KR102032125B1 - 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 chemical formula 1, and an organic light emitting device including the same. Therefore, the hole transport compound of the present invention is characterized by having high hole transport characteristics and a relatively low ionization potential.

Description

Hole transport compound and organic light-emitting diodes using the same

The present invention relates to a hole transport compound and an organic light emitting device including the same, and more particularly, based on high hole transport properties and relatively low ionization potential and an arylamino group group introduced into the carbazole core to form crystallization. The present invention relates to a hole transport compound and an organic light emitting device including the same, which reduces and reduces ionization potential, thereby improving hole transport ability and exhibiting characteristics having a long lifespan.

An electroluminescent device (EL device) is a self-luminous display device having 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 materials for forming an emitting layer. Herein, the organic EL device has an advantage of excellent luminance, driving voltage, and response speed, and multicoloring, compared to the inorganic EL device.

A general organic EL device has an anode 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 made of an organic compound.

The driving principle of the organic EL element having the structure as described above is as follows. When a voltage is applied between the anode and the cathode, holes injected from the anode are moved to the light emitting layer via the hole transport layer. On the other hand, electrons are injected into the light emitting layer from the cathode via the electron transport layer, and carriers are recombined in the light emitting layer to generate excitons. The excitons change from the excited state to the ground state, whereby the molecules of the light emitting layer emit light to form an image. The light emitting material is classified into a fluorescent material using excitons in a singlet state and a phosphorescent material using a triplet state according to its light emitting mechanism.

Until now, a lot of amine derivatives having a carbazole skeleton have been studied in the hole transport material used in the organic light emitting device, but there are many difficulties in practical use due to the higher driving voltage, lower efficiency and shorter lifetime.

Therefore, efforts have been made to develop organic light emitting devices having low voltage driving, high brightness and long life using materials having excellent properties.

Republic of Korea Patent Publication No. 10-1631507

In order to solve the above problems, the present invention is based on high hole transport characteristics and relatively lower ionization potential and arylamino group group is introduced into the carbazole core to reduce the crystal formation and ionization potential to reduce the hole transport ability It is an object of the present invention to provide a hole transport compound and an organic light emitting device including the same, which improves the efficiency and exhibits a long lifespan.

In order to solve the above problems, the present invention is a hole transport compound represented by the formula (1):

[Formula 1]

In the above formula,

R 1, R 2, R 3 and R 4 are each independently hydrogen, phenyl, phenyl carbazole derivatives, or phenyl carboline derivatives,

At least one of R 1, R 2, R 3 and R 4 is a phenyl carbazole derivative or a phenyl carboline derivative.

In order to solve the above problems, the hole transport compound represented by the formula (2):

[Formula 2]

In the above formula,

R 1, R 2, R 3 and R 4 are each independently hydrogen, phenyl, phenyl carbazole derivatives, or phenyl carboline derivatives,

At least one of R 1, R 2, R 3 and R 4 is a phenyl carbazole derivative or a phenyl carboline derivative.

In order to solve the above problems, the present invention is an organic light emitting device including a hole transport layer between a pair of electrodes, characterized in that the hole transport layer comprises a hole transport compound according to the chemical chamber 1 or formula (2) An organic light emitting device is provided.

The hole transport compound according to the present invention is based on a high hole transport property and relatively lower the ionization potential and an arylamino group group is introduced into the carbazole core to reduce the crystal formation and to reduce the ionization potential to improve the hole transport capacity The effect which has a long life can be exhibited.

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

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

When described in detail with reference to the accompanying drawings a preferred embodiment of the present invention. Prior to the detailed description of the present invention, the terms or words used in the specification and claims described below should not be construed as being limited to the ordinary or dictionary meanings. Therefore, the embodiments described in the specification and the drawings shown in the drawings are only one of the most preferred embodiments of the present invention and do not represent all of the technical idea of the present invention, various modifications that can be replaced at the time of the present application It should be understood that there may be equivalents and variations.

The materials, or compounds, used in the major transport layer serve as one of the light emitting materials in the OLED device.

Specifically, the hole transport layer corresponds to a layer that functions to smoothly move holes transferred from the anode through the hole injection layer to the light emitting layer, and simultaneously binds electrons transferred from the cathode to the light emitting layer.

On the other hand, the electro-transport layer materials have a great influence on the performance of the OLED device, and the performance of the overall OLED device may vary greatly depending on how the material is designed and synthesized.

The basic requirement of the hole transport layer is high hole mobility. In order to exhibit these characteristics, it has to have a work function located between the hole injection layer and the light emitting layer, and requires a low LUMO value to bind the electrons to the light emitting layer. desirable.

In addition, in order to have physically high thermal stability, the film must have a high glass transition temperature and the film must be transparent in the visible region so that visible light can pass through the visible region.

In order to satisfy the above requirements, the hole transport compound of the present invention was derived.

Specifically, in the hole transport compound according to the present invention, an arylamino group group is introduced into the carbazole core to reduce crystal formation and reduce ionization potential, thereby improving hole transport ability.

In addition, by applying a triphenyl amine derivative it was possible to secure a long life device.

On the other hand, the hole transport compound according to the present invention having the structure as described above is a conventional carbazole such as a carbazole derivative by binding directly to bromobenzene or 4-bromo-1,1'-biphenyl to benzidine The method of synthesizing a hole transport compound comprising a has a problem that the synthesis is not smooth or the yield is significantly lowered even if synthesized.

On the other hand, in the present invention, in order to solve this problem, a halogen group or an amine group is first introduced into the carbazole derivative, and then aniline or biphenyl-4-amine is connected, followed by a pairing reaction using 4,4'-dibromobiphenyl. By inducing it could be obtained a hole transport compound according to the invention the target compound in a relatively stable yield and high purity.

Specifically, the hole transport compound according to an embodiment of the present invention has a structure of Formula 1:

[Formula 1]

In the above formula,

R 1, R 2, R 3 and R 4 are each independently hydrogen, phenyl, phenyl carbazole derivatives, or phenyl carboline derivatives,

At least one of R 1, R 2, R 3 and R 4 is a phenyl carbazole derivative or a phenyl carboline derivative.

In addition, the hole transport compound according to an embodiment of the present invention has a structure of Formula 2:

[Formula 2]

In the above formula,

R 1, R 2, R 3 and R 4 are each independently hydrogen, phenyl, phenyl carbazole derivatives, or phenyl carboline derivatives,

At least one of R 1, R 2, R 3 and R 4 is a phenyl carbazole derivative or a phenyl carboline derivative.

In the compound according to the embodiment of the present invention, the arylamino group group is introduced into the carbazole core to reduce crystal formation and to reduce the ionization potential, thereby improving the hole transporting ability, and by applying a triphenyl amine derivative to ensure long-term device life. can do.

Compounds according to preferred embodiments of the present invention can be represented according to the following formula.

Compounds according to preferred embodiments of the present invention can be represented according to the following formula.

Compounds according to preferred embodiments of the present invention can be represented according to the following formula.

Compounds according to preferred embodiments of the present invention can be represented according to the following formula.

Compounds according to preferred embodiments of the present invention can be represented according to the following formula.

Compounds according to preferred embodiments of the present invention can be represented according to the following formula.

Compounds according to preferred embodiments of the present invention can be represented according to the following formula.

The compound having the structure of the above formula has a favorable HOMO energy level in hole transport, and also has a high LUMO energy level can block the movement of electrons. Therefore, the compound having the structure according to the above formulas is better than TAPC, N [B, BPBPA, which is generally used as the hole transport layer in overall hole transport characteristics, and has a high energy efficiency and glass transition temperature, thereby ensuring stability and lifetime. great.

The hole transport compound according to the embodiments of the present invention is a compound used in the hole transport layer, the hole transport layer to move the holes transferred from the anode through the hole injection layer more smoothly to the light emitting layer and the electrons transferred from the cathode to the light emitting layer It is the layer that plays the role of having a function to bind to.

The basic requirement of the hole transport layer (HTL) is to have a high hole mobility, and therefore an effective hole injection from the anode to the light emitting layer (EML) must be made.

Well-known materials such as aromatic amine-based materials having an amine structure should form a film that does not crystallize during the deposition of the material, and have high thermal stability and excellent contact / flatness with the anode. It should be transparent when the thin film is formed in the visible light region.

The hole transport compound according to the embodiments of the present invention corresponds to a compound derived based on the following three properties in order to promote the material properties of the hole transport layer as described above.

1) Excellent efficiency and long lifespan

2) high transition temperature to avoid crystallization during deposition

3) Exclusion of sp3 carbon structure for smooth hole flow

To this end, the hole transport compound according to the embodiments of the present invention is a structure connected by inserting a phenyl structure without directly connecting a double bond structure to a central phenylamine structure.

That is, the hole transport compound according to the embodiments of the present invention has a structure in which at least one of R1 to R4 has a phenyl structure inserted between a phenylamine structure and phenyl-carbazole or phenylcarboline.

If the double bond structure is directly connected to the central phenylamine structure, a high transition temperature (Tg) cannot be obtained due to the planarity of the molecular structure. That is, when the carbazole group or the carboline group is directly connected to the central phenylamine structure, the carbazole known as an electron donor has a disadvantage in that its role is halved by the proximity of the nitrogen of the central phenylamine structure and the nitrogen of the carbazole group.

In the present invention, in order to eliminate such disadvantages, by removing the unstable backbond, inserting a phenyl structure without directly connecting a carbazole group or a carboline group, by connecting a carbazole group or a carboline group to the mother nucleus, the flow of electrons or holes more smoothly Let

As such, the hole transport compound according to the embodiments of the present invention has a long service life and has high efficiency and high efficiency by inducing a secondary twist structure rather than a primary twist structure without breaking the basic structure of the planar structure by inserting a phenyl structure. The effect which has a transition temperature Tg can be exhibited.

According to the ease of internal electron transfer as described above the present invention can have a clear difference in the distribution of electrons in the HOMO, LUMO state. In addition, in the present invention, since the longest effective conjugation in which a large number of phenyl groups effectively participates is achieved, the length and the length of the group participating in the effective conjugation are different from those of the general hole transport compound, so that the structure is more preferable and efficient in terms of life. Even in the long life.

Organic light emitting device

Hereinafter, the structure and manufacturing method of an organic light emitting device employing the compound for phosphorescent host according to the present invention.

The organic light emitting device according to the present invention may adopt a structure of a conventional light emitting device, the structure may be changed as necessary. Basically, the organic light emitting device has a structure including an organic film (light emitting layer) between the first electrode (anode electrode) and the second electrode (cathode electrode), and includes a hole injection layer, a hole transport layer, a hole suppression layer, an electron injection layer, or An electron transport layer may be further included. Reference is made to FIG. 1 to describe the structure of the light emitting device of the present invention.

Referring to FIG. 1, an organic light emitting diode according to the present invention has a structure including a light emitting layer 50 between an anode electrode 20 and a cathode electrode 80, and between the anode electrode 20 and the light emitting layer 50. The hole injection layer 30 and the hole transport layer 40 are included, and the electron transport layer 50 and the 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 Figure 1 according to an embodiment of the present invention is manufactured through the following process, which is not limited to this method only one example is described in detail.

First, the anode electrode 20 is formed by coating an anode electrode material on the substrate 10. Here, the substrate 10 may be a substrate generally used in this field, and a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is particularly preferable. In addition, as the anode electrode material formed on the substrate, transparent and excellent indium tin oxide (ITO), tin oxide (SnO 2), zinc oxide (ZnO), and the like may be used, but is not limited thereto.

A hole injection layer (HIL) 30 is selectively formed on the anode electrode 20. In this case, the hole injection layer is formed through a conventional method such as vacuum deposition or spin coating. The material for the hole injection layer is not particularly limited, but CuPc (copper phthalocyanine) or IDE 406 (Idemitsu Kosan) may be used.

Subsequently, the hole transport layer (HTL) 40 is formed on the hole injection layer 30 through a conventional method such as vacuum deposition or spin coating. As the material for the hole transport layer, generally, N, N'-diphenyl-N, N'-bis (1-naphthyl) -1,1'-biphenyl-4,4'-diamine (NPB) N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-biphenyl] -4,4'-diamine (TPD), N, N'-di (naphthalen-1-yl) -N, N'-diphenylbenzidine, N, N'-di (naphthalen-1-yl) -N, N'-diphenyl-benzidine: α-NPD) and the like can be used, but in the embodiment of the present invention It includes a hole transport compound according to the above formula.

Subsequently, an emission layer (EML) 50 is formed on the hole transport layer 40. The light emitting layer forming material may include at least one selected from phosphorescent host compounds as a light emitting host material, and may have a single layer or a multilayer structure of two or more layers. In this case, the compound of Formula 1 may be included alone or in combination with other compounds known in the art, for example, a blue light emitting dopant (iridium compound such as FIrppy or FIrpic). The phosphorescent host compound in the light emitting layer may be included in the range of 1 to 95% by weight based on the total weight of the material constituting the light emitting layer.

The phosphorescent host compound may be formed by a vacuum deposition method, may also be deposited through a wet process such as spin coating, and laser thermal transfer (LITI) may be used.

Optionally, a hole suppression layer (HBL) may be formed on the emission layer 50 to prevent excitons formed from the emission material from moving to the electron transport layer or to prevent holes from moving to the electron transport layer 60. Although it does not restrict | limit especially as a substance for hole suppression layers, A phenanthroline type compound (for example, BCP) etc. can be used. This can be formed through a vacuum deposition method or a spin coating method.

In addition, an electron transport layer (ETL) 60 may be formed on the emission layer 50, and a vacuum deposition method or a spin coating method may be used. Although it does not restrict | limit especially as an electron carrying layer material, For example, TBPI and an aluminum complex (For example, Alq3 (tris (8-quinolinolato) -aluminum)) can be used.

An electron injection layer (EIL) 70 may be formed on the electron transport layer 60 by using a method such as vacuum deposition or spin coating, and the material for the electron injection layer 70 is not particularly limited, but may be LiF, Materials such as NaCl and CsF can be used.

Subsequently, the cathode electrode 80 is formed on the electron injection layer 70 through vacuum deposition to complete the light emitting device. The metal for the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg -Ag) and the like.

In addition, the organic light emitting device according to the present invention has a laminated structure as shown in Fig. 1, and it is also possible to further form one or two intermediate layers, for example, a hole suppression layer, if necessary. In addition, the thickness of each layer of the light emitting device may be determined as needed within the range generally used in the art.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Synthesis Example of Hole Transport Compound According to the Present Invention

Synthesis Example 1

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

16.8 g (0.052 mol) of 3-bromo-9-phenyl-9H-carbazole, 15.7 g (0.062 mol) of bis (pinacyrate) diborane, 10.1 g (0.103 mol) of potashyan acetate and tetrakistriphenyl After dissolving 3.4 g (0.003 mol) of phosphine palladium (0) in 400 ml of 1,4-oxane, the mixture was heated and stirred at 110 ° C. for 8 hours. After confirming the completion of the reaction, the reaction solution was filtered through silica, 500 mL of ethyl acetate was added, washed twice with saturated brine, extracted, and then washed once with water. The organic layer was treated with anhydrous magnesium sulfate, filtered, and the organic layer was concentrated under reduced pressure. The residue obtained was purified by silica gel chromatography with dichloromethane and n-hexane 1: 5 mixed solution with eluent, to obtain the title compound 9-phenyl-3- (4, 11.1 g (57.8%) of 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole were obtained.

Synthesis Example 2

9-phenyl-6- (4,4,5,5- Tetramethyl -1,3,2- Dioxaboloran 2-yl) -9H- Of pyrido [2,3-b] indole  synthesis

16.8 g (0.052 mol) of 6-bromo-9-phenyl-9H-pyrido [2,3-b] indole, 15.7 g (0.062 mol) of bis (pinacolato) diborane, 10.1 g of potashyan acetate ( 0.103 mol) and 3.4 g (0.003 mol) of tetrakistriphenyl phosphine palladium (0) were dissolved in 300 ml of 1,4-oxane and then heated and stirred at 110 ° C. for 12 hours. After confirming the reaction, the reaction solution was filtered through silica, 1L of ethyl acetate was added, washed twice with saturated brine, extracted, and then washed once with water. The organic layer was treated with anhydrous magnesium sulfate, the organic layer was concentrated under reduced pressure after filtration, and the residue was purified by silica gel chromatography with dichloromethane and n-hexane 1:10 mixed solution with eluent to yield the title compound 9-phenyl-6- (4, 11.2 g (58.4%) of 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-pyrido [2,3-b] indole were obtained.

Synthesis Example 3

Synthesis of 9-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-pyrido [3,4-b] indole

16.8 g (0.052 mol) of 6-bromo-9-phenyl-9H-pyrido [3,4-b] indole, 15.7 g (0.062 mol) of bis (pinacolato) diborane, 10.1 g of potashyan acetate 0.103 mol) and 3.4 g (0.003 mol) of tetrakistriphenyl phosphine palladium (0) were dissolved in 300 ml of 1,4-oxane and then heated and stirred at 110 ° C. for 10 hours. After confirming the completion of the reaction, the residue obtained in the same manner as in Synthesis Example 11 was subjected to silica gel chromatography using dichloromethane and n-hexane 1: 7 mixed solution as eluent to obtain the target compound 9-phenyl-6- (4,4,5) as off-white crystals. 12.2 g (63.2%) of, 5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-pyrido [3,4-b] indole were obtained.

Synthesis Example 4

5-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxolan-2-yl) -5H-pyrido [4,3-b] indole

Synthesis of

16.8 g (0.052 mol) of 8-bromo-5-phenyl-5H-pyrido [4,3-b] indole, 15.7 g (0.062 mol) of bis (pinacolato) diborane, 10.1 g of potashyan acetate ( 0.103 mol) and 3.4 g (0.003 mol) of tetrakistriphenyl phosphine palladium (0) were dissolved in 300 ml of 1,4-oxane and then heated and stirred at 110 ° C. for 10 hours. After confirming the completion of the reaction, the residue obtained in the same manner as in Synthesis Example 11 was subjected to silica gel chromatography using dichloromethane and n-heptane 1: 5 mixed solution as eluent to obtain the target compound of the off-white crystals, 5-phenyl-8- (4,4,5). 12.2 g (63.2%) of , 5-tetramethyl-1,3,2-dioxolan-2-yl) -5H-pyrido [4,3-b] indole were obtained.

Synthesis Example 5

Synthesis of 5-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-pyrido [3,2-b] indole

8-bromo-5-phenyl-5H-pyrido [3,2-b] indole 6.8 g (0.052 mol), bis (pinacyrate) diborane 15.7 g (0.062 mol), potashyan acetate 10.1 g (0.103 mol) ) And 3.4 g (0.003 mol) of tetrakistriphenyl phosphine palladium (0) were dissolved in 300 ml of 1,4-oxane and then heated and stirred at 110 ° C. for 10 hours. After confirming the completion of the reaction, the residue obtained in the same manner as in Synthesis Example 11 was subjected to silica gel chromatography using dichloromethane and n-heptane 1: 5 mixed solution as eluent to obtain the target compound of the off-white crystals, 5-phenyl-8- (4,4,5). 13.8 g (71.5%) of, 5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-pyrido [3,2-b] indole were obtained.

Synthesis Example 6

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 11.8 g (0.032 mol), 1-bromo 11.8 g (0.032 mol) of -4-iodobenzene, 9.05 g (0.032 mol) and 1.87 g (0.002 mol) of tetrakistriphenyl phosphine paladin (0) were added to 200 ml of tetrahydrofuran and dissolved, followed by stirring for 30 minutes. . 200 ml of 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 methylene chloride was added to the residue obtained by distillation under reduced pressure, washed several times with water, and then the organic layer was treated with anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure after filtration to obtain ethyl acetate and n-hexane 1: 5. The mixed solution was chromatographed on silica gel with eluent to obtain 8.4 g (65.8%) of the title compound 3- (4-bromophenyl) -9-phenyl-9H-carbazole as white crystals.

Synthesis Example 7

Synthesis of 6- (4-bromophenyl) -9phenyl-9H-pyrido [2,3-b] indole

11.85 g 9-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-pyrido [2,3-b] indole 0.032 mol), 11.8 g (0.032 mol) of 1-bromo-4-iodobenzene, 9.05 g (0.032 mol), tetrakistriphenyl phosphine paladin (0) 1.87 g (0.002 mol) 200 ml of tetrahydrofuran It was dissolved in and stirred for 30 minutes. 200 ml of 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 methylene chloride was added to the residue obtained by distillation under reduced pressure, washed several times with water, and then the organic layer was treated with anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure after filtration to obtain ethyl acetate and n-hexane 1: 4. The mixed solution was subjected to silica gel chromatography with eluent to obtain 9.3 g (72.8%) of target compound 6- (4-bromophenyl) -9phenyl-9H-pyrido [2,3-b] indole as white crystals.

Synthesis Example 8

Synthesis of 6- (4-bromophenyl) -9-phenyl-9H-pyrido [3,4-b] indole

9-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-pyrido [3,4-b] indole11.85 g ( 0.032 mol), 11.8 g (0.032 mol) of 1-bromo-4-iodobenzene, 9.05 g (0.032 mol), tetrakistriphenyl phosphine paladin (0) 1.87 g (0.002 mol) 200 ml of tetrahydrofuran The resulting residue was dissolved and added to the residue. The residue obtained was treated in the same manner as in Synthesis example 7. The mixed solution of ethyl acetate and n-heptane 1: 4 was purified by silica gel chromatography with eluent to give the title compound 6- (4-bromophenyl) -9. 10.2 g (79.9%) of -phenyl-9H-pyrido [3,4-b] indole was obtained.

Synthesis Example 9

Synthesis of 8- (4-bromophenyl) -5-phenyl-5H-pyrido [4,3-b] indole

5-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxolan-2-yl) -5H-pyrido [4,3-b] indole 11.85 g (0.032 mol) ), 1-bromo-4-iodobenzene 11.8 g (0.032 mol), 9.05 g (0.032 mol), tetrakistriphenyl phosphine paladin (0) 1.87 g (0.002 mol) was added to 200 ml of tetrahydrofuran After dissolving, the residue obtained by treating in the same manner as in Synthesis Example 7 was purified by silica gel chromatography with ethyl acetate and n-heptane 1: 6 mixed solution with eluent to obtain the title compound 8- (4-bromophenyl) -5-phenyl as a white crystal. 8.8 g (68.9%) of -5H-pyrido [4,3-b] indole was obtained.

Synthesis Example 10

Synthesis of 8- (4-bromophenyl) -5-phenyl-5H-pyrido [3,2-b] indole

11.85 g of 5-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-pyrido [3,2-b] indole ( 0.032 mol), 11.8 g (0.032 mol) of 1-bromo-4-iodobenzene, 9.05 g (0.032 mol), tetrakistriphenyl phosphine paladin (0) 1.87 g (0.002 mol) 200 ml of tetrahydrofuran The resulting residue was dissolved in, and treated in the same manner as in Synthesis example 7. The resulting mixture was purified by silica gel chromatography with ethyl acetate and n-hexane 1: 5 in an eluent to yield the title compound 8- (4-bromophenyl) -5. 9.87 g (77.3%) of -phenyl-5H-pyrido [3,2-b] indole were obtained.

Synthesis Example 11

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 Heated to. To the reaction solution was added a solution of 0.253 g (1.2 mmol) of tri-tert-butylphosphine and 0.14 g (0.25 mmol) of bis (dibenzylideneacetone ) paldium ( 0) at once, followed by stirring under reflux for 24 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, the reaction product was filtered through silica, 200 mL of ethyl acetate was added, washed with water several times, the organic layer was treated with anhydrous magnesium sulfate, the organic layer was concentrated under reduced pressure, and the obtained residue was dissolved by adding a small amount of ethyl acetate. An excess of 300 mL n-heptane was added thereto, followed by strong stirring at 0 ° C. for 1 hour. 4.2g (40.6%) was obtained

Synthesis Example 12

Synthesis of N-phenyl-4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) aniline

6- (4-bromophenyl) -9phenyl-9H-pyrido [2,3-b] indole 10 g (0.025 mol), aniline 2.58 g (0.028 mol), sodium tert-butoxide 2.91 g (0.03 mol) Is added to 100 mL of toluene and heated to 60 ° C. To the reaction solution was added a solution of 0.253 g (1.2 mmol) of tri-tert-butylphosphine and 0.14 g (0.25 mmol) of bis (dibenzylideneacetone ) paldium ( 0) at once, followed by stirring under reflux for 24 hours. After confirming the completion of the reaction, the reaction mixture was cooled to room temperature, the reaction mixture was filtered through silica, and the filtrate was distilled under reduced pressure, 500 ml of methylene chloride was added to the residue on the obtained oil, washed several times with water. The obtained residue was dissolved by adding a small amount of tetrahydrofuran, 200 mL n-heptane was added thereto, and vigorously stirred at 0 ° C. for 1 hour. The resulting crystals were filtered to give N-phenyl-4- (9-phenyl-9H as a target compound as white crystals. 5.8 g (56.06%) of pyrido [2,3-b] indol-6-yl) aniline was obtained

Synthesis Example 13

Synthesis of N-phenyl-4- (9-phenyl-9H-pyrido [3,4-b] indol-6-yl) aniline

6- (4-bromophenyl) -9-phenyl-9H-pyrido [3,4-b] indole 10 g (0.025 mol), aniline 2.58 g (0.028 mol), sodium tert-butoxide 2.91 g (0.03 mol) ) Is added to 100 mL of toluene and heated to 60 ° C. A solution of 0.253 g (1.2 mmol) of tri-tert-butylphosphine and 0.14 g (0.25 mmol) of bis (dibenzylideneacetone ) paldium ( 0) was added to the reaction solution at the same time. To give 6.2 g (60.0%) of the target compound N-phenyl-4- (9-phenyl-9H-pyrido [3,4-b] indol-6-yl) aniline as white crystals.

Synthesis Example 14

Synthesis of N-phenyl-4- (5-phenyl-5H-pyrido [4,3-b] indol-8-yl) aniline

6- (4-bromophenyl) -9-phenyl-9H-pyrido [4,3-b] indole 10 g (0.025 mol), aniline 2.58 g (0.028 mol), sodium tert-butoxide 2.91 g (0.03 mol) ) Is added to 100 mL of toluene and heated to 60 ° C. A solution of 0.253 g (1.2 mmol) of tri-tert-butylphosphine and 0.14 g (0.25 mmol) of bis (dibenzylideneacetone ) paldium ( 0) was added to the reaction solution at the same time. To give 6.2 g (60.0%) of the title compound of N-phenyl-4- (5-phenyl-5H-pyrido [4,3-b] indol-8-yl) aniline white crystals.

Synthesis Example 15

Synthesis of N-phenyl-4- (5-phenyl-5H-pyrido [3,2-b] indol-8-yl) aniline

8- (4-bromophenyl) -5-phenyl-5H-pyrido [3,2-b] indole 10 g (0.025 mol), aniline 2.58 g (0.028 mol), sodium tert-butoxide 2.91 g (0.03 mol) ) Is added to 100 mL of toluene and heated to 60 ° C. A solution of 0.253 g (1.2 mmol) of tri-tert-butylphosphine and 0.14 g (0.25 mmol) of bis (dibenzylideneacetone ) paldium ( 0) was added to the reaction solution at the same time. To obtain 8.3g (80.7%) of the target compound N-phenyl-4- (5-phenyl-5H-pyrido [3,2-b] indol-8-yl) aniline as white crystals

Synthesis Example 16

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

10 g (0.025 mol) of 3- (4-bromophenyl) -9-phenyl-9H-carbazole, 5.1 g (0.030 mo) of biphenyl-4-amine, 3.62 g (0.038 mol) of sodium-tert-butoxide Toluene was added to 150 mL and stirred at room temperature for 30 minutes. To the reaction solution was added a solution of 0.144 g (0.25 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.253 g (0.63 mmol) of tri-tert-butylphosphine (50% xylene), followed by stirring under reflux for 22 hours. It was. After confirming the completion of the reaction, the mixture was cooled to room temperature, filtered through silica, and the filtrate was distilled under reduced pressure. Then, 300 mL of methylene chloride was added to the obtained gel-like residue, and washed several times with water. The organic layer was treated with anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure. A small amount of tetrahydrofuran was added to the residue, followed by 500 mL of n-hexane, followed by vigorous stirring for 2 hours. The resulting crystals were filtered and washed with a small amount of cold methanol to obtain light brown crystals. N- (4- (9-phenyl-9H- 6 g (49.1%) of carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine were obtained.

Synthesis Example 17

Synthesis of N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl)-[1,1'-biphenyl] -4-amine

6- (4-bromophenyl) -9phenyl-9H-pyrido [2,3-b] indole 10 g (0.025 mol), biphenyl-4-amine 5.1 g (0.030 mo), sodium-tert-butoxide 3.62 g (0.038 mol) was added to 150 mL of toluene and stirred for 30 minutes at room temperature. To the reaction solution was added a solution of 0.144 g (0.25 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.253 g (0.63 mmol) of tri-tert-butylphosphine (50% xylene), followed by stirring under reflux for 22 hours. It was. After confirming the completion of the reaction, the mixture was cooled to room temperature, filtered through silica, and the filtrate was distilled under reduced pressure. Then, 300 mL of methylene chloride was added to the obtained gel-like residue, and washed several times with water. The organic layer was treated with anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure. A small amount of tetrahydrofuran was added to the residue, and 500 mL of a mixed solution of n-heptane: ethyl acetate 9: 1 was added thereto, followed by strong stirring at 5 ° C. for 2 hours. The resulting crystals were filtered and washed with a small amount of cold methanol to obtain light brown crystals. N 7.8 g (64.0%) of-(4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl)-[1,1'-biphenyl] -4-amine were obtained.

Synthesis Example 18

Synthesis of N- (4- (9-phenyl-9H-pyrido [3,4-b] indol-6-yl) phenyl)-[1,1'-biphenyl] -4-amine

6- (4-bromophenyl) -9-phenyl-9H-pyrido [3,4-b] indole 10 g (0.025 mol), biphenyl-4-amine 5.1 g (0.030 mo), sodium-tert-butoxide 3.62 g (0.038 mol) of side was added to 150 mL of toluene and stirred for 30 minutes at room temperature. To the reaction solution was added 0.144 g (0.25 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.253 g (0.63 mmol) of tri-tert-butylphosphine (50% xylene). Target compound of light brown crystals by treatment with N- (4- (9-phenyl-9H-pyrido [3,4-b] indol-6-yl) phenyl)-[1,1'-biphenyl]- 8.4 g (67.0%) of 4-amine were obtained.

Synthesis Example 19

Synthesis of N- (4- (5-phenyl-5H-pyrido [4,3-b] indol-8-yl) phenyl)-[1,1'-biphenyl] -4-amine

6- (4-bromophenyl) -9-phenyl-9H-pyrido [4,3-b] indole 10 g (0.025 mol), biphenyl-4-amine 5.1 g (0.030 mo), sodium-tert-butoxide 3.62 g (0.038 mol) of side was added to 150 mL of toluene and stirred for 30 minutes at room temperature. To the reaction solution was added 0.144 g (0.25 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.253 g (0.63 mmol) of tri-tert-butylphosphine (50% xylene). Target compound of light brown crystals by the method N- (4- (5-phenyl-5H-pyrido [4,3-b] indol-8-yl) phenyl)-[1,1'-biphenyl]- 8.7 g (71.40%) of 4-amine were obtained.

Synthesis Example 20

Synthesis of N- (4- (5-phenyl-5H-pyrido [3,2-b] indol-8-yl) phenyl)-[1,1'-biphenyl] -4-amine

8- (4-bromophenyl) -5-phenyl-5H-pyrido [3,2-b] indole 1 0 g (0.025 mol), biphenyl-4-amine 5.1 g (0.030 mo), sodium-tert- 3.62 g (0.038 mol) of butoxide was added to 150 mL of toluene and stirred at room temperature for 30 minutes. To the reaction solution was added 0.144 g (0.25 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.253 g (0.63 mmol) of tri-tert-butylphosphine (50% xylene). Target compound of light brown crystals by treatment with N- (4- (5-phenyl-5H-pyrido [3,2-b] indol-8-yl) phenyl)-[1,1'-biphenyl]- 9.0 g (71.8%) of 4-amines were obtained.

Synthesis Example 21

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

10 g (0.025 mol) of 3- (3-bromophenyl) -9-phenyl-9H-carbazole, 5.1 g (0.030 mo) of biphenyl-4-amine, and 3.62 g (0.038 mol) of sodium-tert-butoxide Toluene was added to 150 mL and stirred at room temperature for 30 minutes. A solution of 0.144 g (0.25 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.253 g (0.63 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, followed by 12 hours at 120 ° C. After confirming the completion of the reaction, the mixture was filtered under hot conditions to remove the solids, the filtrate was distilled under reduced pressure, and 500 mL of methylene chloride was added thereto, washed several times with water. The organic layer was treated with anhydrous magnesium sulfate, filtered and the organic layer was concentrated under reduced pressure. To methylene chloride: n-hexane = 1: 4 mixed solution was purified by silica gel chromatography with eluent to give the title compound N- (3- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1, 5.5 g (45%) of 1'-biphenyl] -4-amine were obtained.

Synthesis Example 22

Synthesis of N- (3- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl)-[1,1'-biphenyl] -4-amine

10 g (0.025 mol) of 3- (3-bromophenyl) -9-phenyl-9H-carbazole, 5.1 g (0.030 mo) of biphenyl-4-amine, and 3.62 g (0.038 mol) of sodium-tert-butoxide Toluene was added to 150 mL and stirred at room temperature for 30 minutes. To the reaction solution was added 0.144 g (0.25 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.253 g (0.63 mmol) of tri-tert-butylphosphine (50% xylene). Treated by one method, the desired compound of white crystals N- (3- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl)-[1,1'-biphenyl]- 5.9 g (48.4%) of 4-amine were obtained.

Synthesis Example 23

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

20 g (0.086 mol) of 4-bromo-1,1'biphenyl, 17.42 g (0.103 mo) of [1,1'-bisphenyl] -4-amine, and 9.90 g (0.103 mol) of sodium-tert-butoxide Toluene was added to 400mL and stirred for 30 minutes at room temperature. A solution of 0.495 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, followed by 12 hours at 120 ° C. After confirming the completion of the reaction, the silica was filtered in a hot state to remove solids, and the filtrate was stirred at room temperature for 1 hour, and the resulting crystals were filtered and washed with cold toluene. 21.3 g (77.1%) of -biphenyl] -4-yl) amine were obtained.

Synthesis Example 24

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

7.64 g (0.031 mol) N-phenyl- [1,1'-biphenyl] -4-amine, 10.47 g (0.037 mol) 1-bromo-4-iodo benzene, 3.88 g sodium-tert-butoxide 0.04 mol) was added to 150 mL of toluene and stirred at room temperature for 30 minutes. A solution of 0.28 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, followed by 10 hours at 100 ° C. Reacted. After confirming the completion of the reaction, the mixture was filtered under a hot state to remove solids, the filtrate was distilled under reduced pressure, 200 mL of methylene chloride was added thereto, washed several times with water, the organic layer was treated with anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure. : n-hexane = 1: 2 mixture solution was purified by silica gel chromatography with eluent to give the title compound N- (4-bromophenyl) -N-phenyl- [1,1'-biphenyl] -4-amine as a white crystal 9.85 g (79.4%) was obtained

Synthesis Example 25

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

7.64 g (0.031 mol) N-phenyl- [1,1'-biphenyl] -4-amine, 10.47 g (0.037 mol) 1-bromo-3-iodo benzene, 3.88 g sodium-tert-butoxide 0.04 mol) was added to 150 mL of toluene and stirred at room temperature for 30 minutes. To the reaction solution was added 0.28 g (0.31 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.32 g (1 mmol) of tri-tert-butylphosphine (50% xylene), followed by the same method as in Synthesis Example 24. 8.97 g (72.3%) of the target compound N- (3-bromophenyl) -N-phenyl- [1,1'-biphenyl] -4-amine as white crystals was obtained by treatment with

Synthesis Example 26

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

9.97 g (0.031 mol) di ([1,1'-biphenyl] -4-yl) amine, 10.47 g (0.037 mol) 1-bromo-4-iodo benzene, 3.88 g sodium-tert-butoxide 0.04 mol) was added to 150 mL of toluene and stirred at room temperature for 30 minutes. A solution of 0.28 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, followed by the same method as in Synthesis Example 23. N-([1,1'-biphenyl] -4-yl) -N- (4-bromophenyl)-[1,1'-biphenyl] -4-amine 9.54 g (64.6%) was obtained

Synthesis Example 27

9.97 g (0.031 mol) of di ([1,1'-biphenyl] -4-yl) amine, 10.47 g (0.037 mol) of 1-bromo-3-iodo benzene, 3.88 g of sodium-tert-butoxide 0.04 mol) was added to 150 mL of toluene and stirred at room temperature for 30 minutes. To the reaction solution was added 0.28 g (0.31 mmol) of bis (dibenzylideneacetone) palladium (0) in 0.32 g (1 mmol) of tri-tert-butylphosphine (50% xylene), followed by the same method as in Synthesis Example 24. Target compound of white crystals N-([1,1'-biphenyl] -4-yl) -N- (4-bromophenyl)-[1,1'-biphenyl] -4-amine 9.14 g (62.2%) was obtained.

Synthesis Example 28

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-4-io 10.47 g (0.037 mol) of benzene and 3.88 g (0.04 mol) of sodium-tert-butoxide were added to 150 mL of toluene and stirred at room temperature for 30 minutes. 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, followed by 12 hours at 100 ° C. After confirming the completion of the reaction, the mixture was filtered under a hot state to remove solids, the filtrate was distilled under reduced pressure, 200 mL of methylene chloride was added thereto, washed several times with water, the organic layer was treated with anhydrous magnesium sulfate, and the organic layer was filtered with a small amount of tetrahydrofuran. 500 mL of n-hexane was added thereto, followed by vigorous stirring for 2 hours. The resulting crystals were filtered and washed with a small amount of cold methanol to obtain the target compound N- (4-bromophenyl) -N- (4- (9-phenyl 10.4 g (52.4%) of -9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine was obtained.

Synthesis Example 29

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-3-io 10.47 g (0.037 mol) of benzene and 3.88 g (0.04 mol) of sodium-tert-butoxide were added to 120 mL of toluene and stirred for 30 minutes at room temperature. 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. Target compound of light brown crystals by the method N- (3-bromophenyl) -N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] 10.8 g (54.4%) of 4-amine were obtained.

Synthesis Example 30

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-iodo benzene 10.47 g (0.037 mol), sodium-tert-butoxide 3.88 g (0.04 mol) of side was added to 150 mL of toluene and stirred for 30 minutes at room temperature. 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, followed by the same procedure as in Synthesis Example 29. 9.94 g (56.7%) of the title compound 4-bromo-N-phenyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) aniline of light brown crystals was obtained by the method.

Synthesis Example 31

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-3-iodo benzene 10.47 g (0.037 mol), sodium-tert-butoxide 3.88 g (0.04 mol) of side was added to 150 mL of toluene and stirred for 30 minutes at room temperature. 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, followed by the same procedure as in Synthesis Example 29. 8.88 g (50.7%) of target compound 3-bromo-N-phenyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) aniline as light brown crystals was obtained by the method.

Synthesis Example 32

Synthesis of 4-bromo-N-phenyl-N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl) aniline

N-phenyl-4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) aniline 12.8 g (0.031 mol), 1-bromo-4-iobenzene 10.47 g (0.037 mol) ), Sodium-tert-butoxide, 3.88 g (0.04 mol) was added to 150 mL of toluene and stirred at room temperature for 30 minutes. A solution of 0.28 g (0.31 mmol) of bis (dibenzylideneacetone) paldium (0) in 0.3 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, followed by 10 hours at 100 ° C. After confirming the completion of the reaction, a small amount of ethyl acetate was added to the residue, which was treated in the same manner as in Synthesis Example 24, and then dissolved. Then, 500 mL of n-heptane was added thereto, followed by strong stirring for 2 hours. Target compound of pale white crystals 4-bromo-N-phenyl-N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl) aniline 11.9 g (68.2 Got%)

Synthesis Example 33

N- (4-bromophenyl) -N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl)-[1,1'-biphenyl]- Synthesis of 4-amine

15.1 g (0.031 mol) of N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl)-[1,1'-biphenyl] -4-amine, 10.47 g (0.037 mol) of 1-bromo-4-iodo benzene and 13.28 g (0.037 mol) of sodium-tert-butoxide were added to 150 mL of toluene and stirred at room temperature for 30 minutes. A solution of 0.28 g (0.31 mmol) of bis (dibenzylideneacetone) paldium (0) in 0.3 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, followed by 10 hours at 100 ° C. After confirming the completion of the reaction, the target compound of light white crystals was treated by the same method as in Synthesis Example 32. N- (4-bromophenyl) -N- (4- (9-phenyl-9H-pyrido [2, 3-b] indol-6-yl) phenyl)-[1,1'-biphenyl] -4-amine 10.4 g (52.4%) was obtained.

Synthesis Example 34

N- (3-bromophenyl) -N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl)-[1,1'-biphenyl]- Synthesis of 4-amine

15.1 g (0.031 mol) of N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl)-[1,1'-biphenyl] -4-amine, 10.47 g (0.037 mol) of 1-bromo-3-iodo benzene and 13.28 g (0.037 mol) of sodium-tert-butoxide were added to 150 mL of toluene and stirred at room temperature for 30 minutes. A solution of 0.28 g (0.31 mmol) of bis (dibenzylideneacetone) paldium (0) in 0.3 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution, followed by 10 hours at 100 ° C. After confirming the completion of the reaction, the target compound of light white crystals was treated by the same method as in Synthesis Example 31. N- (3-bromophenyl) -N- (4- (9-phenyl-9H-pyrido [2, 3-b] indol-6-yl) phenyl)-[1,1'-biphenyl] -4-amine 10.0 g (50.4%) was obtained.

Synthesis Example 35

Synthesis of N-([1,1'-biphenyl] -4-yl) -N- (4-bromo-2,5-dimethylphenyl)-[1,1'-biphenyl] -4-amine

Di (([1,1'-biphenyl] -4-yl) amine, 10 g (0.031 mol), 1-bromo-4-iodo-2,5-dimethylbenzene 6.81 g (0.037 mol) sodium-tert 3.88 g (0.04 mol) of butoxide was added to 150 mL of toluene and stirred for 30 minutes at room temperature Bis (dibenzylideneacetone) palladium in 0.32 g (1 mmol) of tri-tert-butylphosphine (50% xylene) was added to the reaction solution. (0) A solution obtained by adding 0.28 g (0.31 mmol) was added thereto, and the residue obtained by treatment in the same manner as in Synthesis Example 23 was subjected to silica gel chromatography using a mixed solution of methylene chloride: n-hexane = 1: 4 as eluent to obtain light brown crystals. 6.61 g of compound N-([1,1'-biphenyl] -4-yl) -N- (4-bromo-2,5-dimethylphenyl)-[1,1'-biphenyl] -4-amine (42.3.0%) was obtained.

Synthesis Example 36

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

7.7 g (0.012 mol) 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 6.4 (0.013 mol), sodium tert-butoxide 1.5 g (0.016 mol) is added to 50 ml of toluene and heated to 60 ° C. To the reaction solution was added 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene). Reaction was time. After confirming the completion of the reaction, silica solid was removed by hot filtration to remove the solid, 600 mL of chloroform was added to the residue obtained by concentrating the filtrate under reduced pressure, washed several times with water, and then the organic layer was treated with anhydrous magnesium sulfate, and the residue obtained by filtration and concentrated under reduced pressure. The resulting solid was obtained by sublimation purification of a mixture of dichloromethane, ethyl acetate, and n-heptic acid 1: 2: 4 with silica gel by eluent to give the title compound N1, N4-di ([1,1'-biphenyl] as white crystals. 3.14 g (25.0%) of 4-yl) -N1, N4-bis (4- (9-phenyl-9H-carbazol-3-yl) phenyl) benzene-1,4-diamine were obtained.

Synthesis Example 37

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

7.7 g (0.012 mol) 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 6.4 (0.013 mol), sodium tert-butoxide 1.5 g (0.016 mol) is added to 50 ml of toluene and heated to 60 ° C. To the reaction solution was added 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) in 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene). Reaction was time. After confirming the completion of the reaction, silica solid was removed by hot filtration to remove the solid, 600 mL of chloroform was added to the residue obtained by concentrating the filtrate under reduced pressure, washed several times with water, and then the organic layer was treated with anhydrous magnesium sulfate, and the residue obtained by filtration and concentrated under reduced pressure. The resulting solid was obtained by sublimation purification of a mixture of dichloromethane, ethyl acetate, and n-heptic acid 1: 2: 4 by silica gel chromatography with eluent to give the title compound N1, N3-di ([1,1'-biphenyl] as white crystals. 2.36 g (18.8%) of 4-yl) -N1, N3-bis (4- (9-phenyl-9H-carbazol-3-yl) phenyl) benzene-1,3-diamine were obtained.

Synthesis Example 38

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

16.5 g (0.034 mol) of N- (3- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine, 1,4-dibromo benzene 3.8 g (0.016 mol) and sodium tert-butoxide 3.85 g (0.04 mol) are added to 50 ml of toluene and heated to 60 ° C. To the reaction solution, a solution of 0.147 g (0.16 mmol) of tris (dibenzylideneacetone) dipalladium (0) was added to 0.32 g (0.8 mmol) of tri-tert-butylphosphine (50% xylene). The residue obtained by treatment in the same manner was subjected to silica gel chromatography of a dichloromethane: n-hexane 1: 4 mixed solution with an eluent to sublimate and purify the solid to obtain the target compound N1, N4-di ([1,1'-) as white crystals. 3.37 g (20.1%) of biphenyl] -4-yl) -N1, N4-bis (3- (9-phenyl-9H-carbazol-3-yl) phenyl) benzene-1,4-diamine were obtained.

Synthesis Example 39

N1, N1, N4-tri ([1,1'-biphenyl] -4-yl) -2,5-dimethyl-N4- (3 '-(9-phenyl-9H-carbazol-3-yyl) Synthesis of-[1,1'-biphenyl] -4-yl) benzene-1,4-diamine

4.04 g of N-([1,1'-biphenyl] -4-yl) -N- (4-bromo-2,5-dimethylphenyl)-[1,1'-biphenyl] -4-amine ( 0.008 mol), N- (3- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine 4.26 (0.009 mol), sodium tert-butoxide 1.0 g (0.0104 mol) is added to 80 ml of toluene and heated to 60 ° C. To the reaction solution was added 0.07 g (0.08 mmol) of tris (dibenzylideneacetone) dipalladium (0) in 0.08 g (0.2 mmol) of tri-tert-butylphosphine (50% xylene). Reaction was time. After confirming the completion of the reaction, the solid was removed by filtration through silica in a hot state, and then 800 ml of dichloromethane was added to the residue obtained by concentrating the filtrate under reduced pressure, washed several times with water, and then the organic layer was treated with anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure. The residue was sublimed and purified by silica gel chromatography using dichloromethane, ethyl acetate, and n-hexane 1: 1: 3 mixed solution as eluent to give the title compound N1, N1, N4-tri ([1,1'-) as white crystals. Biphenyl] -4-yl) -2,5-dimethyl-N4- (3 '-(9-phenyl-9H-carbazol-3-yyl)-[1,1'-biphenyl] -4-yl 1.73 g (22.0%) of benzene-1,4-diamine were obtained.

Synthesis Example 40

N1, N1, N4-tri ([1,1'-biphenyl] -4-yl) -2,5-dimethyl-N4- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) Synthesis of Benzene-1,4-diamine

4.04 g of N-([1,1'-biphenyl] -4-yl) -N- (4-bromo-2,5-dimethylphenyl)-[1,1'-biphenyl] -4-amine ( 0.008 mol), N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine 4.26 (0.009 mol), sodium tert-butoxide 1.0 g (0.0104 mol) is added to 80 ml of toluene and heated to 60 ° C. To the reaction solution, 0.07 g (0.08 mmol) of tris (dibenzylideneacetone) dipalladium (0) was added to 0.08 g (0.2 mmol) of tri-tert-butylphosphine (50% xylene). Treated in the same manner to give the desired compound N1, N1, N4-tri ([1,1'-biphenyl] -4-yl) -2,5-dimethyl-N4- (4- (9-phenyl-9H-carbazole 1.82 g (23.1%) of 3-yl) phenyl) benzene-1,4-diamine were obtained.

Synthesis Example 41

N1, N4-di ([1,1'-biphenyl] -4-yl) -N1- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -N4- (4- (9 Synthesis of -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) cyclohexa-2,4-dien-1-yl) 7.7 g (0.012 mol),-[1,1'-biphenyl] -4-amine, N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-bi 6.4 (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 heated to 60 ° C. To the reaction solution, 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) was added to 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene). Treated in the same manner to give the desired compound N1, N4-di ([1,1'-biphenyl] -4-yl) -N1- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)- 3.14 g (25.0%) of N4- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl) benzene-1,4-diamine were obtained.

Synthesis Example 42

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

0.94 g (0.004 mol) of 1,4-dibromo benzene, N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl)-[1,1 ' 4.4 g (0.009 mol) of -biphenyl] -4-amine and 1 g (0.01 mol) of sodium-tert-butoxide were added to 80 mL of toluene and stirred at room temperature for 30 minutes. After heating the reaction solution to 40 ° C, 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. After the solution was added, the mixture was stirred at reflux for 30 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, filtered with silica, 800 mL of chloroform was added, washed several times with water, the organic layer was treated with anhydrous magnesium sulfate, filtered and the organic layer was concentrated under reduced pressure, and then dichloromethane, tetrahahydrofuran, n-hexane 1 Sublimation and purification of the solid obtained by the silica gel chromatography of the 1: 1 mixed solution with the eluent gave the target compound N1, N4-di ([1,1'-biphenyl] -4-yl) -N1, N4-bis as a white crystal. 1.07 g (24.3%) of (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl) benzene-1,4-diamine were obtained.

Synthesis Example 43

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

4,4'-dibromobiphenyl 1.3 g (0.004 mol), N- (4- (9-phenyl-9H-pyrido [3,4-b] indol-6-yl) phenyl)-[1,1 4.4 g (0.009 mol) of '-biphenyl] -4-amine and 1 g (0.01 mol) of sodium-tert-butoxide were added to 80 mL of toluene, and it stirred at room temperature for 30 minutes. After heating the reaction solution to 40 ° C, 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 was added and treated in the same manner as in Synthesis Example 41 to obtain the title compound N4, N4'-di ([1,1'-biphenyl] -4-yl) -N4, N4'-bis (4- ( 1.0 g (24.6%) of 9-phenyl-9H-pyrido [3,4-b] indol-6-yl) phenyl) benzene-1,4'-diamine was obtained.

Synthesis Example 44

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

4,4'-dibromobiphenyl 1.3 g (0.004 mol), N- (4- (5-phenyl-5H-pyrido [4,3-b] indol-8-yl) phenyl)-[1,1 4.4 g (0.009 mol) of '-biphenyl] -4-amine and 1 g (0.01 mol) of sodium-tert-butoxide were added to 80 mL of toluene, and it stirred at room temperature for 30 minutes. After heating the reaction solution to 40 ° C, 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 was added and treated in the same manner as in Synthesis example 42 to obtain the target compound of white crystals N4, N4'-di ([1,1'-biphenyl] -4-yl) -N4, N4'-bis (4- ( 1.03 g (25.0%) of 5-phenyl-5H-pyrido [4,3-b] indol-8-yl) phenyl) benzene-1,4'-diamine was obtained.

Synthesis Example 45

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

4,4'-dibromobiphenyl 1.3 g (0.004 mol), N- (4- (5-phenyl-5H-pyrido [3,2-b] indol-8-yl) phenyl)-[1,1 4.4 g (0.009 mol) of '-biphenyl] -4-amine and 1 g (0.01 mol) of sodium-tert-butoxide were added to 80 mL of toluene, and it stirred at room temperature for 30 minutes. After heating the reaction solution to 40 ° C, 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 was added and treated in the same manner as in Synthesis example 42 to obtain the target compound of white crystals N4, N4'-di ([1,1'-biphenyl] -4-yl) -N4, N4'-bis (4- ( 1.04 g (25.3%) of 5-phenyl-5H-pyrido [3,2-b] indol-8-yl) phenyl) benzene-1,4'-diamine was obtained.

Synthesis Example 46

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

4'-bromo-N-phenyl-N- (4- (9-phenyl-9H-carbazol-3-yl) cyclohexa-2,4-dien-1-yl) aniline6.81 g (0.012 mol), 6.33 g of N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine

(0.013 mol), 1.5 g (0.016 mol) of sodium tert-butoxide are added to 50 ml of toluene and heated to 60 ° C. To the reaction solution was added 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) to 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene). Treated in the same manner to give the target compound of white crystals N1-([1,1'-biphenyl] -4-yl) -N4-phenyl-N1, N4-bis (4- (9-phenyl-9H-carbazole- 2.31 g (18.8%) of 3-yl) phenyl) benzene-1,4-diamine were obtained.

Synthesis Example 47

N1-([1,1'-biphenyl] -4-yl) -N4-phenyl-N1- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -N4- (4- ( Synthesis of 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) cyclohexa-2,4-dien-1-yl) 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), 1.5 g (0.016 mol) of sodium tert-butoxide are added to 50 ml of toluene and heated to 60 ° C. To the reaction solution was added 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) to 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene). Target compound N1-([1,1'-biphenyl] -4-yl) -N4-phenyl-N1- (4- (9-phenyl-9H-carbazol-3-yl) as a target for white crystals by treatment in the same manner 2.71 g (23.2%) of phenyl) -N4- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl) benzene-1,4-diamine

Synthesis Example 48

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

4-bromo-N-phenyl-N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) cyclohexa-2,4-dien-1-yl) aniline 6.82 g (0.012 mol), N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl)-[1,1'-biphenyl] -4-amine 6.34 g (0.013 mol) and sodium tert-butoxide 1.5 g (0.016 mol) are added to 50 ml of toluene and heated to 60 ° C. To the reaction solution was added 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) to 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene). Treated in the same manner to give the target compound of the white crystals 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 obtained 1.91 g (16.4%).

Synthesis Example 49

N1-([1,1'-biphenyl] -4-yl) -2,5-dimethyl-N4-phenyl-N1, N4-bis (4- (9-phenyl-9H-carbazol-3-yl) Synthesis of Phenyl) benzene-1,4-diamine

4-bromo-2,5-dimethyl-N-phenyl-N- (4- (9-phenyl-9H-carbazol-3-yl) cyclohexa-2,4-dien-1-yl) aniline 7.15 g (0.012 mol), N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine 6.33 g (0.013 mol), sodium tert- 1.5 g (0.016 mol) of butoxide is added to 50 ml of toluene and heated to 60 ° C. To the reaction solution, 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) was added to 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene). Treated in the same manner as the target compound of the white crystals N1-([1,1'-biphenyl] -4-yl) -2,5-dimethyl-N4-phenyl-N1, N4-bis (4- (9-phenyl 2.06 g (17.2%) of -9H-carbazol-3-yl) phenyl) benzene-1,4-diamine were obtained.

Synthesis Example 50

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

N- (3-bromophenyl) -N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) cyclohexa-2,4-dien-1-yl) 7.7 g (0.012 mol),-[1,1'-biphenyl] -4-amine, N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-bi 6.4 (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 heated to 60 ° C. In the reaction solution tree -tert- butylphosphine (50% xylene), 0.12g (0.3mmol) of tris (dibenzylideneacetone) dipalladium (0) and after Synthesis Example 36 was added to a solution of 0.12g (0.13mmol) Treated in the same manner to give the desired compound N1, N3-di ([1,1'-biphenyl] -4-yl) -N1- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)- 3.14 g (25.0%) of N3- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl) benzene-1,4-diamine were obtained.

Synthesis Example 51

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

N- (3-bromophenyl) -N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) cyclohexa-2,4-dien-1-yl) 7.7 g (0.012 mol),-[1,1'-biphenyl] -4-amine, N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl) 6.4 (0.013 mol) of-[1,1'-biphenyl] -4-amine and 1.5 g (0.016 mol) of sodium tert-butoxide are added to 50 ml of toluene and heated to 60 ° C. To the reaction solution, 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) was added to 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene). Treatment was carried out in the same manner to give the desired compound N1, N3-di ([1,1'-biphenyl] -4-yl) -N1, N3-bis (4- (9-phenyl-9H-pyrido [2,3- b] 3.03 g (25.0%) of indol-6-yl) phenyl) benzene-1,3-diamine was obtained.

Synthesis Example 52

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

3-bromo-N-phenyl-N- (4- (9-phenyl-9H-carbazol-3-yl) cyclohexa-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), sodium tert- 1.5 g (0.016 mol) of butoxide is added to 50 ml of toluene and heated to 60 ° C. To the reaction solution, 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) was added to 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene). Treated in the same manner to give the desired compound N1-([1,1'-biphenyl] -4-yl) -N3-phenyl-N1, N3-bis (4- (9-phenyl-9H-carbazol-3-yl 2.45 g (21.0%) of phenyl) benzene-1,3-diamine were obtained.

Synthesis Example 53

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

3-bromo-N-phenyl-N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) cyclohexa-2,4-dien-1-yl) aniline Synthesis of 6.82 g (0.012 mol), N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine 6.3 g (0.013 mol) 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, 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) was added to 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene). Treated in the same manner to give the desired compound N1-([1,1'-biphenyl] -4-yl) -N3-phenyl-N1- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) 2.57 g (22.0%) of -N3- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl) benzene-1,3-diamine were obtained.

Synthesis Example 54

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

3-bromo-N-phenyl-N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) cyclohexa-2,4-dien-1-yl) aniline 6.82 g (0.012 mol), N- (4- (5-phenyl-5H-pyrido [3,2-b] indol-8-yl) phenyl)-[1,1'-biphenyl] -4-amine 6.4 g (0.013 mol), sodium tert-butoxide 1.5 g (0.016 mol) are added to 50 ml of toluene and heated to 60 ° C. To the reaction solution, 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) was added to 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene). By the same method as the target compound N1-([1,1'-biphenyl] -4-yl) -N3-phenyl-N1- (4- (5-phenyl-5H-pyrido [3,2-b ] Indol-8-yl) phenyl) -N3- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl) benzene-1,3-diamine 2.15 g (18.4 %) Was obtained.

Synthesis Example 55

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

5-Bromo-2,4-dimethyl-N-phenyl-N- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) cyclohexa-2,4-diene -1-yl) aniline 7.16 g (0.012 mol), N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)-[1,1'-biphenyl] -4-amine 6.3 g (0.013 mol), 1.5 g (0.016 mol) of sodium tert-butoxide are added to 50 ml of toluene and heated to 60 ° C. To the reaction solution, 0.12 g (0.13 mmol) of tris (dibenzylideneacetone) dipalladium (0) was added to 0.12 g (0.3 mmol) of tri-tert-butylphosphine (50% xylene). Treated in the same manner as the target compound N1-([1,1'-biphenyl] -4-yl) -4,6-dimethyl-N3-phenyl-N1- (4- (9-phenyl-9H-carbazole -3-yl) phenyl) -N3- (4- (9-phenyl-9H-pyrido [2,3-b] indol-6-yl) phenyl) benzene-1,3-diamine 2.09 g (17.4%) Got

Compounds according to embodiments of the present invention, for example, a hole transport compound having a structure of Formula 1 to 2 will be easily synthesized by those skilled in the art with reference to the synthesis examples 1 to 55.

Synthesis Example  Synthesized by 36 to 55 Hole transport  Experimental results of the compound itself

Representative physical properties of Compounds 1 to 20 (Synthesis Examples 36 to 55) prepared in Synthesis Example were evaluated, and the results are shown in Table 1 below.

Properties UVmax
(nm) PLmax
(nm) HOMO
(eV) LUMO
(eV Band gap
(eV) T1
(eV) TID
(℃) Tg
(℃) Compound 1
Synthesis Example 36 349,286 421 5.66 2.59 3.07 2.52 584 165 Compound 2
Synthesis Example 37 337,288 413 5.81 2.63 3.18 2.48 521 136 Compound 3
Synthesis Example 38 340,286 426 5.77 2.66 3.11 2.39 592 154 Compound 4
Synthesis Example 39 340,278 424 5.83 2.70 3.13 2.22 487 149 Compound 5
Synthesis Example 40 340,279 424 5.74 2.68 3.06 2.41 503 161 Compound6
Synthesis Example 41 352,278 420 5.58 2.49 3.09 2.36 485 159 Compound7
Synthesis Example 42 352,278 422 5.62 2.51 3.11 2.24 460 148 Compound 8
Synthesis Example 43 353,280 422 5.63 2.57 3.06 2.26 479 142 Compound 9
Synthesis Example 44 352,278 423 5.63 2.62 3.01 2.39 491 146 Compound 10
Synthesis Example 45 353,279 422 5.59 2.51 3.08 2.31 477 140 Compound 11
Synthesis Example 46 352,279 411 5.39 2.28 3.11 2.61 561 162 Compound 12
Synthesis Example 47 353,280 418 5.43 2.33 3.10 2.59 555 163 Compound 13
Synthesis Example 48 353,278 420 5.48 2.41 3.07 2.46 487 159 Compound 14
Synthesis Example 49 340,279 397 5.48 2.31 3.17 2.50 512 158 Compound 15
Synthesis Example 50 352,277 420 5.49 2.31 3.18 2.40 483 148 Compound 16
Synthesis Example 51 353,280 422 5.55 2.48 3.07 2.33 462 152 Compound 17
Synthesis Example 52 337,288 417 5.39 2.13 3.26 2.51 519 153 Compound 18
Synthesis Example 53 338,289 420 5.43 2.22 3.21 2.50 508 141 Compound 19
Synthesis Example 54 337,288 422 5.49 2.28 3.21 2.46 500 139 Compound 20
Synthesis Example 55 353,280 416 5.52 2.34 3.18 2.44 483 147

UVmax: Absorption wavelength of material measured from spectrometer and cyclic voltametry

PLmax: emission wavelength of material measured from spectrometer and cyclic voltametry

HOMO, LUMO, Bandgap: Measured from Spectrometer and Cyclic Voltametry

T1: Triplet energy in the form of a film (checked by phosphorescence measurement at 77K)

TID: degradation temperature of the material (confirmed by TGA)

Tg: glass transition temperature

As shown in Table 1, the hole transport compound according to the embodiments of the present invention has an overall high glass transition temperature, has an advantageous HOMO energy level in hole transport, and has a high LUMO energy level. can confirm. In addition, in TID, it corresponds to 500 degreeC or more, and can confirm that it has a characteristic close to 600 degreeC.

In addition, the materials have an advantage that can be produced in a high yield by the above-described synthesis examples.

Synthesis Example  Synthesized by 36 to 55 Hole transport  Experimental Results of Organic Light-Emitting Device Using Compound

Comparative example

The ITO substrate was cleaned after patterning the light emitting area to a size of 3 mm x 3 mm. After mounting the substrate in a vacuum chamber, the base pressure was 1 × 10 −6 torr and DNTPD was vacuum deposited to a thickness of 60 nm with a hole injection material on the anode ITO. BPBPA was deposited to a thickness of 30 nm with the hole transport layer. After that, DBTTP1 and Ir (ppy) 3 as a dopant were formed on the hole transport layer at a thickness of 30 nm with a dopant concentration of 10%. ZADN was vacuum deposited on the electron transport layer to form a thickness of 30 nm, LiF, an electron injection layer, was formed to a thickness of 1.0 nm, and then Al was formed to a thickness of 100 nm to produce an organic light emitting device. To evaluate the lifespan of the device by measuring the relative changes in the current, voltage and brightness in real time and the results are shown in Table 2 below.

Example  1 to 20

The ITO substrate was cleaned after patterning the light emitting area to a size of 3 mm x 3 mm. After mounting the substrate in a vacuum chamber, the base pressure was 1 × 10 −6 torr, and DNTPD was vacuum deposited to a thickness of 60 nm with a hole injection material on the anode ITO. To compound) was formed into a film with a thickness of 30 nm. After that, DBTTP1 and Ir (ppy) 3 as a dopant were formed on the hole transport layer at a thickness of 30 nm with a dopant concentration of 10%. ZADN was vacuum deposited on the electron transport layer to form a thickness of 30 nm, LiF, an electron injection layer, was formed to a thickness of 1.0 nm, and then Al was formed to a thickness of 100 nm to produce an organic light emitting device. To evaluate the lifespan of the device by measuring the relative changes in the current, voltage and brightness in real time and the results are shown in Table 2 below.

Item
Voltage
[V] Current density
[mA / cm2] Luminance
[Cd / m2] Current efficiency
Cd / A Power efficiency
[Lm / W] Quantum efficiency
[%] life span
(LT90,3000Cd / m2)
[h] Compound 1
Synthesis Example 36 5.0 2.07 1000 58.6 36.8 16.2 63.9 Compound 2
Synthesis Example 37 5.7 2.88 1000 34.2 18.8 9.8 3.8 Compound 3
Synthesis Example 38 5.7 2.62 1000 36.6 22.8 10.5 23.1 Compound 4
Synthesis Example 39 5.5 2.43 1000 39.9 22.8 11.4 56.2 Compound 5
Synthesis Example 40 5.1 2.13 1000 46.2 31.2 13.9 56.1 Compound6
Synthesis Example 41 4.9 2.08 1000 52.7 31.7 14.6 58.2 Compound7
Synthesis Example 42 4.8 2.07 1000 58.6 36.8 16.2 61.2 Compound 8
Synthesis Example 43 5.0 2.11 1000 56.1 34.1 15.3 54.6 Compound 9
Synthesis Example 44 4.9 2.06 1000 55.3 32.2 14.1 47.3 Compound 10
Synthesis Example 45 4.9 2.09 1000 56.9 33.6 14.9 48.7 Compound 11
Synthesis Example 46 5.1 2.03 1000 49.0 30.3 13.6 51.0 Compound 12
Synthesis Example 47 4.6 2.06 1000 49.9 33.5 13.9 49.9 Compound 13
Synthesis Example 48 4.5 1.98 1000 58.9 31.2 16.3 60.3 Compound 14
Synthesis Example 49 5.0 2.09 1000 47.4 29.8 13.1 53.6 Compound 15
Synthesis Example 50 5.5 2.71 1000 35.9 19.5 10.6 6.2 Compound 16
Synthesis Example 51 5.4 2.54 1000 38.1 21.3 11.1 9.8 Compound 17
Synthesis Example 52 5.6 2.86 1000 34.3 19.9 10.4 10.9 Compound 18
Synthesis Example 53 5.5 2.80 1000 36.0 21.4 12.0 14.6 Compound 19
Synthesis Example 54 5.5 2.77 1000 35.9 20.8 11.6 13.5 Compound 20
Synthesis Example 55 5.3 2.67 1000 34.8 20.9 10.7 8.8 Comparative example 5.7 2.73 1000 36.4 23.0 9.9 35.9

As shown in Tables 2 and 3, the hole transport compound according to an embodiment of the present invention has a HOMO energy level that is easier to inject holes than BPBPA materials, which are commonly commercialized materials, and has a high LUMO energy level that can block electrons. With excellent hole transport characteristics, it can be confirmed that when applied to the hole transport layer of the organic light emitting device has a high energy efficiency, high Tg stability and long life.

As described above, the best embodiment has been disclosed in the drawings and the specification. The present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the spirit of the present invention, and the true technical protection of the present invention. The scope should be defined by the spirit of the appended claims.

10: Substrate
20: anode electrode
30: hole injection layer
40: hole transport layer
50: light emitting layer
60: electron transport layer
70: electron injection layer
80: cathode electrode

Claims (9)

A hole transport compound, characterized in that represented by any one of the following formula:

In an organic light emitting device comprising a hole transport layer between a pair of electrodes,
The organic light emitting device, characterized in that the hole transport layer comprises a hole transport compound according to claim 1.
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