KR20240063766A - Novel organic compounds and an organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention provides an organic compound represented by the following formula (1) and an organic electroluminescent device containing the same:
[Formula 1]

Description

Novel organic compounds and an organic electroluminescent device comprising the same}

The present invention relates to the field of displays, and more specifically, to organic compounds that can be used in the manufacture of organic electroluminescent devices, which are a type of display, and organic electroluminescent devices containing the same.

Liquid crystal displays account for most of the flat displays to date, but efforts are being made around the world to develop new flat displays that are more economical, have better performance, and are differentiated from liquid crystal displays. Organic electroluminescent devices, which have recently been in the spotlight as next-generation flat displays, have advantages such as low driving voltage, fast response speed, and wide viewing angle compared to liquid crystal displays.

The structure of an organic electroluminescent device consists of a substrate, an anode, a hole injection layer that accepts holes from the anode, a hole transport layer that transports holes, an electron blocking layer that blocks electrons from entering the hole transport layer from the light emitting layer, and holes and electrons combine to produce light. It consists of a light emitting layer that emits light, a hole blocking layer that blocks the entry of holes from the light emitting layer to the electron transport layer, an electron transport layer that accepts electrons from the cathode and transports them to the light emitting layer, an electron injection layer that accepts electrons from the cathode, and a cathode. In some cases, a light-emitting layer may be formed by doping a small amount of fluorescent or phosphorescent dye into the electron transport layer or hole transport layer without a separate light-emitting layer. When polymers are used, one polymer generally serves as the hole transport layer, light-emitting layer, and electron transport layer. can be performed simultaneously. The organic thin film layers between the two electrodes are formed by methods such as vacuum deposition, spin coating, inkjet printing, or laser thermal transfer. The reason why organic electroluminescent devices are manufactured with a multi-layer thin film structure is to stabilize the interface between the electrode and the organic material. Also, in the case of organic materials, the difference in movement speed between holes and electrons is large, so an appropriate hole transport layer and electron transport layer are used to This is because luminous efficiency can be increased by effectively transferring excess electrons to the light emitting layer and balancing the densities of holes and electrons.

The driving principle of the organic electroluminescent device 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 injection layer and the hole transport layer. Meanwhile, electrons are injected into the light-emitting layer from the cathode via the electron injection layer and the electron transport layer, and carriers recombine in the light-emitting layer area to generate excitons. This exciton changes from the excited state to the ground state, and as a result, the fluorescent molecules in the light-emitting layer emit light, forming an image. At this time, light emission as the excited state falls to the ground state through a singlet excitation state is called “fluorescence,” and light emission as the excited state falls to the ground state through a triplet excitation state is called “phosphorescence.” In the case of fluorescence, the probability of a singlet excited state is 25% (75% of a triplet state), and there is a limit to the luminous efficiency, whereas when using phosphorescence, up to 75% of the triplet state and 25% of the singlet excited state can be used for luminescence. Therefore, theoretically, internal quantum efficiency of up to 100% is possible.

The biggest problems with these organic electroluminescent devices are lifespan and efficiency, but as displays become larger in area, these efficiency and lifespan issues must be resolved.

In particular, in the case of blue, materials such as ADN and DPVBi are used as host materials, and aromatic amine compounds, copper phthalocyanine compounds, carbazole derivatives, perylene derivatives, and coumarin are used as dopants. Although materials such as coumarine-based derivatives and pyrene-based derivatives are used, there is a problem in that it is difficult to obtain deep blue and the luminescence lifetime becomes shorter as the wavelength increases.

Therefore, in order to implement a natural full color display, the development of deep blue materials with a long lifespan and other organic materials with energy levels matching these blue materials are required.

Republic of Korea Patent No. 10-0846221

The present invention was devised to solve the above problems of the prior art,

The purpose is to provide a novel organic compound that can be used as a blue dopant material to improve the luminous efficiency and luminous lifetime of organic electroluminescent devices.

Additionally, the present invention aims to provide an organic electroluminescent device with improved driving voltage, luminous efficiency, and luminous lifetime by including the blue dopant material as described above.

In addition, the purpose of the present invention is to provide an organic electroluminescent device with further improved driving voltage, device efficiency, and lifespan by including the blue dopant material and a specific hole transport layer material in combination.

The present invention provides an organic compound represented by the following formula (1):

[Formula 1]

In the above equation

Ar1, Ar2, Ar3 and Ar4 are each independently selected from deuterium, CN, straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl , biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, It is an aromatic hydrocarbon group having 6 to 60 carbon atoms that is substituted or unsubstituted with one or more selected from the group consisting of pyrazinyl, pyrimidinyl, and quinolinyl groups, or

Deuterium, CN, straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, phenyl group. Substituted anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group , and a quinolinyl group. It is a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms, which is substituted or unsubstituted with one or more elements selected from the group consisting of S, O, N, and Si,

B1 and B2 are each independently selected from straight-chain or branched alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthra Cenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and It is an aromatic hydrocarbon group having 6 to 60 carbon atoms that is substituted or unsubstituted with one or more selected from the group consisting of quinolinyl groups,

n and m are each independently 0 and 1,

R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen, deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , and have 1 to 40 carbon atoms. straight-chain or branched-chain alkyl, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, or cycloalkyl group with 3 to 40 carbon atoms,

F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, carbon number 3 to 40 cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, It is an aromatic hydrocarbon group having 6 to 60 carbon atoms that is substituted or unsubstituted with one or more selected from the group consisting of pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group, or

F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, carbon number 3 to 40 cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[fluorene], carbazolyl, Substituted or unsubstituted with one or more selected from the group consisting of dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group, and from the group consisting of S, O, N, and Si It is a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more selected elements, or

F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, and Phenyl, biphenyl, naphthyl, anthracenyl, substituted or unsubstituted with one or more types selected from the group consisting of cycloalkyl groups having 3 to 40 carbon atoms, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9 -It is an amino group substituted with one or more types selected from the group consisting of dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups.

In addition, the present invention relates to an organic electroluminescent device in which an organic thin film layer consisting of one or multiple layers including at least a light-emitting layer is laminated between a cathode and an anode,

An organic electroluminescent device is provided, wherein the light-emitting layer contains the organic compound of the present invention alone or in combination of two or more types.

In the organic electroluminescent device, the organic thin film layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer,

The hole transport layer may contain one type of organic compound of the following formula (2) alone or in a combination of two or more types:

[Formula 2]

In the above equation,

R1, R2, R3 and R4 are each independently hydrogen; A straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms; Aromatic hydrocarbon having 6 to 60 carbon atoms substituted or unsubstituted with one or more selected from the group consisting of C1 to C10 straight or branched alkyl, C1 to C10 alkoxy, halogen, CN, CF ₃ and Si(CH ₃ ) ₃ group energy; or substituted or unsubstituted with one or more selected from the group consisting of C1~C10 straight or branched alkyl, C1~C10 alkoxy, halogen, CN, CF ₃ and Si(CH ₃ ) ₃ groups, S, O, N and a heteroaromatic hydrocarbon group having 5 to 60 carbon atoms containing at least one element selected from the group consisting of Si;

R1, R2, R3, and R4 may each independently combine with the phenyl group of the basic structure to form an aromatic hydrocarbon or heteroaromatic hydrocarbon.

The present invention provides a novel organic compound that is used as a blue dopant material to improve the luminous efficiency and luminous lifetime of organic electroluminescent devices.

In addition, the present invention provides an organic electroluminescent device with improved driving voltage, luminous efficiency, and luminous lifetime by including the blue dopant material as described above.

In addition, the present invention provides an organic electroluminescent device with further improved driving voltage, device efficiency, and lifespan by including the blue dopant material and a specific hole transport layer material in combination.

The present invention relates to a novel organic compound represented by the following formula (1):

[Formula 1]

In the above equation

Ar1, Ar2, Ar3 and Ar4 are each independently selected from deuterium, CN, straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl , biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, It is an aromatic hydrocarbon group having 6 to 60 carbon atoms that is substituted or unsubstituted with one or more selected from the group consisting of pyrazinyl, pyrimidinyl, and quinolinyl groups, or

Deuterium, CN, straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, phenyl group. Substituted anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group , and a quinolinyl group. It is a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms, which is substituted or unsubstituted with one or more elements selected from the group consisting of S, O, N, and Si,

B1 and B2 are each independently selected from straight-chain or branched alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthra Cenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and It is an aromatic hydrocarbon group having 6 to 60 carbon atoms that is substituted or unsubstituted with one or more selected from the group consisting of quinolinyl groups,

n and m are each independently 0 and 1,

R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen, deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , and have 1 to 40 carbon atoms. straight-chain or branched-chain alkyl, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, or cycloalkyl group with 3 to 40 carbon atoms,

F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, carbon number 3 to 40 cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, It is an aromatic hydrocarbon group having 6 to 60 carbon atoms that is substituted or unsubstituted with one or more selected from the group consisting of pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group, or

F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, carbon number 3 to 40 cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[fluorene], carbazolyl, Substituted or unsubstituted with one or more selected from the group consisting of dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group, and from the group consisting of S, O, N, and Si It is a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more selected elements, or

F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, and Phenyl, biphenyl, naphthyl, anthracenyl, substituted or unsubstituted with one or more types selected from the group consisting of cycloalkyl groups having 3 to 40 carbon atoms, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9 -It is an amino group substituted with one or more types selected from the group consisting of dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups.

Specific examples of the organic compounds include any one of the following compounds 1 to 156.

The organic compound can be used as a blue dopant material.

The present invention also,

In an organic electroluminescent device in which an organic thin film layer consisting of one or multiple layers including at least a light-emitting layer is laminated between the cathode and the anode,

It relates to an organic electroluminescent device, wherein the light-emitting layer contains the organic compound alone or in combination of two or more kinds.

The organic thin film layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer,

The hole transport layer may contain one type of organic compound of the following formula (2) alone or in a combination of two or more types:

[Formula 2]

In the above equation,

R1, R2, R3 and R4 are each independently hydrogen; A straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms; Aromatic hydrocarbon having 6 to 60 carbon atoms substituted or unsubstituted with one or more selected from the group consisting of C1 to C10 straight or branched alkyl, C1 to C10 alkoxy, halogen, CN, CF ₃ and Si(CH ₃ ) ₃ group energy; or substituted or unsubstituted with one or more selected from the group consisting of C1~C10 straight or branched alkyl, C1~C10 alkoxy, halogen, CN, CF ₃ and Si(CH ₃ ) ₃ groups, S, O, N and a heteroaromatic hydrocarbon group having 5 to 60 carbon atoms containing at least one element selected from the group consisting of Si;

R1, R2, R3, and R4 may each independently combine with the phenyl group of the backbone to form an aromatic hydrocarbon or heteroaromatic hydrocarbon.

More preferably in the above formula,

R1, R2, R3 and R4 may each independently be a phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl carbazole or pyrenyl group,

R1, R2, R3, and R4 may each independently combine with a phenyl group in the basic structure to form naphthalene, anthracene, or phenanthrene.

Specific examples of the organic compounds include any one of the following compounds 157 to 168.

Below, the organic electroluminescent device of the present invention will be described as an example. However, the contents illustrated below do not limit the organic electroluminescent device of the present invention.

In the method of manufacturing an organic electroluminescent device according to the present invention, an anode is first formed by coating the surface of a substrate with an anode material in a conventional manner. At this time, the substrate used is preferably a glass substrate or a transparent plastic substrate with excellent transparency, surface smoothness, ease of handling, and waterproofness. In addition, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, can be used as materials for the anode.

Next, a hole injection layer (HIL) material is vacuum thermally deposited or spin coated on the surface of the anode using a conventional method to form a hole injection layer. Such hole injection layer materials include copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris(3-methylphenyl) Amino)phenoxybenzene (m-MTDAPB), starburst type amines 4,4',4"-tri(N-carbazolyl)triphenylamine (TCTA), 4,4',4"-tris Examples include (N-(2-naphthyl)-N-phenylamino)-triphenylamine (2-TNATA) or IDE406 available from Idemitsu.

A hole transport layer (HTL) material is vacuum thermally deposited or spin coated on the surface of the hole injection layer using a conventional method to form a hole transport layer. At this time, the hole transport layer materials include bis(N-(1-naphthyl-n-phenyl))benzidine (α-NPD), N,N'-di(naphthalen-1-yl)-N,N'-biphenyl -Benzidine (NPB) or N,N'-biphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), More preferably, the compound of formula 2 of the present invention can be used.

An emitting layer (EML) material is formed on the surface of the hole transport layer by vacuum thermal evaporation or spin coating using a conventional method. At this time, examples of the light-emitting materials used include phosphorescent fluorescent materials, fluorescent whitening agents, laser dyes, organic scintillator, and reagents for fluorescence analysis. Specifically, carbazole-based compounds, phosphine oxide-based compounds, carbazole-based phosphine oxide compounds, bis ((3,5-difluoro-4-cyanophenyl) pyridine) iridium picolinate (FCNIrpic), tris ( 8-hydroxyquinoline) aluminum (Alq3), polyaromatic compounds such as anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene and quinacridone, oligophenylene compounds such as quiterphenyl, 1, 4-bis (2-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, 1,4-bis (4-methyl-5-phenyl-2-oxazolyl) benzene, 1,4 -bis(5-phenyl-2-oxazolyl)benzene, 2,5-bis(5-t-butyl-2-benzoxazolyl)thiophene, 1,4-diphenyl-1,3-butadiene, 1, Scintillator for liquid scintillation such as 6-diphenyl-1,3,5-hexatriene, 1,1,4,4-tetraphenyl-1,3-butadiene, metal complex of auxin derivative, coumarin pigment, dicyano Methylenepyran dye, dicyanomethylenethiopyran dye, polymethine dye, oxobenzanthracene dye, xanthene dye, carbostyryl dye, perylene dye, oxazine compound, stilbene derivative, spiro compound, oxadiazole compound, etc. can be mentioned. In particular, in the case of a blue organic electroluminescent device, it may be desirable to use the organic compound of Formula 1 of the present invention as a dopant.

Optionally, an electron blocking layer (EBL) may be additionally formed between the hole transport layer and the light emitting layer.

An electron transport layer (ETL) material is vacuum thermally deposited or spin coated on the surface of the light emitting layer using a conventional method to form an electron transport layer. At this time, the electron transport layer material used is not particularly limited, and tris(8-hydroxyquinolinolato)aluminum (Alq ₃ ) is preferably used.

Optionally, by additionally forming a hole blocking layer (HBL) between the light emitting layer and the electron transport layer and using a phosphorescent dopant in the light emitting layer, diffusion of triplet excitons or holes into the electron transport layer can be prevented.

The formation of the hole blocking layer can be performed by vacuum thermal evaporation and spin coating of the hole blocking material by conventional methods. The hole blocking material is not particularly limited, but is preferably (8-hydroxyquinolinola). To) Lithium (Liq), bis(8-hydroxy-2-methylquinolinolnato)-aluminum biphenoxide (BAlq), bathocuproine (BCP), and LiF can be used.

An electron injection layer (EIL) material is vacuum thermally deposited or spin coated on the surface of the electron transport layer using a conventional method to form an electron injection layer. At this time, materials such as LiF, Liq, Li ₂ O, BaO, NaCl, and CsF may be used as the electron injection layer material.

A cathode is formed by vacuum heat deposition of a cathode material on the surface of the electron injection layer using a conventional method.

At this time, the cathode materials used are lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), and magnesium-silver. (Mg-Ag) etc. may be used. Additionally, in the case of a top-emitting organic electroluminescent device, indium tin oxide (ITO) or indium zinc oxide (IZO) can be used to form a transparent cathode through which light can transmit.

A capping layer (CPL) may be formed on the surface of the cathode using the composition for forming a capping layer of the present invention.

The organic electroluminescent device according to the present invention may be manufactured in the order described above, that is, anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode, and vice versa, cathode/electron injection layer/cathode. It may be manufactured in the following order: electron transport layer/light emitting layer/hole transport layer/hole injection layer/anode.

Next, the synthesis method of the compounds of Formula 1 and Formula 2 will be described using representative examples. However, the method of synthesizing the compounds of the present invention is not limited to the methods exemplified below, and the compounds of the present invention can be prepared by the methods exemplified below and methods known in the field.

<Synthesis of compound of formula 1>

<Synthesis of Intermediate-1>

100g (480mmol) of 1,2,3,6,7,8-hexahydropyrene was dissolved in 1L of MC, and then 48ml of Bromine was dissolved in 200ml of MC and slowly added. After 30 minutes, the resulting solid was washed with Ethanol, filtered, and dried to obtain 60g of Intermediate-1 (33% yield).

Intermediate-1 MS (FAB): 366 (M ⁺ )

<Synthesis of Intermediate-2>

60g (163.9mmol) of Intermediate-1 was dissolved in 2L of Toluene, then 120mg of DDQ was added and refluxed for 4 hours. After completion of the reaction, toluene was distilled and columnarized to obtain 23g of Intermediate-2 (39% yield).

Intermediate-2 MS (FAB): 360 (M ⁺ )

<Synthesis of Intermediate-3>

23 g (63.88 mmol) of Intermediate-2 was dissolved in 100 ml of THF and maintained at -78 degrees in an Acetone/dryice bath. 56ml (140mmol) of 2.5M n-BuLi was slowly dropped and stirred for 30 minutes. After adding 22.7 g (160 mmol) of iodomethane, the temperature was gradually raised to room temperature. The organic layer was extracted by adding 300ml of EA and 300ml of H ₂ O and then distilled. By column, 9.4g (64% yield) of intermediate-3 was obtained.

Intermediate-3 MS (FAB): 230 (M ⁺ )

<Synthesis of Intermediate-4>

After dissolving 9.4 g (40.8 mmol) of Intermediate-3 in 100 ml of MC, 14.35 g (89.8 mmol) of Bromine was slowly added. After 6 hours, completion of the reaction was confirmed, MC was distilled, and column was used. 3.6g (23% yield) of intermediate-4 was obtained.

Intermediate-4 MS(FAB): 388(M ⁺ )

<Synthesis of Intermediate-5>

100 g (277.7 mmol) of Intermediate-2 and 74.5 g (611.0 mmol) of phenylboronic acid were dissolved in 600 ml of Toluene and 60 ml of Ethanol. 611 ml of 2M K ₂ CO ₃ and 16.04 g (13.9 mmol) of Pd(PPh ₃ ) ₄ were added and refluxed for 12 hours. After completion of the reaction, the toluene layer was extracted and silica filtered. Recrystallized with n-hexane/MC to obtain 64g (65% yield) of Intermediate-5.

Intermediate-5 MS(FAB): 354(M ⁺ )

<Synthesis of Intermediate-6>

After dissolving 64g (180.57mmol) of Intermediate-5 in 1000ml of MC, 63.5g (397.25mmol) of Bromine was slowly added. After 6 hours, completion of the reaction was confirmed, MC was distilled, and column was used. Intermediate-6 66.6g (72% yield) was obtained.

Intermediate-6 MS(FAB): 512(M ⁺ )

<Synthesis of Intermediate-7>

After dissolving 100 g (494.4 mmol) of pyrene in 1000 ml of MC, 158 g (988.8 mmol) of bromine was slowly added. After 6 hours, completion of the reaction was confirmed, MC was distilled, and column was used. 71.2g (40% yield) of intermediate-7 was obtained.

Intermediate-7 MS(FAB): 360(M ⁺ )

<Synthesis of Intermediate-8>

After dissolving 100 g (434.2 mmol) of Intermediate-3 in 1000 ml of MC, 138.8 g (868.4 mmol) of Bromine was slowly added. After 6 hours, completion of the reaction was confirmed, MC was distilled, and column was used. 27.0g (16% yield) of Intermediate-8 was obtained.

Intermediate-8 MS(FAB): 388(M ⁺ )

<Synthesis of Intermediate-9>

27 g (69.6 mmol) of Intermediate-8 was dissolved in 100 ml of THF and maintained at -78 degrees in an Acetone/dryice bath. 61ml (153.1mmol) of 2.5M n-BuLi was slowly dropped and stirred for 30 minutes. After adding 22.7 g (160 mmol) of iodomethane, the temperature was gradually raised to room temperature. The organic layer was extracted by adding 300ml of EA and 300ml of H ₂ O and then distilled. By column, 9.7g (54% yield) of intermediate-9 was obtained.

Intermediate-9 MS(FAB): 258(M ⁺ )

<Synthesis of Intermediate-10>

After dissolving 9.7g (37.5mmol) of Intermediate-9 in 1000ml of MC, 12.6g (78.8mmol) of Bromine was slowly added. After 6 hours, completion of the reaction was confirmed, MC was distilled, and column was used. 14.7g (94% yield) of intermediate-10 was obtained.

Intermediate-10 MS(FAB): 416(M ⁺ )

<Synthesis of Intermediate-11>

100 g (277.8 mmol) of Intermediate-2 was dissolved in 1000 ml of THF and maintained at -78 degrees in an Acetone/dryice bath. 122ml (305.6mmol) of 2.5M n-BuLi was slowly dropped and stirred for 30 minutes. After adding 47.3g (333.4mmol) of iodomethane, the temperature was slowly raised to room temperature. After THF distillation, 1000 ml of EA and 100 ml of H ₂ O were added to extract the organic layer and then distilled. By column, 55.7g (68% yield) of intermediate-11 was obtained.

Intermediate-11 MS(FAB): 295(M ⁺ )

<Synthesis of Intermediate-12>

55.7 g (188.9 mmol) of Intermediate-11 was dissolved in 500 ml of THF, and then 2.58 g (3.8 mmol) of NiCl ₂ dppf was added. 190ml of Cyclohexylmagnesium chloride (1M) was slowly added at room temperature. The mixture was stirred at room temperature for 6 hours, and after completion of the reaction, 500 ml of H2O was slowly added to quench. THF was distilled and extracted by adding 500 ml of MC. By column, 25.9g (46% yield) of intermediate-12 was obtained.

Intermediate-12 MS(FAB): 298(M ⁺ )

<Synthesis of Intermediate-13>

After dissolving 25.9 g (86.9 mmol) of Intermediate-12 in 500 ml of MC, 30.6 g (191.2 mmol) of Bromine was slowly added. After 6 hours, completion of the reaction was confirmed, MC was distilled, and column was used. 10.3g (26% yield) of intermediate-13 was obtained.

Intermediate-13 MS(FAB): 456(M ⁺ )

<Synthesis of Intermediate-14>

100 g (404.7 mmol) of 4-bromodibenzofuran and 54.7 g (404.7 mmol) of 4-isopropylaniline were dissolved in 500 ml of toluene, and then 58.3 g (607.1 mmol) of sodium tert-butoxide was added. Palladium acetate 1.82g (8.1mmol) and tri-tert-butylphosphine (50% in toluene) 6.55g (16.2mmol) were added and refluxed for 3 hours. After completion of the reaction, it was cooled to room temperature, 500 ml of water was added, and the organic layer was extracted. Recrystallized with N-hexane/MC to obtain 122g (63% yield) of Intermediate-14.

Intermediate-14 MS(FAB): 301(M ⁺ )

<Synthesis of Intermediate-15>

100g (739.6mmol) of 4-isopropylaniline was dissolved in 1L of DMF and maintained at -20 degrees using an ice salt bath. NCS 98.8g (739.6mmol) was slowly added and the temperature was gradually raised to room temperature. After completion of the reaction, 2L of EA and 2L of water were added to extract the EA layer and then distilled. By column, 41.4g (33% yield) of intermediate-15 was obtained.

Intermediate-15 MS(FAB): 169(M ⁺ )

<Synthesis of Intermediate-16>

60.3 g (244 mmol) of 4-bromodibenzofuran and 41.4 g (244 mmol) of intermediate-15 were dissolved in 600 ml of toluene, and then 117.2 g (1220 mmol) of sodium tert-butoxide was added. Palladium acetate 1.64g (7.32mmol) and t-Bu ₃ PHBF ₄ 2.12g (7.32mmol) were added and refluxed for 6 hours. After completion of the reaction, it was cooled to room temperature and the organic layer was extracted by adding 1L of EA and 1L of water. After column recrystallization with n-hexane/MC, 59g (72% yield) of Intermediate-16 was obtained.

Intermediate-16 MS(FAB): 335(M ⁺ )

<Synthesis of Intermediate-17>

59 g (175.7 mmol) of Intermediate-16 was dissolved in 600 ml of DMA, and then 33.8 g (351.4 mmol) of sodium tert-butoxide was added. Palladium acetate 1.18g (5.27mmol) and t-Bu ₃ PHBF ₄ 1.53g (5.27mmol) were added and refluxed for 6 hours. After completion of the reaction, it was cooled to room temperature, 500 ml of EA and 1 L of water were added, and the EA layer was extracted. After column recrystallization with n-hexane/MC, 30.5 g (58% yield) of Intermediate-17 was obtained.

Intermediate-17 MS(FAB): 299(M ⁺ )

<Synthesis of Intermediate-18>

100g (306.8mmol) of 4,6-dibromodibenzofuran was added to a 2L high pressure reactor, and then 1200ml of PEG 300 and 400ml of ammonium hydroxide (30% aq) were added. After adding 584 mg (3.07 mmol) of copper(I) iodide, reaction was performed at 130 degrees for 24 hours. After completion of the reaction, it was cooled to room temperature and the organic layer was extracted by adding 500 ml of EA and 500 ml of water. After silica filter, 57.8g (95% yield) of intermediate-18 was obtained by recrystallization with n-hexane/MC.

Intermediate-18 MS(FAB): 198(M ⁺ )

<Synthesis of Intermediate-19>

57.8 g (291.6 mmol) of Intermediate-18 was dissolved in 600 ml of DMF and maintained at -20 degrees using an ice-salt bath. 103.8 g (583.2 mmol) of NBS was slowly added and the temperature was gradually raised to room temperature. After completion of the reaction, 1L of EA and 1L of water were added, and the organic layer was extracted. After column recrystallization with n-hexane/MC, 84.1g (81% yield) of intermediate-19 was obtained.

Intermediate-19 MS(FAB): 356(M ⁺ )

<Synthesis of Intermediate-20>

84.1 g (236.2 mmol) of Intermediate-19 was added to 1 L of Ethanol, and then 100 ml of H ₂ SO ₄ was slowly added. 48.9 g (708.6 mmol) of NaNO ₂ was slowly added. After refluxing for 2 hours, completion of the reaction was confirmed and cooled to room temperature. After adding 1L of EA and 2L of water, the organic layer was extracted. By column with N-hexane, 24.6g (32% yield) of intermediate-20 was obtained.

Intermediate-20 MS(FAB): 325(M ⁺ )

<Synthesis of Intermediate-21>

24.6 g (75.6 mmol) of 1,9-dibromodibenzofuran and 10.2 g (75.6 mmol) of 4-isopropylaniline were dissolved in 300 ml of toluene, and then 36.3 g (378 mmol) of sodium tert-butoxide was added. Palladium acetate 510mg (2.27mmol) and t-Bu3PHBF4 660mg (2.27mmol) were added and refluxed for 3 hours. After completion of the reaction, it was cooled to room temperature and the organic layer was extracted by adding 1L of EA and 1L of water. After column recrystallization with n-hexane/MC, 16.1g (56% yield) of Intermediate-21 was obtained.

Intermediate-21 MS(FAB): 380(M ⁺ )

<Synthesis of Intermediate-22>

16.1 g (42.3 mmol) of Intermediate-21 was dissolved in 300 ml of DMA, and then 8.1 g (84.6 mmol) of sodium tert-butoxide was added. Palladium acetate 285mg (1.27mmol) and t-Bu3PHBF4 370mg (1.27mmol) were added and refluxed for 6 hours. After completion of the reaction, it was cooled to room temperature, 300 ml of EA and 500 ml of water were added, and the EA layer was extracted. After column recrystallization with n-hexane/MC, 5.45 g (43% yield) of Intermediate-22 was obtained.

Intermediate-22 MS(FAB): 299(M ⁺ )

<Synthesis of Intermediate-23>

100 g (404.7 mmol) of 3-bromodibenzofuran and 74 g (607.1 mmol) of phenylboronic acid were dissolved in 600 ml of Toluene and 60 ml of Ethanol. 607ml of 2M K ₂ CO ₃ and 23.4 g (20.2 mmol) of Pd(PPh ₃ ) ₄ were added and refluxed for 12 hours. After completion of the reaction, the toluene layer was extracted and silica filtered. Recrystallized with n-hexane/MC to obtain 83g (84% yield) of Intermediate-23.

Intermediate-23 MS(FAB): 244(M ⁺ )

<Synthesis of Intermediate-24>

83 g (340 mmol) of Intermediate-23 was dissolved in 500 ml of THF and maintained at -78 degrees using an acetone/dryice bath.

After slowly adding 150ml (374mmol) of 2.5M n-BuLi, the bath was removed and the temperature was raised to room temperature. After 1 hour, the temperature was maintained at -78 degrees using an acetone/dryice bath, and 38.9 g (374 mmol) of trimethylborate was added. After removing the bath, the reaction was terminated by raising the temperature to room temperature. 1L of EA and 1L of water were added to extract the organic layer, then distilled and columned to obtain 38.2g (39% yield) of Intermediate-24.

Intermediate-24 MS(FAB): 288(M ⁺ )

<Synthesis of Intermediate-25>

After dissolving 100 g (739.6 mmol) of 4-isopropylaniline in 1 L of DMF, 131.6 g (739.6 mmol) of NBS was slowly added at 0 degrees. After removing the bath, the temperature was raised to room temperature to complete the reaction, and 2L of EA and 2L of water were added. The organic layer was extracted, distilled, and columned to obtain 139.4 g (88% yield) of Intermediate-25.

Intermediate-25 MS(FAB): 214(M ⁺ )

<Synthesis of Intermediate-26>

After dissolving 38.2 g (132.6 mmol) of Intermediate-24 and 28.4 g (132.6 mmol) of Intermediate-25 in 300 ml of MC, 482 mg (2.65 mmol) of Cupper acetate was added and reacted for 24 hours while blowing air. After completion of the reaction, 52g (86% yield) of Intermediate-26 was obtained by column.

Intermediate-26 MS(FAB): 456(M ⁺ )

<Synthesis of Intermediate-27>

52 g (114 mmol) of Intermediate-26 was dissolved in 500 ml of DMA, and then 21.9 g (228 mmol) of sodium tert-butoxide was added. Palladium acetate 768mg (3.42mmol) and t-Bu ₃ PHBF ₄ 992mg (3.42mmol) were added and refluxed for 6 hours. After completion of the reaction, it was cooled to room temperature, 1000 ml of EA and 1000 ml of water were added, and the EA layer was extracted. After column recrystallization with n-hexane/MC, 22.3g (52% yield) of Intermediate-27 was obtained.

Intermediate-27 MS(FAB): 375(M ⁺ )

<Synthesis of Intermediate-28>

100 g (306.8 mmol) of 1,9-dibromodibenzofuran and 233.7 g (920.3 mmol) of B2pin2 were dissolved in 1 L of 1,4-dioxane, and then 150.5 g (1534 mmol) of potassium acetate was added. After adding 6.89g (30.68mmol) of palladium acetate and 17g (30.68mmol) of dppf, it was refluxed for 12 hours. After completion of the reaction, the solvent was distilled and column was used to obtain 56.7 g (44% yield) of Intermediate-28.

Intermediate-28 MS(FAB): 420(M ⁺ )

<Synthesis of Intermediate-29>

After dissolving 100 g (739.6 mmol) of 4-isopropylaniline in 1 L of DMF, 166.4 g (739.6 mmol) of NIS was slowly added at 0 degrees. After removing the bath, the temperature was raised to room temperature to complete the reaction, and 2L of EA and 2L of water were added. The organic layer was extracted, distilled, and columned to obtain 166.1 g (86% yield) of Intermediate-29.

Intermediate-29 MS(FAB): 261(M ⁺ )

<Synthesis of Intermediate-30>

100 g (383 mmol) of Intermediate-29 and 76.9 g (383 mmol) of (2-bromophenyl)boronic acid were dissolved in 600 ml of Toluene and 60 ml of Ethanol. 383ml of 2M K2CO3 and 22.1g (19.15mmol) of Pd( _PPh3 ) ₄ were added and refluxed for 12 hours. After completion of the reaction, the toluene layer was extracted and silica filtered. Recrystallized with n-hexane/MC to obtain 84.5g (76% yield) of Intermediate-30.

Intermediate-30 MS(FAB): 290(M ⁺ )

<Synthesis of Intermediate-31>

56.7 g (135 mmol) of Intermediate-28 and 39.2 g (135 mmol) of Intermediate-30 were dissolved in 500 ml of Toluene and 50 ml of Ethanol. 135 ml of 2M K2CO3 and 7.8 g (6.75 mmol) of Pd(PPh ₃ ) ₄ were added and refluxed for 12 hours. After completion of the reaction, the toluene layer was extracted and columnarized to obtain 24.5g (36% yield) of Intermediate-31.

Intermediate-31 MS(FAB): 503(M ⁺ )

<Synthesis of Intermediate-32>

24.5 g (48.6 mmol) of Intermediate-31 was dissolved in 300 ml of MC, then 177 mg (0.97 mmol) of Cupper acetate was added, and the mixture was reacted for 24 hours while blowing air. After completion of the reaction, 15.3 g (84% yield) of Intermediate-32 was obtained by column.

Intermediate-32 MS(FAB): 375(M ⁺ )

<Synthesis of Intermediate-33>

100 g (404.7 mmol) of 3-bromodibenzofuran was dissolved in 1000 ml of THF and maintained at -78 degrees using an acetone/dryice bath. 445ml (445mmol) of 1.0M LDA was slowly added and stirred for 1 hour. While maintaining -78 degrees, 147.6 g (445.2 mmol) of CBr ₄ was added. The bath was removed, the temperature was raised to room temperature, and the reaction was terminated by stirring for 1 hour. 1L of EA and 1L of water were added to extract the organic layer, then distilled and columned to obtain 83.1g (63% yield) of Intermediate-33.

Intermediate-33 MS(FAB): 325(M ⁺ )

<Synthesis of Intermediate-34>

83.1 g (255 mmol) of Intermediate-33 and 54.6 g (255 mmol) of Intermediate-25 were dissolved in 300 ml of NMP, and then 166.2 g (510 mmol) of Cesium carbonate was added. After stirring at 180 degrees for 3 hours to confirm the completion of the reaction, it was cooled to room temperature. The organic layer was extracted by adding 300ml of EA and 300ml of water. Column, 69.1g (59% yield) of intermediate-34 was obtained.

Intermediate-34 MS(FAB): 459(M ⁺ )

<Synthesis of Intermediate-35>

95.7g (306.8mmol) of 2,2'-dibromo-1,1'-biphenyl and 233.7g (920.3mmol) of B2pin2 were dissolved in 1L of 1,4-dioxane, and then 150.5g (1534mmol) of potassium acetate was added. After adding 6.89g (30.68mmol) of palladium acetate and 17g (30.68mmol) of dppf, it was refluxed for 12 hours. After completion of the reaction, the solvent was distilled and column was used to obtain 51.1 g (41% yield) of Intermediate-35.

Intermediate-35 MS(FAB): 406(M ⁺ )

<Synthesis of Intermediate-36>

69g (150.3mmol) of Intermediate-34 and 61g (150.3mmol) of Intermediate-35 were dissolved in 1000ml of Toluene and 100ml of Ethanol. 300ml of 2M K ₂ CO ₃ and 17.4 g (15.03 mmol) of Pd(PPh ₃ ) ₄ were added and refluxed for 12 hours. After completion of the reaction, the toluene layer was extracted and columnarized to obtain 23.8g (35% yield) of Intermediate-36.

Intermediate-36 MS(FAB): 451(M ⁺ )

<Synthesis of Intermediate-37>

20 g (51.5 mmol) of Intermediate-4 and 15.4 g (51.5 mmol) of Intermediate-22 were dissolved in 500 ml of toluene, and then 19.8 g (206.1 mmol) of sodium tert-butoxide was added. Palladium acetate 231mg (1.03 mmol) and Tri-tert-butylphosphine 417mg (2.06mmol) were added and refluxed for 12 hours. After completion of the reaction, it was cooled to room temperature, and 500 ml of water was added to extract the organic layer. After column recrystallization with n-hexane/MC, 13.4 g (43% yield) of Intermediate-37 was obtained.

Intermediate-37 MS(FAB): 606(M ⁺ )

<Synthesis of Intermediate-38>

Dissolve 200g (386.2mmol) of 1,3,6,8-tetrabromopyrene and 129.2g (772.5mmol) of carbazole in 500ml of nitrobenzene. Add 7.36g (115.9mmol) of copper powder and 160.1g (1158.7mmol) of potassium carbonate and reflux for 6 hours. After completion of the reaction, cool to room temperature and nitrobenzene is distilled. After washing with MC, celite filter, and column, 34.7 g (13% yield) of intermediate-38 was obtained.

Intermediate-38 MS(FAB): 690(M ⁺ )

<Synthesis of Compound-1>

20 g (43.8 mmol) of Intermediate-13 and 29.1 g (96.4 mmol) of Intermediate-14 were dissolved in 500 ml of toluene, and then 21 g (219 mmol) of sodium tert-butoxide was added. Palladium acetate 197mg (0.88mmol) and Tri-tert-butylphosphine 709mg (1.75mmol) were added and refluxed for 12 hours. After completion of the reaction, it was cooled to room temperature and 500 ml of water was added to extract the organic layer. After column recrystallization with n-hexane/MC, 21.9g (56% yield) of Compound-1 was obtained.

^1H NMR (DMSO, 300Hz): δ(ppm)=8.32-8.09(d, 1H), 8.03-7.91(d, 2H), 7.86-7.71(m, 2H), 7.68-7.47(m, 7H), 7.43-7.16(m, 10H), 7.13-6.87(m, 6H), 3.21-2.52(m, 6H), 1.94-1.51(m, 5H), 1.38-1.03(d, 17H)

MS(FAB): 896(M ⁺ )

<Synthesis of Compound-13>

20 g (51.5 mmol) of intermediate-4 and 32.4 g (108.2 mmol) of intermediate-17 were dissolved in 500 ml of toluene, and then 19.8 g (206.1 mmol) of sodium tert-butoxide was added. Palladium acetate 231mg (1.03 mmol) and Tri-tert-butylphosphine 417mg (2.06mmol) were added and refluxed for 12 hours. After completion of the reaction, it was cooled to room temperature and 500 ml of water was added to extract the organic layer. After column recrystallization with n-hexane/MC, 22.1g (52% yield) of Compound-13 was obtained.

¹ H NMR (DMSO, 300Hz): δ(ppm)= 9.12-8.87(s, 2H), 8.35-8.09(m, 2H), 8.03-7.92(m, 6H), 7.88-7.74(d, 2H), 7.68-7.46(m, 6H), 7.42-7.16(m, 4H), 7.13-6.92(m, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 824(M ⁺ )

<Synthesis of Compound-25>

20 g (51.5 mmol) of intermediate-4 and 32.4 g (108.2 mmol) of intermediate-22 were dissolved in 500 ml of toluene, and then 19.8 g (206.1 mmol) of sodium tert-butoxide was added. Palladium acetate 231mg (1.03 mmol) and Tri-tert-butylphosphine 417mg (2.06mmol) were added and refluxed for 12 hours. After completion of the reaction, it was cooled to room temperature and 500 ml of water was added to extract the organic layer. After column recrystallization with n-hexane/MC, 17.8g (42% yield) of Compound-25 was obtained.

¹ H NMR (DMSO, 300Hz): δ(ppm)=8.31-8.02(m, 4H), 7.98-7.87(d, 2H), 7.81-7.62(m, 6H), 7.58-7.45(m, 4H), 7.37-7.11(m, 6H), 7.13-6.92(d, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 825(M ⁺ )

<Synthesis of Compound-37>

20 g (51.5 mmol) of intermediate-4 and 40.6 g (108.2 mmol) of intermediate-27 were dissolved in 500 ml of toluene, and then 19.8 g (206.1 mmol) of sodium tert-butoxide was added. Palladium acetate 231mg (1.03 mmol) and Tri-tert-butylphosphine 417mg (2.06mmol) were added and refluxed for 12 hours. After completion of the reaction, it was cooled to room temperature and 500 ml of water was added to extract the organic layer. After column recrystallization with n-hexane/MC, 19.1g (38% yield) of Compound-37 was obtained.

^1H NMR (DMSO, 300Hz): δ(ppm)=8.25-7.88(m, 10H), 7.82-7.74(d, 2H), 7.71-7.63(d, 2H), 7.58-7.46(m, 10H), 7.42-7.21(m, 6H), 7.18-6.97(d, 2H), 3.21-2.51(m, 8H), 1.36-1.03(d, 12H)

MS(FAB): 977(M ⁺ )

<Synthesis of Compound-49>

20 g (51.5 mmol) of intermediate-4 and 48.9 g (108.2 mmol) of intermediate-36 were dissolved in 500 ml of toluene, and then 19.8 g (206.1 mmol) of sodium tert-butoxide was added. Palladium acetate 231mg (1.03 mmol) and Tri-tert-butylphosphine 417mg (2.06mmol) were added and refluxed for 12 hours. After completion of the reaction, it was cooled to room temperature and 500 ml of water was added to extract the organic layer. After column recrystallization with n-hexane/MC, 13.4g (23% yield) of Compound-49 was obtained.

NMR (DMSO, 300Hz): δ(ppm)= 8.21-7.93(m, 6H), 7.86-7.77(d, 2H), 7.73-7.65(d, 2H), 7.62-7.51(m, 6H), 7.38- 7.22(m, 22H), 7.18-6.96(d, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 1128(M ⁺ )

<Synthesis of Compound-61>

20 g (51.5 mmol) of intermediate-4 and 40.6 g (108.2 mmol) of intermediate-32 were dissolved in 500 ml of toluene, and then 19.8 g (206.1 mmol) of sodium tert-butoxide was added. Palladium acetate 231mg (1.03 mmol) and Tri-tert-butylphosphine 417mg (2.06mmol) were added and refluxed for 12 hours. After completion of the reaction, it was cooled to room temperature and 500 ml of water was added to extract the organic layer. After column recrystallization with n-hexane/MC, 29.1g (50% yield) of Compound-61 was obtained.

^1H NMR (DMSO, 300Hz): δ(ppm)=8.34-8.08(m, 4H), 8.04-7.91(d, 2H), 7.71-7.61(m, 6H), 7.58-7.44(m, 4H), 7.39-7.21(m, 14H), 7.05-6.92(d, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 976.40(M ⁺ )

<Synthesis of Compound-73>

20 g (39 mmol) of Intermediate-6 and 24.5 g (82 mmol) of Intermediate-17 were dissolved in 500 ml of toluene, and then 15 g (156.2 mmol) of sodium tert-butoxide was added. Palladium acetate 175mg (0.78 mmol) and Tri-tert-butylphosphine 316mg (1.56mmol) were added and refluxed for 12 hours. After completion of the reaction, it was cooled to room temperature and 500 ml of water was added to extract the organic layer. After column recrystallization with n-hexane/MC, 20.8g (56% yield) of Compound-73 was obtained.

¹ H NMR (DMSO, 300Hz): δ(ppm)= 9.11-8.89(s, 2H), 8.23-8.02(m, 4H), 7.98-7.88(m, 6H), 7.84-7.74(m, 6H), 7.58-7.26(m, 14H), 7.18-7.02(d, 2H), 3.05-2.72(m, 2H), 1.36-1.03(d, 12H)

MS(FAB): 948(M ⁺ )

<Synthesis of Compound-75>

13.4 g (22.1 mmol) of Intermediate-37 and 7.3 g (24.3 mmol) of Intermediate-14 were dissolved in 200 ml of toluene, and then 8.5 g (88.4 mmol) of sodium tert-butoxide was added. Palladium acetate 100mg (0.44 mmol) and Tri-tert-butylphosphine 179mg (0.88mmol) were added and refluxed for 12 hours. After completion of the reaction, it was cooled to room temperature and 500 ml of water was added to extract the organic layer. After column recrystallization with n-hexane/MC, 10.4g (57% yield) of Compound-75 was obtained.

^1H NMR (DMSO, 300Hz): δ(ppm)=8.24-7.95(m, 4H), 7.89-7.81(d, 1H), 7.75-7.48(m, 9H), 7.44-7.24(m, 6H), 7.22-7.13(d, 2H), 7.10-7.01(d, 2H), 6.98-6.91(m, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 826(M ⁺ )

<Synthesis of Compound-87>

15 g (21.7 mmol) of intermediate-38 and 14.3 g (47.8 mmol) of intermediate-17 were dissolved in 300 ml of toluene, and then 8.4 g (86.9 mmol) of sodium tert-butoxide was added. Palladium acetate 98mg (0.43mmol) and Tri-tert-butylphosphine 176mg (0.87mmol) were added and refluxed for 12 hours. After completion of the reaction, it was cooled to room temperature and 500 ml of water was added to extract the organic layer. After column recrystallization with n-hexane/MC, 6.1g (25% yield) of Compound-87 was obtained.

¹ H NMR (DMSO, 300Hz): δ(ppm)= 9.12-8.88(s, 2H), 8.62-8.51(d, 2H), 8.31-8.12(d, 2H), 8.09-7.81(m, 10H), 7.78-7.68(s, 4H), 7.62-7.44(m, 8H), 7.42-7.28(m, 6H), 7.26-7.02(m, 6H), 3.05-2.72(m, 2H), 1.37-1.03(d) , 12H)

MS(FAB): 1126(M ⁺ )

<Synthesis of Compound-100>

15 g (21.7 mmol) of intermediate-38 and 14.4 g (47.8 mmol) of intermediate-14 were dissolved in 300 ml of toluene, and then 8.4 g (86.9 mmol) of sodium tert-butoxide was added. Palladium acetate 98mg (0.43mmol) and Tri-tert-butylphosphine 176mg (0.87mmol) were added and refluxed for 12 hours. After completion of the reaction, it was cooled to room temperature and 500 ml of water was added to extract the organic layer. After column recrystallization with n-hexane/MC, 8.8g (36% yield) of Compound-100 was obtained.

¹ H NMR (DMSO, 300Hz): δ(ppm)=8.61-8.51(d, 2H), 8.27-8.12(d, 2H), 8.08-7.91(m, 4H), 7.82-7.54(m, 14H), 7.48-7.12(m, 16H), 7.10-7.01(m, 4H), 6.98-6.88(d, 2H), 3.05-2.72(m, 2H), 1.37-1.03(d, 12H)

MS(FAB): 1130(M ⁺ )

<Synthesis of Compound-123>

20 g (48.1 mmol) of Intermediate-10 and 30.2 g (100.9 mmol) of Intermediate-17 were dissolved in 500 ml of toluene, and then 18.5 g (192.2 mmol) of sodium tert-butoxide was added. Palladium acetate 216mg (0.96mmol) and Tri-tert-butylphosphine 389mg (1.92mmol) were added and refluxed for 12 hours. After completion of the reaction, it was cooled to room temperature and 500 ml of water was added to extract the organic layer. After column recrystallization with n-hexane/MC, 21.7g (53% yield) of Compound-123 was obtained.

¹ H NMR (DMSO, 300Hz): δ(ppm)= 9.13-8.89(s, 2H), 8.05-7.95(m, 4H), 7.91-7.78(m, 4H), 7.62-7.46(m, 6H), 7.42-7.27(m, 4H), 7.16-7.04(d, 2H), 3.21-2.52(m, 14H), 1.37-1.03(d, 12H)

MS(FAB): 852(M ⁺ )

<Synthesis of compound of formula 2>

<Synthesis of Intermediate-39>

Under nitrogen, 1.69 g (10 mmol) of [1,1'-biphenyl]-4-amine and 3.56 g (10 mmol) of 4-iodo-1,1':4',1''-terphenyl were injected and 50 ml of toluene was added. After dissolving in , 0.18 g (0.2 mmol) of Pd ₂ dba ₃ , 0.4 ml (0.4 mmol) of 1M t-Bu ₃ P, and 2.88 g (30 mmol) of t-BuONa were added, respectively, and then refluxed for 8 hours.

When the reaction is completed, the temperature of the reactant is cooled to room temperature, extracted using 200 ml of toluene and 200 ml of H ₂ O, a small amount of water in the organic layer is removed with anhydrous MgSO ₄ , and after filtration under reduced pressure, the organic solvent is concentrated, and the resulting compound is Hex. : EA = 4: 1 column was used to obtain 3.02 g (76%) of intermediate-39.

Intermediate-39 MS(FAB): 397(M ⁺ )

<Synthesis of Intermediate-40>

Inject 3.21 g (10 mmol) of di([1,1'-biphenyl]-4-yl)amine and 3.59 g (10 mmol) of 4-bromo-4'-iodo-1,1'-biphenyl under nitrogen. After dissolving in 60ml of toluene, 0.18g (0.2mmol) of Pd ₂ dba ₃ , 0.4ml (0.4mmol) of 1M t-Bu ₃ P, and 2.88g (30mmol) of t-BuONa were added, respectively, and then refluxed for 8 hours.

When the reaction is completed, the temperature of the reactant is cooled to room temperature, extracted using 200 ml of toluene and 200 ml of H ₂ O, a small amount of water in the organic layer is removed with anhydrous MgSO ₄ , and after filtration under reduced pressure, the organic solvent is concentrated, and the resulting compound is Hex. : EA = 3: 1 column was used to obtain 3.98 g (72%) of Intermediate-40.

Intermediate-40 MS(FAB): 552(M ⁺ )

<Synthesis of Intermediate-41>

Under nitrogen, 0.93 g (10 mmol) of aniline and 3.56 g (10 mmol) of 4-iodo-1,1':4',1''-terphenyl were injected and dissolved in 50 ml of toluene, and then 0.18 g (0.2 g) of Pd ₂ dba ₃ mmol), 0.4 ml (0.4 mmol) of 1M t-Bu ₃ P, and 2.88 g (30 mmol) of t-BuONa were added, respectively, and then refluxed for 8 hours.

When the reaction is completed, the temperature of the reactant is cooled to room temperature, extracted using 200 ml of toluene and 200 ml of H ₂ O, a small amount of water in the organic layer is removed with anhydrous MgSO ₄ , and after filtration under reduced pressure, the organic solvent is concentrated, and the resulting compound is Hex. : EA = 5: 1 column was used to obtain 2.38 g (74%) of intermediate-41.

Intermediate-41 MS(FAB): 321(M ⁺ )

<Synthesis of Intermediate-42>

Under nitrogen, 0.93 g (10 mmol) of aniline and 2.80 g (10 mmol) of 4-iodo-1,1'-biphenyl were injected and dissolved in 50 ml of toluene, followed by 0.18 g (0.2 mmol) of Pd ₂ dba ₃ and 1M t-Bu. _3P 0.4ml (0.4mmol) and t-BuONa 2.88g (30mmol) were added, respectively, and then refluxed for 8 hours.

When the reaction is completed, the temperature of the reactant is cooled to room temperature, extracted using 200 ml of toluene and 200 ml of H ₂ O, a small amount of water in the organic layer is removed with anhydrous MgSO ₄ , and after filtration under reduced pressure, the organic solvent is concentrated, and the resulting compound is Hex. : EA = 5: 1 column was used to obtain 1.99 g (81%) of Intermediate-42.

Intermediate-42 MS(FAB): 245(M ⁺ )

<Synthesis of Intermediate-43>

Under nitrogen, 2.45 g (10 mmol) of intermediate-42 and 3.59 g (10 mmol) of 4-bromo-4'-iodo-1,1'-biphenyl were injected and dissolved in 60 ml of toluene, and then 0.18 g of Pd ₂ dba ₃ ( 0.2 mmol), 0.4 ml (0.4 mmol) of 1M t-Bu ₃ P, and 2.88 g (30 mmol) of t-BuONa were added, respectively, and then refluxed for 8 hours.

When the reaction is completed, the temperature of the reactant is cooled to room temperature, extracted using 200 ml of toluene and 200 ml of H ₂ O, a small amount of water in the organic layer is removed with anhydrous MgSO ₄ , and after filtration under reduced pressure, the organic solvent is concentrated, and the resulting compound is Hex. : EA = 4: 1 column was used to obtain 3.57 g (75%) of intermediate-43.

Intermediate-43 MS(FAB): 476(M ⁺ )

<Synthesis of Compound 157>

Under nitrogen, 5.53 g (10 mmol) of intermediate-40 and 3.98 g (10 mmol) of intermediate-39 were injected and dissolved in 80 ml of toluene, followed by 0.18 g (0.2 mmol) of Pd ₂ dba ₃ and 0.4 ml (0.4 mmol) of 1M t-Bu ₃ P. ), 2.88 g (30 mmol) of t-BuONa were added respectively, and then refluxed for 8 hours.

When the reaction is completed, the temperature of the reactant is cooled to room temperature, extracted using 250 ml of toluene and 250 ml of H ₂ O, a small amount of water in the organic layer is removed with anhydrous MgSO ₄ , and after filtration under reduced pressure, the organic solvent is concentrated, and the resulting compound is filtered through Hex. : EA = 3: 1 column was used to obtain 6.69 g (77%) of Compound-157.

Compound-157 MS(FAB): 869(M ⁺ )

<Synthesis of Compound 159>

Under nitrogen, 5.53 g (10 mmol) of intermediate-40 and 3.21 g (10 mmol) of intermediate-41 were injected and dissolved in 70 ml of toluene, followed by 0.18 g (0.2 mmol) of Pd ₂ dba ₃ and 0.4 ml (0.4 mmol) of 1M t-Bu ₃ P. ), 2.88 g (30 mmol) of t-BuONa were added respectively, and then refluxed for 8 hours.

When the reaction is completed, the temperature of the reactant is cooled to room temperature, extracted using 250 ml of toluene and 250 ml of H ₂ O, a small amount of water in the organic layer is removed with anhydrous MgSO ₄ , and after filtration under reduced pressure, the organic solvent is concentrated, and the resulting compound is filtered through Hex. : EA = 3: 1 column was used to obtain 5.95 g (75%) of Compound-159.

Compound-159 MS(FAB): 793(M ⁺ )

<Synthesis of Compound-168>

Under nitrogen, 4.76 g (10 mmol) of intermediate-43 and 3.21 g (10 mmol) of intermediate-41 were injected and dissolved in 60 ml of toluene, followed by 0.18 g (0.2 mmol) of Pd ₂ dba ₃ and 0.4 ml (0.4 mmol) of 1M t-Bu ₃ P. ), 2.88 g (30 mmol) of t-BuONa were added respectively, and then refluxed for 8 hours.

When the reaction is completed, the temperature of the reactant is cooled to room temperature, extracted using 200 ml of toluene and 200 ml of H ₂ O, a small amount of water in the organic layer is removed with anhydrous MgSO ₄ , and after filtration under reduced pressure, the organic solvent is concentrated, and the resulting compound is Hex. : EA = 4: 1 column was used to obtain 5.59 g (78%) of Compound-168.

Compound-168 MS(FAB): 716(M ⁺ )

The compound of Formula 2 is a known compound, and its synthesis method may be performed using a method disclosed in a known literature.

Hereinafter, the present invention will be described in more detail through examples and experimental examples of organic electroluminescent devices. Since these examples and experimental examples are only for illustrating the present invention, the scope of the present invention is not limited to these examples and experimental examples.

<Manufacture of organic electroluminescent devices>

Example 1

An anode was formed with ITO on the substrate with a reflective layer, and the surface was treated with N ₂ plasma or UV-Ozone. On top of this, HAT-CN was deposited to a thickness of 10 nm as a hole injection layer (HIL). Next, NPD was deposited to a thickness of 120 nm as a hole transport layer (HTL). On the hole transport layer, 9,10-bis(2-naphthyl)anthracene (ADN), which can form blue EML, was deposited at 25 nm as a light emitting layer (EML), and about 5% of Compound 1 as the compound of Formula 1 of the present invention as a dopant. It was doped by about %. An electron transport layer (ETL) was deposited to a thickness of 30 nm by mixing anthracene derivative and LiQ in a 1:1 ratio, and LiQ was deposited to a thickness of 10 nm as an electron injection layer (EIL) on top of this. Afterwards, a 9:1 mixture of magnesium and silver (Ag) was deposited to a thickness of 15 nm as a cathode, and N4,N4′-bis[4-[bis(3-methylphenyl) was deposited on the cathode as a capping layer. Amino]phenyl]-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (DNTPD) was deposited to a thickness of 65 nm. An organic electroluminescent device was manufactured by attaching a seal cap containing a moisture absorbent to the top using a UV curing adhesive to protect the organic electroluminescent device from O ₂ or moisture in the atmosphere.

Examples 2 to 15

In Example 1, instead of compound 1 of formula 1 as the dopant of blue EML, compounds 8, 11, 13, 25, 37, 49, 54, 61, 73, 75, 87, 100, 114, and 123 of formula 1 were used, respectively. Organic electroluminescent devices of Examples 2 to 15 were manufactured in the same manner as Example 1, except that the compound was used.

Example 16

An anode was formed with ITO on the substrate with a reflective layer, and the surface was treated with N ₂ plasma or UV-Ozone. On top of this, HAT-CN was deposited to a thickness of 10 nm as a hole injection layer (HIL). Next, Compound 157 as the compound of Chemical Formula 2 was deposited to a thickness of 120 nm as a hole transport layer (HTL). On the hole transport layer, 9,10-bis(2-naphthyl)anthracene (ADN), which can form blue EML, was deposited at 25 nm as a light emitting layer (EML), and about 5% of Compound 1 as the compound of Formula 1 of the present invention as a dopant. It was doped by about %. An electron transport layer (ETL) was deposited to a thickness of 30 nm by mixing anthracene derivative and LiQ in a 1:1 ratio, and LiQ was deposited to a thickness of 10 nm as an electron injection layer (EIL) on top of this. Afterwards, a 9:1 mixture of magnesium and silver (Ag) was deposited to a thickness of 15 nm as a cathode, and N4,N4'-bis[4-[bis(3-methylphenyl) was deposited on the cathode as a capping layer. Amino]phenyl]-N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (DNTPD) was deposited to a thickness of 65 nm. An organic electroluminescent device was manufactured by attaching a seal cap containing a moisture absorbent to the top using a UV curing adhesive to protect the organic electroluminescent device from O ₂ or moisture in the atmosphere.

Examples 17 to 30

In Example 8, instead of compound 1 of formula 1 as the dopant of blue EML, compounds 8, 11, 13, 25, 37, 49, 54, 61, 73, 75, 87, 100, 114, and 123 of formula 1 were used, respectively. Organic electroluminescent devices of Examples 17 to 30 were manufactured in the same manner as Example 16, except that the compound was used.

Example 31

An anode was formed with ITO on the substrate with a reflective layer, and the surface was treated with N ₂ plasma or UV-Ozone. On top of this, HAT-CN was deposited to a thickness of 10 nm as a hole injection layer (HIL). Next, Compound 159, a compound of Chemical Formula 2, was deposited to a thickness of 120 nm as a hole transport layer (HTL). On the hole transport layer, 9,10-bis(2-naphthyl)anthracene (ADN), which can form blue EML, was deposited at 25 nm as a light emitting layer (EML), and about 5% of Compound 1 as the compound of Formula 1 of the present invention as a dopant. It was doped by about %. An electron transport layer (ETL) was deposited to a thickness of 30 nm by mixing anthracene derivative and LiQ in a 1:1 ratio, and LiQ was deposited to a thickness of 10 nm as an electron injection layer (EIL) on top of this. Afterwards, a 9:1 mixture of magnesium and silver (Ag) was deposited to a thickness of 15 nm as a cathode, and N4,N4′-bis[4-[bis(3-methylphenyl) was deposited on the cathode as a capping layer. Amino]phenyl]-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (DNTPD) was deposited to a thickness of 65 nm. An organic electroluminescent device was manufactured by attaching a seal cap containing a moisture absorbent to the top using a UV curing adhesive to protect the organic electroluminescent device from O ₂ or moisture in the atmosphere.

Example 32

An anode was formed with ITO on the substrate with a reflective layer, and the surface was treated with N ₂ plasma or UV-Ozone. On top of this, HAT-CN was deposited to a thickness of 10 nm as a hole injection layer (HIL). Next, Compound 168 as a compound of Chemical Formula 2 was deposited to a thickness of 120 nm as a hole transport layer (HTL). On the hole transport layer, 9,10-bis(2-naphthyl)anthracene (ADN), which can form blue EML, was deposited at 25 nm as a light emitting layer (EML), and about 5% of Compound 1 as the compound of Formula 1 of the present invention as a dopant. It was doped by about %. An electron transport layer (ETL) was deposited to a thickness of 30 nm by mixing anthracene derivative and LiQ in a 1:1 ratio, and LiQ was deposited to a thickness of 10 nm as an electron injection layer (EIL) on top of this. Afterwards, a 9:1 mixture of magnesium and silver (Ag) was deposited to a thickness of 15 nm as a cathode, and N4,N4′-bis[4-[bis(3-methylphenyl) was deposited on the cathode as a capping layer. Amino]phenyl]-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (DNTPD) was deposited to a thickness of 65 nm. An organic electroluminescent device was manufactured by attaching a seal cap containing a moisture absorbent to the top using a UV curing adhesive to protect the organic electroluminescent device from O ₂ or moisture in the atmosphere.

Examples 33 to 40

Example 31 and Example 31, except that compounds of Chemical Formulas 134, 138, 140, 142, 144, 149, 153, and 156 of Chemical Formula 1 were used instead of Compound 1 of Chemical Formula 1 as the dopant of blue EML. Organic electroluminescent devices of Examples 33 to 40 were manufactured in the same manner.

Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that 2,5,8,11-Tetra-butyl-Perylene (t-Bu-Perylene) was used as a dopant of blue EML as an emitting layer (EML). Manufactured.

Comparative Example 2

An organic electroluminescent device was manufactured in the same manner as in Example 16 except that 2,5,8,11-Tetra-butyl-Perylene (t-Bu-Perylene) was used as a dopant of blue EML as an emitting layer (EML). Manufactured.

Comparative Example 3

An organic electroluminescent device was manufactured in the same manner as in Example 31 except that 2,5,8,11-Tetra-butyl-Perylene (t-Bu-Perylene) was used as a dopant of blue EML as an emitting layer (EML). Manufactured.

The compounds used in Examples 1 to 40 and Comparative Examples 1, 2, and 3 are shown below.

Test example: Evaluation of characteristics of organic electroluminescent devices

1. Evaluation of properties of organic electroluminescent devices of Examples 1 to 15 and Comparative Example 1

The characteristics of the organic electroluminescent devices manufactured in Examples 1 to 15 and Comparative Example 1 were measured at a current density of 10 mA/cm ² , and the results are shown in Table 1 below.

Voltage
(V) Efficiency
(Cd/A) CIE_x CIE_y T ₉₅ (hr) Example 1 4.0 6.2 0.136 0.057 152 Example 2 3.6 5.9 0.135 0.059 161 Example 3 3.8 6.3 0.138 0.055 158 Example 4 3.7 5.8 0.137 0.056 166 Example 5 3.8 5.9 0.137 0.056 160 Example 6 3.6 6.1 0.136 0.058 174 Example 7 4.1 6.3 0.137 0.054 155 Example 8 4.2 6.4 0.136 0.057 161 Example 9 4.0 6.1 0.135 0.056 156 Example 10 3.6 5.9 0.136 0.058 170 Example 11 3.8 5.5 0.136 0.058 164 Example 12 3.7 5.9 0.135 0.057 168 Example 13 3.8 5.8 0.135 0.058 166 Example 14 3.9 5.9 0.135 0.058 162 Example 15 3.6 5.8 0.136 0.057 172 Comparative Example 1 4.8 4.2 0.135 0.063 94

As a result of the above experiment, the organic electroluminescent devices of Examples 1 to 15, which included the organic compound of Formula 1 of the present invention as a dopant in the light emitting layer, showed improved results in efficiency and voltage characteristics compared to the conventional organic electroluminescent device of Comparative Example 1. It seemed.

In addition, as a result of measuring the afterimage lifespan ( _T95 ), it was confirmed that the organic electroluminescent device of Comparative Example 1 had a lifespan of less than 100 hours, while Examples 1 to 15 had a long lifespan of more than 150 hours. In particular, the organic electroluminescent devices of Examples 6, 10, and 15 were confirmed to have a long lifespan of more than 170 hours.

Therefore, it can be seen that the organic electroluminescent device containing the organic compound of Formula 1 of the present invention as a dopant in the light-emitting layer has excellent efficiency, voltage, and lifespan characteristics.

2. Evaluation of properties of organic electroluminescent devices of Examples 16 to 30 and Comparative Example 2

The characteristics of the organic electroluminescent devices manufactured in Examples 16 to 30 and Comparative Example 2 were measured at a current density of 10 mA/cm ² , and the results are shown in Table 2 below.

Voltage
(V) Efficiency
(Cd/A) CIE_x CIE_y T ₉₅ (hr) Example 16 3.9 6.3 0.136 0.057 168 Example 17 3.5 6.0 0.135 0.059 176 Example 18 3.6 6.3 0.138 0.055 172 Example 19 3.7 5.9 0.138 0.055 179 Example 20 3.6 6.0 0.137 0.056 176 Example 21 3.5 6.2 0.136 0.058 188 Example 22 3.8 6.5 0.137 0.054 174 Example 23 3.9 6.6 0.136 0.057 178 Example 24 3.9 6.3 0.135 0.056 175 Example 25 3.5 6.0 0.136 0.058 186 Example 26 3.7 5.7 0.136 0.058 179 Example 27 3.6 6.0 0.136 0.057 184 Example 28 3.6 5.9 0.135 0.058 179 Example 29 3.8 6.1 0.135 0.058 177 Example 30 3.6 6.0 0.137 0.057 189 Comparative Example 2 4.6 4.3 0.135 0.063 98

As a result of the above experiment, the organic electroluminescent devices of Examples 16 to 30 in which the compounds of Formula 1 and Formula 2 of the present invention were used in the light-emitting layer and the hole transport layer were improved in efficiency and voltage characteristics compared to the conventional organic electroluminescent device of Comparative Example 2. Significantly improved results were seen. In particular, the organic electroluminescent devices of Examples 18 and 21 showed significantly improved voltage characteristics and luminous efficiency.

In addition, as a result of measuring the afterimage lifespan ( _T95 ), it was confirmed that the organic electroluminescent device of Comparative Example 2 had a lifespan of less than 100 hours, while Examples 16 to 30 had a long lifespan of more than 160 hours. In particular, the organic electroluminescent devices of Examples 21, 25, 27, and 30 were confirmed to have a long lifespan of more than 180 hours.

Therefore, it can be seen that the organic electroluminescent device of the present invention containing the organic compound of Formula 1 as a dopant in the light-emitting layer and the compound of Formula 2 in the hole transport layer has significantly superior efficiency, voltage, and lifespan characteristics compared to the conventional technology. there is.

3. Evaluation of properties of organic electroluminescent devices of Examples 1, 16, 31, 32 and Comparative Examples 1 and 2

The characteristics of the organic electroluminescent devices manufactured in Examples 1, 16, 31, and 32 and Comparative Examples 1 and 2 were measured at a current density of 10 mA/cm ² , and the results are shown in Table 3 below.

Voltage
(V) Efficiency
(Cd/A) CIE_x CIE_y T ₉₅ (hr) Example 1 4.0 6.2 0.136 0.057 152 Example 16 3.9 6.3 0.136 0.057 168 Example 31 3.7 6.5 0.135 0.057 181 Example 32 3.7 6.3 0.136 0.058 186 Comparative Example 1 4.8 4.2 0.135 0.063 94 Comparative Example 2 4.6 4.3 0.135 0.063 98

As a result of the above experiment, the organic electroluminescent devices of Examples 16, 31, and 32 in which the compounds of Formula 1 and Formula 2 of the present invention were used in the light-emitting layer and the hole transport layer, as well as Comparative Examples 1 and 2, were the organic compounds of Formula 1 of the present invention. Compared to Example 1, which included in the light emitting layer as a dopant, it showed significantly superior voltage characteristics, luminous efficiency, and lifespan characteristics. These results are also clearly confirmed through comparison between Example 2 and Example 17, Example 3 and Example 18, Example 4 and Example 19, and Example 5 and Example 20.

4. Evaluation of properties of organic electroluminescent devices of Examples 33 to 40 and Comparative Example 3

The characteristics of the organic electroluminescent devices manufactured in Examples 33 to 40 and Comparative Example 3 were measured at a current density of 10 mA/cm ² , and the results are shown in Table 4 below.

Voltage
(V) Efficiency
(Cd/A) CIE_x CIE_y T ₉₅ (hr) Example 33 3.6 6.4 0.138 0.050 195 Example 34 3.7 6.7 0.139 0.048 183 Example 35 3.6 6.3 0.138 0.050 180 Example 36 3.7 6.6 0.138 0.051 218 Example 37 3.6 6.4 0.136 0.051 194 Example 38 3.7 6.5 0.137 0.052 189 Example 39 3.8 6.3 0.137 0.056 205 Example 40 3.9 6.7 0.136 0.057 201 Comparative Example 3 4.3 4.4 0.135 0.062 99

As a result of the above experiment, the organic electroluminescent devices of Examples 33 to 40 in which the compounds of Formula 1 and Formula 2 of the present invention were used in the light-emitting layer and the hole transport layer were improved in efficiency and voltage characteristics compared to the conventional organic electroluminescent device of Comparative Example 3. Significantly improved results were seen. In particular, the organic electroluminescent devices of Examples 34 and 40 showed significantly improved voltage characteristics and luminous efficiency.

In addition, as a result of measuring the afterimage lifespan ( _T95 ), it was confirmed that the organic electroluminescent device of Comparative Example 3 had a lifespan of less than 100 hours, while those of Examples 33 to 40 had a long lifespan of more than 180 hours. In particular, the organic electroluminescent devices of Examples 36, 39, and 40 were confirmed to have a long lifespan of more than 200 hours.

In addition, as a result of measuring the color coordinates, it was confirmed that Examples 34 to 38 had a deeper blue color compared to the organic electroluminescent device of Comparative Example 3, especially Examples 33, 34, and The organic electroluminescent device of 35 was confirmed to have a deeper blue color.

Therefore, it can be seen that the organic electroluminescent device of the present invention containing the organic compound of Formula 1 as a dopant in the light-emitting layer and the compound of Formula 2 in the hole transport layer has significantly superior efficiency, voltage, and lifespan characteristics compared to the conventional technology. there is.

The above results can be seen as being obtained by using the compound of formula 2, which responds well to the dopant structure of the compound of formula 1, as a hole transport material.

In the case of a general organic light emitting device, as deterioration progresses at the interface between the hole transport layer and the light emitting layer, electrons diffuse into the hole transport layer through the interface, thereby accelerating the deterioration and reducing the lifespan of the organic light emitting device.

However, in the present invention, by using the compound of formula 2 as a hole transport material, the charge balance of the device is achieved and excitons are prevented from moving within the light-emitting layer, thereby improving the efficiency of the organic electroluminescent device. In addition, the compound of Formula 2 appears to have increased the lifespan of the organic electroluminescent device by preventing overall deterioration by preventing excitons from diffusing into the hole transport layer.

Claims (6)

Organic compounds represented by the following formula (1):
[Formula 1]

In the above equation
Ar1, Ar2, Ar3 and Ar4 are each independently selected from deuterium, CN, straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl , biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, It is an aromatic hydrocarbon group having 6 to 60 carbon atoms that is substituted or unsubstituted with one or more selected from the group consisting of pyrazinyl, pyrimidinyl, and quinolinyl groups, or
Deuterium, CN, straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, phenyl group. Substituted anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group , and a quinolinyl group. It is a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms, which is substituted or unsubstituted with one or more elements selected from the group consisting of S, O, N, and Si,
B1 and B2 are each independently selected from straight-chain or branched alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthra Cenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and It is an aromatic hydrocarbon group having 6 to 60 carbon atoms that is substituted or unsubstituted with one or more selected from the group consisting of quinolinyl groups,
n and m are each independently 0 and 1,
R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen, deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , and have 1 to 40 carbon atoms. straight-chain or branched-chain alkyl, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, or cycloalkyl group with 3 to 40 carbon atoms,
F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, carbon number 3 to 40 cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, It is an aromatic hydrocarbon group having 6 to 60 carbon atoms that is substituted or unsubstituted with one or more selected from the group consisting of pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group, or
F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, carbon number 3 to 40 cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[fluorene], carbazolyl, Substituted or unsubstituted with one or more selected from the group consisting of dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group, and from the group consisting of S, O, N, and Si It is a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more selected elements, or
F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, and Phenyl, biphenyl, naphthyl, anthracenyl, substituted or unsubstituted with one or more types selected from the group consisting of cycloalkyl groups having 3 to 40 carbon atoms, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9 -It is an amino group substituted with one or more types selected from the group consisting of dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups. In claim 1,
The organic compound is any one of the following compounds 1 to 156.



















































In an organic electroluminescent device in which an organic thin film layer consisting of one or multiple layers including at least a light-emitting layer is laminated between the cathode and the anode,
An organic electroluminescent device characterized in that the light-emitting layer contains the organic compound of claim 1 alone or in a combination of two or more types. According to claim 3,
The organic thin film layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer,
The hole transport layer is an organic electroluminescent device characterized in that it contains one type of organic compound of the following formula (2) alone or in a combination of two or more types:
[Formula 2]

In the above equation,
R1, R2, R3 and R4 are each independently hydrogen; A straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms; Aromatic hydrocarbon having 6 to 60 carbon atoms substituted or unsubstituted with one or more selected from the group consisting of C1 to C10 straight or branched alkyl, C1 to C10 alkoxy, halogen, CN, CF ₃ and Si(CH ₃ ) ₃ group energy; or substituted or unsubstituted with one or more selected from the group consisting of C1~C10 straight or branched alkyl, C1~C10 alkoxy, halogen, CN, CF ₃ and Si(CH ₃ ) ₃ groups, S, O, N and a heteroaromatic hydrocarbon group having 5 to 60 carbon atoms containing at least one element selected from the group consisting of Si;
R1, R2, R3, and R4 may each independently combine with the phenyl group of the basic structure to form an aromatic hydrocarbon or heteroaromatic hydrocarbon. In claim 4,
R1, R2, R3 and R4 are each independently a phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl carbazole or pyrenyl group,
An organic electroluminescent device wherein R1, R2, R3, and R4 are each independently combined with a phenyl group of the basic structure to form naphthalene, anthracene, or phenanthrene. In claim 4,
The organic compound is characterized in that it is any one of the following compounds 157 to 168: