TWI735871B - Hole transfer compound and organic light-emitting diodes using the same - Google Patents

Abstract

The present invention relates to a hole transport compound represented by the following chemical formula 1 and an organic light emitting element containing the compound:

Description

Hole transport compound and organic light emitting element containing the compound

The present invention relates to a hole-transporting compound and an organic light-emitting element containing the compound. More specifically, it relates to a hole-transporting compound and an organic light-emitting element containing the compound: on the basis of high hole transport, relatively low free potential It has the characteristics of introducing aromatic amino groups into the carbazole core to reduce the formation of crystals, reduce the free potential, and improve the hole transport ability, with long-term life characteristics.

Electroluminescent device (hereinafter referred to as "EL device") as a self-luminous display device has the advantages of wide viewing angle, excellent contrast, and fast response time.

EL elements are classified into inorganic EL elements and organic EL elements according to the molding material of the emitting layer. Here, compared with inorganic EL elements, organic EL elements not only have excellent characteristics such as brightness, driving voltage, and response speed, but also have the advantage of being able to achieve full color.

A general organic EL element has an anode formed on the upper part of a substrate, and has a structure in which a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially formed on the upper part of the anode. Here, the hole transport layer, the light emitting layer, and the electron transport layer are organic thin films formed of organic compounds.

The driving principle of the organic EL element having the above-mentioned structure is as follows: a voltage is applied between the anode and the cathode, and the holes injected from the anode move to the light emitting layer through the hole transport layer. On the other hand, electrons are injected into the light-emitting layer from the cathode through the electron transport layer, and recombine with the carrier in the light-emitting layer region to generate excitons. The excitons are converted from the excited state to the ground state, so that the molecules of the light-emitting layer emit light and form an image. According to the principle of light emission, luminescent materials are classified into fluorescent materials using singlet state excitons and phosphorescent materials using triplet state.

So far, for hole transport materials using such organic light-emitting elements, many amine derivatives having a carbazole skeleton have been studied, but due to high driving voltage, low efficiency, and short life, it is difficult to put into practical use.

Therefore, continuous efforts are being made to develop organic light-emitting elements with low driving voltage, high brightness, and long life using materials with excellent characteristics.

(Prior Art Document)

(Patent Document)

(Patent Document 1) Korean Registered Patent Publication No. 10-1631507.

In order to solve the above-mentioned problems, the subject of the present invention is to provide a hole-transporting compound and an organic light-emitting device containing the compound. On the basis of the high hole-transporting characteristic, the characteristic of relatively reducing the free potential is introduced into the carbazole core. Aromatic amino groups reduce the formation of crystals, lower the free potential, improve the hole transport ability, and have long-term life characteristics.

In order to solve the above-mentioned problems, the hole transport compound of the present invention is as follows: represented by the following chemical formula 1,

In the chemical formula, the R1, R2, R3, and R4 are independently hydrogen, a phenyl group, a phenylcarbazole derivative or a phenylcarboline derivative; at least one of the R1, R2, R3, and R4 One is a phenylcarbazole derivative or a phenylcarboline derivative.

In order to solve the above-mentioned problems, the present invention provides the following organic light-emitting element: In an organic light-emitting element including a hole transport layer between a pair of electrodes, the hole transport layer includes the hole transport compound of Chemical Formula 1 .

The hole transport compound of the present invention can exert the following effects: on the basis of high hole movement characteristics, the characteristics of relatively reducing the free potential, the introduction of aryl amino groups into the carbazole core reduces the formation of crystals, reduces the free potential, and improves the hole transport ability , With long-term life characteristics.

10‧‧‧Substrate

20‧‧‧Anode electrode

30‧‧‧Electric hole injection layer

40‧‧‧Hole Transmission Layer

50‧‧‧Light-emitting layer

60‧‧‧Electron transport layer

70‧‧‧Electron injection layer

80‧‧‧Cathode electrode

FIG. 1 is a cross-sectional view showing the structure of an organic light emitting device according to an embodiment of the present invention.

Hereinafter, the present invention will be explained in more detail.

The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Before explaining the present invention, the terms or words used in this specification and the scope of the patent application shall not be limited and interpreted by ordinary or dictionary meanings. Therefore, the embodiments described in this specification and the structure shown in the drawings are only the best embodiments of the present invention, and do not represent all the technical ideas of the present invention. Therefore, when submitting this application, it should be understood that there may be alternatives. Various equivalents of these.

The material or compound used in the hole transport layer performs the role of one of the light-emitting materials in the OLED device.

Specifically, the hole transport layer corresponds to a layer that performs the function of allowing holes transferred from the anode through the hole injection layer to more smoothly move to the light-emitting layer while blocking electrons transferred from the cathode while the light-emitting layer functions.

On the other hand, the hole transport layer material has a great influence on the performance of the OLED device, and the overall performance of the OLED device changes greatly depending on how to design and synthesize the material.

The basic requirement of the hole transport layer is high hole mobility. In order to exhibit this characteristic, it is preferable to have a work function between the hole injection layer and the light-emitting layer, and in order to block electrons in the light-emitting layer, a Lowest Unoccupied Molecular Orbital (LUMO) is required. When forming a thin film, it has non-crystalline characteristics without crystallinity.

In addition, in order to have high thermal stability physically, the film should have light transmittance in the visible light region, so that it has a high glass transition temperature and can transmit visible light in the visible light region.

In order to meet the above requirements, the hole transport compound of the present invention has been derived.

Specifically, the hole transport compound of the present invention introduces an arylamino group into the carbazole core, reduces the formation of crystals, reduces the free potential, and improves the hole transport ability.

In addition, the use of triphenylamine derivatives can ensure a long device life.

On the other hand, the hole-transporting compound of the present invention having the above-mentioned structure directly binds bromobenzene or 4-bromo-1,1'-biphenyl to benzidine to bind carbazole derivatives. The method for synthesizing the hole transport compound of carbazole has a problem that it cannot be synthesized smoothly or the yield is reduced even if it is synthesized.

On the contrary, in order to solve such a problem, in the present invention, a halogen group or an amine group is first introduced into the carbazole derivative, and then aniline or benzidine-4-amine is connected, and then 4,4'-dibromobiphenyl is used to induce induction. The coupling reaction, in turn, can obtain the target compound, that is, the hole transport compound of the present invention, with a relatively stable yield and high purity.

Specifically, the hole transport compound of an embodiment of the present invention has the structure of the following chemical formula 1.

In the chemical formula, the R1, R2, R3, and R4 are each a single hydrogen, a phenyl group, a phenylcarbazole derivative or a phenylcarboline derivative; one of the R1, R2, R3, and R4 The above are phenylcarbazole derivatives or phenylcarboline derivatives.

According to the compound of the embodiment of the present invention, an arylamino group is introduced into the carbazole core, which reduces crystal formation, reduces free potential, and improves hole transport ability, and uses triphenylamine derivatives to ensure a long device life.

The compounds of the preferred embodiments of the present invention can be represented according to the following chemical formula:

The compound according to the preferred embodiment of the present invention can be represented according to the following chemical formula:

The compound according to the preferred embodiment of the present invention can be represented according to the following chemical formula:

For the compound with the above chemical formula structure, it has a favorable Highest Occupied Molecular Orbital (HOMO) energy level in hole transport, and has a high LUMO energy level, which can block the movement of electrons. Therefore, the overall hole transport properties of the compound with the structure of the above chemical formula are better than those of TAPC, NPB, and BPBPA commonly used as hole transport layers, and have high energy efficiency and glass transition temperature, as well as excellent stability and lifetime. .

The hole transport compound according to the embodiment of the present invention is used as a compound for the hole transport layer. The hole transport layer is implemented to make the holes transferred from the anode through the hole injection layer more smoothly move to the light emitting layer and block the light emitting layer. The function layer of electrons transferred from the cathode.

The basic requirement of the hole transport layer HTL is to have high hole mobility, and the hole injection from the anode to the light emitting layer EML should be effectively performed.

The well-known material for these materials is an aromatic amine material with an amine structure. The material should form a thin film that will not crystallize during the material deposition process, and should have high thermal stability and excellent contact with the anode. Flatness, and should have transparent properties when forming a thin film in the visible light region.

In order to achieve the material properties of the hole transport layer as described above, the hole transport compound according to the embodiment of the present invention is a compound derived from the following three characteristics: 1) Excellent efficiency and long life; 2) Used in the deposition process The high conversion temperature at which crystallization does not occur; 3) The sp3 carbon structure is eliminated to make the holes flow smoothly.

For this reason, the hole transport compound according to the embodiment of the present invention is a structure in which the aniline structure in the center is not directly connected to the double bond structure but is inserted and connected to the phenyl group.

That is, the hole transport compound of the embodiment of the present invention has a structure in which one or more of the above-mentioned R1 to R4 have a phenyl group inserted between the aniline structure and the phenyl-carbazole or phenylcarboline.

If the double bond structure is directly connected to the central aniline structure, there is a disadvantage that a high transition temperature Tg cannot be obtained due to the planarity of the molecular structure. That is, in the case of an aniline in which a carbazolyl group or a carboline group is directly connected to the center, there is a carbazole known as an electron donor because the nitrogen of the central aniline structure is close to the nitrogen of the carbazolyl group and the effect is halved. Shortcomings.

In order to solve the above-mentioned shortcomings in the present invention, the unstable backbond is eliminated, and the carbazolyl or carbolinyl group is not directly connected, but the carbazolyl or carbolinyl group is inserted into the phenyl structure. Connecting to the mother core can make the flow of electrons or holes smoother.

As described above, the hole transport compound of the embodiment of the present invention inserts a phenyl structure, thereby substantially not destroying the basic structure of the planar structure, while inducing a secondary deformation structure instead of a primary deformation structure, and can exhibit a long life and excellent structure. Efficiency, the effect of high conversion temperature Tg.

According to the ease of internal electron migration as described above, the present invention can have a clear difference in electron distribution in HOMO and LUMO states. In addition, in the present invention, the longest effective conjugation (longest effective conjugation) in which multiple phenyl groups are effectively involved is realized. Therefore, when compared with common hole transport compounds, the groups involved in effective conjugation are different from their lengths. Therefore, it is a more effective and better structure for electron movement, and it also has a long life on the life side.

Organic light-emitting element

Hereinafter, the structure and manufacturing method of an organic light-emitting element using the phosphorescent host compound of the present invention will be described.

According to the organic light emitting element of the present invention, a common light emitting element structure can be adopted, and the structure can be changed according to requirements. Generally, an organic light-emitting element has a structure including an organic film (light-emitting layer) between the first electrode (anode electrode) and the second electrode (cathode electrode), and may also include: a hole injection layer, a hole transport layer, and a hole blocking layer. Layer, electron injection layer or electron transport layer. The structure of the light-emitting element of the present invention will be described with reference to FIG. 1.

1, the organic light-emitting element according to the present invention has a structure of a light-emitting layer 50 between the anode electrode 20 and the cathode electrode 80, and a hole injection layer 30 and a hole transport layer 40 are included between the anode electrode 20 and the light-emitting layer 50, and An electron transport layer 50 and an electron injection layer 70 are included between the light emitting layer 50 and the cathode electrode 80.

On the other hand, the organic light emitting device of FIG. 1 according to an embodiment of the present invention is manufactured through the following process. Here, it is only an example, and is not limited to this method.

First, an anode electrode material is applied to the upper part of the substrate 10 to form the anode electrode 20. Here, the substrate 10 can be a substrate commonly used in this field, and is particularly preferably a glass substrate or a transparent plastic substrate with excellent transparency, surface smoothness, ease of handling, and water resistance. In addition, as the anode material formed on the substrate, transparent and excellent conductive indium tin oxide ITO, tin oxide SnO ₂ , zinc oxide ZnO, etc. can be used, but it is not limited to this.

A hole injection layer HIL30 can be selectively formed on the upper portion of the anode electrode 20. At this time, the hole injection layer is formed by a normal method such as a vacuum evaporation method or a spin coating method. There is no particular limitation on the material for the hole injection layer, and copper phthalocyanine (CuPc) or IDE406 (Idemitsu Kosan) can be used.

Next, the hole transport layer THL40 is formed on the upper portion of the hole injection layer 30 by a normal method such as a vacuum evaporation method or a spin coating method. For the material for the hole transport layer, N,N'-diphenyl-N, N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-bis Amine NPB, N,N'-bis(3-methylbenzene)-N,N'-diphenyl-[1,1-diphenyl]-4,4'-diamine TPD, N,N'- Di(naphthalene-1-yl)-N,N'-diphenylbenzidine, N,N'-bis(naphthalene-1-yl)-N,N'-diphenyl-benzidine α-NPD, etc., The embodiment of the present invention includes the hole transport compound of the above chemical formula.

Next, a light-emitting layer EML50 is formed on the hole transport layer 40. The light-emitting layer forming material may include one or more light-emitting host substances selected from the phosphorescent host compound, and may have a single layer or a multilayer structure of two or more layers. At this time, the compound of Chemical Formula 1 alone or the mixture includes other compounds well-known in the art, for example, blue light-emitting dopants (iridium compounds such as FIrppy or FIrpic) and the like. Based on the total weight of the constituent materials of the light-emitting layer, the content of the phosphorescent host compound of the light-emitting layer may be in the range of 1 to 95% by weight.

The phosphorescent host compound can be formed by a vacuum evaporation method, and can be evaporated by a wet process such as a spin coating method, or a laser induction thermal imaging method LITI can be used.

A hole blocking layer HBL that prevents excitons formed in the light-emitting substance from moving to the electron transport layer or prevents holes from moving to the electron transport layer 60 may be selectively formed on the upper portion of the light emitting layer 50. Regarding the material for the hole blocking layer, there is no particular limitation, but a phenanthroline compound (for example, BCP) or the like can be used. This can be formed by a vacuum evaporation method or a spin coating method.

In addition, the electron transport layer ETL60 may be formed on the light-emitting layer 50, and a vacuum evaporation method or a spin coating method may be used. The material for the electron transport layer is not particularly limited, and TBPI, aluminum composite (for example, ALq ₃ (tris(8-hydroxyquinoline) aluminum)) can be used.

The electron injection layer EIL70 can be formed on the upper part of the electron transport layer 60 by a vacuum evaporation method or a spin coating method. The material for the electron injection layer 70 is not particularly limited, and LiF, NaCl, CsF and the like can be used.

Next, a cathode electrode 80 is formed on the upper portion of the electron injection layer 70 by vacuum evaporation, thereby completing the light-emitting element. Here, as the metal for the cathode, lithium Li, magnesium Mg, aluminum Al, aluminum-lithium Al-Li, calcium Ca, magnesium-indium Mg-In, and magnesium-silver Mg-Ag can be used.

In addition, the organic light-emitting element according to the present invention has a laminated structure as shown in FIG. In addition, the thickness of each layer of the light-emitting element can be determined according to requirements within the usual range in the field.

The present invention will be explained in more detail through examples, but the present invention is not limited to the following examples.

Synthesis example of hole transport compound of the present invention

Synthesis example 1

Synthesis of 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole

Combine 16.8g (0.052mol) of 3-bromo-9-phenyl-9H-carbazole, 15.7g (0.062mol) of di(pinacol) diboron, 10.1g (0.103mol) of potassium acetate, and tetrakis(triphenyl) After dissolving 3.4 g (0.003 mol) of phosphonium palladium (0) in 400 ml of 1,4-oxopropane, it was heated and stirred at 110° C. for 8 hours. After confirming the completion of the reaction, the reaction solution was filtered with silica, then 500 mL of ethyl acetate was added, and the extraction was performed after washing with saturated brine twice, and then washing again with water. The organic layer was treated with anhydrous magnesium sulfate and filtered, and then the residue obtained by concentrating the organic layer under reduced pressure was subjected to silica gel chromatography using a 1:5 mixture of dichloromethane and n-hexane as the eluent to obtain the target compound as white crystals. That is, 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 11.1g (57.8%).

Synthesis Example 2

Synthesis of 3-(4-bromophenyl)-9-phenyl-9H-carbazole

9-Phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 11.8g (0.032mol), 1-bromo-4-iodobenzene 11.8g (0.032mol), 9.05g (0.032mol), tetrakis (triphenylphosphine) palladium (0) 1.87g (0.002mol) added to 200ml of tetrahydrofuran to dissolve and then stirred for 30 minutes . 200 ml of a 2N-potassium carbonate aqueous solution was added to the reaction solution, followed by vigorous stirring at 70°C for 18 hours. After confirming the completion of the reaction, 500 mL of dichloromethane was added to the residue obtained by distillation of the reaction solution under reduced pressure, and the organic layer was washed with water, then the organic layer was treated with anhydrous magnesium sulfate and filtered, and then the organic layer was concentrated under reduced pressure. Silica gel chromatography was performed with a 1:5 mixture of dichloromethane and n-hexane as the eluent to obtain the target compound as white crystals, namely 3-(4-bromophenyl)-9-phenyl-9H-carbazole 8.4 g(65.8%).

Synthesis Example 3

Synthesis of N-phenyl-4-(9-phenyl-9H-carbazol-3-yl)aniline

Add 10g (0.025mol) of 3-(4-bromophenyl)-9-phenyl-9H-carbazole, 2.58g (0.028mol) of aniline, and 2.91g (0.03mol) of sodium tert-butoxide to 100mL of toluene and heat To 60°C. A solution in which 0.253 g (1.2 mmol) of tri-tert-butylphosphine and 0.14 g (0.25 mmol) of bis(dibenzylideneacetone)palladium(0) was dissolved was added to the reaction solution all at once, and then stirred in circulation for 24 hours. After confirming the completion of the reaction, the reactant was cooled to room temperature and filtered with silica, then 200 mL of ethyl acetate was added and washed with water several times, and the organic layer was treated with anhydrous magnesium sulfate, then filtered, and then the residue obtained by concentrating the organic layer under reduced pressure Add a small amount of ethyl acetate to dissolve the substance, and add 300 mL of excess n-heptane, stir vigorously at 0°C for 1 hour to form crystals, and filter the resulting crystals to obtain white crystals of the target compound, namely phenyl-4-(9- Phenyl-9H-carbazol-3-yl)aniline 4.2 g (40.6%).

Synthesis Example 4

Synthesis of N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine

Add 10g (0.025mol) of 3-(4-bromophenyl)-9-phenyl-9H-carbazole, 5.1g (0.030mol) of benzidine-4-amine, 3.62g (0.038mol) of sodium tert-butoxide After 150 mL of toluene, it was stirred at room temperature for 30 minutes. Then, to the reaction solution was added a solution in which 0.253 g (0.63 mmol) of tri-tert-butylphosphine (50% xylene) was dissolved in 0.144 g (0.25 mmol) of bis(dibenzylideneacetone)palladium(0), followed by circulating stirring for 22 Hour. After confirming the completion of the reaction, it was cooled to room temperature and filtered with silica, the remaining liquid was distilled under reduced pressure to obtain a residue in a gel state. After adding 300 mL of dichloromethane to the residue, the residue was washed with water several times, and then the organic layer was washed with anhydrous sulfuric acid Treated with magnesium and filtered, and concentrated the organic layer under reduced pressure to obtain the residue, and added a small amount of tetrahydrofuran and 500 mL of n-hexane to the residue, then vigorously stirred for 2 hours to form crystals, filtered the crystals and washed with a small amount of cold ethanol to obtain a light brown The crystalline target compound, N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 6g (49.1%).

Synthesis Example 5

Synthesis of N-(3-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine

Add 10g (0.025mol) of 3-(3-bromophenyl)-9-phenyl-9H-carbazole, 5.1g (0.030mol) of benzidine-4-amine, 3.62g (0.038mol) of sodium tert-butoxide After 150 mL of toluene, it was stirred at room temperature for 30 minutes. Then, a solution of 0.144 g (0.25 mmol) of bis(dibenzylideneacetone)palladium (0) dissolved in 0.253 g (0.63 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then heated at 120°C. Stir for 12 hours. After confirming the completion of the reaction, filter to remove the solid matter under the hot state and distill the remaining liquid under reduced pressure, then add 500 mL of dichloromethane, wash the base layer with water several times, treat it with anhydrous magnesium sulfate and filter, then concentrate under reduced pressure The residue obtained from the base layer was passed into and out of silica gel chromatography with a 1:4 mixed solution of dichloromethane and n-hexane to obtain the target compound of white crystals, namely N-(3-(9-phenyl-9H-carbazole-3) -Yl)phenyl)-[1,1'-biphenyl]-4-amine 5.5 g (45%).

Synthesis Example 6

Synthesis of bis([1,1'-biphenyl]-4-yl)amine

Add 20g (0.086mol) of 4-bromo-1,1'-biphenyl, 17.42g (0.103mol) of [1,1'-diphenyl]-4-amine, and 9.90g (0.103mol) of sodium tert-butoxide After 400 mL of toluene, it was stirred at room temperature for 30 minutes. Then, after adding 0.87 g (2.15 mmol) of tri-tert-butylphosphine (50% xylene) to the reaction solution, 0.495 g (0.86 mmol) of bis(dibenzylideneacetone)palladium (0) was added at 120°C. React for 12 hours. After confirming the completion of the reaction, perform silica filtration under hot conditions to remove solids, and stir the remaining liquid at room temperature for 1 hour to form crystals. The formed crystals are filtered and washed with cold toluene to obtain white crystals of the target compound, namely two ([1,1'-biphenyl]-4-yl)amine 21.3g (77.1%).

Synthesis Example 7

Synthesis of N-(4-bromophenyl)-N-phenyl-[1,1'-biphenyl]-4-amine

Combine N-phenyl-[1,1'-biphenyl]-4-amine 7.64g (0.031mol), 1-bromo-4-iodobenzene 10.47g (0.037mol), sodium tert-butoxide 3.88g (0.04 mol) was added to 150 mL of toluene and stirred at room temperature for 30 minutes. Then, a solution of 0.28 g (0.31 mmol) of bis(dibenzylideneacetone) palladium (0) dissolved in 0.32 g (1 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then the temperature was kept at 100°C. React for 10 hours. After confirming the completion of the reaction, filtration was performed under hot conditions to remove solid materials and pressure distillation of the remaining liquid. Then 200 mL of dichloromethane was added and washed with water several times, and the organic layer was treated with anhydrous magnesium sulfate and filtered, and the pressure was reduced. The organic layer was concentrated to obtain the residue, and then the residue was chromatographed with a 1:2 mixture of dichloromethane: n-hexane as the eluent silica gel chromatography to obtain white crystals of the target compound, namely N-(4-bromophenyl)- N-phenyl-[1,1'-biphenyl]-4-amine 9.85 g (79.4%).

Synthesis Example 8

Synthesis of N-(3-bromophenyl)-N-phenyl-[1,1'-biphenyl]-4-amine

Combine N-phenyl-[1,1'-biphenyl]-4-amine 7.64g (0.031mol), 1-bromo-4-iodobenzene 10.47g (0.037mol), sodium tert-butoxide 3.88g (0.04 mol) was added to 150 mL of toluene and stirred at room temperature for 30 minutes. Then, a solution of 0.32 g (1 mmol) of tri-tert-butyl phosphine (50% xylene) dissolved in 0.28 g (0.31 mmol) of bis(dibenzylideneacetone) palladium (0) was added to the reaction solution, and then the same as the synthesis example 7 The same method was performed to obtain the target compound as white crystals, namely N-(3-bromophenyl)-N-phenyl-[1,1'-biphenyl]-4-amine 8.97 g (72.3%).

Synthesis Example 9

Synthesis of N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-[1,1'-biphenyl]-4-amine

Di([1,1'-biphenyl]-4-yl)amine 9.97g (0.031mol), 1-bromo-4-iodobenzene 10.47g (0.037mol), sodium tert-butoxide 3.88g (0.04mol) ) After adding to 150 mL of toluene, the mixture was stirred at room temperature for 30 minutes. Then, a solution of 0.32 g (1 mmol) of tri-tert-butyl phosphine (50% xylene) dissolved in 0.28 g (0.31 mmol) of bis(dibenzylideneacetone) palladium (0) was added to the reaction solution, and then the same as the synthesis example 7 The same method is performed to obtain the target compound as white crystals, namely N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-[1,1'-biphenyl Yl]-4-amine 9.54 g (64.6%).

Synthesis Example 10

Di([1,1'-biphenyl]-4-yl)amine 9.97g (0.031mol), 1-bromo-4-iodobenzene 10.47g (0.037mol), sodium tert-butoxide 3.88g (0.04mol) ) After adding to 150 mL of toluene, the mixture was stirred at room temperature for 30 minutes. Then, a solution of 0.32 g (1 mmol) of tri-tert-butyl phosphine (50% xylene) dissolved in 0.28 g (0.31 mmol) of bis(dibenzylideneacetone) palladium (0) was added to the reaction solution, and then the same as the synthesis example 7 The same method is performed to obtain the target compound as white crystals, namely N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-[1,1'-biphenyl Yl]-4-amine 9.14 g (62.2%).

Synthesis Example 11

Synthesis of N-(4-bromophenyl)-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine

N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 15.1g (0.031mol), 1-bromo- After adding 10.47 g (0.037 mol) of 4-iodobenzene and 3.88 g (0.04 mol) of sodium tert-butoxide to 150 mL of toluene, the mixture was stirred at room temperature for 30 minutes. Then, after adding 0.3 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene) to the reaction solution, 0.28 g (0.31 mmol) of bis(dibenzylideneacetone)palladium(0) was dissolved at 100°C. React for 12 hours. After confirming the completion of the reaction, filter under the hot state to remove the solid matter and distill the remaining liquid under pressure, then add 200 mL of dichloromethane and wash with water several times, and the organic layer is treated with anhydrous magnesium sulfate and filtered, and the organic layer is treated with anhydrous magnesium sulfate and filtered. Add a small amount of tetrahydrofuran and 500 mL of n-hexane to the layer and then vigorously stir for 2 hours to form crystals, then filter the formed crystals and wash with a small amount of cold methanol to obtain the target compound as pale white crystals, namely N-(4-bromophenyl)-N- (4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 10.4 g (52.4%).

Synthesis Example 12

Synthesis of N-(3-bromophenyl)-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine

N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 15.1g (0.031mol), 1-bromo- 10.47 g (0.037 mol) of 3-iodobenzene and 3.88 g (0.04 mol) of sodium tert-butoxide were added to 120 mL of toluene and then stirred at room temperature for 30 minutes. Then, to the reaction solution was added a solution of 0.3 g (0.8 mmol) of tri-tert-butyl phosphine (50% xylene) dissolved in 0.28 g (0.31 mmol) of bis(dibenzylideneacetone) palladium (0), and then combined with the synthesis Example 11 was processed in the same way to obtain the target compound with light brown crystals, namely N-(3-bromophenyl)-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)- [1,1'-Biphenyl]-4-amine 10.8 g (54.4%).

Synthesis Example 13

Synthesis of 4-bromo-N-phenyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)aniline

Combine N-phenyl-4-(9-phenyl-9H-carbazol-3-yl)aniline 12.73g (0.031mol), 1-bromo-4-iodobenzene 10.47g (0.037mol), tert-butanol After adding 3.88 g (0.04 mol) of sodium to 150 mL of toluene, the mixture was stirred at room temperature for 30 minutes. Then, to the reaction solution was added a solution of 0.3 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene) dissolved in 0.28 g (0.31 mmol) of bis(dibenzylideneacetone)palladium(0), and then used and synthesized Example 11 was processed in the same way to obtain the target compound with light brown crystals, namely 4-bromo-N-phenyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)aniline 9.94 g(56.7%).

Synthesis Example 14

Synthesis of 3-bromo-N-phenyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)aniline

Combine N-phenyl-4-(9-phenyl-9H-carbazol-3-yl)aniline 12.73g (0.031mol), 1-bromo-4-iodobenzene 10.47g (0.037mol), tert-butanol After adding 3.88 g (0.04 mol) of sodium to 150 mL of toluene, the mixture was stirred at room temperature for 30 minutes. To the reaction solution was added a solution of 0.3 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene) dissolved in 0.28 g (0.31 mmol) of bis(dibenzylideneacetone)palladium (0), and then used and Synthesis Example 11 The same method was carried out to obtain the target compound of light brown crystals, namely 3-bromo-N-phenyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)aniline 8.88g( 50.7%).

Synthesis Example 15

Synthesis of N-(4-(9H-carbazol-9-yl)phenyl)-[1,1'-biphenyl]-4-amine

9-(4-bromophenyl)-9H-carbazole 8.0g (0.025mol), benzidine-4-amine 5.1g (0.030mol), 3.62g (0.038mol) sodium tert-butoxide added to 150mL of toluene, Stir at room temperature for 30 minutes. Then, after adding 0.144 g (0.25 mmol) of bis(dibenzylideneacetone) palladium (0) 0.144 g (0.25 mmol) in tri-tert-butylphosphine (50% xylene) 0.253 g (0.63 mmol) to the reaction solution, it was stirred for 22 hours in a circular flow. . After confirming the completion of the reaction, after cooling to room temperature, filtering with silica and distilling the remaining liquid under reduced pressure to obtain a residue in a gel state, and then recrystallize the residue in a gel state with 50 mL of ethyl acetate to obtain a white crystal. The compound, namely N-(4-(9H-carbazol-9-yl)phenyl)-[1,1'-biphenyl]-4-amine 5.70g (55.5%).

Synthesis Example 16

Synthesis of N1,N4-bis([1,1'-biphenyl]-4-yl)-N1,N4-bis(4-(9-phenyl-9H-carbazol-3-yl)phenyl)benzene- 1,4-diamine

Add N-(4-bromophenyl)-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 7.7 g(0.012mol), N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 6.4(0.013mol), 1.5 g (0.016 mol) of sodium tert-butoxide was added to 50 mL of toluene and then heated to 60°C. Then, add 0.12g (0.3mmol) of tri-tert-butylphosphine (50% xylene) to the reaction solution to dissolve 0.12g (0.13mmol) of tris(dibenzylideneacetone)dipalladium (0), and then add a solution of 0.12g (0.13mmol) of tri-tert-butylphosphine (50% xylene) React for 12 hours at °C. After confirming the completion of the reaction, it was filtered under the hot state to remove the solid matter, and the remaining liquid was concentrated under reduced pressure to obtain a residue. 600 mL of dichloromethane was added to the residue and washed with water several times. After that, the organic layer was treated with anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain a residue. The obtained residue was subjected to silica gel chromatography with a 1:2:4 mixed solution of dichloromethane, ethyl acetate, and n-heptane as a separating liquid to obtain a solid substance. The solid substance was sublimed to crystallize the target compound as white crystals, namely N1,N4-bis([1,1'-biphenyl]-4-yl)-N1,N4-bis(4-(9-phenyl-9H- Carbazol-3-yl)phenyl)benzene-1,4-diamine 3.14g (25.0%).

Synthesis Example 17

Synthesis of N1,N1,N4-tris([1,1'-biphenyl]-4-yl)-N4-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)benzene-1 ,4-Diamine

Bis([1,1'-biphenyl]-4-yl)amine 3.85g (0.012mol), N-(4-bromophenyl)-N-(4-(9-phenyl-9H-carbazole- 3-yl)phenyl)-[1,1'-biphenyl]-4-amine 8.34 g (0.013 mol) and 1.5 g (0.016 mol) of sodium tert-butoxide were added to 50 mL of toluene and heated to 60°C. Then, a solution of 0.12 g (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) dissolved in 0.12 g (0.3 mmol) of tri-tert-butyl phosphine (50% xylene) was added to the reaction solution, and then the mixture with The same method as in Example 16 was carried out to obtain the target compound of white crystals, namely N1,N1,N4-tris([1,1'-biphenyl]-4-yl)-N4-(4-(9-phenyl- 9H-carbazol-3-yl)phenyl)benzene-1,4-diamine 1.87g (17.7%).

Synthesis Example 18

Synthesis of N1,N4-bis([1,1'-biphenyl]-4-yl)-N1-phenyl-N4-(4-(9-phenyl-9H-carbazol-3-yl)phenyl) Benzene-1,4-diamine

N-phenyl-[1,1'-biphenyl]-4-amine 2.94g (0.012mol), N-(4-bromophenyl)-N-(4-(9-phenyl-9H-carb Azol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 8.34g (0.013mol), 1.5g (0.016mol) of sodium tert-butoxide added to 50mL of toluene and heated to 60℃ . A solution of 0.12 g (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) dissolved in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then the same as in the example 16 The same method was performed to obtain the target compound as white crystals, namely N1,N4-bis([1,1'-biphenyl]-4-yl)-N1-phenyl-N4-(4-(9-phenyl) -9H-carbazol-3-yl)phenyl)benzene-1,4-diamine 1.57g (16.2%).

Synthesis Example 19

Synthesis of N1-(4-(9H-carbazol-9-yl)phenyl)-N1,N4-bis([1,1'-biphenyl]-4-yl)-N4-(4-(9-benzene) -9H-carbazol-3-yl)phenyl)benzene-1,4-diamine

N-(4-(9H-carbazol-9-yl)phenyl)-[1,1'-biphenyl]-4-amine 4.92g (0.012mol), N-(4-bromophenyl) -N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 8.34g (0.013mol), sodium tert-butoxide 1.5 g (0.016 mol) was added to 50 mL of toluene and then heated to 60°C. A solution of 0.12 g (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) dissolved in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then the same as in the example 16 The same method was performed to obtain the target compound of white crystals, namely N1-(4-(9H-carbazol-9-yl)phenyl)-N1,N4-bis([1,1'-biphenyl]-4 -Yl)-N4-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)benzene-1,4-diamine 2.13 g (18.3%).

Synthesis Example 20

Synthesis of N1,N3-bis([1,1'-biphenyl]-4-yl)-N1,N3-bis(4-(9-phenyl-9H-carbazol-3-yl)phenyl)benzene- 1,3-diamine

N-(3-bromophenyl)-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 7.7g (0.012mol), N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 6.4 (0.013mol), tertiary 1.5 g (0.016 mol) of sodium butoxide was added to 50 mL of toluene and then heated to 60°C. Then, add 0.12g (0.3mmol) of tri-tert-butylphosphine (50% xylene) to the reaction solution to dissolve 0.12g (0.13mmol) of tris(dibenzylideneacetone)dipalladium (0), and then add a solution of 0.12g (0.13mmol) of tri-tert-butylphosphine (50% xylene) React for 12 hours at °C. After confirming the completion of the reaction, the silica was filtered to remove the solid matter under the hot state, and the remaining liquid was concentrated under reduced pressure. Then 600 mL of dichloromethane was added to the residue and washed with water several times, and then the organic layer was treated with anhydrous magnesium sulfate and combined After filtration, the organic layer was concentrated under reduced pressure, and then the residue was subjected to silica gel chromatography with a 1:2:4 mixed solution of dichloromethane, ethyl acetate, and n-hexane as the separating liquid to obtain a solid substance, and then the solid substance was purified by sublimation The target compound is obtained as white crystals, namely N1,N3-bis([1,1'-biphenyl]-4-yl)-N1,N3-bis(4-(9-phenyl-9H-carbazole-3- (Yl)phenyl)benzene-1,3-diamine 2.36g (18.8%).

Synthesis Example 21

Synthesis of N1,N4-bis([1,1'-biphenyl]-4-yl)-N1,N3-bis(3-(9-phenyl-9H-carbazol-3-yl)phenyl)benzene- 1,3-diamine

N-(3-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 16.5g (0.034mol), 1,4- 3.8 g (0.016 mol) of dibromobenzene and 3.85 g (0.04 mol) of sodium tert-butoxide were added to 50 mL of toluene and heated to 60°C. Then, to the reaction solution, a solution of 0.32 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene) dissolved in 0.147 g (0.16 mmol) of tris(dibenzylideneacetone)dipalladium (0) was added to the reaction solution. Process in the same way as Synthesis Example 20, and then use a 1:4 dichloromethane:n-hexane mixed solution as the separation solution to obtain a solid substance by silica gel chromatography. The solid substance is sublimated and purified to obtain the target of white crystals. Compound, namely N1,N4-bis([1,1'-biphenyl]-4-yl)-N1,N4-bis(3-(9-phenyl-9H-carbazol-3-yl)phenyl) Benzene-1,4-diamine 3.37g (20.1%).

Synthesis Example 22

Synthesis of N1,N4-bis([1,1'-biphenyl]-4-yl)-N1-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-N4-(4 -(9-Phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)benzene-1,4-diamine

N-(4-bromophenyl)-N-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)cyclohexane-2,4-diene -1-yl)-[1,1'-biphenyl]-4-amine 7.7g (0.012mol), N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl) -[1,1'-biphenyl]-4-amine 6.4 (0.013 mol), 1.5 g (0.016 mol) of sodium tert-butoxide were added to 50 mL of toluene and then heated to 60°C. Then, a solution of 0.12 g (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) dissolved in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution. The same method as in Example 16 was carried out to obtain the target compound, namely N1,N4-bis([1,1'-biphenyl]-4-yl)-N1-(4-(9-phenyl-9H-carbazole- 3-yl)phenyl)-N4-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)benzene-1,4-diamine 3.14g (25.0%).

Synthesis Example 23

Synthesis of N1,N4-bis([1,1'-biphenyl]-4-yl)-N1,N4-bis(4-(9-phenyl-9H-pyrido[2,3-b]indole- 6-yl)phenyl)benzene-1,4-diamine

1,4-Dibromobenzene 0.94g (0.004mol), N-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)-[1, 4.4 g (0.009 mol) of 1'-biphenyl]-4-amine and 1 g (0.01 mol) of sodium tert-butoxide were added to 80 mL of toluene and then stirred at room temperature for 30 minutes. The reaction solution was heated to 40°C, and then 0.083g (0.09mmol) of tris(dibenzylideneacetone)dipalladium (0) was dissolved in 0.1g (0.23mmol) of tri-tert-butylphosphine (50% xylene) in the reaction solution. The solution of) was then stirred in circulation for 30 hours. After confirming the completion of the reaction, after cooling to room temperature, the silica was filtered and 800 mL of chloroform was added, and then washed with water several times. After that, the organic layer was treated with anhydrous magnesium sulfate and filtered. The organic layer was concentrated under reduced pressure. The mixed solution of methyl chloride, tetrahydrofuran, and n-hexane is used as the separation liquid to perform silica gel chromatography to obtain a solid substance. The solid substance is sublimated and purified to obtain the target compound of white crystals, namely N1,N4-bis([1,1'-biphenyl] -4-yl)-N1,N4-bis(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)benzene-1,4-diamine 1.07 g(24.3%).

Synthesis example 24

Synthesis of N4,N4'-bis([1,1'-biphenyl]-4-yl)-N4,N4'-bis(4-(9-phenyl-9H-pyrido[3,4-b]indole Dol-6yl)phenyl)benzene-1,4'-diamine

4,4'-Dibromobiphenyl 1.3g (0.004mol), N-(4-(9-phenyl-9H-pyrido[3,4-b]indol-6-yl)phenyl)-[ 4.4 g (0.009 mol) of 1,1'-biphenyl]-4-amine and 1 g (0.01 mol) of sodium tert-butoxide were added to 80 mL of toluene and then stirred at room temperature for 30 minutes. Then, the temperature of the reaction solution was raised to 40°C, and then 0.083 g of tris(dibenzylideneacetone)dipalladium (0) 0.083g ( 0.09mmol) solution, followed by treatment in the same manner as in Synthesis Example 23 to obtain the target compound as white crystals, namely N4,N4'-bis([1,1'-biphenyl]-4-yl)-N4,N4 '-Bis(4-(9-phenyl-9H-pyrido[3,4-b]indol-6yl)phenyl)benzene-1,4'-diamine 1.0g (24.6%).

Synthesis Example 25

Synthesis of N4,N4'-bis([1,1'-biphenyl]-4-yl)-N4,N4'-bis(4-(5-phenyl-5H-pyrido[4,3-b]indole Dol-8-yl)phenyl)benzene-1,4'-diamine

4,4'-Dibromobiphenyl 1.3g (0.004mol), N-(4-(5-phenyl-5H-pyrido[4,3-b]indol-8-yl)phenyl)-[ 4.4 g (0.009 mol) of 1,1'-biphenyl]-4-amine and 1 g (0.01 mol) of sodium tert-butoxide were added to 80 mL of toluene and then stirred at room temperature for 30 minutes. Then, the temperature of the reaction solution was raised to 40°C, and then 0.083 g of tris(dibenzylideneacetone)dipalladium (0) 0.083g ( 0.09mmol) solution, followed by treatment in the same manner as in Synthesis Example 23 to obtain the target compound as white crystals, namely N4,N4'-bis([1,1'-biphenyl]-4-yl)-N4,N4 '-Bis(4-(5-phenyl-5H-pyrido[4,3-b]indol-8-yl)phenyl)benzene-1,4'-diamine 1.03g (25.0%).

Synthesis Example 26

Synthesis of N4,N4'-bis([1,1'-biphenyl]-4-yl)-N4,N4'-bis(4-(5-phenyl-5H-pyrido[3,2-b]indole Dol-8-yl)phenyl)benzene-1,4'-diamine

4,4'-Dibromobiphenyl 1.3g (0.004mol), N-(4-(5-phenyl-5H-pyrido[3,2-b]indol-8-yl)phenyl)-[ 4.4 g (0.009 mol) of 1,1'-biphenyl]-4-amine and 1 g (0.01 mol) of sodium tert-butoxide were added to 80 mL of toluene and then stirred at room temperature for 30 minutes. The reaction solution was heated to 40°C, and then 0.083g (0.09mmol) of tris(dibenzylideneacetone)dipalladium (0) was dissolved in 0.1g (0.23mmol) of tri-tert-butylphosphine (50% xylene) in the reaction solution. ) Solution, and then processed in the same manner as in Synthesis Example 23 to obtain the target compound as white crystals, namely N4,N4'-bis([1,1'-biphenyl]-4-yl)-N4,N4'- Bis(4-(5-phenyl-5H-pyrido[3,2-b]indol-8-yl)phenyl)benzene-1,4'-diamine 1.04 g (25.3%).

Synthesis Example 27

Synthesis of N1-([1,1'-biphenyl]-4-yl)-N4-phenyl-N1,N4-bis(4-(9-phenyl-9H-carbazol-3-yl)phenyl) Benzene-1,4-diamine

4'-bromo-N-phenyl-N-(4-(9-phenyl-9H-carbazol-3-yl)cyclohex-2,4-dien-1-yl)aniline 6.81g (0.012mol ), N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 6.33g (0.013mol), tert-butanol 1.5 g (0.016 mol) of sodium was added to 50 mL of toluene and then heated to 60°C. Then, a solution of 0.12 g (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) dissolved in 0.12 g (0.3 mmol) of tri-tert-butyl phosphine (50% xylene) was added to the reaction solution, and then the mixture with The same method in Example 16 was carried out to obtain the target compound of white crystals, namely N1-([1,1'-biphenyl]-4-yl)-N4-phenyl-N1,N4-bis(4-(9- Phenyl-9H-carbazol-3-yl)phenyl)benzene-1,4-diamine 2.31g (18.8%).

Synthesis Example 28

Synthesis of N1-([1,1'-biphenyl]-4-yl)-N4-phenyl-N1-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-N4- (4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)benzene-1,4-diamine

4-bromo-N-phenyl-N-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)cyclohex-2,4-diene-1- Yl)aniline 6.82g (0.012mol), N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 6.33g (0.013 mol), 1.5 g (0.016 mol) of sodium tert-butoxide were added to 50 mL of toluene and then heated to 60°C. Then, a solution of 0.12 g (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) dissolved in 0.12 g (0.3 mmol) of tri-tert-butyl phosphine (50% xylene) was added to the reaction solution, and then the mixture with The same method as in Example 16 was carried out to obtain the target compound of white crystals, namely N1-([1,1'-biphenyl]-4-yl)-N4-phenyl-N1-(4-(9-phenyl- 9H-carbazol-3-yl)phenyl)-N4-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)benzene-1,4 -Diamine 2.71g (23.2%).

Synthesis Example 29

Synthesis of N1-([1,1'-biphenyl]-4-yl)-N4-phenyl-N1,N4-bis(4-(9-phenyl-9H-pyrido[2,3-b]indole Dol-6-yl)phenyl)benzene-1,4-diamine

4-bromo-N-phenyl-N-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)cyclohex-2,4-diene-1- Yl)aniline 6.82g (0.012mol), N-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)-[1,1'- Phenyl]-4-amine 6.34 g (0.013 mol) and sodium tert-butoxide 1.5 g (0.016 mol) were added to 50 mL of toluene and then heated to 60°C. Then, a solution of 0.12 g (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) dissolved in 0.12 g (0.3 mmol) of tri-tert-butyl phosphine (50% xylene) was added to the reaction solution, and then the mixture with The same method in Example 16 was carried out to obtain the target compound of white crystals, namely N1-([1,1'-biphenyl]-4-yl)-N4-phenyl-N1,N4-bis(4-(9- Phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)benzene-1,4-diamine 1.91 g (16.4%).

Synthesis Example 30

Synthesis of N1,N3-bis([1,1'-biphenyl]-4-yl)-N1-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-N3-(4 -(9-Phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)benzene-1,4-diamine

The N-(3-bromophenyl)-N-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)cyclohex-2,4-diene- 1-yl)-[1,1'-biphenyl]-4-amine 7.7g (0.012mol), N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)- [1,1'-biphenyl]-4-amine 6.4 g (0.013 mol) and sodium tert-butoxide 1.5 g (0.016 mol) were added to 50 mL of toluene and heated to 60°C. Then, a solution of 0.12 g (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) dissolved in 0.12 g (0.3 mmol) of tri-tert-butyl phosphine (50% xylene) was added to the reaction solution, and then the mixture with The same method as in Example 16 was carried out to obtain the target compound, namely N1,N3-bis([1,1'-biphenyl]-4-yl)-N1-(4-(9-phenyl-9H-carbazole- 3-yl)phenyl)-N3-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)benzene-1,4-diamine 3.14g (25.0%).

Synthesis Example 31

Synthesis of N1,N3-bis([1,1'-biphenyl]-4-yl)-N1,N3-bis(4-(9-phenyl-9H-pyrido[2,3-b]indole- 6-yl)phenyl)benzene-1,3-diamine

The N-(3-bromophenyl)-N-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)cyclohex-2,4-diene- 1-yl)-[1,1'-biphenyl]-4-amine 7.7g (0.012mol), N-(4-(9-phenyl-9H-pyrido[2,3-b]indole -6-yl)phenyl)-[1,1'-biphenyl]-4-amine 6.4 g (0.013 mol) and 1.5 g (0.016 mol) of sodium tert-butoxide were added to 50 mL of toluene and heated to 60°C. Then, a solution of 0.12 g (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) dissolved in 0.12 g (0.3 mmol) of tri-tert-butyl phosphine (50% xylene) was added to the reaction solution, and then the mixture with The same method as in Example 16 was carried out to obtain the target compound, namely N1,N3-bis([1,1'-biphenyl]-4-yl)-N1,N3-bis(4-(9-phenyl-9H- Pyrido[2,3-b]indol-6-yl)phenyl)benzene-1,3-diamine 3.03g (25.0%).

Synthesis example 32

Synthesis of N1-([1,1'-biphenyl]-4-yl)-N3-phenyl-N1,N3-bis(4-(9-phenyl-9H-carbazol-3-yl)phenyl) Benzene-1,3-diamine

6.8g (0.012mol ), N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4-amine 6.3g (0.013mol), tert-butanol 1.5 g (0.016 mol) of sodium was added to 50 mL of toluene and then heated to 60°C. Then, a solution of 0.12 g (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) dissolved in 0.12 g (0.3 mmol) of tri-tert-butyl phosphine (50% xylene) was added to the reaction solution, and then the mixture with The same method as in Example 16 was carried out to obtain the target compound, namely N1-([1,1'-biphenyl]-4-yl)-N3-phenyl-N1,N3-bis(4-(9-phenyl- 9Hcarbazol-3-yl)phenyl)benzene-1,3-diamine 2.45g (21.0%).

Synthesis Example 33

Synthesis of N1-([1,1'-biphenyl]-4-yl)-N3-phenyl-N1-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-N3- (4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)benzene-1,3-diamine

3-bromophenyl-N-phenyl-N-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)cyclohex-2,4-diene -1-yl)aniline 6.82g (0.012mol), N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]-4- Amine 6.3 g (0.013 mol) and sodium tert-butoxide 1.5 g (0.016 mol) were added to 50 mL of toluene and heated to 60°C. Then, a solution of 0.12 g (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) dissolved in 0.12 g (0.3 mmol) of tri-tert-butyl phosphine (50% xylene) was added to the reaction solution, and then the mixture with The same method as in Example 16 was carried out to obtain the target compound, namely N1-([1,1'-biphenyl]-4-yl)-N3-phenyl-N1-(4-(9-phenyl-9H-carb Azol-3-yl)phenyl)-N3-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)benzene-1,3-diamine 2.57g (22.0%).

Synthesis Example 34

Synthesis of N1-([1,1'-biphenyl]-4-yl)-N3-phenyl-N1-(4-(5-phenyl-5H-pyrido[2,3-b]indole-8 -Yl)phenyl)-N3-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl)benzene-1,3-diamine

3-bromophenyl-N-phenyl-N-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)cyclohex-2,4-diene -1-yl)aniline 6.82g (0.012mol), N-(4-(5-phenyl-5H-pyrido[2,3-b]indol-8-yl)phenyl)-[1,1 '-Biphenyl]-4-amine 6.4 g (0.013 mol) and sodium tert-butoxide 1.5 g (0.016 mol) were added to 50 mL of toluene and then heated to 60°C. Then, a solution of 0.12 g (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) dissolved in 0.12 g (0.3 mmol) of tri-tert-butyl phosphine (50% xylene) was added to the reaction solution, and then the mixture with The same method as in Example 16 was carried out to obtain the target compound, namely N1-([1,1'-biphenyl]-4-yl)-N3-phenyl-N1-(4-(5-phenyl-5H-pyridine) And [3,2-b]indol-8-yl)phenyl)-N3-(4-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)phenyl ) Benzene-1,3-diamine 2.15g (18.4%).

Ordinary technicians can easily synthesize the compounds of the examples of the present invention with reference to the synthesis examples 1 to 34. For example, a hole transport compound having the structure of the chemical formula 1.

Experimental results of the hole transport compounds synthesized from Synthesis Examples 16 to 34

The representative physical properties of the compounds 1 to 19 (Synthesis Examples 16 to 34) produced by the synthesis examples were evaluated, and the results are shown in Table 1.

As shown in Table 1, it can be confirmed that the hole transport compound of the embodiment of the present invention has a high glass transition temperature as a whole, which is beneficial for having a HOMO energy level and a high LUMO energy level in hole transport. In addition, it can be confirmed that the TID has characteristics of 500°C or higher and almost 600°C.

In addition, the above-mentioned substance can be produced in a high yield through the above-mentioned synthesis example.

Experimental results of organic light-emitting devices to which the hole-transporting compounds synthesized in Synthesis Examples 16 to 34 are applied

Comparative example

The ITO substrate was patterned to have a light-emitting area of 3 mm×3 mm and then washed. Then, the substrate was installed in a vacuum chamber to adjust the base pressure to 1×10-6 torr, and then DNTPD was vacuum deposited on the anode ITO with a thickness of 60 nm of the hole injection material. BPBPA was used to form a hole transport layer with a thickness of 30 nm. Subsequently, DBTTP1 and Ir(ppy)3 as a dopant were deposited on the upper part of the hole transport layer to form a film with a thickness of 30 nm as a light-emitting layer, in which the concentration of the dopant was 10%. On this upper part, ZADN was vacuum deposited to form a 30nm thick film as an electron transport layer, a 1.0nm thick film was formed with LiF as an electron injection layer, and a 100nm thick film was formed with Al as a cathode, thereby fabricating an organic light-emitting element. Then, the light-emitting characteristics of the light-emitting element were evaluated, the relative changes in current, voltage, and brightness were measured immediately, and the life of the element was evaluated, and the results are shown in Table 2 below.

Examples 1 to 20

The ITO substrate was patterned to have a light-emitting area of 3 mm×3 mm and then washed. Then, after mounting the substrate in a vacuum chamber, the base pressure was adjusted to 1×10-6 torr, and then DNTPD was vacuum deposited on the anode ITO with a thickness of 60 nm of the hole injection material. A hole transport layer having a thickness of 30 nm was formed using the compounds 1 to 19 (compounds manufactured by Synthesis Examples 16 to 34). Subsequently, DBTTP1 and Ir(ppy)3 as a dopant were deposited on the upper part of the hole transport layer to form a film with a thickness of 30 nm as a light-emitting layer, in which the concentration of the dopant was 10%. On this upper part, ZADN was vacuum deposited to form a 30nm thick film as an electron transport layer, a 1.0nm thick film was formed with LiF as an electron injection layer, and a 100nm thick film was formed with Al as a cathode, thereby fabricating an organic light-emitting element. Then, the light-emitting characteristics of the light-emitting element were evaluated, the relative changes in current, voltage, and brightness were measured immediately, and the life of the element was evaluated, and the results are shown in Table 2 below.

As shown in Table 2, it can be confirmed that compared with the BPBPA material that is commonly used in practice, the hole transport compound of the present invention has a HOMO energy level that is easy for hole injection and a high LOMO energy level that can block electrons. Moreover, it has excellent hole transport characteristics, high energy efficiency when applied to the hole transport layer of organic light-emitting devices, stability and long life due to high Tg.

Above, the drawings and description together disclose the best embodiments. The present invention is not limited to the above-mentioned embodiments, and within the scope of the idea of the present invention, those with ordinary knowledge in the technical field of the present invention can make various changes and modifications. The true technical protection scope of the present invention should be applied for a patent. The technical thinking definition of the scope.

10‧‧‧Substrate

20‧‧‧Anode electrode

30‧‧‧Electric hole injection layer

40‧‧‧Hole Transmission Layer

50‧‧‧Light-emitting layer

60‧‧‧Electron transport layer

70‧‧‧Electron injection layer

80‧‧‧Cathode electrode

Claims (2)

A hole-transporting compound represented by any of the following chemical formulas:

An organic light-emitting device includes a hole transport layer between a pair of electrodes, wherein the hole transport layer contains the hole transport compound according to the first item of the patent application.

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