TW201947009A - Hole transfer compound and organic light-emitting diodes using the same - Google Patents

Abstract

The present invention provides a hole transfer compound represented by formula (1) and an organic light-emitting diodes including the same.

Description

   Hole transporting compound and organic light emitting element containing the same   

The present invention relates to a hole-transporting compound and an organic light-emitting element containing the compound, and more particularly, to the following hole-transporting compound and an organic light-emitting element containing the compound: on the basis of high hole-transmission, relatively reducing the free potential It has the characteristics of introducing arylamino groups to the carbazole core to reduce crystal formation, reduce free potential, improve hole transport capacity, and have long life characteristics.

As a self-luminous display element, an electroluminescent device (hereinafter referred to as “EL element”) 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 emitting layer molding material. Compared with inorganic EL elements, organic EL elements are not only excellent in characteristics such as brightness, driving voltage, and response speed, but also have the advantage of being full-colored.

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

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

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

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

(Prior art literature)

(Patent Literature)

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

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

In order to solve the problems described above, the hole-transporting compound of the present invention is represented by the following Chemical Formula 1,

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

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

The hole-transporting compound of the present invention can exert the following effects: on the basis of high hole-moving characteristics, the characteristics of relatively reducing the free potential, the introduction of an arylamino group to the carbazole core reduces the formation of crystals, reduces the free potential, and improves the hole-transporting ability With long life characteristics.

10‧‧‧ substrate

20‧‧‧Anode electrode

30‧‧‧ Hole injection layer

40‧‧‧ Hole Transmission Layer

50‧‧‧Light emitting layer

60‧‧‧ electron transmission layer

70‧‧‧ electron injection layer

80‧‧‧ cathode electrode

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

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

The preferred embodiments of the present invention will be described in detail below with reference to the drawings. Before explaining the present invention, the terms or words used in the scope of the present specification and patent application shall not be limited and explained by ordinary or dictionary meanings. Therefore, the embodiments described in the present specification and the structures shown in the drawings are only the best embodiments of the present invention, and do not represent all 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 for the hole transport layer performs one of the functions of a light emitting material in the OLED element.

Specifically, the hole transporting layer corresponds to a layer that performs the function of moving the hole transferred from the anode through the hole injection layer to the light emitting layer more smoothly, and blocks the function of the electrons transferred from the cathode in the light emitting layer.

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

The basic requirement for 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 Value, and when forming a thin film, it has amorphous properties that do not appear crystalline.

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

In order to satisfy the requirements as described above, the hole-transporting compound of the present invention is derived.

Specifically, the hole-transporting 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-transporting ability.

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

On the other hand, the hole-transporting compound of the present invention having the structure as described above includes conventional methods such as a method in which bromobenzene or 4-bromo-1,1'-biphenyl is directly bonded to benzidine to bind a carbazole derivative. A method for synthesizing a hole-transporting compound of carbazole has problems in that it cannot be smoothly synthesized 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 a carbazole derivative, then an aniline or a biphenyl-4-amine is attached, and then induced by 4,4'-dibromobiphenyl The coupling reaction can further obtain the target compound, that is, the hole transporting compound of the present invention, in a relatively stable yield and high purity.

Specifically, the hole-transporting compound according to an embodiment of the present invention has a structure of the following Chemical Formula 1,

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

In the compound according to the embodiment of the present invention, the arylamino group is introduced into the carbazole core, which reduces crystal formation, reduces free potential, improves hole transport ability, and uses a triphenylamine derivative to further ensure long-term device life.

The compound of 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:

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

For compounds having the above-mentioned chemical formula structure, they have favorable highest Occupied Molecular Orbital (HOMO) energy levels in hole transport, and have high LUMO energy levels, thereby blocking electron movement. Therefore, the compound with the above-mentioned chemical structure has better hole-transport characteristics than the conventional TAPC, NPB, and BPBPA used as hole-transport layers, and has high energy efficiency and glass transition temperature, and further has excellent stability and life. .

The hole-transporting compound according to the embodiment of the present invention is used as a compound for the hole-transporting layer. The hole-transporting layer performs the function of moving the hole transferred from the anode through the hole injection layer to the light-emitting layer more smoothly and blocking the light-emitting layer. A functioning layer of electrons transferred from the cathode.

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

A well-known material as these materials is an aromatic amine-based material having an amine structure. The material should form a thin film that does not crystallize during the material deposition process, and has 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.

The hole-transporting compounds according to the embodiments of the present invention are derived from the following three characteristics in order to achieve the material characteristics of the hole-transporting layer as described above: 1) excellent efficiency and long life; 2) used in the deposition process High crystallization temperature does not appear in the crystal; 3) Sp3 carbon structure is eliminated to make the holes flow smoothly.

For this reason, the hole-transporting compound according to the embodiment of the present invention is a structure in which an aniline structure at the center is not directly connected to a double bond structure but is inserted and connected to a 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 is a phenyl group inserted between an aniline structure and a phenyl-carbazole or a phenylcarboline.

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

In the present invention, in order to solve the above-mentioned disadvantages, unstable backbonds are excluded, and carbazolyl or carbolinyl is not directly connected, but a phenyl structure is inserted into the carbazolyl or carbolinyl Connected to the mother core, which can make electrons or holes flow more smoothly.

As described above, the hole-transporting compound of the embodiment of the present invention is inserted into the phenyl structure, and thus does not substantially damage the basic structure of the planar structure, and induces a secondary deformation structure instead of a primary deformation structure, thereby exhibiting a long life and excellent Efficiency, high conversion temperature Tg effect.

According to the ease of internal electron migration as described above, the present invention may have a clear difference in the electron distribution in the HOMO and LUMO states. In addition, in the present invention, the longest effective conjugation in which a plurality of phenyl groups are effectively involved is realized. Therefore, when compared with a general hole-transporting compound, since the groups participating in effective conjugation are different in length from each other Therefore, it is a more effective and better structure in electronic movement, and also has a long life in terms of life.

    Organic light emitting element    

Hereinafter, the structure and manufacturing method of an organic light-emitting device using the compound for a phosphorescent host 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 a first electrode (anode electrode) and a second electrode (cathode electrode), and may further include a hole injection layer, a hole transport layer, and a hole barrier. Layer, electron injection layer, or electron transport layer. A light-emitting element structure of the present invention will be described with reference to FIG. 1.

Referring to FIG. 1, an organic light emitting element according to the present invention has a structure of a light emitting layer 50 between an anode electrode 20 and a cathode electrode 80. A hole injection layer 30 and a hole transport layer 40 are included between the anode electrode 20 and the light emitting layer 50. 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 by the following process. Here, it is only an example, and is not limited to this method.

First, a substance for an anode electrode is coated on the substrate 10 to form an anode electrode 20. Here, the substrate 10 can be a substrate generally used in this field, and particularly preferably a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and water resistance. In addition, as the anode substance formed on the substrate, indium tin oxide ITO, tin oxide SnO ₂ , zinc oxide ZnO, or the like can be used, but is not limited thereto.

A hole injection layer HIL30 may be selectively formed on the anode electrode 20. At this time, the hole injection layer is formed by a general method such as a vacuum evaporation method or a spin coating method. The substance for the hole injection layer is not particularly limited, and copper phthalocyanine (CuPc) or IDE406 (Idemitsu Kosan) can be used.

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

Next, a light emitting layer EML 50 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 phosphorescent host compounds, and may have a single-layer structure or a multilayer structure of two or more layers. At this time, the compound or mixture containing Chemical Formula 1 alone includes other compounds known in the art, for example, blue light emitting dopants (iridium compounds such as FIrppy or FIrpic) and the like. The content of the phosphorescent host compound of the light-emitting layer may be in a range of 1 to 95% by weight based on the total weight of the constituent materials of the light-emitting layer.

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

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. The substance for the hole barrier layer is not particularly limited, but a phenanthroline compound (for example, BCP) can be used. This can be formed by a vacuum evaporation method or a spin coating method.

In addition, an 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 and an aluminum composite (for example, ALq ₃ (tris (8-hydroxyquinoline) aluminum) can be used.

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

Next, a cathode electrode 80 is formed on the electron injection layer 70 by vacuum evaporation, thereby completing a light emitting element. Here, as the cathode metal, 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. 1, and one or two intermediate layers can be formed according to requirements. For example, a hole blocking layer or the like can be additionally formed. In addition, the thickness of each layer of the light-emitting element can be determined within the ordinary range in the field according to requirements.

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

    Synthesis example of hole transporting compound of the present invention    

Synthesis Example 1

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

16.8 g (0.052 mol) of 3-bromo-9-phenyl-9H-carbazole, 15.7 g (0.062 mol) of di (pinacol) diboron, 10.1 g (0.103 mol) of potassium acetate, tetrakis (triphenyl) After dissolving 3.4 g (0.003 mol) of palladium (0) 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, 500 mL of ethyl acetate was added, washed twice with saturated brine, and then extracted, and then washed 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 an eluent to obtain the target compound as white crystals. That is, 11.1-g (57.8%) of 9-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-diheteropentylborane-2-yl) -9H-carbazole.

Synthesis Example 2

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

11.8 g (0.032 mol) of 9-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-diheteropentylborane-2-yl) -9H-carbazole, 1-bromo-4-iodobenzene 11.8 g (0.032 mol), 9.05 g (0.032 mol), tetrakis (triphenylphosphine) palladium (0) 1.87 g (0.002 mol) was added to 200 ml of tetrahydrofuran to dissolve, and stirred for 30 minutes . 200 ml of 2N-potassium carbonate aqueous solution was added to the reaction solution, and it stirred vigorously at 70 degreeC for 18 hours. After confirming the completion of the reaction, 500 mL of dichloromethane was added to the residue obtained by distilling the reaction solution under reduced pressure, and the organic layer was washed with water. After that, the organic layer was treated with anhydrous magnesium sulfate and filtered, and the organic layer was concentrated under reduced pressure to obtain the obtained residue. Silica gel chromatography using a 1: 5 mixture of dichloromethane and n-hexane as the eluent gave 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

10 g (0.025 mol) of 3- (4-bromophenyl) -9-phenyl-9H-carbazole, 2.58 g (0.028 mol) of aniline, 2.91 g (0.03 mol) of sodium tert-butoxide were added to 100 mL of toluene, and then heated To 60 ° C. To the reaction solution, a solution of 0.253 g (1.2 mmol) of tri-tert-butylphosphine and 0.14 g (0.25 mmol) of bis (dibenzylideneacetone) palladium (0) was added all at once, followed by stirring for 24 hours in a circulating manner. After confirming the completion of the reaction, the reaction was cooled to normal temperature, and then filtered with silica, and then 200 mL of ethyl acetate was added and washed several times with water. The organic layer was treated with anhydrous magnesium sulfate and then filtered, and the residue obtained by concentrating the organic layer under reduced pressure was removed. A small amount of ethyl acetate was added to dissolve the mixture, and an excess of 300 mL of n-heptane was added. The mixture was vigorously stirred at 0 ° C for 1 hour to generate crystals. The resulting crystals were filtered to obtain the target compound as white crystals, 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 10 g (0.025 mol) of 3- (4-bromophenyl) -9-phenyl-9H-carbazole, 5.1 g (0.030 mol) of biphenyl-4-amine, 3.62 g (0.038 mol) of sodium tert-butoxide 150 mL of toluene was stirred at room temperature for 30 minutes. Then, a solution of 0.253 g (0.63 mmol) of tri-tert-butylphosphine (50% xylene) in 0.144 g (0.25 mmol) of bis (dibenzylideneacetone) palladium (0) was added to the reaction solution, and the mixture was stirred in a circulating manner for 22 hours. hour. After confirming the completion of the reaction, the mixture was cooled to normal temperature, and then filtered through silica. The remaining liquid was distilled under reduced pressure to obtain a gel-like residue. After the residue was added with 300 mL of dichloromethane, the residue was washed with water several times, and then the organic layer was treated with anhydrous sulfuric acid. Magnesium treatment and filtration, and the organic layer was concentrated under reduced pressure to obtain a residue. A small amount of tetrahydrofuran and 500 mL of n-hexane were added to the residue, followed by vigorous stirring for 2 hours to produce crystals. After filtering the crystals, washing with a small amount of cold ethanol gave a light brown The target compound, which was crystallized, was 6 g (49.1%) of N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine.

Synthesis Example 5

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

10g (0.025mol) of 3- (3-bromophenyl) -9-phenyl-9H-carbazole, 5.1g (0.030mol) of biphenyl-4-amine, 3.62g (0.038mol) of sodium tert-butoxide were added 150 mL of toluene was stirred at room temperature for 30 minutes. Next, a solution of 0.244 g (0.63 mmol) of tri-tert-butylphosphine (50% xylene) in bis (dibenzylideneacetone) palladium (0) (0.144 g (0.25 mmol)) was added to the reaction solution, and the temperature was then increased to 120 ° C. Stir for 12 hours. After confirming the completion of the reaction, the solids were filtered in a hot state to remove the solids and the remaining liquid was distilled under reduced pressure. Then, 500 mL of dichloromethane was added. The base layer was washed with water several times, treated with anhydrous magnesium sulfate and filtered, and then concentrated under reduced pressure. The residue obtained from the base layer was subjected to silica gel chromatography using a mixed solution of dichloromethane and n-hexane of 1: 4 to obtain the target compound as 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

20 g (0.086 mol) of 4-bromo-1,1'-biphenyl, 17.42 g (0.103 mol) of [1,1'-diphenyl] -4-amine, and 9.90 g (0.103 mol) of sodium tert-butoxide were added After 400 mL of toluene, the mixture was stirred at room temperature for 30 minutes. Then, a solution of 0.47 g (0.86 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.87 g (2.15 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution at 120 ° C. Reaction for 12 hours. After confirming the completion of the reaction, the solid matter was filtered under a hot state to remove solid matter, and the remaining liquid was stirred at room temperature for 1 hour to produce crystals. The generated crystals were filtered and washed with cold toluene to obtain the target compound as white crystals, namely ([1,1'-Biphenyl] -4-yl) amine 21.3 g (77.1%).

Synthesis Example 7

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

N-phenyl- [1,1'-biphenyl] -4-amine 7.64 g (0.031 mol), 1-bromo-4-iodobenzene 10.47 g (0.037 mol), sodium tert-butoxide 3.88 g (0.04 mol) was added to 150 mL of toluene, followed by stirring at normal temperature for 30 minutes. Then, a solution of 0.22 g (0.31 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.32 g (1 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then at 100 ° C. Reaction for 10 hours. After confirming the completion of the reaction, the solids were filtered in a hot state to remove the solid matter and the remaining liquid was distilled under pressure. Then, 200 mL of dichloromethane was added and washed several times with water. The organic layer was treated with anhydrous magnesium sulfate and filtered, and the pressure was reduced. The organic layer was concentrated to obtain a residue, and the residue was subjected to silica gel chromatography using a mixed solution of dichloromethane: n-hexane of 1: 2 as an eluent to obtain the target compound as white crystals, 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

N-phenyl- [1,1'-biphenyl] -4-amine 7.64 g (0.031 mol), 1-bromo-4-iodobenzene 10.47 g (0.037 mol), sodium tert-butoxide 3.88 g (0.04 mol) was added to 150 mL of toluene, followed by stirring at normal temperature for 30 minutes. Then, a solution of 0.22 g (0.31 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.32 g (1 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution. 7 The same method was used 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 9.97 g (0.031 mol), 1-bromo-4-iodobenzene 10.47 g (0.037 mol), sodium tert-butoxide 3.88 g (0.04 mol) ) Added to 150 mL of toluene and stirred at room temperature for 30 minutes. Then, a solution of 0.22 g (0.31 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.32 g (1 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution. 7 The same method was used to obtain the target compound as white crystals, namely N-([1,1'-biphenyl] -4-yl) -N- (4-bromophenyl)-[1,1'-biphenyl Alkyl] -4-amine 9.54 g (64.6%).

Synthesis Example 10

Di ([1,1'-biphenyl] -4-yl) amine 9.97 g (0.031 mol), 1-bromo-4-iodobenzene 10.47 g (0.037 mol), sodium tert-butoxide 3.88 g (0.04 mol) ) Added to 150 mL of toluene and stirred at room temperature for 30 minutes. Then, a solution of 0.22 g (0.31 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.32 g (1 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution. 7 The same method was used to obtain the target compound as white crystals, namely N-([1,1'-biphenyl] -4-yl) -N- (4-bromophenyl)-[1,1'-biphenyl Methyl] -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 15.1 g (0.031 mol), 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, a solution of 0.28 g (0.31 mmol) of bis (dibenzylideneacetone) palladium (0) dissolved in 0.3 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution at 100 ° C. Reaction for 12 hours. After confirming the end of the reaction, it was filtered in a hot state to remove solid matter and the remaining liquid was distilled under pressure. Then, 200 mL of dichloromethane was added and washed several times with water. The organic layer was treated with anhydrous magnesium sulfate and filtered. After adding a small amount of tetrahydrofuran and 500 mL of n-hexane to the layer, the mixture was stirred vigorously for 2 hours to produce crystals. Then, the generated crystals were filtered and washed with a small amount of cold methanol to obtain the target compound, 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 15.1 g (0.031 mol), 1-bromo- After adding 10.47 g (0.037 mol) of 3-iodobenzene and 3.88 g (0.04 mol) of sodium tert-butoxide to 120 mL of toluene, the mixture was stirred at room temperature for 30 minutes. Then, a solution of 0.28 g (0.31 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.3 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then synthesized with Example 11 was treated in the same manner to obtain the target compound as light brown crystals, that is, 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

N-phenyl-4- (9-phenyl-9H-carbazol-3-yl) aniline 12.73 g (0.031 mol), 1-bromo-4-iodobenzene 10.47 g (0.037 mol), 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, a solution of 0.28 g (0.31 mmol) of bis (dibenzylideneacetone) palladium (0) dissolved in 0.3 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then used and synthesized Example 11 was treated in the same manner to obtain the target compound as 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

N-phenyl-4- (9-phenyl-9H-carbazol-3-yl) aniline 12.73 g (0.031 mol), 1-bromo-4-iodobenzene 10.47 g (0.037 mol), 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, a solution of 0.28 g (0.31 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.3 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene) was added. The same method was used to obtain the target compound as light brown crystals, namely 3-bromo-N-phenyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) aniline 8.88 g ( 50.7%).

Synthesis Example 15

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

8.0 g (0.025 mol) of 9- (4-bromophenyl) -9H-carbazole, 5.1 g (0.030 mol) of biphenyl-4-amine, and 3.62 g (0.038 mol) of sodium tert-butoxide were added to 150 mL of toluene. Stir for 30 minutes at normal temperature. Then, a solution of 0.153 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 the mixture was stirred in a circulating manner for 22 hours. . After confirming the completion of the reaction, the mixture was cooled to normal temperature, filtered through silica, and the remaining liquid was distilled under reduced pressure to obtain a gel-like residue. Then, the gel-like residue was recrystallized with 50 mL of ethyl acetate to obtain a white crystal. Compound, N- (4- (9H-carbazol-9-yl) phenyl)-[1,1'-biphenyl] -4-amine 5.70 g (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

N- (4-Bromophenyl) -N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine g (0.012 mol), N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine 6.4 (0.013 mol), After 1.5 g (0.016 mol) of sodium tert-butoxide was added to 50 mL of toluene, it was 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, and then 120 g The reaction was carried out at 12 ° C for 12 hours. After confirming the completion of the reaction, the solution was filtered in a hot state to remove 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 the residue was washed with water several times. After filtration, the organic layer was concentrated under reduced pressure to obtain a residue. The obtained residue was subjected to silica gel chromatography using a mixed solution of dichloromethane, ethyl acetate, and n-heptane of 1: 2: 4 as a release solution to obtain a solid substance. The solid substance was sublimated and crystallized to give 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 3.14 g (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

Di ([1,1'-biphenyl] -4-yl) amine 3.85 g (0.012 mol), 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) in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then Example 16 was treated in the same manner to obtain the target compound as 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 1.87 g (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 2.94 g (0.012 mol), N- (4-bromophenyl) -N- (4- (9-phenyl-9H-carb Azol-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. . To the reaction solution was added a solution of 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) in 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0), followed by the same procedure as in Example. 16 The same method was used 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 1.57 g (16.2%).

Synthesis Example 19

Synthesis of N1- (4- (9H-carbazole-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 4.92 g (0.012 mol), N- (4-bromophenyl) -N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine 8.34 g (0.013 mol), sodium tert-butoxide After 1.5 g (0.016 mol) was added to 50 mL of toluene, it was heated to 60 ° C. To the reaction solution was added a solution of 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) in 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0), followed by the same procedure as in Example. 16 The same method was used to obtain the target compound as 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 7.7 g (0.012 mol), N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine 6.4 (0.013 mol), tertiary After 1.5 g (0.016 mol) of sodium butoxide was added to 50 mL of toluene, it was 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, and then 120 g The reaction was carried out at 12 ° C for 12 hours. After confirming the completion of the reaction, the silica was filtered in a hot state to remove solid matter, and the remaining liquid was concentrated under reduced pressure. Then, 600 mL of dichloromethane was added to the residue and washed several times with water. Then, the organic layer was treated with anhydrous magnesium sulfate and After filtration, the organic layer was concentrated under reduced pressure, and the residue was subjected to silica gel chromatography using a mixed solution of dichloromethane, ethyl acetate, and n-hexane of 1: 2: 4 as a release solution to obtain a solid substance, which was then sublimated and purified. The target compound was obtained as white crystals, namely N1, N3-bis ([1,1'-biphenyl] -4-yl) -N1, N3-bis (4- (9-phenyl-9H-carbazole-3- Phenyl) phenyl) benzene-1,3-diamine 2.36 g (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 16.5 g (0.034 mol), 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 then heated to 60 ° C. Next, a solution in which 0.32 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene) was dissolved in 0.12 g (0.16 mmol) of tris (dibenzylideneacetone) dipalladium (0) was added to the reaction solution, and then Synthesis Example 20 was treated in the same manner, and the obtained residue was subjected to a silica gel chromatography using a mixed solution of dichloromethane: n-hexane of 1: 4 as the release liquid to obtain a solid substance. The solid substance was sublimated to obtain a white crystal. 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 3.37 g (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] indole-6-yl) phenyl) benzene-1,4-diamine

N- (4-bromophenyl) -N- (4- (9-phenyl-9H-pyrido [2,3-b] indole-6-yl) cyclohexane-2,4-diene -1-yl)-[1,1'-biphenyl] -4-amine 7.7 g (0.012 mol), N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -[1,1'-biphenyl] -4-amine 6.4 (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 in which 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) was dissolved in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution. Example 16 was treated in the same manner to obtain the target compound, that is, 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] indole-6-yl) phenyl) benzene-1,4-diamine 3.14 g (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 0.94 g (0.004 mol), N- (4- (9-phenyl-9H-pyrido [2,3-b] indole-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, followed by stirring at room temperature for 30 minutes. The reaction solution was heated to 40 ° C, and then 0.083 g (0.09 mmol) of tris (dibenzylideneacetone) dipalladium (0) was dissolved in 0.1 g (0.23 mmol) of tri-tert-butylphosphine (50% xylene) in the reaction solution. The solution of) was stirred in a circle for 30 hours. After confirming the completion of the reaction, the silica was filtered after cooling to normal temperature, 800 mL of chloroform was added, and then washed several times with water. After that, the organic layer was treated with anhydrous magnesium sulfate and filtered, and the organic layer was concentrated under reduced pressure. A mixed solution of methyl chloride, tetrahydrofuran, and n-hexane was used as a release solution, and silica gel chromatography was performed to obtain a solid substance. The solid substance was sublimated and purified to obtain the target compound as white crystals, namely 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 1.07 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] in Indole-6yl) phenyl) benzene-1,4'-diamine

1.3 g (0.004 mol) of 4,4'-dibromobiphenyl, N- (4- (9-phenyl-9H-pyrido [3,4-b] indole-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, followed by stirring at room temperature for 30 minutes. Then, the reaction solution was heated to 40 ° C, and then 0.083 g of tris (dibenzylideneacetone) dipalladium (0) was dissolved in 0.1 g (0.23 mmol) of tri-tert-butylphosphine (50% xylene) in the reaction solution ( 0.09 mmol) solution, followed by treatment in the same manner as in Synthesis Example 23 to give the target compound as white crystals, namely N4, N4'-bis ([1,1'-biphenyl] -4-yl) -N4, N4 1.0 g (24.6%) of '-bis (4- (9-phenyl-9H-pyrido [3,4-b] indole-6yl) phenyl) benzene-1,4'-diamine.

Synthesis Example 25

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

1.3 g (0.004 mol) of 4,4'-dibromobiphenyl, N- (4- (5-phenyl-5H-pyrido [4,3-b] indole-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, followed by stirring at room temperature for 30 minutes. Then, the reaction solution was heated to 40 ° C, and then 0.083 g of tris (dibenzylideneacetone) dipalladium (0) was dissolved in 0.1 g (0.23 mmol) of tri-tert-butylphosphine (50% xylene) in the reaction solution ( 0.09 mmol) solution, followed by treatment in the same manner as in Synthesis Example 23 to give the target compound as white crystals, namely N4, N4'-bis ([1,1'-biphenyl] -4-yl) -N4, N4 1.03 g (25.0%) of '-bis (4- (5-phenyl-5H-pyrido [4,3-b] indole-8-yl) phenyl) benzene-1,4'-diamine.

Synthesis Example 26

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

1.3g (0.004mol) of 4,4'-dibromobiphenyl, N- (4- (5-phenyl-5H-pyrido [3,2-b] indole-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, followed by stirring at room temperature for 30 minutes. The reaction solution was heated to 40 ° C, and then 0.083 g (0.09 mmol) of tris (dibenzylideneacetone) dipalladium (0) was dissolved in 0.1 g (0.23 mmol) of tri-tert-butylphosphine (50% xylene) in the reaction solution. ) 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'- 1.04 g (25.3%) of bis (4- (5-phenyl-5H-pyrido [3,2-b] indole-8-yl) phenyl) benzene-1,4'-diamine.

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-diene-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 After 1.5 g (0.016 mol) of sodium was added to 50 mL of toluene, it was heated to 60 ° C. Then, a solution of 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then Example 16 was treated in the same manner to obtain the target compound as 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 2.31 g (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] indole-6-yl) phenyl) benzene-1,4-diamine

4-bromo-N-phenyl-N- (4- (9-phenyl-9H-pyrido [2,3-b] indole-6-yl) cyclohex-2,4-diene-1- Group) aniline 6.82 g (0.012 mol), N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine 6.33 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) in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then Example 16 was treated in the same manner as in Example 16 to obtain the target compound as 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] indole-6-yl) phenyl) benzene-1,4 -Diamine 2.71 g (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] in Indol-6-yl) phenyl) benzene-1,4-diamine

4-bromo-N-phenyl-N- (4- (9-phenyl-9H-pyrido [2,3-b] indole-6-yl) cyclohex-2,4-diene-1- Phenyl) aniline 6.82 g (0.012 mol), N- (4- (9-phenyl-9H-pyrido [2,3-b] indole-6-yl) phenyl)-[1,1'-bi 6.34 g (0.013 mol) of phenyl] -4-amine and 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) in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then Example 16 was treated in the same manner to obtain the target compound as white crystals, namely N1-([1,1'-biphenyl] -4-yl) -N4-phenyl-N1, N4-bis (4- (9- Phenyl-9H-pyrido [2,3-b] indole-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] indole-6-yl) phenyl) benzene-1,4-diamine

N- (3-bromophenyl) -N- (4- (9-phenyl-9H-pyrido [2,3-b] indole-6-yl) cyclohex-2,4-diene- 1-yl)-[1,1'-biphenyl] -4-amine 7.7 g (0.012 mol), N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)- 6.4 g (0.013 mol) of [1,1'-biphenyl] -4-amine 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) in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then Example 16 was treated in the same manner to obtain the target compound, that is, 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] indole-6-yl) phenyl) benzene-1,4-diamine 3.14 g (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

N- (3-bromophenyl) -N- (4- (9-phenyl-9H-pyrido [2,3-b] indole-6-yl) cyclohex-2,4-diene- 1-yl)-[1,1'-biphenyl] -4-amine 7.7 g (0.012 mol), 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) in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then Example 16 was treated in the same manner to obtain the target compound, that is, 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 3.03 g (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

3-Bromo-N-phenyl-N- (4- (9-phenyl-9H-carbazol-3-yl) cyclohex-2,4-dien-1-yl) aniline 6.8 g (0.012 mol ), N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine 6.3 g (0.013 mol), tert-butanol After 1.5 g (0.016 mol) of sodium was added to 50 mL of toluene, it was heated to 60 ° C. Then, a solution of 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then Example 16 was treated in the same manner to obtain the target compound, that is, N1-([1,1'-biphenyl] -4-yl) -N3-phenyl-N1, N3-bis (4- (9-phenyl- 9H carbazol-3-yl) phenyl) benzene-1,3-diamine 2.45 g (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] indole-6-yl) phenyl) benzene-1,3-diamine

3-Bromophenyl-N-phenyl-N- (4- (9-phenyl-9H-pyrido [2,3-b] indole-6-yl) cyclohex-2,4-diene -1-yl) aniline 6.82 g (0.012 mol), N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4- After adding 6.3 g (0.013 mol) of amine and 1.5 g (0.016 mol) of sodium tert-butoxide to 50 mL of toluene, the mixture was heated to 60 ° C. Then, a solution of 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) in 0.12 g (0.3 mmol) of tri-t-butylphosphine (50% xylene) was added to the reaction solution, and then Example 16 was treated in the same manner to obtain the target compound, that is, 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] indole-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] indole-6-yl) phenyl) benzene-1,3-diamine

3-Bromophenyl-N-phenyl-N- (4- (9-phenyl-9H-pyrido [2,3-b] indole-6-yl) cyclohex-2,4-diene -1-yl) aniline 6.82 g (0.012 mol), N- (4- (5-phenyl-5H-pyrido [2,3-b] indole-8-yl) phenyl)-[1,1 6.4 g (0.013 mol) of '-biphenyl] -4-amine and 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) in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, and then Example 16 was treated in the same manner to obtain the target compound, that is, N1-([1,1'-biphenyl] -4-yl) -N3-phenyl-N1- (4- (5-phenyl-5H-pyridine) Benzo [3,2-b] indole-8-yl) phenyl) -N3- (4- (9-phenyl-9H-pyrido [2,3-b] indole-6-yl) phenyl ) Benzene-1,3-diamine 2.15 g (18.4%).

Ordinary skilled persons 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-transporting compound having the structure of Chemical Formula 1.

    Experimental results of the hole transporting compound itself synthesized in Synthesis Examples 16 to 34    

The representative physical properties of 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 above, it can be confirmed that the hole-transporting compound of the embodiment of the present invention has a high glass transition temperature as a whole, which is beneficial to having a HOMO energy level and a high LUMO energy level in the hole transmission. In addition, it was confirmed that the TID has a characteristic of 500 ° C or higher and almost 600 ° C.

In addition, according to the above-mentioned synthesis examples, the above-mentioned substances can be produced in a high yield.

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

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

Above, the drawings and the specification disclose the preferred embodiment together. The present invention is not limited to the embodiments described above, and a person skilled in the art in the technical field to which the present invention pertains can make various changes and modifications within the scope of the idea of the present invention. The true technical protection scope of the present invention should be covered by the patent application. Definition of technical ideas in scope.

Claims (5)

A hole transporting compound, represented by the following chemical formula 1,

In the chemical formula 1, the R1, R2, R3, and R4 are respectively hydrogen, a phenyl, a phenylcarbazole derivative, or a phenylcarboline derivative; One or more is a phenylcarbazole derivative or a phenylcarboline derivative. The hole-transporting compound according to item 1 of the scope of patent application, wherein it is represented by any one of the following chemical formulas:

The hole-transporting compound according to item 1 of the scope of patent application, wherein it is represented by any one of the following chemical formulas:

. The hole-transporting compound according to item 1 of the scope of patent application, wherein it is represented by any one of the following chemical formulas:

    An organic light-emitting element includes a hole-transporting layer between a pair of electrodes, wherein the hole-transporting layer includes the hole-transporting compound according to any one of claims 1 to 4 in the scope of the patent application.