tetrahydrofuran, extract the residue with dichloromethane and water, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then slurry and purify with 100ml of petroleum ether to obtain about 27.48g of compound 37-2, with a yield of 71.5%. MS: 548.93.

[0150] Synthesis of compound 37-3:

[0151] Accurately weigh compound 2.2-dibromobiphenyl (25g, 80mmol) and 250ml of anhydrous tetrahydrofuran, place in a 500ml three-necked flask, stir and dissolve, replace nitrogen three times, cool the reaction solution to -78°C, then slowly add 36ml of butyl lithium (2.5M) to control the temperature and react for 1h, then add a solution of compound 37-2 (22g 40mmol) in anhydrous tetrahydrofuran, remove the cooling device after the addition is complete, and the reaction solution is warmed to room temperature. After 2h, TLC shows that the reaction is over. Add 100ml of water to the reaction solution under stirring, then concentrate to remove the solvent tetrahydrofuran, extract the residue with dichloromethane and water, combine the organic phases, wash the organic phase with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then slurry and purify with a mixed solvent of petroleum ether and dichloromethane in a ratio of 5:1 (volume ratio), to obtain a total of 14.15g of compound 37-3, with a yield of 56.1%. MS:630.18.

[0152] Synthesis of compound (37):

[0153] Accurately weigh compound 37-3 (12.59 g, 20 mmol) and 150 ml of anhydrous dichloromethane, place in a 500 ml three-necked flask, stir and dissolve, cool the reaction solution to 5°C, then slowly drop 20 ml of hydrogen peroxide (36%), remove the cooling device after the dropwise addition is complete, and the reaction solution is warmed to room temperature. The reaction ends after 2 hours. Add 100 ml of water to the reaction solution under stirring, combine the organic phases, wash the organic phases with saturated sulfurous acid aqueous solution and saturated salt water in turn, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, and then recrystallize with toluene to obtain 10.51 g of compound (37), with a yield of 81.3%. MS: 646.43.

[0154] Preparation and characterization examples of OLED devices:

[0155] Device Example 1

[0156] like Figure 1 The OLED device structure shown is:

[0157] Substrate 101 / Anode layer 102 / Hole injection layer 103 (5nm) / First hole transport layer 104 (30nm) / Second hole transport layer 105 (15nm) / Emitting layer 106 (45nm) / Electron transport layer 107 (40nm) / Electron injection layer 108 (2nm) / Cathode layer 109 (100nm)

[0158] Its preparation method comprises the following steps:

[0159] a. Cleaning of ITO conductive glass substrate: Clean the anode layer of ITO conductive glass with detergent, rinse it clean, and then ultrasonically clean it with deionized water, acetone, and isopropanol for 15 minutes, then blow it dry with nitrogen and treat it in a plasma cleaner for 5 minutes to improve the electrode work function.

[0160] b. Preparation of hole injection layer: The ITO conductive glass substrate was moved into a vacuum vapor deposition device and placed in a high vacuum (1×10 -6 Under the condition of 200 mbar, the hole injection layer material HATCN was evaporated with a thickness of 10 nm.

[0161] c. Preparation of the first hole transport layer: On the hole injection layer, a hole transport material compound TAPC is evaporated to a thickness of 30 nm to form the first hole transport layer.

[0162] d. Preparation of the second hole transport layer: TCTA was evaporated on the first hole transport layer with a thickness of 15 nm to form the second hole transport layer.

[0163] e. Preparation of the light-emitting layer: a light-emitting layer is deposited on the second hole transport layer, wherein the host material is selected from compound (1), the guest light-emitting material is selected from EM1, the mass ratio of the host material to the guest light-emitting material is 95:5, and the thickness is 30 nm, to form a light-emitting layer;

[0164] f. Preparation of electron transport layer: vacuum evaporation is performed on the light-emitting layer to form an electron transport layer with a thickness of 40 nm.

[0165] g. Forming an electron injection layer: forming an electron injection layer with a thickness of 1 nm on the electron transport layer by vacuum evaporating an electron injection material Liq.

[0166] h. Forming a cathode layer: Al is deposited on the electron injection layer by vacuum evaporation to obtain an Al cathode with a thickness of 100 nm.

[0167] i. Packaging: The device is packaged with UV-curable resin in a nitrogen glove box.

[0168] The structural formula of the compound involved:

[0169] .

[0170] Device Examples 2-9:

[0171] The preparation methods of device examples 2-9 are the same as those of device example 1, except that the main materials in the light-emitting layer are different, and the organic compound (1) in device example 1 is replaced by organic compound (3), organic compound (12), organic compound (13), organic compound (15), organic compound (23), organic compound (27), organic compound (31) and organic compound (37), respectively. See Table 1 for details.

[0172] The current-voltage (JV) characteristics of each OLED device were characterized by a characterization device, and the LT95 lifetime and luminous efficiency were recorded at the same time. LT95 represents the time required for the device brightness to decay to 95% of the initial brightness. The results are shown in Table 1.

[0173] Table 1

[0174]

[0175] It can be seen from the results in Table 1 that the organic compound provided by the present invention is used as a phosphorescent host material in an organic electroluminescent device, and the device exhibits good photoelectric performance.

[0176] It should be noted that the present invention is particularly described using individual embodiments. However, without departing from the principles of the present invention, a person skilled in the art may make various improvements in form or detail to the present invention, and these improvements also fall within the scope of protection of the present invention.

Claims

1. An organic compound, characterized in that: The organic compound has a structure as shown in the general formula (I): （I） Where: -Z- each occurrence is selected from none or a single bond; Each occurrence of R1, R2, R3, and R5 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, substituted or unsubstituted straight-chain alkyl having 1 to 20 carbon atoms, substituted or unsubstituted straight-chain or cyclic alkyl having 3 to 20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms; Each occurrence of R4 is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, substituted or unsubstituted straight chain alkyl having 1 to 20 carbon atoms, substituted or unsubstituted straight chain or cyclic alkyl having 3 to 20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms; m is selected from 0, 1, 2, 3, 4 or 5; "Substituted or unsubstituted" means that the defined group is unsubstituted or substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a straight-chain or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups.

2. The organic compound according to claim 1, characterized in that: The organic compound has a structure as shown in the general formula (II-1) or (II-2): 。 3. The organic compound according to claim 1, characterized in that: The organic compound is selected from any of the following general formulas: 。 4. The organic compound according to claim 1, characterized in that: Each occurrence of R1, R2, R3, and R5 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, substituted or unsubstituted straight-chain alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted straight-chain or cyclic alkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms, and substituted or unsubstituted heteroaromatic groups having 5 to 10 ring atoms.

5. The organic compound according to claim 4, characterized in that: Each occurrence of R1 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched-chain alkyl group or a cyclic alkyl group having 3 to 6 carbon atoms, a phenyl group, a pyridyl group, or a group formed by a combination of the above groups; And / or, each occurrence of R2 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 6 carbon atoms, a phenyl group, a pyridyl group, or a group formed by a combination of the above groups.

6. The organic compound according to claim 4, characterized in that: Each occurrence of R3 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 6 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, phenyl, pyridyl, or a group formed by a combination of the above groups; and / or, each occurrence of R4 is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a linear alkyl group having 1 to 6 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, phenyl, pyridyl, naphthyl, or a group formed by a combination of the above groups; And / or, each occurrence of R5 is independently selected from --H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 6 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms.

7. The organic compound according to claim 1, characterized in that: The organic compound is selected from any of the following general formulas: ； in: Each occurrence of R1 is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched-chain alkyl group or a cyclic alkyl group having 3 to 6 carbon atoms, a phenyl group, a pyridyl group, or a group formed by a combination of the above groups; Each occurrence of R2 is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 6 carbon atoms, phenyl, pyridyl, or a group formed by a combination of the above groups.

8. The organic compound according to claim 1, characterized in that: The organic compound is selected from any of the following structures: 。 9. A mixture, characterized in that: The mixture comprises the organic compound according to any one of claims 1 to 8 and at least one organic functional material.

10. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a cathode, an anode and at least one functional layer located between the cathode and the anode, wherein the at least one functional layer comprises the organic compound according to any one of claims 1 to 8.

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